PVC FACT BOOK - VEC · 2018-01-17 · Four years have passed since the publication of the first PVC...

PVC FACT BOOK2008 Edition

VINYL ENVIRONMENTAL COUNCIL (VEC)

Four years have passed since the publication of the first PVC Fact Book. The handbook was intended to improve the public understanding of PVC, in particular, the environmental advantages of PVC, and to clear misunderstandings about the relation between PVC and dioxins, and furthermore, to promote the use of PVC.

We are encouraged to see that many have visited our website and have appreciated the PVC Fact Book. We hope that the revised handbook helps you to know PVC better and to give you clearer ideas on how PVC can effectively contribute to sustainable development.

August 2008Shigetaka Seki, Executive Director

Vinyl Environmental Council

The 2008 Edition of the PVC Fact Book

The origin of the Vinyl Environmental Council goes back to the PVC Association of Japan which was established in 1953. Along with the development of the Japanese PVC industry, last year marked our organization’s 50th anniversary.

Cumulative production of PVC in the past 50 years is estimated to be 64 million tons in Japan. Not only did the Japanese PVC industry contribute significantly to the lives of citizens and the development of the national economy, but also, along with the internationalization of the economy, had a significant effect on the economical development abroad, including Asia and surrounding countries.

Within such historical background, the serviceability of PVC and its converted products is widely known today throughout the world. However, in recent years, issues have arisen regarding appropriate treatment after use of PVC and safety of chemical substances used as additives in PVC. There is an increasing need for us to share a broad range of information both domestic and abroad.

Our organization published the "PVC Fact Book" last year as a public relations material based on facts and data, which was prepared to serve as a tool for communication towards society. Based on it, we created this English version for international communication.

May this brochure be of some use to readers upon acquiring knowledge and understanding of PVC and its related industries.

Foreword

August 2004Shigeaki Nakahara,

Chairman*Vinyl Environmental

Publication of the English Version of the "PVC Fact Book"

* as of 2004

Foreword

The history of the Japanese PVC industry began in 1941, which is 63 years ago, when Nippon Chisso Hiryo K.K. industrialized production of PVC by acetylene synthesis method. From then on, production and consumption increased along with the rise of the Japanese industries and economy. Since PVC is superior in convertibility and durability among general purpose plastics, domestic production marked 2.6 million tons in 1997.

However, due to increasing consumer consciousness on the environment and safety, the issue of dioxins generation from waste incineration had drawn attention within Japan during the latter half of the 90s. There had been excessive attention towards PVC as a chlorine source upon dioxins generation. Also, plasticizers added to PVC were among the center of focus regarding the endocrine disrupting substances debate.

In the past, there had been incinerators in Japan that generated excessive amounts of dioxins due to lack of appropriate incineration control. During that time, there had been no efficient regulations to cut back dioxins generation. Furthermore, there were no scientific evaluations regarding the effect of plasticizers on the endocrine system, all of which resulted in the inclination towards PVC avoidance among consumers and switch towards other resins. Ultimately, the domestic demand for PVC declined.

The Law Concerning Special Measures against Dioxins was enacted thereafter, and a limit was set to the level of dioxins generations at incinerators accordingly. The Ministry of Environment announced last year that dioxins emission at the end of fiscal 2002 was predicted to be cut down to below 10% as compared with the level in 1997. As for the alleged endocrine disruptive effect of plasticizers on the ecosystem, which was initially a concern among the public, tests were conducted and no apparent endocrine disrupting effects were proven.

At the same time, the “Reduce, Reuse and Recycle” scheme had been promoted from the standpoint of effective use of resources and cutting back of environmental burdens. Recycling laws related to packaging, household electrical appliances, automobiles and construction materials have been laid down. There has been an increasing expectation for plastics recycling. Also, in line with the promotion of measures against global warming based on the Kyoto Protocol, there is an increasing trend towards adopting PVC window profiles with double glazing in order to boost thermal insulation in housing.

In this way, the climate has changed dramatically regarding the PVC situation in Japan. In order for the industry to develop in harmony with the environment and citizen’s health, it is essential for us to gain understanding from the PVC user industries, consumers and the media, about the status of PVC - it is crucial for us to share accurate information with the public. It is also increasingly important for us to share such information not only within Japan but internationally, and to put such information to use.

In this brochure we included the basic information regarding PVC in Japan. We sincerely hope that users of PVC, as well as those who have interest in PVC, would further gain a deeper understanding for this versatile material.

August 2004Tetsuo Nishide,

Executive Director*Vinyl Environmental Council

Our Strive Towards Gaining a Deeper Understanding of PVC

* as of 2004

TABLE OF CONTENTS

(1) Linkage of PVC related industries(2) Production process of raw material for PVC (VCM)(3) PVC production processes(4) PVC as petrochemical product(5) PVC as chlorine product

(1) Chemical stability(2) Mechanical stability(3) Processability and moldability(4) Others (versatility in designing through compounding)

(1) Production safety(2) Safety upon use(3) Evaluation of carcinogenicity(4) Residual monomers in PVC

(1) The Japanese Industrial Standard (JIS) for PVC(2) JIS for PVC products(3) Applications of PVC (PVC products)

1. What is PVC?2. Production of PVC

3. Characteristics of PVC

4. Safety of PVC

5. JIS and PVC Applications

(1) Role of plasticizers(2) Type of plasticizers (3) Safety of plasticizers(4) Regulation of plasticizers used for some PVC products by revision of the Food Sanitation Law (Public Notification No.267 by the MHLW, August 2, 2002)

(1) Role of stabilizers (2) Types of Stabilizers(3) Hazard data of compounds used in stabilizers(4) Stabilizer by applications(5) Demand trends in PVC stabilizers

1. Safety of Plasticizers

2. Safety of Stabilizers

(1) LCI data for PVC(2) LCI data for PVC products(3) LCI data for mechanical recycling

(1) PVC and PVC products(2) Characteristics of PVC products(3) Advantages and disadvantages of PVC products(4) Physical properties of PVC products(5) Property modification of PVC products

1. Effect of PVC and PVC Products on the Global Environment　 2. LCA for PVC and PVC Products

3. Characteristics and Property Modification of PVC

(1) Initial phase (1937~1951)(2) Development phase (1952~1965)(3) Boom phase (1966~1974)(4) Structural reform phase (1975~1990)(5) Restructuring and counter-environmental issues phase (1991~2003)(6) Our stride towards future developments

1. Brief History of the Japanese PVC Industry through Production Volume

2. PVC Related Data

(1) Actual condition of dioxins emissions to the environment(2) Dioxins generation from incineration and control measures(3) Regulations set by the "Law Concerning Special Measures against Dioxins" (The Dioxin Law)(4) Total emission of dioxins(5) Dioxin levels in the environment(6) Dioxins emission from vinyl chloride monomer (VCM) manufacturing facilities(7) The toxicity of dioxins

(1) Brief history of the endocrine disrupter issue(2) What are "endocrine disrupters"?(3) Actions taken by the Japanese government(4) Results of assessment for endocrine disruptive effects

(1) What is the sick house syndrome?(2) Possible causes behind the sick house syndrome(3) Governmental actions(4) Guideline values for indoor concentration of chemical substances(5) Facts from results of survey for indoor concentration of DEHP

(1) Establishment of measures against exhaust gases(2) Major causes of acid rain

2

34567

9111112

12121314

151516

2224

2425252526

27272829

3030303132

333334

1. Dioxins Issues

2. Endocrine Disrupter Issues

3. Sick House Syndrome Issues

4. Hydrogen Chloride from Incineration

5. Impacts on the PVC Industry

CHAPTER 1: INTRODUCTION TO POLYVINYL CHLORIDE

CHAPTER 2: ENVIRONMENTAL ISSUES AND CURRENT STATUS OF PVC AND PVC PRODUCTS　

CHAPTER 4: THE SAFETY OF ADDITIVES

CHAPTER 5: SERVICEABILITY OF PVC AND PVC PRODUCTS

CHAPTER 6: BRIEF HISTORY AND DATA REGARDING THE JAPANESE PVC INDUSTRY

OUTLINE OF THE VINYL ENVIRONMENTAL COUNCIL

CHAPTER 3: ENVIRONMENTAL ACTIVITIES BY THE PVC INDUSTRY

(1) Pollutant Release and Transfer Register (PRTR) in the PVC industry(2) Dioxins emissions from VCM production facilities

(1) Status and activities(2) Mechanical recycling(3) Feedstock recycling(4) Recycling under new technologies

(1) Recycling "PVC construction material wastes" generated from the western Tottori prefecture earthquake(2) Recycling of "PVC construction material wastes" recovered from demolition sites of residential buildings owned by the Tokyo Metropolitan Government (TMG): an example of public-private sector cooperation(3) Recycling of PVC profiles(4) Recycling of PVC flooring(5) Recycling of PVC wallcoverings(6) Recycling of refrigerator door gaskets

525253

56

5656575758

60

626366

6767686976

80808282838485

91

3839

40404243

44

454647484949

1. Responsible Care

2. Recycling of PVC Products

3. Constructing Social Systems

4. PVC Products and Recycling Related Laws

CHAPTER 1: INTRODUCTION TO POLYVINYL CHLORIDE

Polyvinyl chloride (PVC) was first manufactured in Germany in 1931 as a robust and lightweight new plastic. This breakthrough material was brought about to substitute for metals, glass, wood, natural fibers, papers and fabrics. Over 30 million tons of PVC is used around the globe today, both in industrialized and developing countries, due to its cost efficiency, durability, self-extinguishing properties, processability, and resources saving features.

Owing to its safe, healthy, convenient and aesthetical advantages, PVC products support daily life in a wide variety of fields including urban infrastructures, electronic products, and consumer goods.

For example, PVC can be found in public lifelines such as water supply, sewage pipes, or power lines. It is also used in building materials such as sidings, furniture, spouts, window profiles, flooring, decking boards, and roofing sheets. Agricultural and industrial applications include green house sheets, semi-conductor cleansing facilities, exhaust ducts, and parts for automobile and home electrical appliances. Consumer products include food wraps, synthetic leather and stationery. As you can see, PVC, or polyvinyl chloride/vinyl chloride resin, is a raw material used in a vast range of applications.

General information on PVC is provided here in Chapter 1, followed by introductions on four aspects of PVC; production, characteristics, safety and applications.

Thermosetting resin

Fig.1-1 Synthetic resin and their raw materials

Source: "Dictionary of plastics in use", Industrial Research Center of Japan, Inc. Production Goods Work Station (1993)

Thermoplastic resin

Raw material (monomers)Vinyl chloride monomer (Vinyl chloride: VCM)

Ethylene

Propylene

Styrene monomer

Acrylonitrile/Butadiene/Styrene

Bisphenol A/Carbonyl chloride

Hexamethylenediamine/Adipic acid

Methyl methacrylic acid

Ethylene/Terephthalic acid

Phenol/Formaldehyde

Melamine/Formalin

Caprolactam/Hexamethylenediamine

Trienediisocyanate/Propylene glycol

Bisphenol A/Epichlorohydrin

Dimethylsiloxane 　　　　　

Maleic anhydride/Styrene monomer

Synthetic resin (polymers)Polyvinyl chloride (PVC)

Polyethylene (PE)

Polypropylene (PP)

Polystyrene (PS)

Acrylonitrile-Butadiene-Styrene Resin (ABS)

Polycarbonate (PC)

Polyamide resin (PA:Nylon)

Methacrylic resin (PMMA)

Polyethylene terephthalate (PET)

Phenol resin

Melamine resin

Polyamide resin (PA : Nylon)

Polyurethane (PU : Urethane resin)

Epoxy resin

Silicone resin (SI)

Unsaturated polyester resin (FRP)

2

CHAPTER 1 : INTRODUCTION TO POLYVINYL CHLORIDE

■ A thermoplastic resinPlastics are also called synthetic resins and are

broadly classified into two categories; thermosetting resins and thermoplastic resins(Fig.1-1). The thermosetting resins include phenol resin and melamine resin, which are thermally hardened and never soften again. Thermoplastic resins include PVC, polyethylene(PE), polystyrene(PS) and polypropylene(PP), which can be softened again by heating.　

Usually, thermoplastics are supplied in the form of pelletized material (compounds) with additives (anti-oxidants, etc.) already blended in it. However, PVC is supplied in powder form and long term storage is possible since the material is resistant to oxidizing and degradation. Various additives and pigments are added to PVC during the processing stage, and then molded and fabricated into PVC products.

PVC is better known as bineel (vinyl) in Japan. This is due to the fact that PVC products, in the form of films or sheets, were widely used among the public after World War II, and these products were simply called bineel. When these PVC products that are soft to the touch first landed Japan, where only rigid thermosetting resins had been known, they left a very strong impression among the population. This is how bineel mistakenly became a synonym for all soft films including polyethylene films.

■ A safe synthetic resin made from vinyl chloride monomers (VCM)

Most synthetic resins are made up from single molecule units, called monomers. Through a chemical

reaction known as polymerization, these single molecules are branched into long chains to form polymers (which are also called macromolecules). PVC is also a type of polymer made from VCM through polymerization (Fig.1-1).

Some monomers exist in the form of unstable gaseous chemical substances, and some of these may cause health hazards when in direct contact with humans. In these cases they are manufactured and processed under strict control for safety. On the other hand, polymers, which are manufactured from monomers through polymerization, are solid and chemically stable substances, therefore do not affect human health. VCM, which is the raw material for PVC, is a high-pressure gas that can pose risks on human health such as carcinogenicity, but PVC does not have such carcinogenicity.

As you can see, plastics possess completely different chemical properties before and after polymerization. Since names of these substances sound unfamiliar, misunderstandings tend to occur regarding their attributes and safety. Also due to the fact that the Japanese terms Enbi polymer (PVC) and Enbi monomer (VCM) are both frequently called Enbi, there has been further confusion in Japan.

One example of such confusion is an erroneous report made in Japan on February 2003, which ran "Carcinogenic Enbi (PVC) emissions into the air and soil" - this of course, is a serious misunderstanding.

■ Resource saving and fire resistant properties

Only 40% of PVC's composition is petroleum-

1. What is PVC?

2. Production of PVC

3

derived. PVC is less dependent on petroleum, which is a natural resource that may one day be depleted. Therefore PVC can be regarded as a natural resource saving plastic, in contrast to plastics such as PE, PP and PS, which are totally dependent on petroleum.

Also, PVC contains components derived from industrial grade salt. Thus, PVC is a fire resistant plastic with properties of chlorine containing substances. When PVC is set on fire, the flames go out as the fire source is removed due to its self-extinguishing properties.

■ One of four major plastics with the longest historyPlastics production in Japan for 2007 was

approximately 15 million tons, out of which 70% is represented by PE, PP, PVC and PS (Fig.1-2). PVC is a general purpose plastic with the longest history in industrial production both domestic and abroad.

Due to its low price, excellent durability and processability, PVC became widely used since around 1948 in commonplace consumer applications, such as air inflated toys including floats and beach balls, films and sheets such as raincoats, bags, containers, or synthetic leather in the form of shoes, hand bags and furniture surfaces. Around that time, PVC began to be used for electrical wire covering. Today, PVC is widely used within civil engineering and construction materials that require durability. Examples include drinking water and sewage pipes, optical fiber protective pipes, wallcovering, flooring, window profiles (PVC saches), and furniture.

■ Contributes to energy saving and reduces CO2 emissions

Production of PVC requires little energy due to

the manufacturing process of its raw material, VCM. According to the results of survey by the Plastic Waste Management Institute, PVC requires only about 70% of energy required for production of other plastics. This means less CO2 emissions occur from production processes, thus contributing to the prevention of global warming.

Furthermore, as PVC products have the required strength, durability, and low thermal conductivity, its heat-insulating efficiency is three times as high as that of metal such as aluminum when used as window profiles and siding boards. Therefore consumption of fossil fuels such as petroleum can be cut back, which contributes to further reduction of CO2 emissions.

(1) Linkage of PVC related industries

■ Upstream of the PVC industry (the basic petrochemical industry, the soda industry)※ Ethylene and chlorine are raw materials for PVC.

Therefore, industries positioned upstream of the PVC industry are the basic petrochemical industry, which supplies ethylene, and the soda industry, which supplies chlorine.

※ By thermal cracking of naphtha, the basic petrochemical industry manufactures ethylene and propylene, etc. Naphtha is mainly supplied from the petroleum refinery industry, which uses imported crude oil as raw material.

※ The soda industry produces caustic soda, chlorine

and hydrogen via electrolysis using industrial grade salt as main raw material.

■ The PVC industryThe PVC industry produces an intermediate raw

material called ethylene dichloride (EDC) using ethylene and chlorine, the former of which is supplied by the basic petrochemical industry and the latter being supplied by the soda industry. EDC is then thermally cracked to produce VCM. Finally, VCM is polymerized to produce PVC (Fig.1-3).

Naphtha :Crude oil is heated for refining at the refinery to obtain heavy oil, light oil, kerosene, gasoline, naphtha fractions, and LP gas. Naphtha is transferred to petrochemical plants, where ethylene, propylene, butylene etc. are obtained by thermal cracking.

22.1%30.0%

70.0%

21.1%12.0%

14.8%

100%

Fig.1-2 Production ratio of four major plastics (2007)

PE (total of HDPE and LDPE)

Total plastics 14.61

million tons

Other

PVC

PP

PS (including ABS and AS)

Total of fourmajor plastics

Source: "Yearbook of Chemical Industries Statistics 2007", METI

4


■ Downstream of the PVC industry (the PVC converter industry)

PVC is supplied downstream to the PVC converter industries, where various additives including stabilizers and plasticizers are blended, of which are then converted by extrusion molding and calendering. Resulting products are further fabricated into construction and civil work materials, agricultural and industrial materials, parts for the assembly industry,

and consumer products. The PVC industry and the PVC converter industry

are closely associated with each other, and in some cases, both are called the PVC industries collectively. According to a rough calculation of the industrial statistics for 1998, the number of businesses is 4,600; the number of employees is 72,000, and the shipped value amounts to ¥1.5 trillion, or 15% of the total shipment value of all plastics.

(2) Production process of raw material for PVC (VCM)

VCM is a high pressure gas with a molecular weight of 62.5 and boiling point of - 13.9℃ , therefore it is manufactured under strict quality and safety control.

There are two ways to manufacture VCM; the direct chlorination method and oxychlorination method. Under the direct chlorination method, ethylene (obtained from thermal cracking of naphtha) and chlorine (obtained from electrolysis of salt) reacts within a catalyst-containing reactor to form the intermediate material EDC. EDC is then thermally

cracked to yield VCM at a few hundred ℃ (① in Fig.1-4).

When the hydrogen chloride obtained as by-product from the above method reacts with ethylene in the presence of catalyst and air (or oxygen), EDC is obtained again. This is called the oxychlorination process (② in Fig.1-4). When EDC from the oxychlorination process is dehydrated and then thermally cracked (likewise with the EDC from the direct chlorination process), VCM is obtained.

These two methods are combined thus at the major VCM plants in Japan. Fig.1-5 is a flow chart of VCM manufacturing processes shown in Fig.1-4.

EDC PVC

Fig.1-4 VCM production method

②Oxychlorination

①Direct chlorination

Ethylene

Air (Oxygen)

Ethylene Chlorine

EDC

Hydrogen chloride Thermal cracking

Thermal cracking

Polymerization VCM

Source: Prepared from material by the Japan Petroleum Institute (JPI)

Fig.1-3 Linkage of PVC related industries

Naphtha NaphthaPetroleum

Petroleum refiningindustry

Sea water

Rock saltSalt industry

(Installation, Assembly, Consumption)

End user industry, Consumer

●Upstream

Basic petrochemical industry

EthyleneEthylene

(Electrolysis)

PVC industryIndustrialgrade salt

Industrialgrade salt

Caustic sodaChlorine

Soda industry

EDC VCM PVC PVCindustries

Chlorine

(Processing Fabrication)

PVCPVC productsPVC converter industry

●Downstream

5

(3) PVC production processes

Generally, the suspension polymerization process is adopted to manufacture PVC. First, the raw material VCM is pressurized and liquefied, and then fed into the polymerization reactor, which contains water and suspending agent in advance. Through high-speed agitation within the reactor, micro particles of VCM are obtained. Next, the initiator for polymerization is fed into the reactor, and PVC is produced by reaction under a few atmospheric pressures at 40 - 60℃.　 PVC obtained through suspension polymerization is

suspended in water as micro particles of 50~200 µm diameter (in slurry form). Therefore, slurry discharged from the polymerization reactor is dehydrated, dried and the particle size matched by screening to yield PVC in the form of white powder. The unreacted VCM is entirely recovered through the stripping process, and after refining, recycled as raw material for reuse in this process (Fig.1-6). Emulsion polymerization process and bulk polymerization process are also adopted.

Recovered VCM storage tank

RecoveredVCM

storage tank

VCM tank

Volumeter CatalystPolymerization reactor

Additives

Gasholder

Crude VCMstorage tank

VCM purification column

Vacuumpump

Compressor Purified water Stripping

Tank

Centrifuge

Slurry tank

Fluidized-bed dryer

Screen

PVC storage tank

PVC

Source: Prepared from material by the JPI

Fig.1-6 PVC polymerization process flow diagram

Fig.1-5 Process flow diagram for VCM

Chlorine

Ethylene

chlorination reactor Air

(oxygen)

Ethylene

Oxychlorinationreactor

Direct Caustic sodaQuench column

Caustic soda washing column

Decanter

Dehydrating column

Low boiling point fraction collection column

High boiling point fraction collection column

Recovery column

Cracking furnace

Quenchcolumn

Hydrochloric acid removalcolumn

Monomer recovery column

Caustic soda washing columnVCM

Source: Prepared from material by the JPI

6


(4) PVC as petrochemical product

■ A petrochemical product manufactured from ethylene

PVC is a petrochemical product, since its intermediate raw material, EDC, is manufactured from ethylene (Fig.1-7). 13% of all ethylene demand during 2001 was used for production of EDC (ethylene requirement breakdown). Almost all of EDC is used for PVC production in Japan, although a small portion is used for manufacturing of ethylenediamine, organic solvents and various pharmaceutical products.

Four major applications, i.e., low-density polyethylene (LDPE), high-density polyethylene (HDPE), EDC and styrene monomer (SM) comprise about 70% of all ethylene consumption (almost all styrene is used for PS).

■ PVC industry and petrochemical complexes The petroleum refining industry and the basic

232,153 thousand kl 7,739

3,8903,603 3,142 2,162

2,097

1,135

698754

3,533

1,749

125

547

727

230

58,403 thousand kl (25%)





966

537

261

734587

367

6,286

7,337

4,487

295

3,087

281

235

1,6551,024

16

961

270

520

743

12,888

295

418

1,254

Fig.1-8 Production flow of typical petrochemical complex (focus on ethylene derivatives 2007)

Crude oil

Gasoline

Naphtha

Kerosene

Light oil

Heavy oil

Chlorine

Caustic soda

Industrial grade salt

Ethylene

Ethylene oxide

Ethyl benzene

Acetaldehyde

EDC

Organic solvents

Propylene

Butadiene

Aromatics

Others

Unit: 1,000 tons/year

Ethylene glycol

Styrene monomer

Butanol

Ethyl acetate

Acetic acid Vinyl acetate

VCM PVC

Phenol

Octanol

Propylene oxide

Acrylonitrile

Benzene, Toluene, Xylene

Ethylenediamine PP

Phenolic resin

Phthalates*

*(for Plastcizers)

Acrylic fiber

Urethane foam

High purity terephthalic acid

Synthetic rubber

Polycarbonate

Polyester fiber

LDPE

HDPE

PET

PS

Acrylonitrile-Styrene

ABS

MBS

SBR

Polyvinyl acetate

Sources: Present Status of Petrochemical Industry: 2008 by the Japan Petrochemical Industry Association, Yearbook of Chemical Industries Statistics 2007 by the METI Guidebook for the Soda Industry by the JSIANOTE: 1. Imported naphtha of 26,873 thousand kl is not shown here. Total naphtha supply of 49,503 thousand kl is a sum of 22,630 thousand kl of domestic naphtha and imported naphtha. 2. Derivatives having two or more raw materials are shown against the major raw material. 3. Figures does not represent yields from each material substances.

LDPE

HDPE

1.95

1.25 EDC (PVC,

Ethylenediamine, others) 0.98

SM 0.85

Ethyl acetate 0.75

Others (Acetaldehyde, etc.)

1.58

Source: Prepared from chemical industry statistics by the Japan Petrochemical Industry Association, materials by the METI

Fig.1-7 Breakdown of ethylene applications (2001) (ethylene requirement)

Ethylenedemand

7.38(100%)

(13%)

(17%)

(27%) (21%)

(10%)

(12%)

Unit : Million tons

7

petrochemical industry in Japan are located at coastal areas, where there is easy access to imported natural resources such as crude oil, in the same way as energy industries such as the thermal power generation industry. They form petrochemical complexes, where refineries, ethylene centers and the petrochemical plants are connected by pipelines. Likewise, the soda industry is located together with petrochemical complexes in many cases, since it is preferable for large-sized soda plants to be at the coastal areas for easier access to imported salt and consumption of

caustic soda's by-product, chlorine.VCM plants, which use ethylene and chlorine as

major raw materials, and PVC plants, are generally located in the petrochemical complex due to this background. Fig.1-8 focuses on the flow of ethylene which is one of five types of products that are yielded by cracking of naphtha, and downstream on to the production of petrochemical products such as general-purpose plastics. Figures show the production volume in 2007.

(5) PVC as a chlorine product

■ Ratio of VCM within the total 　 chlorine demands

Ethylene and chlorine are the major raw materials for VCM. Therefore, VCM is affected by the supply-demand situations of both ethylene and chlorine, respectively. As already mentioned, in Japan the share of VCM amount to 13% of all ethylene use (ethylene requirement). In contrast, VCM amounts to 40% of all chlorine use. Therefore, the demand-supply situation of chlorine has more impact on VCM than that of ethylene (Fig.1-9).

■ The balance between chlorine and caustic sodaChlorine is a by-product of caustic soda production,

generated at a ratio of 0.88:1. As applications for chlorine and caustic soda are totally different, one striking a balance between supply and demand does not necessarily mean the other would also. In fact, until 1970, the demand for chlorine was weaker than that of caustic soda, therefore, caustic

soda production was adjusted to meet the chlorine demand, and the resulting shortage of caustic soda was supplemented by imports. Afterwards, chlorine became short of supply since demand for PVC grew year by year (Fig.1-10). In order to make up for the chlorine shortage, EDC, which is comparatively easy to transport, was imported.

Fig.1-9 VCM share in total chlorine demand (fiscal 2006)

VCM 40%

Food 1% Solvent 2%

Chloromethane 5%

Source: Japan Soda Industry Association (JSIA)

Propylene oxide 5%

TDI/MDI (raw material for urethane) 8%

Others 39%

Chlorine demand Domestic chlorine supply Chlorine import ( )

'82 '83 '84 '85 '86 '87 '88 '89 '90 91 '92 '93 '94 '95 '96 '97 '98 '99 '00 01 '02

2,781

2,391

390

3,025

2,530

495

3,163

2,681

482

3,253

2,666

587

3,292

2,715

577

3,502

2,901

601

3,763

3,119

644

3.921

3,271

650

4,043

3,445

598

3,967

3,407

560

3,914

3,361

553

3,737

3,269

468

3,943

3,367

576

4,188

3,544

644

4,328

3,598

730

4,423

3,861

562

4,203

3,684

519

4,419

3,903

516

4,285

3,883

402

4,042

3,689

353

4,074

3,806

268

'03 '04 05 '06

4,048

3,822

224

4,092

3,936

156

4,096

3,894

202

4,121

3,898

223

2,000

0

3,000

4,000

5,000

fiscal year

1,000 tons

Chlorine demand

Chlorine import

Domestic chlorine supply

NOTE: 1. The chlorine demand represents the "net demand" derived by subtracting the recovered chlorine from the gross domestic chlorine demand. 2. The chlorine import is derived from all imported chlorine products in terms of chlorine requirement.

Source: JSIA

Fig.1-10 Transition of the balance between chlorine and caustic soda

8


■ Dependency of VCM production on imported EDCEspecially during the mid 1980s, imports of EDC

increased year by year in order to make up for the grave shortage in chlorine due to the growth of domestic demand for VCM and also the increased export of VCM to China. The import of EDC marked an all time high of 842 thousand tons in 1996. As a result, the dependency of VCM production on imported EDC (i.e., the ratio of VCM manufactured with imported EDC) reached 34% (Fig.1-11).

After 1997 when VCM production hit its peak, the dependency of VCM on imported EDC started to decline. The decline resulted from the price hike of imported EDC partially due to growth in worldwide VCM demand; domestic VCM manufacturers had boosted production based on domestic chlorine.

After 2000, the import of EDC decreased to less than 500 thousand tons per year along with the

decline of PVC production. This was partially due to the general economic recession in Japan and reduced domestic demands (secondary converters had moved abroad). In 2004, the import of EDC further declined to 200 thousand tons, shifting the dependency ratio on imported EDC to below 10%. The price increase of imported EDC and domestic chlorine was partially responsible for the deficit of the Japanese PVC Industry after the latter half of 1990s. Thus, the balance between chlorine and caustic soda as well as the supply-demand situation of VCM both domestic and abroad are the dominant factors for the amount of EDC imported as raw material and the domestic shipment/export amount of VCM.

Crystalline :Molecules are aligned in a regular grid pattern when the substance is in solid form and stable. PVC has a dominant amorphous molecular structure, with only 5~10% of crystalline components.

Polarity : Tendency within parts of the molecule to be slightly charged positively and negatively. Parts within the molecule that are charged are called polar parts, as opposed to nonpolar parts where there is very little electrical charge.

0

500

1,000

1,500

2,000

2,500

3,000

Imported EDC

PVC production

VCM production

VCM production (EDC requirement)*

　 EDC dependency ratio (%)**

(1,000 tons)

1994

586

2,111

2,318

1,942

30

1995

723

2,274

2,586

2,167

33

1996

842

2,511

2,921

2,448

34

1997

696

2,626

3,124

2,618

27

1998

570

2,457

2,995

2,510

23

1999

553

2,461

3,124

2,618

21

2000

417

2,410

3,032

2,541

16

2001

383

2,195

2,895

2,426

16

2002

295

2,225

2,970

2,489

12

2003

256

2,164

2,948

2,470

10

2004

185

2,153

2,977

2,495

7

2005

153

2,151

3,038

2,546

6

2006

318

2,146

3,228

2,705

12

2007

223

2,162

3,142

2,633

8

15

20

25

0

5

10

30

35

40（％）

1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007

1,000 tons Imported EDC EDC dependency ratio VCM production (EDC requirement)

x 100VCM production (EDC requirement)

** EDC Dependency Ratio =

* VCM production (EDC requirement) = VCM production x 0.838Imported EDC

Source; Yearbook of Chemical Industries Statistics, METI Trade Statistics of Japan, Ministry of Finance

Fig.1-11 Transition of EDC import and dependency ratio on imports

3. Characteristics of PVC

9

PVC, PE, PP and PS are called general-purpose plastics. The features of the plastic are determined by the chemical composition and type of molecular structure (molecular formation: crystalline /amorphous structure)(Fig.1-12).

PVC has a unique amorphous structure with polar chlorine atoms in the molecular structure. Having chlorine atoms and the amorphous molecular structure are inseparably related. Although plastics seem very similar in the daily use context, PVC has completely different features in terms of performance and functions as compared with olefin plastics which have only carbon and hydrogen atoms in their molecular structures.

(1) Chemical stability

Chemical stability is a common feature among substances, containing halogens such as chlorine and fluorine. This applies to PVC resins also, which furthermore possess fire retarding properties, durability, and oil/chemical resistance.

■ Fire retarding propertiesPVC has an inherently superior fire

retarding property due to its chlorine atom components, and do not require addition of fire retardants to its products. For example, the ignition temperature of PVC is as high as 455℃ , and is a material with less risk for fire incidents since it is not ignited easily (Fig.1-13).

Furthermore, the heat radiation in burning is considerably low with PVC, when compared with those for PE and PP, and is hard to spread fire to nearby materials even while burning (Fig.1-14). Therefore, PVC is the most suitable plastic to be used in products requiring fire retarding properties such as housing materials.

■ DurabilityUnder normal conditions of use, the factor

most strongly influencing the durability of a material is resistance to oxidation within the air. PVC, having the molecular structure where chlorine atom is bound to every other carbon chains, is very resistant to oxidative reactions, and maintains its performance

500℃

400℃

300℃

200℃

Vinylidene chloride Low flammability Fluoroplastic

PS Hard to ignite

Cellulose acetate

PVC Nylon

PU

PE

Nylon

PVC

PE PU

Methacrylicresin

Pine wood Pine wood Cotton Paper Paper Wool High flammability Easy to ignite

Fig.1-13 Flash ignition and ignition temperatures of mateials

Source: "Technical Information: Five Properties of Polyvinyl Chloride" by the technical committee of the Vinyl Institute, 1988 (PVC and Polymer, Vol.29, No.9, 6-11: No.10, 10-16, 1989)

Vinylidenechloride

Material 91

250

315

746

859

1216

1325

1335

Maximum heat release（kW/m2）

Fig.1-14 Maximum heat release by various materials

PVC

Fire resistant ABS

Fire resistant PS

ABS

PS

Polyester

PE

PP

Source: PVC and polymer Vol.29 (1989)

H

C

H

H

C

H

C

H

H

C

H

C

H H

H

C

H

C

H CH3

H

C

Molecular form Amorphous part

Crystalline part

carbon, hydrogen, chrorine carbon, hydrogen

CrystallineThe crystalline part is fixed, the amorphous part is flexible.

Amorphous

Molecular chains are fixed.

PVC PS PE PP

Chemical composition

Fig.1-12 Molecular structures of general purpose plastics

10


almost semi-permanently. In contrast, other general purpose plastics with structures made up only of carbon and hydrogen are susceptible to deterioration by oxidation in extended use conditions.

According to measurements on underground PVC pipes by the Japan PVC Pipe & Fittings Association, a pipe used underground for 35 years showed no deterioration, and its strength remained the same as with new pipes (Fig.1-15).

A report from Germany, where rigid PVC pipes were used from the early days, states that a PVC pipe used for over 50 years displayed the same strength as with new pipes.

Almost no deterioration was observed upon recovery of three kinds of automobile exterior accessories (flexible PVC products using plasticizers) from end-of-life cars after 13 years of use and upon comparison of physical properties with new products (Fig.1-16). The shortened time for thermal decomposition (loss of durability) is due to the heat history in the re-converting process, and can be recovered to that of the original products by adding

stabilizers. Recovered products can in fact be molded back into the same products through re-converting, regardless of whether they are pipes or automobile parts. The physical properties of these re-converted products are almost the same as with products made from virgin resin, and there is also no problem upon actual use.

As described above, PVC has an outstanding durability and is a suitable material for long service life products, and has an excellent recycleability.

Taking advantage of this characteristic, PVC is used in exhaust gas ducts, sheets used in construction, bottles, tubes and hoses.

■ Oil/Chemical ResistancePVC is resistant to acid, alkali and almost all

inorganic chemicals. Although PVC swells or dissolves in aromatic hydrocarbons, ketones, and cyclic ethers, PVC is hard to dissolve in other organic solvents.

A B C

2000

1500

1000

500

0A B C

25

20

15

10

5

0A B C

120

100

80

60

40

20

0A B C

2

0

-2

-4

-6

-8

-10

13 years later

A B C

400

300

200

100

0A B C

250

200

150

100

50

0A B C

400

300

200

100

0A B C

120

100

80

60

40

20

0

Fig.1-16 Change of physical properties of recovered automobile exterior accessories

Degree of polymerization Original

Plasticizer content (%) Hardness (at 23℃) Brittle temperature (℃)

Sample Sample Sample Sample

SampleSampleSampleSample

Tensile strength (kg/cm2) 100% Modulus (kg/cm2) Elongation (%) Thermal decomposition time (mins)

Source: "PVC and environmental issues" by Tetsuya Makino, Seikei Kakou (a journal of the Japan Society of Polymer Processing), Vol.10, No.1 (1998)

（M

Pa）

100 20 30 40 50

58

60

64

66

62

50

52

56

54

Tens

ile s

treng

th Number of years in use

Fig.1-15 Aging of strength in rigid PVC pipe

Source: Japan PVC Pipe & Fittings Association

11

(2) Mechanical stability

PVC is a chemically stable material, which shows little change in the molecular structure, and also exhibits little change in the mechanical strength. However, high-polymer material is a viscoelastic body and deformed by continuous application of exterior force, even if the applied force is well below its yield point. This is called creep deformation. Although PVC is a viscoelastic body, its creep deformation is very little compared with other plastics due to little molecular motion at ordinary temperature, in contrast to PE and PP, which have greater molecular motion in their amorphous sections. Through a joint research with the Kyoto Institute of Technology, it was found out that the service lives of rigid PVC pipes were over 50 years. Specifically, internal pressure creep tests revealed that rigid PVC pipes retain about three times the designed circumferential stress even after 50

years of service. This is proof that PVC can maintain its mechanical strength for an extended period of time (Fig.1-17).

Viscoelastic body :Refers to material having both viscosity and elasticity. Distortion occurs as soon as external force is applied and thereby absorbing the force (elasticity), but when the force is continuously applied, deformation occurs to a certain extent (viscosity).

Yield point :When external force is applied to a material, elastic deformation (strain) takes place up to the yield point, and the strain disappears as soon as the external force is removed. When the external stress is greater than the yield point, plastic deformation (permanent set) takes place and the material would not recover its original shape even after removal of exterior force.

(3) Processability and moldability

The processability of a thermoplastic material depends largely on its melt viscosity. PVC is not meant for injection molding of large sized products, since its melt viscosity is comparatively high. On the other hand, the viscoelastic behavior of molten PVC is less dependent on temperature and is stable. Therefore PVC is suitable for complex shaped extrusion profiling (e.g., housing materials), as well as calendering of wide films and sheets (e.g., agricultural films and PVC leather). The exterior surfaces of molded PVC products are excellent, and displays superior embossing performance - enabling a wide variety of surface treatments with textures ranging from enamel gloss to the completely delustered suede. Since PVC is an amorphous plastic with no phase transition, molded PVC products have high dimensional accuracy. PVC also exhibits excellent secondary processability in bending fabrication, welding, high-frequency bonding, and vacuum forming, as well as on-site workability.

Paste resin processing such as slush molding, screen-printing and coating is a convenient processing technique that is feasible only with PVC. These processing methods are used in flooring, wall covering, automobile sealants and undercoating.

Interior decoration films

10010 1000 10000 100000 1000000

10

25

100

50

Fig.1-17 Circumferential stress by internal pressure and breaking time of rigid PVC pipes

Circ

umfe

rent

ial s

tress

(MPa

)

Elapsed time (hrs) 50 years

Source: Japan PVC Pipe & Fittings Association

4. Safety of PVC

12


(4) Others (versatility in designing through compounding)

PVC has polar groups (chlorine), and is amorphous, therefore mixes well with various other substances. The required physical properties of end products (e.g., flexibility, elasticity, impact resistance, anti-fouling, anti-bacteria, anti-mist, fire retarding) can be freely designed through formulation with plasticizers and various additives, modifiers, and coloring agents. PVC is the only general purpose plastic that allows free, wide and seamless adjustment of the required physical properties of products such as flexibility, elasticity, and impact resistance, by adding plasticizers, additives, and modifiers.

Since the physical properties of end products are adjustable through compounding, it requires only a few types of resin to cover all the applications of high-polymer materials (fiber, rigid and flexible plastic, rubber, paint, and adhesive). This controllability is also extremely beneficial recycling-wise.

The polar groups in PVC contribute to ease in coloring, printing and adhesion, therefore PVC products do not require pretreatment, which enables a wide variety of designs. PVC is used in various scenes taking full advantage

of its superior printability, adhesion properties and weatherability. Patterns such as wood grain, marble, and metallic tones are possible. Familiar examples include wall coverings and floorings, housing materials, furniture, home electric appliances, or signboards and ads on airplanes, bullet trains, buses and trams.

(1) Production safety

VCM, which is the intermediate raw material for PVC, has a boiling point of - 13.9℃ and a flash point of - 78℃ . Caution is required upon handling since it is a dangerous substance in gaseous form. The PVC industry in Japan handles VCM with utmost care at PVC manufacturing facilities and has safe working environments. No hazard has ever been brought to local communities. Neither has there been any death incidence or sufferers due to improper manufacturing process control throughout the years.

(2) Safety upon use

PVC is a chemically and mechanically stable material with excellent fire retarding properties, and is a safe plastic under normal conditions of use. Fig.1-19 is an excerpt of the Material Safety Data Sheet (MSDS) prepared by PVC manufacturers. The MSDS shows data for the safe use of PVC.

5

4

3

2

1

Fig.1-18 Comparison of physical properties of PVC materials with polyolefin materials

Fire retardance

Oil resistance

Abrasion resistance

Scratch resistance

Adhesion

Gloss

Compression Set

Exterior appearance

Moldability

Tensile strength

PVC materialsPolyolefin materials

Improved polyolefin materials

Source: "PVC and environmental issues" by Tetsuya Makino, Seikei Kakou, Vol.10, No.1 (1998)

13

(3) Evaluation of carcinogenicity

In 1974, cancer incidents were reported among workers who had been employed by the PVC industry in the U.S., and VCM were reported to be responsible. As a result of an epidemiological survey, a very rare type of cancer (angiosarcoma) was identified in workers who had been exposed to high concentrations of VCM for an extended period of time.

Following this report, improvements of work environments were accelerated through closed system EDC/VCM manufacturing processes and automated cleaning of PVC polymerization reactors, in the U.S. and across of the world.

In Japan, a new guideline was introduced in 1975 where the geometrical average was to be within 2ppm in the general work environments and within 5ppm inside the polymerization reactor. Subsequently, better process control technologies were introduced such as enhanced polymerization rates and recovery of unreacted VCM from the reactor. The PVC industry also worked on the reduction plan for hazardous air pollutants in cooperation with administrations (see Chapter 3).

There were once cancer incidents among workers who cleaned polymerization reactors for extended

H

C

H n

H

C

Fig.1-19 Material Safety Data Sheet (MSDS)

References 1) "Plastic Data Handbook" Edited by Kimimasa Itoh. Kogyo Chosakai Publishing Co., Ltd. (1980) P.116 2) Same as above. P.110 Disclaimer The contents herein are based on documents, information and data available at the time of press. However, no guarantee is extended as to the physical/chemical characteristics and dangerousness. Cautions are meant for normal conditions of handling. Appropriate safety measures must be taken for each special conditions of handling.

PVC(White powder)

PVC materialfor molding (Colored pellets)

Product designationDistinction of single/mixed materialChemical nameChemical formulaStructural formula

Classification # in official gazetteCAS No. Classification of hazardousness Title of classification　Danger　HazardousnessFirst aid　If in contact with eye

　If in contact with skin　If swallowedMeasures in case of fire 　Extinguish method　Extinguishing Agent 　Others Measures upon leakageCautions upon handling 　Handling 　Storage

(CH2CHCl)n

Polyvinyl chlorideSingle materialPolyvinyl chloride (PVC)

6-66 (Japanese Chemical Substances Control Law) 9002-86-2

Not applicable to classification standards None None

Do not rub, rinse with water for 15 minsand consult a physicianRinse with waterConsult a physician

Extinguisher must use air breathing apparatus Water, dry chemical, foam Irritant gas is emitted when burnt. Major component of gas: HCl, CO and CO2. Collect the diffused in empty containers

Do not expose to fire. Do not diffuse Avoid exposure to direct sunlight, and store at a well ventilated, cool and dark place

Explosion preventive measures　Concentration control　Permissible Concentration　Measures for facilities

　Protective gears

Physical/Chemical characteristics 　External appearance 　Property　Boiling point 　Vapor pressure 　Volatility 　True specific gravity　Solubility Info on danger (Stability/Reactivity)　Ignition temperature　Flash ignition temperature　Combustibility 　 Oxidative property　Dust explosiveness Stability/ReactivityInfo on hazardousness

Cautions upon disposal

Cautions upon transportation

Applicable laws and regulations

Not applicable None (Japan Society for Occupational Health)Desirable to install local ventilators with dust filters where diffusion tends to occur

White powder

Not applicableNot applicableNot applicable 1.4 (20℃)Not soluble in water

391℃ 1） 454℃ 2）

Stable in room temperatureStable in terms of dust explosiveness Stable under normal handling conditions

None specifically

Use the following protective gears when necessary ●Respirators (dust masks in operation, and air breathing apparatus mask in case of fire)●Protective spectacles (dustproof spectacles)●Protective gloves●Protective clothes (not required generally)

Self-extinguishing resin with oxygen index of approx. 45

Avoid damage to containers and collapse of cargo

Unclear, but no case known to show hazardousness

Incinerate by incinerators with exhaustgas treatment facilities, or landfill as non-dangerous waste

14


periods of time, but after the carcinogenic effects of VCM surfaced, improvements were made immediately for the safety and hygiene in the work environment, and methods to use VCM safely was established within a short period of time.

For reference, the International Agency for Research on Cancer (IARC), which is a branch of the World Health Organization (WHO), classified VCM as substance belonging to Group 1 (Carcinogenic to humans) in June, 2001 (Fig.1-20). On the other hand, PVC was classified as Group 3 (Not-classifiable as to its carcinogenicity to humans), along with tea and caffeine. (WHO is continuing its quantitative risk assessment on carcinogenicity).

(4) Residual monomers in PVC

Trace amounts of unreacted VCM are found in PVC, but their concentrations are not a problem upon processing and use of PVC products. Food packaging and medical appliances require stringent safety measures; therefore the following specifications have been established.

① Specifications for food packaging■ Standards in the Food Sanitation Law

In 1973, a research was conducted in Italy where oral doses of VCM were given to experimental animals, which resulted in manifestation of angiosarcoma. This lead to further investigations on residual VCM in PVC across the world, and the US National Toxicology Program (NTP) was one such example. In Japan, review of the Food Sanitation Law started immediately from a hygienic standpoint. Safety evaluations were made based on residual monomer levels and its relationships

with migration levels. On February, 1977, the Ministry of Health and Welfare set the standard of residual VCM in PVC to be below 1 ppm and announced this through public notification No.17. The notification continues to be effective to date.

■ Voluntary Standard by Japan Hygienic PVC Association (JHP Standard):

In 1970, prior to the abovementioned public notification, Japan Hygienic PVC Association (JHPA), which consists of PVC manufacturers and PVC product manufacturers, had worked out voluntary standards based on the Food Sanitation Law in the form of positive list (JHP standard: recommendable substances for use/guideline upon manufacturing of food packaging) ahead of the Responsible Care concept (see footnote of page 38).

JHPA had decided to work out this voluntary standard when the result of the animal experiment in Italy was reported. By the time the public notification No.17 was announced by the Ministry of Health and

■ Positive list　・A list presenting the designations of chemical substances which can be used as raw materials, their quality, quantity, application and elution limit, etc.　・Polymer (resin), additives, plasticizers, stabilizers, antioxidants, UV absorbers, surfactants, lubricants, colorants and fillers foaming agents, and others■ Material test　・Substances not to be used intentionally or to be included in the product and their test methods are stipulated　・Cadmium, lead, dibutyltin compounds, cresol, phosphates, VCM■ Elution test　・Non-volatile residues, heavy metals, and consumption of KMnO4

The JHP standard by JHPA consists of:1) Positive list (list of recommended 　raw materials to be used), and2) Material test and leach test methods for PVC food packaging based on the Food Sanitation Law. The level of residual VCM is stipulated to be below 1ppm.

Fig.1-21 JHP standard

Source: Prepared based on "Voluntary standards for food sanitation etc. of PVC products, (JHP standard: version 12)" March, 1993, JHPA

Group 1

Group 2A

Group 2B

Group 3

Group 4

Classification

Carcinogenic tohumans

Probably carcinogenic to humans

Possibly carcinogenic to humansNot classifiable as to its carcinogenicity in humans

Probably not carcinogenic to humans

Agents Asbestos, VCM, 2,3,7,8- TCDD, Formaldehyde, Cadmium,Benzene,Benzopyrene, Acrylamide, Ultraviolet radiation Lead & lead compounds (inorganic)Acetaldehyde, Styrene, Lead compounds (organic)Caffeine, Chlorinated drinking-water, DEHP, PVCCaprolactam(raw material for nylon)

MixturesAlcoholic beverages, Tobacco smoke, Soot

Diesel engine exhaust

Coffee, Gasoline, Pickled vegetables (Asian traditional)

Tea (black tea, green tea)

105

66

248

515

1

Fig.1-20 Evaluations of carcinogenicity by the IARC

Source: IARC website

SubstancesNumber

As of Mar. 2008

5. JIS and PVC Applications

15

Welfare in February 1977, reduction of residual VCM had already been achieved.

The voluntary JHP standard is a comprehensive voluntary standard that integrates official regulations, and following the revision of the Food Sanitation Law, the 1ppm limit of residual VCM was immediately adopted (Fig.1-21).

② Standards for medical equipmentAnother example of measures against residual VCM

is the case in medical PVC products including blood

bags, liquid/blood transfusion sets, artificial heart lung apparatus and artificial kidneys. PVC has been used safely for more than 40 years both at home and abroad, in accordance with the Pharmacopoeia of Japan, voluntary standards established by the Japan Medical Devices Manufacturers Association (Fig.1-22), and GMP (Good Manufacturing Practice). PVC resins in compliance with standards shown in Fig.1-22 are used for medical products. The level of residual VCM is set below 1ppm in this application field as well.

(1) The Japanese Industrial Standard (JIS) for PVC

PVC is controlled under the following test methods and shipped in uniform quality. PVC compound is a form of PVC product but it is marketed as an intermediate material to be molded into PVC products. Therefore test methods for compounds are also shown.

(2) JIS for PVC products

PVC has a wide variety of applications, and more than 200 JIS items are relevant. PVC products contribute to society under support by these vast number of standards.

Fig.1-22 Standards for medical apparatus

Test method for transfusion bags (Pharmacopoeia of Japan )

Designation of medical products

Transparency/External appearance

PVC compound I ･ II for medical apparatus (voluntary standards by the Japan Medical Devices Manufacturers Association)

Plasticized PVC transfusion bags

No abnormality by visual inspection Same as with left

Same as with left

Same as with left

Same as with left

VCMbelow 1μg (1 ppm) (others: omitted)

(others: omitted)

△PH, KMnO4 reducing substance, UV absorption spectrum

Acute toxicity tests, Intracutaneous reaction

Tests on eluates

Biological tests

Blood set, Disposable set for artificial heart/lung equipment, Blood tube for hemodialysis, Blood catheter, Transfusion set,Blood transfusion set, Others

Source: Prepared based on the document by the Japan Medical Devices Manufacturers Association

Material tests

Plastics-PVC homopolymer and copolymer: designations, specification, specimen, properties* PVC: Method to measure impurities*Method of viscosity measurement with rotational viscometer*Method to measure apparent density*Method to measure viscosity of diluted solution (reduced viscosity of PVC/K value)*PVC homopolymer and copolymer (method to measure residual VCM)*PVC paste resin (method to measure apparent viscosity)*PVC homopolymer and copolymer (method to measure volatile component/ moisture content)*Method to prepare PVC paste (dissolving method)*Plasticized (flexible) PVC compoundMaterials for molding and extrusion of un-plasticized PVC (PVC-U) (Rigid PVC compound)Plastic: Materials for molding and extrusion of plasticized PVC (PVC-P)

K 6720- 1～2K 6737K 7117-2 K 7365 K 7367-2 K 7380 K 7381 K 7382 K 7383 K 6723 K 6740 K 7366

JIS

* Changeover to a new JIS standard will take place in October 2004 in line with the international standardization towards ISO. 13 other new JIS standards will be introduced.

16


PVC has superior features in one, and is used in various fields ranging from the lifeline (water supply, sewage, electric cable, etc.), basic industries (housing), consumer products, and front line electronics, to medical apparatus and products. The application of PVC is divided, in general, based on the hardness

of products, e.g., rigid, flexible, electric cables and others. The most prominent feature of PVC product is applications requiring long service lives. Fig.1-23 shows the applications in the vertical direction and the service life in the horizontal direction, with some photographs of applicable products.

(3) Applications of PVC (PVC products)

Fig.1-23 Applications and service life of PVC - 1 Long ShortService life

Long term (some years～50 years) Less than a few years

ducts, tanks, semi-conductor cleansing devices,flanges, other facilities/equipments,

anti static plates

■ Industrial

■ General name plates,construction materials,sign boards,stationeries,agricultural applications

Flat

pla

tes

Rig

id p

rod

ucrs

Film

s/S

hee

ts

■ Construction materials

Co

rru

gat

ed s

hee

t

corrugated sheet

■ Agricultural applications

name plates, construction materials

terrace roofing

displays

displays

separated trays

separated trays

blister packs■ Non food packaging

dimpled sheets

packaging (for eggs, tofu, fruits)caps,

food trays

■ Food packaging

■ Others cooling towers, toys,electronic equipment accessories, stationeries,cards,FDJ

terraces, dormer, carports, blinds, sheds, arcades,

accessories

cards

temporary structures, snow fences

casing,lightweight packaging

clean rooms


Long term (several years～50 years) Less than a few years

ducts, tanks, semi-conductor cleansing devices,flanges, other facilities/equipments,

anti static plates

■ Industrial

■ General name plates,construction materials,sign boards,stationeries,agricultural applications

Flat

pla

tes

Rig

id p

rod

ucts

Film

s/S

hee

ts


Co

rru

gat

ed s

hee

ts

corrugated sheet

■ Agricultural applications

name plates, construction materials

terrace roofing

displays

displays

separated trays

separated trays

blister packs■ Non food packaging

dimpled sheets

packaging (for eggs, tofu, fruits)caps,

food trays

■ Food packaging

■ Others cooling towers, toys,electronic equipment accessories, stationeries,cards,FDJ

terraces, dormers, car ports, blinds, sheds, arcades

accessories

cards

temporary structures snow fences

casing,lightweight packaging

clean rooms

17

agricultural water system



Rig

id p

rod

ucts

■ Water supply

■ Agricultural water

■ Sewege

■ Industrial, facility drainage

■ Cable protection

Pip

esFi

ttin

gs

Sp

ou

ts

■ Other applications

power tube

■ Special purposes base pipes for PVC lined steel pipes

adaptor for steel pipes right angle elbow

rainspouts, chicken farm spouts, accessories

plant piping, well drilling, natural gas pipelinesindustrial waterworks, marine structures, componentswater discharge facility buildings, roadworks, railroad sathletic fields, air conditioning, gray waterworkswater draining from retaining walls, highways

electric conduits (telecommunication, signals, indoor wiring, lighting, vehicles)

optical fiberprotection cables

aquacultures, hot springs, coil core

NTT cable protecting tube

power tubes

pipe fittings

paddy field irrigation pipelineirrigation for farmland

waterworksexclusive water works simplified water works

public sewage systemfarm village sewage systemdevelopment of housing premises

Sewage system

waterworks

Y shaped fitting

rainspout

18




Rig

id p

rod

ucts

Pro

file

ext

rusi

on


window profiles, wire screens, girt, bargeboards, fascias, decks, trim, parting, angles, panels, ribs, knobs, accordion doors, sidings window profiles

siding (exterior of housings) siding (exterior of stations) various construction materials

■ Consumer products

drain boards, bath tub lids, rails, hanger,

pen tray

■ E&E wiring ducts, wire protectors, handle for radio-cassette players, battery separators

speakers

IC carriers

IC carriers

■ Furniture/ Wooden product applications

edges, trims, outside corners, squinches, deck plates

decks, etc. counter table

■ Vehicle applications

vehicle interior

interior of JR sleeper express trains

■ For food packaging

soy sauce, Worcester sauce, vinegar, seaweed

■ For non food applications

cosmetics, shampoo, detergents

Other applications valves, flanges, night soil tanks, rain water sumps, wastewater sumps, in-house sumps, keyboards

sumps valves/flanges

various rigid PVC extrusion molded products

various bottlesBlo

w m

old

ed p

rod

uct

s

penholder

19



non woven fabric

Flex

ible

pro

du

cts

Gen

eral

film

s/S

hee

ts

■ Laminated products

printed plywood, PVC laminated steel platesprinted films for interior finishing,printed sheets for exterior finishing

hot springs (ceiling) theaters (walls) stores (exterior wall)

doors (surface)

pianos (surface)

■ Packaging various covers, fabric wrapping blood bags, IV infusion bags, food wraps, stickers (labels)shrink film

waste fluid storage bags

■ Vehicle applications

instrument panels, consoles, door sheets, ceiling, carpet, trunk room sheets, insulating tapes

■ Consumer products

furniture, accessories

Agricultural films green house gardening, vegetables, fruits, paddy, tobacco

Artificial leather wallcovering, vehicle seats, furniture, baggage,bags, garments, stationeries

wallcovering, sofa

baggage, footwear

stationeries, bags, toys, raincoats, umbrellas, adhesive tapes, adhesive plasters

agricultural PVC films

footwear

20




Flex

ible

pro

du

cts

waterstops, industrial hoses/tubes, gaskets (for residences, home electrical appliances, automobiles), machinery/equipment parts,flooring of housings

Extruded profiles medical tubes, garden hoses,tubes for food, skipping ropes

draining hoseshousing material parts

table edges

side molding

artificial heart-lung catheter

various shaped extruded profiles refrigerator door gaskets

Injection-molded products and others

tarpaulins (canvases, tents, sunshades), mattresses, sealing sheets, civil work sheets, roofing sheets, waterproof sheets, insulation sheet

carrier cart bumpers

vacuum cleaners automobile parts

Cable covering electric power cable, machine control cable, construction/housing cable, electric wire for machine/equipment (cords, wires, harnesses),consumer products, telecommunications

high-voltage cables

cables for construction works (low-voltage )

power cords

interfacing cables flat-shaped cablestape/ribbon cables

Ele

ctri

c ca

ble

s an

d o

ther

s

Flooring homogeneous tiles, composite tiles, cushion flooring, long sheet flooring, tile carpet, laminated tile

flooring for stores such as department stores, super markets, and DIY shops

Fiber fishing nets, ropes, insect screens, brushes, wigs

Otherspaints,expanded products (floats, heat insulators, cushion material)

dolls, shoe soles, boots,gloves, industrial tapes

CHAPTER 2: ENVIRONMENTAL ISSUES AND CURRENT STATUS OF PVC AND PVC PRODUCTS

PVC has become widespread among our daily lives and industrial activities in the form of various products. For such reasons, its safety and impact on human health has become the center of concern by the general public. PVC and PVC products have been scrutinized based on the following beliefs:●Dioxins tend to generate when incinerated at inappropriately conditioned waste incinerators● Phthalate plasticizers contained in flexible PVC products are under evaluation as alleged endocrine disrupters● Phthalates are also taken up for evaluation as substances suspected to cause sick-house syndromes ●Hydrogen chloride generated from incineration is regarded as the major contributor to incinerator corrosion and acid rain

However, gradually the record is set straight for PVC and its products as a result of measures taken to solve these issues, such as improvement of incineration systems, progress of scientific researches and accumulation of experimental data.

In this chapter, facts about the environmental issues taken up in relation to PVC and its products are explained with focus on dioxins, endocrine disrupters, the sick-house syndrome and hydrogen chloride generation upon incineration.

22

CHAPTER 2 : ENVIRONMENTAL ISSUES AND CURRENT STATUS OF PVC AND PVC PRODUCTS

1. Dioxins Issues

PVC de-selection campaigns developed on a worldwide basis on assumption that PVC is the source of dioxins generation when incinerated. PVC was perceived as bad, especially in Japan. Also, incineration of PVC waste became a serious social issue due to remarkable advancement of analytical technologies which enabled detection of even trace amounts of dioxins at various segments of the environment including waste incinerators, coupled with the perception that “dioxins are deadly poisonous substances”. The PVC industry has been committed to activities to win correct understanding of PVC, PVC products and dioxins.

(1) Actual condition of dioxins emissions to the environment

When a substance is incinerated in atmospheres that include chlorine compounds, dioxins are generated unintentionally due to incomplete combustion, whatever the incinerated substance may be. For example, dioxins are generated from natural phenomena such as the volcanic activities and forest fires, which have taken place time and again from prehistoric ages. In fact, dioxins have been detected from 8,000 years old sediment at the bottom of Osaka bay, from the soil of the South Pole, and volcanic dusts.

The major contributors of dioxins pollution in Japan and elsewhere in the world are agricultural chemicals (herbicides, etc.) and poly-chlorinated biphenyl (PCB) used in the past, when the presence of dioxins included in them as impurities were yet unknown. Such agricultural chemicals and PCB were banned

in the course of time because of their acute toxicity, carcinogenicity, and accumulation in eco-systems. As shown in Fig.2-1, from its peak value in 1970, dioxins emitted to the environment decreased sharply by 1984 as a result of regulation and emission prevention efforts.

After 1985, dioxins emissions to the environment through agricultural chemicals became negligible, and emissions from waste incinerators were highlighted as the major source. Japan's national land area is modest and population is concentrated in urban areas. Thus, the public sanitation policy to incinerate wastes for volumetric reduction rather than landfilling has been unavoidable. Municipal governments in Japan installed municipal waste incineration facilities according to the volume of waste generated, in order to meet the national policy (Waste Disposal and Public Cleansing Law) which makes municipal governments responsible for domestic waste disposal. As a result, many relatively small-scale waste incinerators are operated in Japan as compared with other major countries (Fig.2-2).

In contrast, the basic policy for waste disposal in the U.S. and Europe is based on wide-area coverage and larger scale incinerators. The number of incinerators is far less than in Japan; therefore not many dioxin issues from waste incineration occurred. Dioxin issues directly relate to the size of national land and the national waste disposal policy.

After peaking in 1997, dioxins emissions in Japan have been reduced remarkably after 1998, through improvement of waste incinerators and incineration conditions following the enactment of the “Air Pollution Control Law” and “Law concerning Special Measures against Dioxins”, along with activities to

Fig. 2-1 Transitions of dioxins emissions into the environment

Agricultural chemical (PCP) Agricultural chemical (CNP) co-PCBs originated from PCB (ex.insulating oil) Industrial waste incinerators Municipal waste incinerators Other sources (industrial etc.)

（g-

TEQ/

year）

0

10,000

20,000

30,000

40,000

50,000

60,000

１９５８

１９５９

１９６０

１９６１

１９６２

１９６３

１９６４

１９６５

１９６６

１９６７

１９６８

１９６９

１９７０

１９７１

１９７２

１９７３

１９７４

１９７５

１９７６

１９７７

１９７８

１９７９

１９８０

１９８１

１９８２

１９８３

１９８４

１９８５

１９８６

１９８７

１９８８

１９８９

１９９０

１９９１

１９９２

１９９３

１９９４

１９９５

１９９６

１９９７

１９９８

１９９９

２０００

２００１

２００２

２００３

２００４

２００５

２００６

※Data source for 1958-1995: trial calculations by Prof. Shigeki Masunaga of Yokohama National University ※No data exists for 1996, therefore the average of '95 and '97 is indicated. ※Data source for 1997-2006, MoE

<Origin of dioxins>

23

reduce waste generation. However, dioxins were detected from the sediments

of bays and lakes including Tokyo Bay and Shinjiko

Lake. Once dioxins are emitted into the environment, they do not decompose easily and they accumulate.

Fig. 2-2 Number of waste incinerators, incineration capacity and regulated dioxins emission value

148

223

0.21

17

71

0.14

1841

20

0.1～10

53

208

0.1

11

255

0.1

21

81

0.1

Germany Netherlands Sweden U.S. Canada Japan

# of waste incinerators

Average incineration capacity(1,000 tons/incinerator/year)Regulated dioxins emission value(ng-TEQ/m3N)

Source: Data from assistant professor S. Sakai of Kyoto University

1967

1962~71

1976

1977

1983

1985

1985

1990

Around 1996

1997

January, 1997

February, 1999

July, 1999

September, 2004

:

:

:

:

:

:

:

:

:

:

:

:

:

:

The cause for mass mortality of chickens in the U.S. (1957) was revealed to be dioxins in the fat mixed in chicken feed. Tremendous amounts of Agent Orange dispersed during the Vietnam War in which dioxins were included as impurities.An agricultural chemical manufacturing plant exploded at Seveso, Italy, where dioxin-containing chemicals were widely released.A scientist in the Netherlands discovered dioxins in waste incinerator ashes for the first time. Professor Tachikawa of Ehime University found dioxins in Japanese municipal waste incinerators. Sweden regulated dioxin concentrations in exhaust gases of waste incinerators to be below 0.1 ng/m3. A technical committee in the Ministry of Health and Welfare (the present MHLW) concluded that the level of dioxins emitted from municipal waste incinerators in Japan pose "no problems to human health". Ministry of Health and Welfare announced an initial guideline to reduce dioxins emission from waste incinerators. It was revealed that dioxins emissions from municipal waste incinerators throughout Japan were extremely higher than levels in the U.S. or Europe.PVC products were highlighted as the cause of dioxin generation, and "PVC = Dioxin" campaign was launched in Japan. Ministry of Health and Welfare announced a "new guideline" for reduction of dioxin generation from waste incinerators.Erroneous media reports on dioxin pollution of vegetables from Tokorozawa in Saitama prefecture. "Law concerning Special Measures against Dioxins" was promulgated (and partially entered into force from January 2000. Full enforcement: December 2002). MoE announced that "the target at the end of Fiscal 2002, which is 90% reduction from the level in 1997, is likely to be attainable".

● Brief chronology of dioxin issues

Isomers Designation

Polychlorinated dibenzo-p-dioxins (PCDDs)Polychlorinated dibenzo furans (PCDFs)Coplanar PCB(Co-PCB)

7513514

71012

Dioxins :

Allegedly toxicisomers

Polychlorinated-dibenzo-p-dioxins (PCDD)

Polychlorinateddibenzofurans (PCDF)

Coplanar-PCB

Cl

9 1 3

4 4

2

5 6

3 2

5 6

9 12

3

4 45 56 6

2

3 77

88

Cl Cl Cl

Cl Cl

C C

C

24


(2) Dioxins generation from incineration and control measures

Through complete combustion, PVC can be broken down into water, carbon dioxide and hydrogen chloride (HCl). However, complete combustion is rarely feasible in reality, and dioxins are unintentionally generated as byproducts according to incineration conditions. For example, trace amounts of dioxins are generated through incineration of newspapers or paraffin which is composed only of carbon and hydrogen. These materials generate the same level of dioxins as with PVC when common salt is added as chlorine source1). Dioxins are composed of carbon, hydrogen, oxygen and chlorine as shown in the structural formulas of the preceding page, and dioxins are generated through incineration when these four elements are present. Chlorine, out of the four elements, is ubiquitous (widely present) in the natural environment as well as in food that are consumed by humans. Therefore, dioxins are generated by incineration of kitchen wastes, paper, wood and waste plastics alike.

Japan, likewise with other major countries of the world, decided to have the incinerators at the clean centers operated in conditions as close to complete

combustion as possible in order to control dioxins generation. The proper incineration conditions set by the Japanese government stipulates temperatures to be over 800℃ , the residence time in the combustion chamber to be over 2 seconds, and sufficient turbulence with air. Furthermore, dioxins emission is controlled through quenching (rapid cooling) of combustion gas downstream the combustion chamber at below 200℃ , and generated soot (fly ash) is to be collected by bag filters etc. The common view expressed from related ministerial offices in Japan is; “if appropriate measures and controls are taken, the influence of PVC and other chlorine containing compounds in waste becomes a relatively smaller factor, and on the other hand, the combustion and waste-gas treatment conditions become more important factors affecting the concentration of dioxins2)”.

Remarkable achievement is shown in the data supplied by the union of public cleansing offices of the 23 wards of metropolitan Tokyo which prove that the concentration of dioxins emission into air from existing waste incinerators is 1/100th to 1/10,000th of the standard value, 1 ng/m3N, set by the law. This improvement was materialized in just in three years from 2000 (website of the union, titled results of dioxin measurements at waste incineration plants, etc., in Japanese only).

(3) Regulations set by the “Law Concerning Special Measures against Dioxins” (The Dioxins Law)

The Dioxins Law was enacted July 1999 in order

“to set up a dioxins reduction target for the end of 2002 and to reduce about 90% from the total dioxin emissions level in 1997 (843~891 g-TEQ/year)”. The law entered into force in January 2000. The law has established the target as the foundation of measures to be taken in order to control and mitigate the environmental pollution by dioxins. The law has also regulated necessary treatment for soil polluted by dioxins.

The Dioxins Law has stipulated Tolerable Daily Intake (TDI) and environmental quality standards as measures to be taken against dioxins. In addition, the law has specified the applicable emission sources, and emission standards for exhaust gas and water discharge. (Further reinforcement has been made possible).

Survey of actual conditions of pollution is conducted throughout Japan. Obligation to monitor dioxin pollutions in air, water and soil has been imposed on both national and municipal governments in each region. Also business entities which own and manage specified emission sources are also obligated under the law to measure at least

once per year the concentration of dioxins in exhaust gas and water.

●Tolerable daily intake (TDI) : 4 pg-TEQ/kg body weight/day

● Environmental quality standards : for ambient air < 0.6 pg-TEQ/m3

(annual average) for water < 1 pg-TEQ/L (annual average) for soil < 1,000 pg-TEQ/g (survey level: 250 pg-TEQ/g)* for sediment < 150 pg-TEQ/g

* If soil monitored exceeds the survey level, an additional survey will be conducted.

Unit : ng-TEQ/m3 N

Types of specified facilities

Waste incinerators(with hearth area of over 0.5 m2 or incineration capacity of over 50 kg/hr)

Electric steel-making furnaces

Sintering facilities for steel industry

Facilities for collecting zinc

Facilities for manufacturing aluminum base alloy

Capacity of incinerators

Standard fornew facilities

Standard for existing facilities2001.1-2002.11 2002.12-

● Standards for exhaust gas :

> 4 t/hr 0.1

1 80

20

2

40

20

5

0.5

0.1

1

1

1

5

10

5

1

10

5

2 t/hr~4 t/hr

< 2 t/hr

25

(4) Total emission of dioxins

The Ministry of the Environment (MoE) has announced the total dioxins emission every year since 1997, in line with “the plan for reducing the release of dioxins generated by business activities in Japan” which was established based on the Dioxins Law.

According to these announcements by the ministry, about 90% of the total dioxins emitted used to originate from waste incinerators in 1997. However, after the introduction of the Dioxins Law and subsequent emission regulations on waste incinerators, the total annual dioxins emissions dropped a remarkable 96% from about 8,100g in 1997 to 317g in 2006 (Fig. 2-3). Dioxins emissions from industrial activities including electric steel making furnaces and

standards for the quality of discharged water under the Dioxins Law is applicable (see 2. Production of PVC within Chapter 1).

During the oxychlorination process in EDC/VCM production processes, it has been known that at 250~300℃ , besides carbon, hydrogen, oxygen and

(5) Dioxin levels in the environment

Fig.2-5 shows the transition of average dioxin concentrations in the environment for 1998~2006, studied by the national and municipal governments. According to the results of research in 2006, average dioxin concentrations in the environment were:0.050 pg-TEQ/m3 in air, 0.21 pg-TEQ/L in water (public water bodies), 6.7 pg-TEQ/g in sediment (public water bodies) and 2.6 pg-TEQ/g in the soil. This proved that the environmental quality standards established by the

0

1000

7,680～8,135

1997 2006

2000

3000

4000

5000

6000

7000

8000

9000

Fig. 2-3 Dioxins emissions per sources

Others

Small-scale wasteincinerators

Industrialsource

IncinerationFacilities ofIndustrial waste

IncinerationFacilities ofMunicipal waste

（g-

TEQ/

year）

Source: Dioxins emission inventory, MoE

700～ 1,153

4707.5

7.0

1,505

5,000

289～317

5463

93

10176～

0

10

20

30

40 39.5

21.1

11.48.1

4.52.0 2.0 1.8 1.1 1.1 0.63 0.36

Fig. 2-4 Dioxins emissions per industrial sector (2006)

（g-

TEQ/

year）


Electr

ic stee

l-mak

ing fu

rnace

s

Sinter

ing pr

oces

s for

steel

indus

try

Alumi

num

refini

ng fa

cility

Zinc r

ecov

ery fa

cility

Ceme

nt pro

ducti

on fa

cility

Autom

obile

man

ufactu

ring f

ac.

Therm

al po

wer s

tation

s

Wrou

ght c

oppe

r prod

ucts

manu

factur

ing fa

c.

Alumi

num

rollin

g fac

ility

Lime p

roduc

tion f

acilit

y

Copp

er ca

ble &

wire

man

ufactu

ring f

ac.

VCM

prod

uctio

n fac

ility

sintering processes for the steel industry are the most dominant (Fig. 2-4). Out of the total emission to the environment, emission to water amounts to only about 0.5%, and the majority of the emission is to air.

In August 2004, the MoE announced that “the reduction target for total emissions of dioxins at the end of fiscal 2002, which is 90% reduction from the level in 1997, is likely to be attainable” 3).

（pg-TEQ/m3）

（pg-TEQ/g）

（pg-TEQ/L）

（pg-TEQ/L）

（pg-TEQ/g）

2000 2001 2002 2003 2004 2005 20061998 1999

0.23

0.40

7.7

0.081

6.5

0.18

0.24

5.4

0.096

-

0.15

0.31

9.6

0.097

6.9

0.13

0.25

8.5

0.074

6.2

0.093

0.25

1.1

0.066

3.8

0.068

0.24

7.4

0.059

4.4

0.059

0.22

7.5

0.063

3.1

0.052

0.21

6.4

0.047

5.9

0.050

0.21

6.7

0.056

2.6

0.6

1

150

1

1000

Fig. 2-5 Transition of dioxin levels in the environment

Medium

Air

Public water bodies

Water

Groundwater

Sediment

Soil

Source: Results of environmental investigations regarding dioxin emissions, MoE

Average Environmental quality standard

government have been met at most monitoring points.

(6) Dioxins emission from vinyl chloride monomer (VCM) manufacturing facilities

The ethylene dichloride (EDC) cleansing facility is one of the specified emission sources, to which the

26


chlorine, catalytic effects of metals such as copper chloride can generate trace amounts of dioxins through side reactions. Fig.2-6 shows the results of surveys on dioxins emission from VCM production facilities during 1997~2006. During the period of this survey, total dioxins emission from VCM facilities was less than 1g per year, which is equivalent to about 0.4% of total emissions from all industries (93.0g-TEQ) and about 0.1% of total emissions including emissions from waste incinerators.

enhance effects of other carcinogens (promotional effects), and have a threshold value.

The informational brochure issued by the Japanese government states, “…present levels of dioxins in the general environment in Japan are lower than those known to cause cancer risks2)”.

3) Tolerable daily intake (TDI)The Japanese government determined the TDI for

dioxins to be 4 pg/kg body weight/day, which will bring forth no hazardous effects through lifetime intake. The TDI value has been determined by taking into consideration the exposure impacts on new born babies, who are thought to be the most vulnerable to exposure. It is thought that there would be no adverse effect on human health even if exposure levels slightly exceed the TDI value for short periods of time during life.

According to the survey by the Ministry of Health, Labour and Welfare (MHLW), 99% of dioxins intake by the Japanese is estimated to be through food. The average daily intake of dioxins by the Japanese population is estimated to be about 1.04g-TEQ per 1kg body weight per day. Dioxin intakes are declining year by year, and are well below the TDI.

1997

0.20

0.54

0.74

1998

0.20

0.53

0.73

1999

0.20

0.55

0.75

2000

0.19

0.20

0.39

2001

0.29

0.58

0.87

2002

0.29

0.16

0.45

2003

0.30

0.10

0.40

2004

0.21

0.07

0.28

2005

0.22

0.10

0.32

2006

0.28

0.08

0.36

Fig. 2-6 Results of dioxins emission survey from VCM production facilities

Unit: g-TEQ/year

Emissions to air

Emissions to water

Total


(7) The toxicity of dioxins

1) Acute toxicityDioxins are said to be “the deadliest poison of all”,

since the median lethal dose (LD50 ) of 2,3,7,8-TCDD for guinea pigs was determined to be 1 µg (one-thousandth of a mg)/kg body weight (Fig.2-7), which is far less than that for sarin or potassium cyanide. However, the LD50 value varies largely among animal species. The Japanese government has referred to the acute toxicity of dioxins to humans as follows, in the governmental brochure: “The toxicity referred to is the acute toxicity that occurs from very high levels of exposure, such as ingesting at one time a dose of some hundred thousand times the regular daily intake” “….the regular levels of daily intake are very unlikely to lead to acute toxicity, such as would happen in the case of accidental ingestion2)”.

2) CarcinogenicityAlthough dioxins are speculated to be carcinogenic

to humans, the International Agency for Research on Cancer (IARC), which is an affiliate organization of the World Health Organization (WHO), has classified 2,3,7,8-TCDD under Group 1:“carcinogenic to humans “, based on the results of animal experiments. On the other hand, there are other PCDDs such as 1,2,3,7,8-PeCDD, which are classified under Group 3:”not classifiable as to its carcinogenicity to humans”.

However, the epidemiological study literature from which IARC drew the above conclusion states that the relative risks for people exposed to 20 years or more in high concentrations of 2,3,7,8-TCDD - up to 100~1,000 times the value for the general public - would be 1.2~1.64). Incidentally, the risk for lung cancer for a cigarette smoker consuming one packet a day is reported to be 4~5 times higher than that of a non-smoker. Furthermore, it is said that 2,3,7,8-TCDD do not have direct carcinogenic effects on genes, but

LD50 (μg/kg)

12245

50～70115284＞500

5000？

＊ Guinea pigsRats

MonkeysRabbitsMiceDogsHamstersHumans

Fig. 2-7 Acute toxicity of 2,3,7,8-TCDD (Oral dosing)

Animal species

* The toxicity is 64,000 times that of sodium cyanide. Death observed after 2-6 weeks.

Source: O.Wada, Journal of Academia, No.830, January, 2001

♂ ♀

2,3,7,8-TCDD :A type of PCDD with additional four chlorine atoms on the basic chemical structure. “2,3,7,8-” indicates parts where chlorine atoms are attached.

LD50 : Value of chemical substances that would result in 50% mortality of experimental animals, expressed in terms of 1kg body weight. It is the most widely used index to express acute toxicity of chemical substances. The smaller the LD50 value, the stronger the toxicity.

Relative risk : Ratio indicating enhanced manifestation of diseases or mortality rates through exposure to the risk element (chemical substances, etc.).

Threshold value : Indicates concentrations that start to exhibit impacts on health. Generally, threshold values are assigned to chemical substances with no carcinogenic effects. No threshold values are set for carcinogens that cause genetic disorder. Threshold values are assigned to chemical substances which do not have gene damaging effects.

27

In the past, the media often reported on the so called risks brought by PVC products, expressing as to contain endocrine disruptive substances. This all started when Di-n-butyl phthalate (DBP), a plasticizer used for paints and adhesives, and Di-(2-ethylhexyl) phthalate (DEHP), the major plasticizer used for soft PVC products, was included in the list of suspected endocrine disrupters under the “Strategic Programs on Environmental Endocrine Disruptors ’98 (SPEED’98)” prepared by the MoE.

The evaluation results by the ministry have already been announced, and suspicions on DBP and DEHP have been cleared. Below is the background to this event.

(1) Brief history of the endocrine disrupter issue

During the early 1990’s, size reduction in penises of male alligators and their decreased headcount at Lake Apopka in Florida was reported, and the correlation between organic chlorine compounds and endocrine disruptive effects became the center of concern (Fig.2-8). In July, 1991, the Wingspread Statement was announced, stating that “The release and use of toxic substances have had substantial unintended consequences affecting human health and the environment”, at a natural science expert meeting held in Wingspread, Wisconsin, U.S.

In 1996, Theo Colborn, current director of the Wildlife and Contaminants

project at the World Wildlife Fund (WWF: the largest environment protection organization in the world), published a book titled Our Stolen Future. In 1997, the Japanese translation of the book was published, and was widely read in Japan. The subtitle of the book reads “A scientific detective story”, insinuating presentation of endocrine disruptor issues based on gathered information and scientific inferences. This was taken up as a realistic issue in Japan together with the easily understandable Japanese term “kankyo horumon(environmental hormones)”.

It developed into an issue of public concern, resulting in de-selection of substances listed as suspected endocrine disrupters in SPEED’98 announced by the MoE in May, 1998, before any plausible results of scientific studies were announced on the suspected substances.

2. Endocrine Disrupter Issues

Sea snails(such as reishia)

Roaches(a kind of carp)

Alligators

Seagulls

Mammals in sea such asdolphins, seals

Source: Food Science Information Center News, vol.1 (April 1999)

Fig. 2-8 Report concerning effects on wildlife

WildlifePlace

PhenomenaAround the world (more than 140 types)Virilescence

River Aire in the UK Hermaphroditism, vitellogenin detectedfrom males (the protein is usually foundin females for producing eggs)Lake Apopka, Florida, U.S.Male penis atrophy, reduced hatchability of ovumThe Great Lakes, U.S.Dying chicks, abnormal behavior such as female pairing, thyroid tumorsNorthern Europe etc.Sharp decline in population

(2) What are “endocrine disrupters”?

When a specific chemical substance is taken into a living organism and affects the inherent hormonal functions, it is scientifically defined as endocrine disrupting chemicals or endocrine disrupters.

Hormones are generally defined as substances secreted by endocrine glands (hormone secreting organs) such as the pituitary and thyroid glands, and

perform unique functions on specific target organs. These substances perform roles such as homeostasis i.e. keeping physical conditions at a constant state in order to cope with the environmental changes, or controlling differentiation and growth of tissues, and controlling the development of reproductive organs.

There are natural substances called phytoestrogens created by plants, which also act like estrogens in the body. The phytoestrogen intake is largely through food such as soy beans. Therefore upon estimating the

Phytoestrogen :In the early 1940’s, infertility was observed in Australian sheep feeding on significant amounts of clover. This was due to the fact that a large quantity of a substance in clover had estrogenic effects. Isoflavones in soybean are well known as phytoestrogen and is also considered as good to the human body.

Lake Apopka : There are many lakes in Florida, but this was the only lake which suffered pollution by water discharge from a nearby agricultural chemical plant. No such abnormalities were observed in alligators in other lakes of the region.

28


effects of endocrine disrupters it is necessary to study the effects of phytoestrogens also.

Millenium Project the Japanese government conducted risk assessments for more than 40 chemical substances from 2000. On March 2005, the MoE published the results to SPEED’98 as well as the future policy called ExTEND2005 on endocrine disruptors, which mainly consists of observation of wildlife and risk assessments.

(3) Actions taken by the Japanese government

The Environment agency (the present MoE) announced “SPEED’98” in 1998 to deal with the endocrine disrupter issue. 67 groups of chemical substances selected for the list were picked up from the literatures both domestic and abroad as “suspected” endocrine disrupters, therefore they were not necessarily asserted as endocrine disrupters at that time. The “SPEED’98” was later reviewed, and only 65 chemical substances were included in the November 2000 Version. In order to avoid such misunderstandings as “the listed substances are dangerous”, a special note was added which read “NOTE: The existence of endocrine-disrupting effects, strength and mechanisms have not been proven or clarified for these substances. These are groups of substances for which continued study and research is a priority. It is expected that the number will be reduced as study and research proceeds”. Through its

●Summary of activities by the government

1997:

May, 1998:

June, 1998:

December, 1998:

November, 2000:

June, 2003:

September, 2004:

March, 2005:

・An informational exchange group organized by the Environment Agency, Ministry of Health and Welfare, Ministry of International Trade and Industry, Ministry of Agriculture, Forestry and Fishery, and Ministry of Labour. ・The Environment Agency established a study

group for the endocrine disrupter issue and evaluated literature and results of environment monitoring both domestic and abroad in order to decide subjects of survey and policy.

・The Environment Agency announced "SPEED '98".

・The Environment Agency established a study committee for endocrine disruptive chemicals issues.

・The Environment Agency organized the International Symposium on Environmental Endocrine Disrupters (held every year thereafter).

・The Environment Agency announced the revised version of "SPEED '98". The number of listed substances was reduced to 65.

・MoE (former Environment Agency) announced the results of risk assessments for 40 chemical substances, and decided to review "SPEED '98".

・MoE summarizes the results of “Speed '98" and publishes a leaflet.

・MoE publishes “ExTEND 2005” which is a future policy for endocrine disruptive chemicals.

Fig. 2-9 Major human endocrine organs

Posterior pituitary

Anterior pituitary

Pituitarygland

Hypothalamus

Cerebrum

Cerebellum

Parathyroidgland

Thyroid gland

Adrenalgland

Adrenal medulla

Adrenal cortex

Kidney

Pancreas

Digestive tract

Testis

(male) (female)

Placenta

Ovary

Source : SPEED '98, MoE

29

(4) Results of assessment for endocrine disruptive effects

■ Results of assessment by the Japan Plasticizer Industry Association(JPIA) and academia

In 1997, JPIA not only conducted in vitro tests but also uterine hypertrophy tests on ovariectomized rats, which was the most advanced test method during that time, and confirmed that phthalate esters including DEHP do not have estrogenic activities.

Similar tests were later repeated in academia also, and it was revealed that even though very weak estrogenic activities were (about one-millionth of female hormone) observed in some in vitro tests, no estrogenic activities were seen for phthalate esters in actual animal tests.

■ Assessment results by the MoEThe MoE conducted studies on 24 prioritized

chemical substances listed in “SPEED’98”, and reported the results in June 2002, which revealed that nonylphenol, octylphenol and bisphenol A possibly

had endocrine disrupting effects on fish (or Oryzias latipes), although the effects were lower compared to 17-　-estradiol (a natural hormone). Regarding human (mammal) impact for DEHP (and 9 other substances tested), there were “no apparent endocrine disruptive effects observed at low-dose6) (comparatively low concentration based on estimated human exposure obtained through literature etc.)”.

Furthermore, the results of tests regarding endocrine disruptive effects to ecological systems (Oryzias latipes) revealed that “even though a few cases of testis ovum manifestation was indeed observed, taking into account the results of additional tests conducted in 2002 regarding the correlation of testis ovum manifestation and fertility, it is hard to conclude that there are adverse effects on fertility, and no apparent endocrine disruptive effect were proven for the 5 tested chemicals (including DEHP)7) ”. This means that the endocrine disruptive effects of DEHP have been denied. Fig.2-10 is a summary of the evaluation results by the MoE.

〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇

〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇

〇〇〇〇

Fig. 2-10 Results of assessment for endocrine disruptive effects of chemicals listed in "SPEED '98 "

DEHP

Butylbenzyl phthalate (BBP)

di-n-butyl phthalate DBP

Dicyclohexyl phthalate (DCHP)

Diethyl phthalate (DEP)

Dipentyl phthalate

Dihexyl phthalate

Dipropyl phthalate

Di-2-ethylhexyl adipate (DEHA)

Tributyl tin

Triphenyl tin

Nonylphenol

Octylphenol

Benzophenon

Octachlorobutylene

Pentachlorophenol

Amitole

Bisphenol A

Dichlorophenol

Nitrotoluene

herachlorobenzene

-hexachlorocyclohexane

PP' - DDT

OP' - DDT

PP' - DDD

General purpose plasticizers used for PVC products Source: 2nd Review session on endocrine desruptive substances, MoE 2005

Plas

ticize

rsOt

hers

Tested chemicals

Tests on endocrine disruptive effectson human health using mammals

No endocrinedisruptive effects

No endocrinedisruptive effects

Test results for endocrine disruptive effectson ecosystems using fish

Endocrine disruptiveeffects observed

30


DEHP used for flexible PVC products is included in the indoor air concentration guideline established by the MHLW. However, the objective of the guideline is “to prevent the indoor air pollution and to secure healthy and comfortable air quality”. The inclusion of DEHP in the guideline does not necessarily mean that the substance is determined as cause for the sick houses syndrome. As with the endocrine disrupter issue, these measures were taken in response to social concerns, such as regulations abroad, public comments and widely used products.

(1) What is the sick house syndrome?

“Sick houses” are residential buildings that induce headaches, eye irritations or nausea on residents. It is a word devised in Japan after sick building which was a social issue in the U.S. and Europe during the 1980s. Similar phenomena seen in school buildings

are called “sick school”. Since 1996, the issue of indoor air pollution by chemical substances has been highlighted, as the number of people with allergies, atopic dermatitis or hypersensitivity to chemical substances has increased.

According a sick house issue study group of the MHLW, the sick house syndrome is defined as follows:

3. Sick House Syndrome Issues

Numerous reports have been made on physical dispositions of residents due to indoor air pollution by chemical substances in newly built or reformed houses or buildings. Improved air-tightness and use of housing and interior materials emit chemical substances. Symptoms vary, and data still insufficient to prevent these problems and to clarify the mechanism of the syndrome development. It is called the sick house syndrome, since various elements are thought to cause the issue.

(2) Possible causes behind the sick house syndrome

The sick house syndrome is not unique to Japan. It is said that the following factors are combined to make matters complex:・Increased use of building materials, furniture, 　consumer products, etc. with high chemical 　substances emission・Emission of combustion gases from heating 　appliances・Changes in design and construction methods that 　increase air-tightness of housing・Changes in the life style, e.g., ventilation ・Individual sensitivity to chemical substancesThe above suggests that the modern way of living

in airtight spaces with less flow of air is quite different from traditional Japanese housing where natural ventilation was inseparable.

(3) Governmental actions

As a result of increased use of new construction materials, new materials in general and various chemical substances, new health issues have been raised. In 1996 the Ministry of Health and Welfare started to consider “guidelines for volatile organic chemicals in residential environments” in their “study group on comfortable and healthy housing”. As a result, “guideline values for indoor concentration of formaldehyde” was established in June 1997.

Later in April 2000, a “study committee for the sick house (indoor air pollution) issues” was established in the ministry, where standards for indoor concentration of volatile organic chemicals, sampling methods, and the analysis methods were established.

On the other hand, from July 1996, a study group for healthy housing was jointly established by the Institute for Building Environment and Energy Conservation (IBEC), experts, related industries, and relevant ministerial offices (Ministry of Construction, Ministry of International Trade and Industry, Ministry of Health and Welfare, and the Forestry Agency) in

Sick building :In the U.S. and Europe, it was revealed that most of the sick buildings were not old buildings but modern buildings with air conditioning facilities constructed after 1977. It is said that the major cause of the sick building issue was the increased number and concentration of pollutants emitted within buildings as a result of reduced ventilation air volume in order to cut back on energy.

Hypersensitivity to chemical substances :Once hypersensitivity develops due to exposure to relatively high concentrations of chemical substances, or after repeated exposure to comparatively low concentrations of chemical substances for extended periods of time, a subsequent exposure to even trace amounts of the same chemical substances may trigger hypersensitivity. Such symptom is called

hypersensitivity to chemical substances. The syndrome may be caused by sick houses, but the same can be observed with workers in chemical products manufacturing industries who are occupationally exposed to high concentrations. Accordingly, “hypersensitivity to chemical substances” is not synonymous with the “sick house syndrome”.

31

order to study measures to reduce health impacts of chemical substances in indoor air of residential buildings. In addition, Ministry of Land, Infrastructure and Transport and five other relevant ministerial offices jointly established a subcommittee for survey of actual conditions under a study committee for indoor air measures in order to conduct nationwide survey and to study concentrations of chemical

substances concentration in indoor air. As the result of the survey in fiscal 2000, it was

revealed that the ratio of residences that exceeded the guideline value for formaldehyde was very high 9) , and it was considered necessary to take immediate countermeasures. Consequently, the Building Standards Law was revised July 2002 to deal with the sick house issue.

The Building Standards Law was partially amended on July 12 2002 in order to introduce hygienic countermeasures for volatile chemical substances inside rooms. The outline of the amendment is as follows:・Concentrations of chlorpyrifos and 　　formaldehyde will be regulated.・Use of chlorpyrifos-containing

　construction materials indoors will be 　prohibited.・Use of formaldehyde-emitting housing 　materials for interior finishing will be 　regulated. ・Installation of ventilation facilities 　indoors will be obligated.

● Revision of the Building Standards Law

(4) Guideline values for indoor concentration of chemical substances

100 μg/m3（0.08 ppm） 1997.6

260 μg/m3（0.07 ppm） 2000.6

870 μg/m3（0.20 ppm） 2000.6

240 μg/m3（0.04 ppm） 2000.6

3.80 mg/m3（0.88 ppm） 2000.12

220 μg/m3（0.05 ppm） 2000.12

1 μg/m3 （0.07 ppb） 2000.12

0.1 μg/m3（0.007 ppb）

220 μg/m3 （0.02 ppm） 2000.12

330 μg/m3 （0.04 ppm） 2001.7

400 μg/m3 2000.12

41μg/m3 （7 ppb） Draft

120 μg/m3 （7.6 ppb） 2001.7

0.29 μg/m3 （0.02 ppb） 2001.7

48 μg/m3 （0.03 ppm） 2002.1

33 μg/m3 （3.8 ppb）

※１mg = 1,000 μg１ppm = 1,000 ppb

2002.1

Formaldehyde

Toluene

Para-dichlorobenzene

Ethylbenzene

Styrene

Chlorpyrifos

for young children

DBP

Tetradecane

TVOC (Total Volatile Organic Compounds)

DEHP

Diazinon

Nonanal

Acetaldehyde

Fenocarb　(BPMC)

Adhesives for plywood and glass fibers, etcSolvent for varnish, paint or wood preserving agents, etc

Solvent for varnish, paint or wood preserving agents, etc

Insecticides and aroma agents for chest of drawersSolvent for paints and adhesivesExpanded polystyrene and polystyrene foam (insulation)

Anti termites (insecticides), etc.

Contained in paints and adhesivesSolvents to substitute toluene or xylene

Generated in the body throughexposure to ozone, aroma oil

Plasticizers for PVC products(flooring, wallcovering).

Contained in insecticides

Contained in adhesives

Irritation to the nasopharyngeal mucosa by human inhalational exposureImpacts on the nervous system/behavior and reproductive fertility by human inhalationImpacts on the development of the centralnervous system of offsprings by inhalational exposure to pregnant ratsImpacts on liver and kidney, etc. by exposurethrough oral dosing to beaglesImpacts on liver and kidney by inhalationalexposure to mice and ratsImpacts on the brain and liver byinhalational exposure to rats

Impacts in the form of genitalia abnormalities etc. of offspring by oral exposure to pregnant ratsImpacts on liver by oral dosing exposure ofC8~C16 mixtures to rats

Will be decided within the lowest range possible,based on the research for actual concentrationsof indoor VOC in JapanToxicological impacts by oral dosing of C8~C12 mixtures to rats

Histopathological impacts on the testes ofrats by oral dosing exposure

Impacts on cholinesterase activities, etc.by oral dosing exposure to rats

Impacts on plasma and erythrocyte cholinesteraseactivities by oral dosing exposure to ratsImpacts on the olfactory epithelium in the nasalcavity by exposure through the trachea to rats

Impacts on the development of the nervous system and morphological impacts on the brain of offsprings by oral exposure topregnant rats

Source: Press release document: interim report by the study committee for sick house issuesNOTE: The figures in ( ) are the converted values at 25℃.

Designation of substance Indoor concentrationguideline value Toxicity index Emission source

As of July, 2003

Month/Year ofestablishment

Agricultural chemicals, anti termites, etc

Fig. 2-11 Concentration guideline values of chemical substances indoors

Provisional target value

Xylene

Room : Defined as spaces continuously used for living, office work, other works, meetings, entertainment, and similar purposes.

Total Volatile Organic Compound (TVOC) :The concentration level of various volatile organic compounds, converted to the toluene equivalent value.

32


Many chemical substances are present within indoor air. Guideline values for indoor concentration of chemical substances have been established to improve indoor air quality and to secure healthy and comfortable air quality by the MHLW (Fig.2-11). The guideline values are established under concentrations thought to be non hazardous to human health upon lifetime exposures based on existing scientific data (formaldehyde is an exception, where the guideline value has been established as an index based on short-term exposure toxicity), and this guideline is not legally binding.

Besides theses guideline values, a provisional value called TVOC (total volatile organic compounds) has been set at 400 µg/m3 for standard indoor air quality. Since this provisional value is not based on toxicological data, it is treated independently from the volatile organic compounds (VOC) guideline values, and research will be conducted in order to make this value formal in the future.

(5) Facts from results of survey for indoor concentration of DEHP

The hygiene bureau of the Tokyo Metropolitan Government measured the indoor concentration of phthalates for the first time as a municipal government, in order to check the pollution level of indoor air (Fig.2-12).

Furthermore, the DEHP concentration in fiscal 2000 was reported to be 0.011~2.38 µg/m3 and more than 85% of DEHP was collected as particulaes10). It was also reported that room concentrations in summertime amounted to twice as much as in the winter.　On the other hand, the report on the measurement of indoor phthalate ester concentration during the August-September 2001 period conducted by the MoE for 71 detached houses and 21 apartments throughout Japan revealed that the indoor concentration of DEHP was 0.023~3.4 µg/m3 (outdoor concentration: 0.04~0.51 µg/m3)11).

In both survey reports, the actual concentration was confirmed to be two orders of magnitude smaller than the guideline for the indoor concentration of 120 µg/m3 established by the MHLW. In other words, no special measures for use of PVC wallcoverings and interior materials are needed, considering the wide disparity between the guideline value and the actual indoor concentrations.

Fig. 2-12 DEHP indoor air concentrations

* Tokyo Metropolitan Government** Ministry of the Environment*** Ministry of Health, Labour and Welfare

Indoor concentration(μg/m3)

(Outdoor concentration)

0.35(0.085)

0.31

0.26

0.04 ～ 0.87(0.023 ～ 0.20)

0.023 ～ 3.4 (0.04 ～ 0.51)

0.052 ～ 2.38

0.011 ～ 0.83

Detached houses (64 rooms)Collective housing (28 rooms)

Detached houses (71 rooms)Collective housing (21 rooms)

About 30 housing

Average(μg/m3) Point of measurement Literature

Tokyo*('00)

MoE**('01)

MHLW***('01)

Buildings (50 rooms)10)

11)

12)

33

4. Hydrogen Chloride from Incineration

(1) Establishment of measures against exhaust gases

When wastes are incinerated for disposal, not only dioxins, as already mentioned, but sulfur oxides (SOX), nitrogen oxides (NOX) cyclic aromatic hydrocarbons and hydrogen chloride are emitted also. Especially with hydrogen chloride, PVC wastes contribute to hydrogen chloride generation in the same way as with kitchen waste and waste paper, all of which are chlorine sources. PVC packaging which was once widely used have been reduced significantly, and the current ratio of waste PVC products in municipal waste is now reduced to below 1%. In Japan, emission of the abovementioned chemical substances from waste incineration facilities is strictly regulated to prevent air pollution. In addition, development of modern incineration facilities has been promoted since 1970, since HCl, SOX and NOX which generate acidic gases are closely associated with the corrosion of conventional furnaces.

The modern waste incinerators are equipped with various facilities to control exhaust gases, including neutralization of acid gas by charging lime and caustic soda, or cracking of NOX by NOX removal equipment downstream the bag filter, etc (Fig2-13). As a result, corrosion of waste incinerators is improved, and the standard value for the hydrogen chloride emission to

煙　突

Fig. 2-13 Simplified flow diagram of a waste incinerator system

Waste

Hopper

Combustor

Boiler

Gascooler

Lime/Causticsoda

De-nitrificationUnit

Stack

Bag filter

SO2 NOx

SO42-,NO3-H2SO4 HNO3

H+,SO42-,NO3-

H+

Fig. 2-14 Atmospheric chemistry for acid rain

Emission Transport /Conversion

Deposition

Gas/Aerosol Cloud Processin cloud

Processunder cloud

Cloud waterdrops(solution)

Rain, etc.

Intake

Intake

Evaporation of water

Evaporation ofwater

Wet depositionDry

depositionEmission of causative agents

Oxidation

ImpactsEmissionsources

Receptive fields soil/plants, inland water, goods, structures, human body, etc.

Source : "Acid rain and the environment" March 1999 by the Acid Deposition and Oxidant Research Center of the Japan Environmental Sanitation Center

(2) Major causes of acid rain

In the past, PVC products were accused of as the “the major cause of acid rain” in Europe and other regions, since hydrogen chloride gas is emitted through incineration of PVC waste. However, according to an intensive survey in Europe to identify the emitted quantities of SOX, NOX and hydrogen chloride, it was revealed that the major cause of acid rain were SOX and NOX emitted mainly from power stations, manufacturing plants and automobiles, not by hydrogen chloride from waste incinerators. Fig.2-14 shows a diagram of acid rain formation based on existing information.

In any case, emission of SOX and NOX which cause air pollution and acid rain is associated with all human activities including production, consumption and waste disposal. In a broad sense, measures to prevent them have a lot to do with energy saving which would reduce fossil fuel consumption.

the air of 700 mg/m3N (430 ppm) (some municipalities have additional values) has been cleared, and the emission value is controlled down to the order of 10 ppm.

Hydrogen chloride : Gas composed of chlorine and hydrogen. Forms hydrochloric acid when dissolved in water. Also major component of gastric acid.

34


0

2

4

6

8

10

12

14

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

Fig. 2-15 Transition of PVC resin production by world regions

(Million tons)

Source: Future demand trends for global petrochemical products 2007, METI

Europe

North America

Asia(excluding Japan)

Other regions

Japan

The dioxin issue and the endocrine disrupter issue shocked the Japanese PVC Industry, and “substitution with alternative materials” started within the consumer products field. Such “PVC de-selection” moves have spread to some parts of the durable product field and the production material field within recent years. After peaking in 1997, the decrease in PVC production onwards owes mainly to the shrinking market due to the recession in general and the transfer of production activities to other countries. As a result, the number of PVC resin manufacturers has decreased to 7 companies as of April 2003 from 15 in 1995, partly due to loss of competitive edge of the

5. Impacts on the PVC Industry

industry.On the other hand, the production of PVC resin

during the 1991~2006 period increased 1.2 times in Europe, 1.5 times in North America, and 4.4 times in Asia (excluding Japan) . Japan's growth was 1.06 times for the same period. But Japan's decline after 1998 has been significant (Fig.2-15). From 2002 onwards, Japanese production has been seesawing, but the declining trend has come to a halt due to the somewhat recovering economy, diffculty to substitute to other materials, and the rise in environment friendly applications such as PVC window frames.

35

References : 1) T. Makino, K. Tsubota et al., Chemosphere 46(2000) 1003~1007 2) Informational brochure “Dioxins 2003” by the Council of Ministries and Agencies on Dioxin Policy 3) Dioxins Emission Inventory, September 27, 2004, MoE 4) O. Wada, Journal of academia 830(2001) 9~19 5) Welfare science project for fiscal 2001, “Survey of dioxins pollution situation and study to reduce intake” 6) Results of SPEED '98, September 2004, MoE 7) Press release document by the MoE “The 1st meeting of study committee for endocrine disruptive substances issue, fiscal 2002” 8) Press release document by the MoE “The 1st meeting of study committee for endocrine disruptive substances issue, fiscal 2003” 9) Study Group for Indoor Air Pollution Countermeasures, Actual Conditions Survey Group “Survey report on situations for 2000: executive summary”10) I. Saito et al., “Measurement of Phthalate Esters in Indoor Air”, Journal of indoor environment academia, 5(1)2002, 13~2211) “The 2nd meeting of study committee for endocrine disruptive substances issue, fiscal 2002” proceeding No.3-212) M.Ando.,“Investigative research on substances in indoor air” Research report 1998-2000, p.120

36


CHAPTER 3: ENVIRONMENTAL ACTIVITIES BY THE PVC INDUSTRY

Disposal of plastic wastes have been a major challenge in the context of waste disposal and prevention of environmental pollution. Issues have been pointed out regarding PVC and PVC products; quite a few of which are based on misunderstanding due to lack of accurate information, especially regarding dioxin formation.

The present status of various activities jointly promoted by the PVC industry, PVC converter organizations, relevant businesses, and the government administrations will be introduced here in chapter 3 in order to provide proper understanding of PVC and PVC products.

7,000

6,000

5,000

4,000

3,000

2,000

1,000

01975 1980 1985 1990 1995 2000 2005

70

60

50

40

30

20

10

0

Responsible Care (RC) :Voluntary control activities of chemical manufac-turers and dealers to conduct and improve envir-onmental, safety and health measures throughout the lifecycle of chemical substances (from R&D to production, logistics, use, consumption, and waste disposal) based on the principles of self-determi-nation and self-responsibility.

Pollutant Release and Transfer Register (PRTR) :A system to track, compile and release to the pub-lic the data regarding various hazardous chemical substances such as emission sources, emissions to environment, or amount transported outside of business premises in the form of wastes.

High production volume (HPV) chemicals :Any existing chemical substance manufactured over 1,000 tons per country per year. The HPV chemicals program by the OECD collects and eval-uates data on safety. In Japan also the Japan Chemical Industry Association mainly undertakes related tasks.

Fig. 3-1: Transition of VCM emission to air and investments for reduction measures

VCM

em

issi

on (t

)

Tota

l inve

stmen

t for

redu

ction

mea

sure

s (￥

billio

n)

General emission (VEC members only)

Gross emission PRTR (Includes related organizations)

￥25 billion

￥33.6 billion

￥44.3 billion

Source: VECfiscal year

　End of 1973: VCM related cancer incidents in the U.S.　Early-1974: VCM emission reduction measures launched in Japan　 Occupational hygiene measures: establishment of the Industrial Safety and Health Law in 1975 　　 Food hygiene measures: establishment of the Food Sanitation Law in 1977　　General environmental measures　 Feb. 1980: Establishment of the "voluntary standards for emissions reduction"　 1988: Degradability tests based on the Japanese Chemical Substances Control Law　 1995: Survey of actual conditions by the Ministry of International Trade and Industry (present METI)　 1997: Start of the 1st reduction plan　 2000: Participation in OECD's investigation of HPV chemicals program　 2000: Start of the 2nd reduction plan

<Total capital investment for reduction measures>　　 Fiscal 1975-1995: ￥25 billion　　　 Fiscal 1997-1999 (1st):￥8.6 billion (including EDC)　 Fiscal 2000-2003(2nd):￥10.7 billion (including EDC)

38

CHAPTER 3 : ENVIRONMENTAL ACTIVITIES BY THE PVC INDUSTRY

1. Responsible Care

geometrical average concentration) were established. The Japanese PVC industry, mainly VEC (then called

the PVC Industry Association) determined its own voluntary rules for reduction of VCM emission and started its 1st voluntary reduction plan in fiscal 1997.

The targets of the voluntary reduction plan were set at 22% reduction for VCM emissions and 30% reduction for EDC within three years. As a result, 24% reduction of VCM and 59% reduction of EDC were achieved, both of which far exceeded the initial targets.

■ The 2nd voluntary emission reduction planVEC has been addressing its 2nd voluntary emission

reduction plan since fiscal 2000, subsequently to its 1st plan. Emissions have been set at 100 g-VCM/t-VCM upon production of VCM, 100 g-VCM/t-VCM for use in suspension polymerization process, and 1,000 g-VCM /t-VCM for use in emulsion polymerization processes. Emission upon EDC production is set at 250 g-EDC/t-EDC. Further reductions are aimed for.

■ Measurement of concentrations in the environment

Since 1997, the Ministry of the Environment is continuing annual measurements of EDC/VCM

(1) Pollutant Release and Transfer Register (PRTR) in the PVC industry

Ethylene dichloride (EDC) and vinyl chloride monomer (VCM), which are raw materials of PVC, have been included in Class I Designated Chemical Substances under the PRTR Law. From fiscal 2002, it has been made mandatory for relevant businesses to report actual emission figures of the preceding year regarding these substances to municipal governments of the region.

Prior to this the Vinyl Environmental Council (VEC) had taken the measures for improvement of emissions based on Responsible Care and made use of the economically viable best available technology (BAT) through its "2nd three-year plan for reduction of EDC/VCM emissions to air" which started from fiscal 2000.

■ Backgrounds of the voluntary standards for EDC/VCM emissions

Carcinogenicity issues upon EDC/VCM manufacturing processes triggered publication of a work environment standard of VCM in Japan in 1975 (work environment; below 2 ppm, inside polymerization reactors; below 5 ppm, both

39

concentrations in the general environment. In fiscal 2006, more than 2,400 samples were taken for measurements of VCM and EDC respectively- from 254 sites for VCM and from 247 sites for EDC (Fig.3-2).

The results of analysis showed that from 1997 to 2006, the average VCM concentration declined from 0.21 µg/m3 to 0.05 µg/m3. As for VCM, annual average concentration in air of 10 µg/m3 (0.0036 ppm) as a guideline was set in 2003, but the present actual concentration is far below this guideline level.

Likewise, the average EDC concentration in the general environment was 0.20 µg/m3 in 1997 but has been reduced to almost one half since 2001.

Furthermore, an annual average concentration guideline in air of 1.6 µg/m3 is set for EDC.

(2) Dioxins emissions from VCM production facilities

Under the Law Concerning Special Measures against Dioxins, every year the Ministry of the Environment (MoE) conducts a survey of the status of dioxins emissions from specified facilities and facilities (industries) likely to be the emission sources based on available information.

Fig.3-3 shows the results of survey for dioxins emission from the VCM production facilities. Emissions from VCM production facilities in 2006 were 0.36g, which amounts to less than 0.4% of emissions from all industries, which totaled 93 g.

■ Emissions to airThe annual emissions to air is calculated per facility

based on the results of voluntary measurements of exhaust gases resulting from liquid waste incineration (7 facilities throughout Japan: 0.019~1.3 ng-TEQ/m3N) and results of voluntary measurements of exhaust gases from waste gas incineration (5 facilities throughout Japan: 0.00025~0.29 ng-TEQ/m3N). The total annual emission is calculated by summing all of these.

The emission per ton of VCM production is 78.2 ng-TEQ/ton in the case of liquid waste incineration (i.e., the total annual emission is divided by the total of annual VCM production of 3,228 thousand tons by the facilities incinerating liquid waste). Likewise, emission per ton VCM production is 6.7 ng-TEQ/ton in the case of waste gas incineration (i.e., the total annual emission is divided by the total of annual VCM production of 2,721 thousand tons.

■ Emissions to waterThe annual emissions to water for 2006 was

estimated by summing the total annual emissions from the eight industrial establishments (0.0017~2.0 pg-TEQ/L) in Japan, owned and operated by the member companies of VEC.

199711

0.210.012

0.9

19981520.13

0.0092.2

19991620.10

0.0081.8

20001690.08

0.0021.1

20011840.07

0.0031.6

19971840.20

0.0172.7

19982120.19

0.0252.6

19992200.15

0.0102.0

20002160.16

0.0082.1

20012270.11

0.0061.1

20022280.10

0.0171.3

20021970.07

0.0022.7

20032330.10

0.0081.0

20032180.05

0.0021.4

20042290.13

0.0051.7

20042190.06

0.0031.8

20052490.10

0.0050.7

20052270.04

0.0020.6

20062260.05

0.0031.5

20062490.13

0.0051.7

Fig. 3-2 VCM and EDC concentrations in the general environment

VCMFiscal year

Fiscal year

Unit: µg/m3

# of sitesAverageMin. valueMax. value

# of sitesAverageMin. valueMax. value

EDC

Source: Monitoring of hazardous air pollutants, MoE

2000

0.19

0.20

0.39

2001

0.29

0.58

0.87

2002

0.29

0.16

0.45

2003

0.30

0.10

0.40

2004

0.21

0.07

0.28

2005

0.22

0.10

0.32

2006

0.28

0.08

0.36

1997

0.20

0.54

0.74

1998

0.20

0.53

0.73

1999

0.20

0.55

0.75

Fig. 3-3 Results of dioxins emission survey from VCM production facilities

Unit: g-TEQ/year

Emissions to airEmissions to water

Total


40


(1) Status and activities

■ Status of recycling, processing and disposal of plastics and PVC products

According to the Plastic Waste Management Institute, the total discharge of plastic waste in 2006 was 10.05 million tons, out of which 2.04 million tons (20%) were treated by mechanical recycling, 280 thousand tons (3%) by feedstock recycling (use in blast furnaces and liquefaction), and 4.89 million tons by thermal recycling (heat recovery)49% . Therefore, the total recycling rate was 72%, and the remaining 28% were either incinerated or disposed in landfills (Fig.3-4).

As for waste PVC products the total discharge was approximately 1.0 million tons, out of which approximately 390 thousand tons (38%) were treated by mechanical recycling. Compared with plastics as a whole, the mechanical recycling of PVC waste is a step ahead. This is because PVC is less affected by contamination of foreign matters and has various

recycling applications.

■ Recycling activities of the PVC industry There are roughly three types of recycling process

for plastics.

2. Recycling of PVC Products

※Mechanical recycling: A recycling process to return the recovered and sorted plastic waste back into plastic material by physical procedures※ Feedstock recycling: A recycling process to convert recovered plastic waste into feedstock through thermal processing, pressurizing and chemical reactions. Plastic waste is converted into reducing agents for blast furnaces, fuel/feedstock for cement kilns, and raw material gas for chemical processes. ※ Thermal recycling:A recycling process where waste plastics are incinerated for thermal energy recovery

The Japanese PVC industry primarily promotes mechanical recycling, but this recycling process is not suitable for excessively deteriorated or fouled plastic waste. Also, since there are still some difficulties in further developing applications and distribution channels, the increase of recycling volume is limited. For such reasons, feedstock recycling is also promoted due to its versatility.

Recycling projects are shared, for instance the Japan PVC Environmental Affairs Council (JPEC) mainly takes charge of mechanical recycling, while VEC mainly takes charge of feedstock recycling.

(2) Mechanical recycling

■ PipesPipes are the largest application for PVC, and

approximately 500,000 tons of PVC pipes (including fittings) are manufactured annually. This amount represents roughly one-third of the annual PVC consumption. The amount of waste pipes are estimated to be about 35,500 tons in 2002, out of which about 48% are recycled back to pipes. In

order to promote recycling of PVC pipes, the Japan PVC Pipe and Fittings Association (JPPFA) took the initiative to establish 10 recycling centers throughout Japan in December 1998 under cooperation with existing recycling business entities. In addition to these recycling centers, intermediate collection facilities were provided for nationwide collection of waste pipes. As of May 2007, 17 recycling centers and 33 collection facilities (a total of 50 facilities) have been established. Along with the conventional

Fig. 3-4 Scheme of the three methods of recycling

Sorting1. Mechanical recycling

Material Pipes

Agro-film

necessary

2. Feedstock recycling

Material PVC waste

Fuel/Feedstock for cement kilns

Chemical raw material gas

mixed plasticwaste ok

mixed plasticwaste ok

3. Thermal recycling

Material PVC waste

Electrical energy

(Physical processing)

Pipes

Flooring

(Chemical processing) Material

Material

Reducing agent for blast furnaces

(Incineration) Energy recoveryThermal energy

41

pipe purchasing system, an intermediary treatment consignment system was newly started from 2003.

The Law Concerning Recycling of Materials from Construction Work (in short, Construction Material Recycling Act) established in 1999 has made mandatory the recycling of specified construction materials. Concrete, asphalt and wood are specified for recycling at the moment, and PVC construction materials are not included.

On the other hand, PVC construction materials are widely used due to their excellent properties as construction materials (fire retarding properties, durability, designability, processability, etc.). VEC, JPPFA, PVC windows industries association, PVC spout manufacturers association, Interiorfloor Industrial Association (flooring), Japan Vinyl Goods Manufacturers Association (wallcovering), and the Japanese Electric Wire & Cable Makers' Association jointly organized a "study group for recycling of PVC construction materials" with participation from the chemical industry division and the ceramics industry division of the Ministry of International Trade and Industry (the present METI). This study group is active to date under the name of "PVC construction material liaison conferece" and continues to contribute to recycling systems within each industry through information sharing and close horizontal communications among the PVC construction material related industries.

This group discussed the ways to promote the recycling activities, and proactively made recommendations to the Japanese government. As a result, the Law for Promotion of Effective Utilization of Resources was enacted in April 2001. Rigid PVC pipes and fittings were specified as products to be recycled under the Law for Promotion of Effective Utilization of Resources, and recycling efforts were made mandatory. Also, rigid PVC pipes, spouts, window profiles, flooring and wallcovering were required to attach the common "∞ PVC" mark to show that they are PVC construction materials.

Following the decision, the PVC construction material industries further promoted recycling activities, and PVC construction materials gained credit as products that are easy to use. Furthermore, sewage pipes and heat insulating window profiles made of recycled rigid PVC material were specified as products to be procured (for public construction projects) under the Law on Promoting Green Purchasing. The recycling activities for PVC flooring installation wastes by 8 PVC flooring manufacturers of the Interiorfloor Industrial Association were given the sanction of specified industrial waste disposer for wide area recycling from the minister of the environment for the first time as a trade organization. The recycling activities have been launched in 2003.

Outer layer(virgin resin)

Tile (Modular) carpets(Recycled agro-filmmaterial is used as

backing )

■ Agricultural PVC films Presently, about 70,000 tons of agricultural PVC

films (agro-films) are discharged per year, out of which about 50% is mechanical recycled.

The mechanical recycling of agro-films started during the mid 60’s. Today, farmers, agricultural organizations, and municipal governments have set up a council in order to systematically collect agro-film waste for appropriate recycling. More than 10 manufacturing centers for recycled raw material products have been established throughout Japan, and a system for recycling has been set up. At these centers, flooring, footwear, sheets and others are manufactured out of the recovered agro-films. In order to further promote the mechanical recycling of agro-films, 7 agro-film producers and the National Federation of Agricultural Cooperative Association (Zen-Noh) established the "Noubi Recycle Acceleration Council (NAC)" in July 1999.

NAC is expected to promote the implementation of nationwide recovery and processing systems in order to develop new agro-film processing technologies and applications, to realize a totally recycle-based society in the future.

■ PVC construction materials

(Nominal diameter) 100, 150, 200 and 300mm(Color) Blue grey

Middle layer(recycled material)

Inner layer(virgin resin)

Homogeneous tiles(Recycled agro-film material is used as backing )

Outer layer(virgin resin)

Recycled three-layer pipes

42


(3) Feedstock recycling

■ Plastic contributing to steel manufacturing - feedstock for blast furnaces

By this recycling technology, coke, which works as a reducing agent to remove oxygen from iron ore in steel manufacturing, can be partially replaced with plastic waste. From the environmental standpoint, various advantages are expected from this technology including saving cokes and CO2 reduction.

The Japanese PVC industry conducted research and development of blast furnace feedstock technologies for plastic waste (including PVC waste), jointly with the present JFE Kankyo. Following pilot tests in 1998 and operations at a demonstration plant in 2000, the preparation for commercial operation is now under way at JFE Kankyo since fiscal 2004.

JEF Steel's Keihin Steelworks (Kawasaki City)

Showa Denko’s Kawasaki plant (Kawasaki City )

■ Generating new chemical raw materials or energy - gasification

By thermal cracking at high temperatures, PVC waste can be recycled into gas components such as hydrogen chloride, hydrogen and carbon monoxide, which can be put to use.

The Japanese PVC industry has been working to materialize gasification technologies to treat various plastic wastes including PVC, jointly with Nippon Steel, Daicel and Sumitomo Metals. Hydrogen and carbon monoxide derived from this process can be used for ammonia and methanol production, or as fuel gas for power plants. Hydrogen chloride (hydrochloric acid) is widely used as chemical raw material or as industrial chemicals. Also, Ube Industries/Ebara Corporation (EUP) and Showa Denko are operating plants with pressurized two-stage gasfication furnaces to meet the requirements of the Container and Packaging Recycling Law.

PVC waste de-HCl HCl Absorption / Purification

Chemical raw material /Industrial chemicals

Reducing agent for blast furnacesFuel / Raw materialfor cement kilns

(HCl)

(Char)

PVC waste Gasificationfacility

HCl Absorption /Purification

Chemical raw material /Industrial chemicals,Fuel gas

Material for roadbeds, etc.

(Syngas)

(HCl)(Molten slag)

43

■ Collection of metals by chlorinated volatization (Kowa Seiko)

This process separates iron and non ferrous metals from iron rich matters (such as dust collected at the collection ducts of steel making plants) by using chlorine. PVC is incinerated to collect thermal energy and at the same time the hydrogen chloride generated is proactively used as the chlorine source for this chlorinated volatilization process. As an example, during the 5 years between 2003 and 2007, 200 tons per year of scrap or waste PVC wallcovering generated from either building or renovating collective housings and buildings were collected and treated under the Wallcovering Association of Japan’s initiative.

(4) Recycling under new technologies

■ Material recycling by dicing and pulverizing technology

Refinverse Inc. had launched the recycling of PVC layers from used modular carpet discharged from office buildings and intermediate processing companies. The technology involves scraping off

Tile carpet waste

Separation of PVC backing

Source: Technical document from Refinverse Inc.

Recycled PVC compound

Recycled PVC backing

Recycled tile carpet

Kowa Seiko(Kitakyushu City)

PVC layers from modular carpets with precision and separating them in powder form to reuse as a raw material component for the manufacture of new tile (modular) carpets. It has been commercialized at their plant in Chiba with an annual processing capacity of 18,000 tons since 2006. This quantity amounts to about 15% of the total modular carpets discharged.

PVC waste

Collection of Metals Chlorinated Volatitization

Metal chloride collecting device

Wet separation process

Metal chloride gas Pelletize

12000 C

HCl

Pb Zn Cu Fe

CaCl2 Ferric oxide containingPb , Zn

Calcinated ferric oxide

Calcium sulphate

Chlorinated volatilization/Rotary kiln calcination

44


(1) Recycling of "PVC construction material wastes" generated from the western Tottori prefecture earthquake

Under cooperation with the Tottori prefecture government, Yonago city authorities, and Sakaiminato city authorities, the Japanese PVC Industry undertook recycling of “PVC construction material wastes" recovered from destroyed houses and buildings by the western Tottori prefecture earthquake (magnitude 7.3), which occurred on October 6, 2000. This was the first case in the world to recycle wastes generated by a natural hazard (not limited to PVC waste, but other plastics as well).

The PVC construction materials waste including pipes, spouts, corrugated sheets, etc. recovered from the collapsed houses and buildings were stored temporarily at the

3. Constructing Social Systems

Temporary collection facilities for wastes

collection facilities in Yonago city and Sakaiminato city, processed into regenerated materials, and then recycled back into PVC pipes by pipe manufacturers. A part of the waste material was reused (by feedstock recycling) as the fuel/raw material for cement kilns.

PVC construction materials waste generated by

natural hazard collected in containers Raw material for pipes

Recycled pipe (3 layer pipe)

Recycled pipe

Fig. 3-5 Recycling flow of PVC construction materials 　　　 waste generated by the earthquake

Temporary collection facilitiesfor PVC construction materials waste

(Yonago city, Sakaiminato city)

Recycle cooperation companies(processing into recycled raw materials)

PVC pipes and fittings manufacturers(production of recycled pipes)

Cement manufacturers(utilization as fuel/raw material

for cement kilns)

Procured by the national governmentand municipal governments

45

VEC, JPPFA, and Sumitomo Metals are promoting the demonstration experiment for feedstock recycling of waste PVC construction materials in cooperation with the TMG.

In July 2002, waste PVC construction materials generated from the demolition site at Niijuku, Katsushika-ku, Tokyo, were processed into raw material for recycled pipes by mechanical recycling ("Recycling model project for residential buildings owned by the housing bureau of TMG"). Also, a part of PVC construction materials waste, which were excessively fouled or mixed with foreign matters, were processed by a pilot gasification melting plant of Sumitomo Metals, in November 2002, for reuse as chemical feedstock. It was confirmed that there was no technical difficulties with the gasification. The results of feedstock recycling as well as mechanical recycling were reflected on the "manual of recycling waste construction

Demolition of residential buildings owned by the TMG

materials from residential building" (edited and published by the technical development division, regional housing department of the housing bureau, TMG. 2003).

Collected PVC waste pipes

Regenerated pipes

Gasification melting plant

Fig. 3-6 Demolition of residential buildings owned by the TMG and recycling

Housing bureau, TMG

PVC wastes generated fromresidential buildings at

Niijuku 6-chome, Katsushika-ku, Tokyo,owned by the TMG

Incorporation of resultsto the recycling manual

VEC

Feedstock recycling

JPPFA Sumitomo Metals(gasification melt plant)

Mechanicalrecycling

Recycled pipesmanufacturers

(2) Recycling of "PVC construction materials wastes" recovered from demolition sites of residential buildings owned by the Tokyo metropolitan government (TMG) : an example of public-private sector cooperation

46


(3) Recycling of PVC Profiles

The PVC sash (PVC profile) is widely used as an energy saving construction material with a high heat-insulating feature. The PVC profile manufacturing industry is specified as the applicable industry along with the PVC pipe and fittings manufacturing industry under a "waste processing and recycling guideline for industries" by the industries structure council, (METI).

The environmental working group which was jointly formed by the technical committee of the PVC Windows Industries Association and the environmental issue committee of the Japan Sash Manufacturers Association tested the physical properties of recycled PVC profiles, and confirmed that there is no problem with the molding operation, and that the physical properties of molded window

frames are enough to meet the JIS standards. Furthermore, the two-layer extrusion molding

technology to use recycled material in the core section and use virgin resin in the surface layer of window profiles has already been put into practice. It has also been confirmed that the color variance of the recycled material with the color of finished product window profiles would not be a major problem for "sash-to-sash" recycling.

For information, this PVC window profiles recycling was selected by the METI as one of the evaluation themes for the ministry's open invitation for fiscal 2002, and evaluated under "PVC profiles recycling system survey", chaired by Mr. Tsuyoshi Seike, assistant professor of Tokyo University. The details of this survey are included in the "Handbook of recycling: 2002 edition" by the Hokkaido municipal government.

Collected waste PVC profiles Washing waste PVC profiles with water

Fig. 3-7 Model scheme of PVC profiles collection and recycling

Scope of activities

Registered demolisherBuilding demolition site

Demolished waste materials including PVCGlass

Construction site of housing

Specified processorSubcontractor

PVC profile manufacturersPrimary intermediate processing

Secondary intermediate processing

Mortar/Caulking, etc.

Auxiliary parts

Aluminum

SteelRoughly crushed waste PVC material

Processing for raw material preparation Molding tests Manufacturers ofextruded products

Scraps frommanufacturing

plantsPVC

profiles

Profile manufacturing plantsRaw materialsRaw materials

PVC product manufacturing plant

47

(4) Recycling of PVC flooring

PVC flooring is an important application that can be derived partially from used agricultural films or used cable covering.

The recycling of waste flooring itself have been initiated from April 2003 within 8 regions of Japan by 8 PVC flooring manufacturers which are members of the Interiorfloor Industries Association. Installation waste discards from new housings and buildings construction and reform sites are sorted and recovered, then recycled into flooring at each

manufacturers after crushing and processing. PVC flooring sheet, cushion flooring and homogeneous flooring tiles are recycled by the above 6 companies and 3 other subcontracted companies.

The feature of this recycling activity is "horizontal recycling from flooring into flooring" by the flooring manufacturers themselves. In March 2003, the Interiorfloor Industrial Association was specified as “industrial waste disposer for wide area recycling" from the Environment minister for the first time as a trade organization, and have launched its activities.

Areas conducting flooring recycling

Saitama

Tokyo

Chiba

KanagawaAichi

Osaka

Hyogo Kyoto

New housings & buildings construction sites,

Building contractors, General contractors,

Housing manufacturers

Discards, scraps

Crushed raw materials

Products

Freighters Flooring manufacturers

Crushing plants

48


(5) Recycling of PVC wallcoverings

It has been over 30 years since PVC wallcovering was first introduced to Japan. Production of wall covering in Japan amounts to about 700 million m3, or about 200 thousand tons. The PVC wallcovering has become an inseparable part of comfortable residences, having durability, serviceability, and fire retarding properties, and has established its own position in the modern life.

On the other hand, recycling of wallcovering was not conducted partially due to the small amount of wastes, due to its long service life of over 10 years.

However, gradual increase of discharged waste wallcovering is expected, in line with the increased number of demolished or renewed houses and buildings after a few tens of years of construction. Labeling of "∞ PVC" mark to PVC wallcoverings is now mandatory in the same way as with PVC pipes and flooring, as a "specified product for indication obligations" under the 1999 revision of the Law for Promotion of Effective Utilization of Resources. As a result, how to cope with social requirements has become a major issue to be tackled by the wallcovering industry.

An experimental recycling model was carried out as preparation for full-scale recycling systems, by the Wallcoverings Association of Japan (WACOA), which is comprised of manufacturers/whole sellers and servicing companies, from April 2003.

Fig.3-8 shows the flow of the recycling scheme. The waste wallcovering collected and sorted by the building contractors were temporarily transferred to collection facilities, compressed/crushed upon

intermediate processing, and then transported to Tobata Plant of Kowa Seiko in Kita-Kyushu City, Fukuoka Prefecture, where wallcovering waste was utilized as heat source for industrial waste processing, or as feedstock to cement kilns. Recovered chlorine from the process was effectively used in the extraction of valuable metals under chlorinated volatilization process. Also, a part of waste PVC wallcovering was utilized as raw material in the manufacturing of boards and blocks by mechanical recycling.

The WACOA of Japan successfully completed this model experiment in 2007, and is currently considering a new business model for wallcovering recycling based on the outcome.

Compressed and packed PVC wallcovering waste

Fig. 3-8 Model scheme of recycling experiment for PVC wallcovering waste

・Heat source for　industrial waste processing・Raw material for　cement manufacturing・Recovery of valuable metals by　chlorinated volatilization process

Recycle processing(Kowa Seiko,Tobata Plant)

Discharge sites(Construction/Remodeling/

Demolition sites,Wholesellers, Plants)

Land transportation

Land transportation

WACOA(Supporters: JPEC, VEC)

Storage(Collection sites)

Intermediate processing(Crushing-Compressing/

Volume reduction orConversion to RDF)

Flow of PVC wallcovering waste

Shipboard(Shinmoji port← Ariake port)

49

(6) Recycling of refrigerator door gaskets

In the past, the municipal governments collected end-of-life refrigerators, TV, air-conditioners and washing machines as large-sized wastes, and the majority of them were disposed in landfills. In April 2001, the Electric Household Appliances Recycling Law was enacted and about 10 million units of these products were recycled at more than 30 recycling plants throughout Japan. Steel for casing and glass used as the cathode-ray tubes were the major materials for recycling.

Although PVC parts were not applicable for recycling under the law, an effort to recycle refrigerator door gaskets made of PVC was initiated by recovering the gaskets and removing magnets from them, as a part of activities to materialize a recycled-oriented society. Recovered door gaskets are crushed into small pieces, molten by heating, and converted into synthetic wood for indoor flooring applications.

■ Basic Law for Establishing a Sound Material -Cycle Society (January 2001)

It is the basic framework law for the realization of a recycle-based society through the promotion of 3Rs (i.e., Reduce, Reuse, and Recycle) and subsequent incineration and volumetric reduction for appropriate disposal by landfill. Also, "the discharger responsibility" of business enterprises and citizens, as well as the concept of Extended Producer Responsibility (EPR) for manufacturers has been clarified. From the standpoint of implementing a recycle-based society, PVC is a plastic which can realize the 3Rs, since PVC products are resources saving, durable and easy to recycle.

■ Law for Promotion of Effective Utilization of Resources (April 2001)

It is a general law showing the basic framework for the promotion of the waste generation reduction (Reduce), the reuse of materials (Reuse), and the re-utilization (Recycle) by converting the materials into resources, and for extended service lives of products. The law has specified the industries which are obligated to manufacture recyclable products, and has specified the products to which identification marks are to be affixed in order to make sorting easier. Of the PVC products, rigid PVC pipes and fittings are specified products for mandatory recycling. PVC pipes

Separation of magnets from PVC gaskets at the recycling plant

Sorted refrigerator door gaskets

Synthetic wood for flooring

4. PVC Products and Recycling Related Laws

are also specified for marking indication. Furthermore, PVC-made spouts, window profiles, wallcovering, and flooring are also specified products for identification mark of "∞ PVC".

■ Containers and Packaging Recycling Law (April 2000)

Of the solid municipal wastes, about 60% by volume and about 25% by weight are containers and packaging. The law was first applied to PET bottles and glass bottles in 1996, and subsequently to plastics in general "as other plastics" and waste paper in April 2000.

Specified business entities, such as the manufacturers of containers, packaging and their contents, are required to entrust recycling to the specified corporate body by paying recycling charges. PVC bottles and sheets for commercial applications have been decreased, and presently they are estimated to occupy only 3-4% of total plastic wastes in solid municipal wastes.

Identification mark

SPI codePVC PVC

Identification marks for containers and packaging

50


■ Home Appliance Recycling Law (April 2001)

The law promotes recycling of 4 large-sized electrical household appliances (i.e., refrigerators, TV, washing machines and air-conditioners) disposed from households as wastes, which had previously been collected and landfilled by municipal governments. The law is now applicable to these waste products from April 2001. Presently, the main materials specified for mandatory recycling are steel and glass, which amount to 50-60% of the total collected volume. Although recycling of PVC materials are not mandatory under the law in the same manner as with other plastics, some of the electric household appliance related companies have started recycling of PVC gaskets on refrigerator doors.

■ Construction Material Recycling Law (May 2002)

The law promotes recycling of construction material waste, amounting to about 20% of the total industrial waste. Waste asphalt, concrete and wood are the 3 items in "specified construction material wastes" to be recycled under the law. Although PVC materials are not included in the specified materials under the law,

recycling systems for waste rigid PVC pipe is readily implemented, and intermediate collection facilities have already been deployed throughout Japan.

■ End-of-Life Vehicles Recycling Law (January 2005)

The law promotes recycling of end-of-life automobiles (5 million cars per year). Collection and recycling of CFC gas, air bag and shredder dust generated in the dismantling operation of waste cars are mandatory under the law.

■ Law on Promoting Green Purchasing (April 2001)

The law is aimed to prioritize procurement by the national and municipal governments of products and services that contribute to the reduction of environmental burdens, specified as "environment compatible products, etc.", and to promulgate information useful for such procurement system. Of the PVC products, heat insulating profiles (February 2002) and recycled rigid PVC pipes for sewage systems (February 2003) have been selected as "specified items for green procurement (for public construction projects)".

Fig. 3-9 Structure of Recycling Related Laws

Put into force:January 2001

Amended:June 2006

Put into force:April 2000


Put into force:May 2001

Put into force:May 2002

Put into force:Jan 2005

Containers andPackaging Recycling Law

Home Appliance Recycling Law

Food Recycling Law

Construction Material Recycling Law

End-of-LifeVehicles Recycling Law

glass bottles, PET bottles, paper & plastic packaging etc.

air conditioners, refrigerators, TV, washing machines

food waste wood, concrete, asphalt

automobiles


Green Purchasing Law (Promotion of procurement of recycled products by the national government on its own initiative)


Fundamental Law for Establishing a Sound Material-Cycle Society

Waste Management Law Law for Promotion of EffectiveUtilization of Resources

<Proper waste management> <Promotion of recycling>

1. Curb generation of waste2. Proper waste disposal (incl. recycling)3. Regulations for waste processors4. Establishment of standards for waste disposal

1. Recycling of recovered resources2. Development of structure/material for easy recycling3. Labeling products for selective collection Identifying mark : ∞ PVC4. Promotion of effective utilization of by-products

Reduce Reuse Recycle (3R)

Recycle (1R)

Regulations in accordance with the characteristics of specific products

(basic framework law)

CHAPTER 4: THE SAFETY OF ADDITIVES

Additives used in plastics consist of “plasticizers” which soften plastics which are inherently hard, “stabilizers” which enhance the heat stability in molding and heating operations, “antioxidants” and “UV absorbents” which prevent quality deterioration during use of plastic products, and “lubricants”, “pigments” and “fillers” which give additional properties to plastic products.

After addition of these various additives, PVC is molded and fabricated into durable products such as pipes for water supplies and sewers, electric cable coverings and construction materials, or agricultural films (agro-films) and medical devices, which have long been used as important materials supporting our society and daily life.

Data revealing the safety of two major additives for PVC, i.e., “plasticizers” and “stabilizers” are shown in this chapter.

52

CHAPTER 4 : THE SAFETY OF ADDITIVES

(1) Role of plasticizers

PVC is basically a hard plastic at ordinary temperature. This is due to the short distances between the molecules since there are strong pulling forces between them (intermolecular forces). When heated, the energies of molecular motions become greater than the intermolecular forces, which widen molecular distances, resulting in softening of the resin. When plasticizers are added to PVC at this stage, the plasticizer molecules make their way between the PVC molecules and prevent the PVC polymer molecules from coming closer with each other. Consequently the polymer molecules are kept apart even at ordinary temperature and softness is kept. This is the role of plasticizers and such process is technically called plasticizing.

PVC polymer molecules have positive and negative polarities within, while plasticizer molecules also have such polar and non-polar parts. The PVC polymer

1. Safety of Plasticizers

molecules and the plasticizer molecules are electrically attracted to each other as shown in Fig.4-1, and the non-polar parts widen the distance among the polymer molecules to keep softness. PVC products which are softened by plasticizers are called soft (flexible) PVC products. About 40% of the total PVC is used for flexible PVC products.

Plasticizers conform well to PVC (compatibility), and keep the required softness at minimal quantity (plasticizing efficiency). Plasticizers should not easily migrate into air or water (low volatility, low migration). The plasticizers widely used for PVC products are di-2-ethylhexyl phthalate (DEHP) and di-isononyl phthalate (DINP), which have well balanced properties described above. These plasticizers account for about 80% of all plasticizers used for PVC. Apart from these two, adipate plasticizers for low temperature resistance and trimellitate plasticizers for heat resistance are used to meet specific requirements.

(2) Type of plasticizers

There are several kinds of plasticizers, such as phthalates, adipates, phosphates and trimellitates, and phthalates account for more than 80% of all plasticizers used (Fig.4-2).

Although the major application of phthalates is plasticizers for PVC, they are also used for other applications as shown in Fig.4-3.

－　　　＋

－　　　＋

＋　　　－

＋　　　－

－　　　＋

－　　　＋

＋　　　－＋　－

＋　　　－

－　　　＋

－　　　＋

＋　　　－

＋　　　－

O

C O CH2 CH

C2H5

CH2 CH2 CH2 CH3

O

C O CH2 CH

C2H5

CH2 CH2 CH2 CH3

Fig. 4-1 PVC molecules, plasticizer molecules and molecular formula of DEHP

PVC molecules PVC molecules

Plasticizermolecules

Polar part Non-polar part

Source: Prepared from the website of JPIA

DEHPDINP 51.2%27.6%

Fig. 4-2 Ratio of phthalates in plasticizer production (2006)

Phthalates

Other phthalates6.6%

Other plasticizers

14.6%

Source: " Plasticizer information No.21", Japan Plasticizer Industry Association

85.4%

53

(3) Safety of plasticizers

This section explains the safety of DEHP which is the most generally used plasticizer amounting to about 50% of all plasticizers, based on the data prepared by Japan Plasticizer Industry Association(JPIA).

① Acute toxicity, skin irritation and mutagenicity

As shown in Fig.4-4, the acute toxicity (LD50) of DEHP is lower than that for common salt or sugar, and is almost equivalent to non-toxic.

Fig.4-5 shows the results of evaluation on the safety of phthalates, mainly DEHP, in terms of acute toxicity and other indexes. The level of skin irritancy is within the range of non-irritancy or slight irritancy, which would not affect the human or animal skin. It has also been confirmed that toxicity upon cutaneous absorption is very low.

As for its mutagenicity (meaning the potency to cause damage to the gene), it has been proven that DEHP is negative through microorganism tests.

② CarcinogenicityIn 1980s, the liver tumor of rats and mice was

reported upon an extremely high concentration dosing of DEHP, but subsequent studies clarified that such effects are unique to rodents such as rats and mice and would not occur in primates such as monkeys.

In 2000, the International Agency for Research on Cancer (IARC: an affiliate organization of World Health Organization: WHO) re-classified DEHP from Group 2B to Group 3 in their carcinogenicity evaluation, thus clearly showing that DEHP is not

carcinogenic to humans. Tea and tap water (drinking water sterilized with chlorine) are also included in Group 3, which means that the carcinogenicity of DEHP is lower than that of coffee (Fig.4-6).

③ Endocrine disruptor issuesIn the past, slightly estrogenic effects of DEHP

were reported as a result of in vitro tests. Therefore the Ministry of the Environment listed DEHP as a suspected endocrine disrupter in its Strategic Programs on Environmental Endocrine Disruptors ’98 (SPEED98). However, JPIA subsequently confirmed that DEHP has no estrogenic effects, likewise with other major phthalates, i.e. DBP, DnOP, DINP or DIDP, through in vitro tests and uterine hypertrophy tests using ovariectomized rats.

A study committee for endocrine disruptive chemical

LD50 :An index for amount of chemical substance rendering 50% death rate in experimental animals, expressed in terms of 1kg body weight (median lethal dose). It is the most widely used index to show acute toxicity of chemical substances. The smaller the LD50 value, the stronger the acute toxicity.

Mutagenicity :The property to damage DNA, and substances with such properties are called mutagenic substances. In the past, mutagenicity was synonymous with carcinogenicity. Subsequently, however, existences of many mutagenic substances that are not carcinogens have been

identified through accumulation of scientific data. Today the two terms are differentiated.

Acetic acid Ethyl alcohol Common salt

Sugar Soap

Citric acid DEHP

0 0.5 5 10 15 20 25 30 35 40

Fig. 4-4 Acute toxicity of DEHP and general substances

Acute toxicity to rat via oral dosing (LD50) (g/kg body weight)

Toxic Slightlytoxic

Practicallynon-toxic

Comparatively harmless

Source: Yearbook of chemical industries statistics 1999, METI

DEHP(DOP)DnOPDINPDNPDIDP610P, 711P, etc.DMPDEPDBPBBP

390390418418446―194222278312

386―403―420―282298339370

di-2-ethylhexyl phthalate di-n-octyl phthalate di-isononyl phthalate di-nonyl phthalate di-isodecyl phthalate mixed alkyl chain phthalates (C6~C11) di-methyl phthalate di-ethyl phthalate di-butyl phthalate butyl-benzyl phthalate

Average Low volatility, Low temperature resistance Low volatility, Low temperature resistance Low migration, Electrical insulation Low volatility, Electrical insulation Low volatility, Low temperature resistance Compatibility Compatibility Processability, Plasticizing efficiency Processability, Oil resistance

General purpose Cables/Wires, Films General purpose Cables/Wires, Flooring Heat resistant cables, Artificial leather General purpose Cellulose acetate, Diluents Cellulose acetate, Polystyrene, Cosmetics Paint, Adhesive Adhesive, Sealants

Fig. 4-3 Characteristics and applications of major phthalates

Name of substance Abbreviation MW bp(℃) Features Major applications

Source: Website of JPIA: General purpose plasticizer used for PVC products

54


Teratogenicity :Degree of occurrence of fetal malformation by exposure of substances through the placenta of the pregnant mother animal. Fetuses in the early phase of pregnancy is said to be more susceptible to the impacts on the organ development.

1)

2)

3)

4)

5)

6)

6)

7)8)

9)10)

Fig. 4-5 Safety of phthalates, mainly of DEHP

Index Evaluation Remarks Reference

Acute toxicity Skin irritation and percutaneous absorption toxicity Metabolism Mutagenicity Teratogenicity Subacute/Chronic toxicity Testiculartoxicity

Carcinogenicity

Endocrine disruptive effects (Endocrine disrupter issues)

Lower acute toxicity than those for general substances such as common salt and sugar Within the range of non-irritation or slight irritation. Toxicity also very low. Metabolism in and excretion from the animal body very rapid

Negative (no damage to DNA) Teratogenicity occurs in mouse by extremely high-concentration dosing to mother mice, but the effect not clear for rats. High concentration dosing affects the liver, the kidney and testes of rats/mice, but no impact confirmed for primates. High concentration dosing introducesthe testicular atrophy of rats/mice,but no such phenomenon confirmedfor primates (Research continued).

No carcinogenicity in humans. (IARC has categorized DEHP as a Group 3, meaning non carcinogenic substance to humans.)

No estrogenic effect thought to exist.

○The LD50 value of DEHP (rat, oral) is 30~34 g/kg body weight. ○The LD50 value of common salt (rat, oral) is 8~10 g/kg body weight, while that of sugar is 8~12 g/kg body weight. ○Toxicity upon percutaneous absorption was tested in the range of 5~20 ml/kg body weight and no mortality in experimental animals observed. It can be said that toxicity is extremely low.

○In the case of oral dosing to dogs, about 90% of the dosed amount is excreted from the body within 24 hours. ○No mutagenicity has been observed in microorganisms 　in tests for 12 major phthalates. ○Fetal toxicity manifests in rats at 856~1,055 mg/kg body weight/day, and for mice, at 191~293 mg/kg body weight/day. ○JPIA conducted 13-week oral repeated administration tests for DEHP and DINP on primates and checked the impacts on respective organs. ○As to testicular toxicity with rats/mice, no damage was observed in sperms themselves or on spermatocytes, and testicular atrophy has also been identified as recoverable. ○In 1980, manifestation of liver tumor was reported upon dosing of an extremely high-concentration of DEHP to rats, but subsequent studies clarified that the mechanism of liver tumor manifestation is unique to rodents. Presently, it is thought that there are no carcinogenic effects on humans. ○Estrogenic effects of 8 major phthalates were studied. BBP, DBP and DHP exhibited a weak estrogenic activity at a high concentration in the in vitro tests. However, all 8 phthalates showed no estrogenic activities in the in vivo tests (uterine hypertrophy tests with ovariectomized rats).

1) JPIA, Q&A on safety of phthalates (PAEs) Part 1 P.89~92, 1974 2) JPIA, Q&A on safety of phthalates (PAEs) Part 2 P.106~107, 1977 3) JPIA, Q&A on safety of phthalates (PAEs) Part 1 P.147~157, 1974 4) T. Otsuka et al., National institute of health sciences report No.93.1, 1975 5) Tyl, R.W. et al., Fundam. Appl. Toxicol. 10, 395~412, 1988 or NTP 86~309, National Toxicology Program, 1986 6) JPIA, Plasticizer information No.7. 1997 7) JPIA, Plasticizer information special edition. 2000 8) Kurata, Y., Kidachi, F. et al., Toxicological Sciences 42. 49~56. 1998 9) JPIA, Q&A on phthalates and endocrine disrupting issue P.8~9. 1998

10) Zacharewski, T., Meek, M.D., Clemons, J.H. et al., Toxicological Sciences, 46. 282~293. 1998

＊DEHP does not affect the testes of primates as 　opposed to the case with rats (rodents), and ＊Behavior of DEHP in the body of primates is quite 　different from that in rats (rodent), including 　accumulation in the testes, etc.

55

substance issues of the Ministry of the Environment also conducted animal experiments with mammal (rodents), fish (medaka, i.e. Orzias latipes) as well as in vitro tests. In June 2002, the committee reported that DEHP (and other 9 chemical substances tested along with DEHP) had shown no apparent endocrine disruptive effects on humans (mammal). Furthermore,

Microphotograph of marmoset testis tissue after 65 weeks of DEHP dosing at the rate of 2,500 mg/kg body weight/day. No abnormality observed.

in June 2003, the committee also reported that DEHP (and other 4 chemical substances tested along with DEHP) had shown no apparent endocrine disruptive effects on the ecosystem. Similar tests were conducted also in other countries on 8 phthalates, with no estrogenic effects observed in the in vivo tests.

④ Reproductive toxicitySome tests in the past reported atrophy of the

testes as a result of high concentration dosing of DEHP to rats and mice. Based on the test results, use of DEHP in toys and food apparatus/food packaging was regulated, effective from August 2003, in Japan.

JPIA, in cooperation with counterpart industries in Europe and the U.S. commissioned a two-year study, titled long-term dosing tests of DEHP to young marmosets to an independent research organization in September 2000, for an overall evaluation of safety of DEHP, including the testes and the behavior of DEHP in the animal body. The result of the study was announced in January, 2003, and the following points were made clear:

Based on the test results on primates, JPIA affirms that the time has come to review the evaluation results in the past which were based on experimental data with rats. Furthermore, it has become clear that carcinogenicity and testes toxicity are apparently different by animal species as seen between rats and primates. Presently, further studies on reproductive toxicity (the impacts on pregnant state) are under way to evaluate the differences between species.

Fig. 4-6 Evaluations of carcinogenicity by the IARC

Souce: IARC

Group/Evaluation Substance / Item

1

2A

2B

3

4

Carcinogenic to humans

Probably carcinogenic to humans

Possibly carcinogenic to humans

Not classifiable as to its carcinogenicity in humans

Probably not carcinogenic to humans

Asbestos, Tobacco smoke, Alcoholic beverages, etc.

Diesel engine exhaust, Lead & lead compounds (inorganic), etc.

Coffee, Pickled vegetables, Gasoline, etc.

DEHP , Tea, Chlorinated drinking water, Lead compounds (organic), etc.

Caprolactam (only one substance)

● Test items of long-term dosing tests of DEHP to young marmosets

● General condition observation and measurement of body weight ● Hematological tests ● Biochemical examination of blood ● Histopathological examination ● Peroxisome proliferator activated receptor α (PPAR-α) assay ● Sperm count ● Pharmacokinetic tests, etc.

56


(4) Regulation of plasticizers used for some PVC products by revision of the Food Sanitation Law (Public Notification No.267 by the MHLW, August 2, 2002)

In June 2000, the Ministry of Health and Welfare (the present MHLW) announced that DEHP had leached from PVC gloves designed for kitchen applications. The Food Sanitation Law was amended on grounds that there could be health risks from the exposure level which exceeded the Tolerable Daily Intake (TDI) for humans estimated based on testicular toxicity and the reproductive toxicity test results with rodents.

The amended Food Sanitation Law became applicable to toys which include DEHP and DINP which are intended to be mouthed by young children for an

extended period of time (mouthing hours), to prevent possible exposure in excess of the TDI.

① Food apparatus and food packagingUse of DEHP to PVC products (i.e., food apparatus

and food packaging), which may come into contact with oil/fat or oil/fat containing food (food with oil/fat content of about 20% or more, excluding the case of dry solid food) was prohibited, effective from August 1, 2003.

② ToysUse of DEHP or DINP containing PVC products to

toys intended to be mouthed by babies and young children under 6 years of age (such as pacifiers and teethers) and use of DEHP containing PVC products to the other toys were prohibited effective from August 1, 2003. Plasticizers other than DEHP and DINP are outside the scope of the modified regulation.

2. Safety of Stabilizers

(1) Role of stabilizers

When PVC is heated to 170~180℃ , chlorine and hydrogen in the molecules are eliminated and release of hydrogen chloride becomes evident. Once such decomposition starts, unstable structure is formed in the molecule, which further accelerates HCl elimination and decomposition. As PVC is heated to

soften during the molding process, prevention of hydrogen chloride elimination due to heat history and subsequent decomposition is required. The stabilizer prevents such initial elimination of hydrogen chloride from PVC. Therefore, use of stabilizers (metal compounds) is essential to prevent the chain reaction of decomposition.

TDI : Abbreviation of Tolerable Daily Intake. An index for the quantity of chemical substances deemed harmless through lifetime intake considering impacts on human health. It is expressed in terms of intake per day per 1 kg of body weight.

Metallic soap : Soap used in our daily life is a sodium salt of fatty acid manufactured from natural oil/fat. Fatty acid salts with calcium, zinc or barium in the place of sodium are called metallic soaps. The abovementioned metal stearate is a typical metal soap.

(2) Types of stabilizers

The major metals contained in stabilizers are lead (Pb), barium (Ba), calcium (Ca), and tin (Sn). The stabilizers are classified into Pb stabilizers, Ba-Zn stabilizers, Ca-Zn stabilizers, and Sn stabilizers.

Ba-Zn stabilizers and Ca-Zn stabilizers are used as metallic soaps such as stearates, while Sn stabilizers are used as organic tin (dialkyl tin compounds). Other than metallic soap, Pb stabilizers are used as basic sulfate, basic carbonate, or basic phosphate.

<Ca-Zn stabilizers>

Ca-Zn stabilizers amount to a little more than 20%

of the total stabilizers for PVC. Use as substitutes for Pb stabilizers is increasing mainly for cable covering in automobiles and household electric appliance fields, except for cables for electric power grids and telecommunications. Also, Ca-Zn stabilizers are mainly used for flexible PVC products, including consumer products and medical devices as non-toxic stabilizers approved by the U.S. Food and Drug Administration (FDA), and Japan Hygienic PVC Association (JHPA).

<Ba-Zn stabilizers>Ba-Zn stabilizers are essential for soft PVC products

such as films and sheets, which require higher transparency, and amount to slightly less than 20% of

57

total stabilizers.

<Sn stabilizers>Sn stabilizers amount to about 10% of all stabilizers.

For rigid PVC products which require higher fabrication temperatures, octyl-Sn (not tributyl-Sn) stabilizers are used to substitute Pb-stabilizers,　 since this type of stabilizer offers better transparency, weatherability and stabilizing effects to PVC products.

<Pb stabilizers>Pb-stabilizers have the longest history as stabilizers

for PVC, and amount to a little more than 40% of total stabilizers. Their stabilizing effects are excellent and used for PVC products with long service life and are required to endure longer fabrication (heating) hours. Also they are used for rigid PVC in construction material applications such as extruded profiles (e.g., window profiles).

(3) Hazard data of compounds used in stabilizers

Fig.4-8 shows the acute toxicity data (LD50) of stearates, which are the major PVC stabilizers. Generally in Japan, chemical compounds with LD50

values below 300 mg are called “toxic substances”, those with 30~300 mg are called “deleterious substance”, and those over 300 mg are called “ordinary substance”. The LD50 values of typical compounds used as PVC stabilizers are over 300 mg, and are classified as “other substances”.

(4) Stabilizer by applications

< Cable/Wire covering>Cable/wire can be classified into various categories,

such as overhead high-voltage cables, high-voltage drop wire, overhead low voltage cables, low-voltage drop wire, low-voltage wire, wire for various equipments, wire for OA equipments, and wire harnesses for automobiles. Pb stabilizers are used for electric power grid cables such as overhead high-voltage cables, which require durability for extended periods of time, weatherability and electric insulating properties.

Although there are moves to avoid use of Pb-containing products from an environmental viewpoint, power cable covering using Pb stabilizers will not be placed in the human mouth, and furthermore the recycling systems for waste cables/wires have been set up within the society and are working well. For applications other than electric cables, Ca-Zn stabilizers are used in the place of the Pb stabilizers for indoor wiring and automobile wire including wire harness.

<Agro-films and flexible sheets >Ca-Zn and Ba-Zn stabilizers are mainly used for

PVC agro-films and wall covering. Especially, Ba-Zn stabilizers are essential for agro-films, which require transparency. Sn stabilizers were used for food wraps and consumer products in the past, but replacement with non PVC alternatives has been promoted rapidly, and not many PVC packaging and consumer products with Sn stabilizers are used today.

<Other flexible PVC products>

Non-toxic Ca-Zn stabilizers conforming to the FDA provisions and specified by JHPA are used for flexible PVC products such as food wraps, containers for toiletry and hoses, which are all used widely in our daily lives.

<Pipes and fittings>In the past, Pb stabilizers were used for almost

all rigid PVC products. Today, octyl-Sn stabilizers conforming to FDA provisions and specified by JHPA

＞ 10 g/kg ＞ 10 g/kg ＞354 mg/kg

2,506 mg/kg 1,832 mg/kg 319 mg/kg 3,600 mg/kg

＞1,241 mg/m3/4H

12,428 mg/kg 10,428 mg/kg

6,000 mg/kg

Fig. 4-7 Acute toxicity data for stearates

Rats LD50 (Oral)Mice LD50 (Oral)Mice LD50 (Intra-abdominal)Guinea pigs LD50 (Oral)Mammal LC (Inhalation)

1) The MSDS search site, The University of Vermont2) Catalogues, etc. of reagent manufacturers

Zn stearate1) Ba stearate1) Pb stearate2)

58


are used in pipes for water supplies subsequent to the revision of drinking water quality standards in 1993. The same trend can be seen with hot water supply systems. On the other hand, Pb stabilizers continue to be used for pipes other than water and hot water supply systems. There is no adverse effect on wastewater or contacting soil, because water does not penetrate into the pipe material and the stabilizers would not elude or migrate out of the pipe. Furthermore, Japan PVC Pipe and Fittings Association have already implemented the recycling systems for end-of-life rigid PVC pipes and fittings, and the systems are functioning satisfactorily.

<Other rigid PVC products>

The major products under this category are window profiles, spouts and sidings. Ca-Zn stabilizers are phasing in increasingly to replace Pb stabilizers which were the main plasticizers used for window profiles. Pb or Sn stabilizers were used for rainwater spouts in the past, but the moves to use non-Pb stabilizers have already been commenced. Sn stabilizers have been used all along for construction materials such as sidings and transparent boards.

(5) Demand trends in PVC stabilizers

Fluctuations of PVC stabilizers are shown in Fig. 4-8. Although Pb stabilizers have superior properties as described above, there are concerns on the toxicity of Pb (metallic lead) used as raw material. The PVC

Pipe and Fittings Association set up a voluntary standard in 1993 for water supply pipes to become Pb-free before the Pb criteria in water quality standard became stricter. As seen in such example, the use of lead stabilizers are declining in recent years, and the demand for Ca-Zn based PVC stabilizers is on the rise.

Fig. 4-8 Transition of shipment of PVC stabilizers

Types

Pb stabilizers

Ba-Zn stabilizers

Ca-Zn stabilizers

Sn stabilizers

Organic stabilizing auxiliary

Total

2000

31,360

9,130

9,614

6,203

4,871

61,178

2001

30,125

8,140

8,750

5,396

4,123

56,534

2002

27,008

8,230

9,281

5,465

3,699

53,683

2003

24,399

8,398

10,614

5,409

3,749

52,569

2004

23,921

8,026

11,666

5,641

3,806

53,060

2005

21,823

7,742

11,383

5,171

4,021

50,140

2006

19,538

7,867

12,260

5,655

4,548

49,868

2007

18,176

6,794

11,967

5,279

4,477

46,693

Unit: Tons

Source: Japan Inorganic Chemical Industry Association

CHAPTER 5: SERVICEABILITY OF PVC AND PVC PRODUCTS

In recent years, the impacts of industrial products and their raw materials on the environment in all phases of production, use and waste disposal have drawn attention from the standpoint of global environment and depletion of natural resources. LCA (Life Cycle Assessment) is highlighted as one of the tools to evaluate quantitative impacts on the environment, and its effectiveness has been demonstrated.

Compared with other plastics, PVC products are less dependent on oil, which is a fossil fuel, and are chemically stable, therefore PVC is a plastic which has suitable characteristics for production of durable products.

In this chapter, the features of PVC and PVC products will be explained based on LCA and physical properties of PVC to help gain understanding on the serviceability of PVC and PVC products.

60

CHAPTER 5 : SERVICEABILITY OF PVC AND PVC PRODUCTS

1. Effect of PVC and PVC Products on the Global Environment

The energy consumption upon production of raw materials and fabrication of plastics is considerably small; therefore the total energy requirement for production of end products is significantly smaller as compared with other materials.

Of all plastics, PVC has excellent environmental features such as low CO2 (carbon dioxide) emissions in the production phase, which contributes to the prevention of global warming and saves resources and energy.

■ Contributes to prevention of global warming Upon considering the global warming issue, the

magnitude of CO2 emission for the material we use throughout its lifecycle, from production to consumption and disposal, is an important index. PVC is proven as a material with minimal environmental load in terms of CO2 emission, when compared with metal or glass products of the same application (Fig.5-1).

■ Contributes to energy savingPVC is an energy efficient plastic which saves

significant amounts of energy in the production stage as compared with other plastics (Fig.5-2).

PVC window profiles have three times the heat insulation efficiency of aluminum profiles, and are compatible with the Next Generation Energy Saving Standard. They cut down energy consumption for heating and air conditioning (Fig.5-3).

■ Contributes to saving natural resources57% of PVC is made up of chlorine, which is derived

from natural salt that is abundant on earth. Therefore PVC contributes significantly to saving oil, which is a limited natural resource, in contrast to other plastics whose composition depends entirely on oil.

0

1

2

3

CO2（×104kg）

CO2（×106kg）

0

2

4

6

8

10

0.78

0.177 0.346

9.500

2.72<Water pipes>

Fig. 5-1 CO2 emissions upon production

PVC Steel

<Agricultural green houses> (per 1 km2)

PVC Polyolefin Glass

Source: Prepared from the survey report by Chem Systems

(15 cm diameter, per 1 km length)

0

5

10

15

20（Mcal/kg）

10.85

14.3515.70 16.25 16.38 16.53 17.26

PVC

PET

HDPE

LDPE

PP PS Expanded PS

Fig. 5-2 Energy consumption up to the production stage of plastics

Source: Prepared from "A report on LCI data for petrochemical products", PWMI

A house with plastic window frames and plastic siding

■ Contributes by producing long life products Plastics are often perceived as symbols of

throwaway or single use. However, in reality plastics are durable materials which do not rust or corrode. PVC is an exceptionally durable plastic, used in water

61

The Next Generation Energy-Saving Standard :The revision of the Japanese Housing Energy Efficiency took place in 1999, triggered by the 1997 Kyoto Protocol which required 6% reduction of CO2 emission from the level in 1990. Reduction standards, etc. for heat loss from openings (e.g., windows and entrances) of housing have been defined.

supply and sewage pipes, which can be used for over 50 years. Much of PVC products are used in durable applications. More than half of all PVC products are long life products with service lives of over 15 years, which ultimately contributes to society (Fig.5-4).

■ Contributes to recycling PVC is a material suitable for recycling. It has the

longest history of recycling among plastics, and it is most advanced in mechanical recycling. For example, about 68% of end-of-life agricultural films (agro-films) were recycled and used for flooring, etc. in 2005 (Fig.5-5).

0 20 40 60 80 100

100

71.4

53.5

35.7

35.7

35.7

( % )*1

Fig. 5-3 Rate of heat loss*1 The heat loss through single glazing aluminum profiles is defined as 100 for comparison.*2 low-e : low emissivity

High LowHeat insulation

Aluminum profiles (single glazing)

Aluminum profiles (double glazing)

PVC & aluminum hybrid profiles (double glazing)

Double profiles (aluminum profile + PVC inner window

(single glazing) (low-e*2 double glazing)

PVC & aluminum hybrid profiles (low-e double glazing)

PVC profiles (low-e double glazing)

Source: Prepared from "A document by the energy saving construction materials promotion center" within the Federation of Construction Material Industries, Japan

Fig. 5-4 Service life of plastics

0 20 40 60 80 100（％）

PVC

HDPE

LDPE

PS

ABS

PP

Source: Prepared from “A plastics demand structure survey report”by the MITI

> 15 years 2 - 15 years < 2 years Other

Fig. 5-5 Recycling of agro-films

recycled

About 68%

60~70 thousand tons(annual discharge quantity)

62


LCA (Life Cycle Assessment) is a quantitative

and objective method to evaluate environmental loads (consumption of resource energy, emission of environmental load substances and wastes), through all phases of a product including resource extraction, production, use and waste disposal. It is important to collect and provide proper LCI (Life Cycle Inventory) data for correct LCA evaluations.

(1) LCI Data for PVC

According to the LCI data worked out by the Plastics Waste Management Institute (PWMI) for general purpose plastics, the process energy from extraction of oil to plastic production is 4.989~6.850 Mcal/kg, and there is no remarkable difference between each plastics. As for resource energy however, the plastics

mainly composed of hydrocarbons from oil require 8.301~10.710 Mcal/kg. PVC, of which more than half of its weight is composed of chlorine, requires 4.857 Mcal/kg, which amounts to less than half the resource energy needed for other plastics, meaning that it takes half the load to the environment. The sum of process energy and resource energy for PVC is 10.849 Mcal/kg, which amounts to 65.6% of the sum needed for low-density polyethylene (LDPE) (16.532 Mcal/kg), which is widely used as packaging. PVC is an excellent material with the least energy load (upper graph of Fig.5-6).

As for the environmental load of PVC, CO2 emission from PVC is 1.430 kg/kg, which is higher than that of polyolefin and lower than that of PS. NOX and SOX emissions from PVC are 2.131 g/kg and 1.941 g/kg respectively, which are the lowest of all other plastics (lower graph of Fig.5-6).

Fig. 5-6 LCI data for production of general purpose plastics

Source: “Survey report for LCI data of petrochemical products” by PWMI, July 1997

181614121086420

LDPE

LDPE

HDPE

HDPE

PP PS Expanded PS PVC PET for bottles

PP PS Expanded PS PVC PET for bottles

5.843 4.989 5.627 6.147 6.850 5.992 6.052

(Mcal/kg) Resource energyProcess energy

<Environmental load of plastics production>

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0

（CO

2=kg

/kg　

NO

X/SO

X=g/

kg）

CO2

NOX

SOX

<Energy consumption for plastics production>

10.689 10.710 10.623 10.233 10.407

4.8578.301

16.532 15.699 16.250 16.381 17.257

10.849

14.352

1.4211.421

2.7062.7062.6322.632 2.356

1.2311.231

2,5342,5342.356

1.3791.379

2.6632.6632.5462.546

1.7561.756

2.7172.7172.8822.882

1.8621.862

2.8712.8713.0153.015

1.4301.430

1.9411.9412.1312.131

1.4161.416

3.2053.2052.5402.540

2. LCA for PVC and PVC Products

Life Cycle Assessment (LCA) :Method to evaluate the magnitude of resources consumption and impacts on the environment for a material or product throughout its whole

life cycle (production, use, waste disposal and recycling) by overall analysis. Rather than focusing on the environmental load alone, it

evaluates from a comprehensive viewpoint. It has been highlighted as a guideline provider for material selection and green procurement.

63

(2) LCI data for PVC products

Flat plates, pipes and agro-films are typical PVC products. According to the results of LCI data research by Japan PVC Environmental Affairs Council (JPEC),

the processing energy is 2.006 Mcal/kg for flat plates, 0.580 Mcal/kg for pipes, and 2.252 Mcal/kg for agro-films. Therefore the environmental load from pipes is the smallest (upper graph of Fig.5-7).

0

1

2

3

4

5

6

Fig.5-7 LCI data for representative PVC products

Source: "Report on Investigation of LCI Data Concerning PVC Products" October 1999, JPEC

<Energy consumption for PVC products>

<Environmental load from PVC products>

14121086420

Rigid PVC flat plates (extruded)

(Mcal/kg)

Rigid PVC pipes (extruded)

Agro-films(calendered)

Processing energyMaterial energy

(CO 2

= kg/k

g NO X

/SOX =

g/kg）

CO2

NOX

SOX

Rigid PVC flat plates (extruded)

Rigid PVC pipes (extruded)

Agro-films(calendered)

9.591 10.27510.959

10.85513.211

2.00611.597

0.5802.252

1.6622.0772.248 1.485

1.9572.1541.662

2.0772.248 1.4851.9572.154

2.3042.304

5.7115.7115.7845.784

Energy consumption from plastic processing originates from electric power requirements. In the case of PVC products, the environmental load differs for processes that require steam (i.e. use of heavy oil) such as calendering, in comparison to extrusion (lower graph of Fig.5-7).

Results of comparison between PVC products and non-PVC products of the same applications revealed that the total energy consumption (sum of material energy and processing energy) of PVC products is lower. Energy consumptions of PVC products amount to the following percentages of products made by other materials - water pipes (small diameter pipes for water supply): 57.7% of polyethylene pipes, water

pipes (medium diameter pipes for water supply): 33.9% of ductile iron pipes, sewage pipes: 30.4% of ductile iron pipes, agro-films: 73.7% of polyolefin films (Upper graphs per product in Fig.5-8).

Similarly, the environmental loads of PVC products are reported to be lower than those made from other materials - water pipes (small diameter pipes for water supply): 81.9% of polyethylene pipes, water pipes (medium diameter pipes for municipal water supply): 28.8% of ductile iron pipes, sewage pipes: 25.7% of ductile iron pipes, agro-films: 51.2% of polyethylene films (Lower graphs per product in Fig.5-8 ).

Life Cycle Inventory (LCI) :Accumulated set of quantitative data of resources and energy consumption and emission in terms of various environmental load items

Resource energy :Evaluation in terms of calorific values of each hydrocarbon sources used as raw materials.

for each phase of the life cycle (production, use, waste disposal) for a product. Provides basic data for life cycle assessments (LCA).

64


Fig. 5-8 Comparison of LCI data between PVC products and non-PVC products

<Medium diameter pipes for water supply>(150 mmφ, per 1 km)

<Agro-film> (per 1 km2)

0

200

400

600

800

1,000

1,200

0

2,000

4,000

6,000

8,000

10,000

PVC pipe Ductile iron pipes

PVC pipes Ductile iron pipes

PVC Polyolefin

PVC Polyolefin0

50,000

100,000

150,000

200,000

250,000

300,000

350,000

374(comparison with

ductile iron pipes 33.9%)

1,102

6,603(comparison withPE films 73.7%)

8,962

Total energy consumption

Total energy consumption

CO2 emission

CO2 emission

0

5,000

10,000

15,000

20,000

30,000

25,000

7,824(comparison with


27,173

<Sewage pipes> (250 mmφ, per 1 km)

0200400600800

1,0001,2001,4001,6001,800



546(comparison with


1,797Total energy consumption

CO2 emission

0

10,000

20,000

30,000

40,000

50,000

11,400(comparison with

ductile iron pipe 25.7%)

44,300

<Small diameter pipes for water supply>(50 mmφ, per 1 km)

0

20

40

60

80

100

Ener

gy

PVC pipes Polyethylene pipes

PVC pipes Polyethylene pipes

56(comparison withPE pipes 57.7%)

97Total energy consumption

CO2 emission

0

300

600

900

1,200

1,500 1,163(comparison with

PE pipe 81.9%)

1,420

177,000(comparison withPE films 51.2%)

346,000

(thousand MJ)

Ene

rgy

(thousand MJ)

Ener

gy

(thousand MJ)

Ener

gy

(thousand MJ)

Envi

ronm

enta

l loa

d

（kg）

Envi

ronm

enta

l loa

d

（kg）

Envi

ronm

enta

l loa

d

（kg）

Envi

ronm

enta

l loa

d

（kg）

Source: Summarized and prepared based on the survey report by Chem Systems

65

●SUMMARY : Comparison of LCI data (PVC products versus non-PVC products)

1) Comparison of environmental loads up to production with other various general purpose plastics

2) LCI data for water pipes, sewage pipe and agro-film

Small diameter (50mmφ)

● Example: pipes for water supply (small diameter, per 1 km)

PVC pipe(1.00 kg/m)

PE pipe(1.22 kg/m)

Energy consumption (MJ)

CO2 (kg)

NOX (kg)

SOX (kg)

CO2 (kg)

NOX (kg)

SOX (kg)

CO2 (kg)

NOX (kg)

SOX (kg)

CO2 (kg)

NOX (kg)

SOX (kg)

Medium diameter (150 mmφ)

● Example: pipes for water supply (medium diameter, per 1 km)

PVC pipes(6.70 kg/m)

ductile iron pipes(23.80 kg/m)


Medium diameter (250 mmφ)

● Example: sewage pipes (per 1 km)

PVC pipes(9.80 kg/m)

ductile iron pipes(38.80 kg/m)


● Example: agro-films (per 1 km2)

PVC(123 t/km2)

polyolefin(96 t/km2)


5.6×104

1,163

8

11

9.7×104

1,420

3

2

37.4×104

7,824

51

76

110.2×104

27,173

77

89

54.6×104

11,400

75

111

179.7×104

44,300

126

144

660.3×104

177,000

690

860

896.2×104

346,000

520

330

66


(3) LCI data for mechanical recycling

Both rigid and flexible PVC waste has been widely recycled from the early days. Compared with other materials, PVC is the most versatile upon mechanical recycling. Specialist recyclers collect PVC waste and distribute them crushed for rigid PVC waste and in the form of sheets or pellets for flexible PVC wastes. These are reused as raw materials. For example, the production energy of recycled pipes made from rigid PVC waste is 2.50 Mcal/kg, which amounts to 20% of the energy required for production of pipes made from virgin (new) PVC. Similarly, comparing environmental loads, CO2 emission from recycled pipes made from rigid PVC waste amounts to fewer than 40% of that required for pipes made from virgin PVC. Likewise, NOX and SOX emissions amount to about 20% respectively. As you can see, recycled PVC can be manufactured with less environmental load, yielding comparable qualities (Fig.5-9(1)).

The intermediate layer used in PVC flooring is manufactured from flexible PVC sheet waste. The production energy required for production of such recycled intermediate layer amounts to about 30% of the energy required for manufacture using virgin PVC, and the environmental load amounts to 20~50% (Fig.5-9(2)).

Furthermore, end-of-life PVC agro-films, which among flexible PVC waste has an advanced track record upon collection and recycling, are reused as material to be molded into new applications, with little environmental load. Its production energy is less than 20% and CO2, NOX and SOX emissions are about 20% as compared to using virgin PVC (depending on the composition of each resin) (Fig.5-9(3)).

Generally, environmental loads resulting from production, processing, and recycling of plastic products are far greater than those from transportation or landfill. Environmental load resulting from production of virgin resin represents the largest proportion.

Mechanical recycling eliminates the environmental load for final treatment such as incineration or landfill, and therefore makes up for the substantial load resulting from virgin material production. Mechanical recycling is the most advanced recycling method for PVC products.

Fig. 5-9 Environmental load of virgin PVC/recycled material

(1) pipes

(2) flooring intermediate layer

12

10

8

6

4

2

0Energy CO2 NOX SOX

CO2 NOX SOX

CO2 NOX SOX

(Energ

y = M

cal/k

g, CO

2 = kg

/kg, N

O X/ S

O X =

g/kg)

(Energ

y = M

cal/k

g, CO

2 = kg

/kg, N

O X/ S

O X =

g/kg)

(Energ

y = M

cal/k

g, CO

2 = kg

/kg, N

O X/ S

O X =

g/kg)

Virgin

Recycled

(3) agro-films

12

10

8

6

4

2

0Energy

Virgin

Recycled

8

6

4

2

0Energy

VirginRecycled

Source: Survey data by VEC

7.06

2.501.485

0.483

2.154

0.499

1.957

0.440

10.86

2.39

1.071 0.517

2.853

0.516

1.703

0.655

10.85

1.60 1.4300.322

2.131

0.304

1.941

0.287

Mechanical recycling :Method of recycling where plastic wastes undergo treatment such as crushing and sorting, and then recycled back into materials for plastic products. PVC shows less degradation of physical

Virgin material :Colloquial term for materials manufactured entirely from unused raw materials, in other words made without using any recycled materials.

properties or loss of functionality due to mixture of foreign matters. Therefore PVC is a material that can be mechanically recycled with ease.

67

(1) PVC and PVC products

PVC is an amorphous thermoplastic with significant polarity within the polymer molecular structure, since hydrogen and chlorine atoms are connected to the main chain made up of carbon atoms. PVC itself comes in the form of white fine powder with the average particle size of 100~150 µm. The apparent density is 0.4~0.7 g/cm2, due to countless micro voids within the particles.

Generally, ancillary materials (called additives) such as thermal stabilizers, lubricants, pigments, and fillers are added before the molding processes. Plasticizers in particular can change the moldability and property of products considerably. It is possible to manufacture products with various physical properties from rigid to flexible, by adding plasticizers at the ratio of 0~120 parts by weight to 100 parts of PVC resin.

At temperatures over its softening point, the

stress-strain behavior of PVC has little temperature dependence. Therefore various molding processes can be employed for PVC:

3. Characteristics and Property Modification of PVC

Calendering process (compression molding) Extrusion molding

Injection moldingInflation moldingBlow molding

rigid/flexible sheets, films

pipes, drain spouts, window profiles, food wrapsfittings, valves, machine partsfilmsbottles

(2) Characteristics of PVC products

Fig.5-10 shows the general properties of rigid/flexible PVC products, respectively. The type and composition of additives used at the time of molding can yield different properties such as moldability, and other characteristics of the molded product.

―

―

―

―

―

―

―

D792

〃

D638

〃

〃

〃

D695

D790

〃

D256A

D2240/D2583

C177

―

D696

D648

〃

D257

D149

D150

〃

〃

〃

〃

〃

D492

D542

―

―

D570

―

D543

〃

〃

〃

〃

72～105

140～205

53～140

149～213

703～2,812

2.0～2.3

0.002～0.006

1.30～1.58

0.77～0.63

415～527

40～80

415～457

24,600～42,200

562～914

703～1,125

21,100～35,200

2.2～12

65～85

（Shore D）

3.5～5.0

0.25～0.35

50～100

60～76

57～82

＞1016

350～500

3.2～4.0

3.0～3.8

2.8～3.1

0.007～0.020

0.009～0.017

0.006～0.019

60～80

1.52～1.55

76～82

8～18

0.04～0.4

Generally changes

None

None-slight

None

None

75～105

140～176

35～140

160～196

562～1,758

2.0～2.3

0.010～0.050

1.16～1.35

0.86～0.74

105～246

200～450

―

―

63～120

―

―

50～100

（Shore A）

3～4

0.3～0.5

70～250

―

―

1011～1015

300～400

5.0～9.0

4.0～8.0

3.3～4.5

0.08～0.15

0.07～0.16

0.04～0.14

―

―

―

―

0.15～0.75

Changes according to stabilizer

None

None-slight

None

None

75～105

140～176

35～140

160～196

70～140

0.2～2.3

0.008～0.035

1.3～1.7

0.77～0.59

70～246

200～400

―

―

70～127

―

―

50～100

（Shore A）

3～4

0.3～0.5

―

―

―

1011～1014

250～300

5.0～6.0

4.0～5.0

3.5～4.5

0.10～1.05

0.09～0.16

0.09～0.10

―

―

―

―

0.50～1.0

None-slight

None

None-slight

None

None

Melting point ℃ Tg (amorphous)

Compression molding temperature ℃

Compression molding pressure kg/cm2

Injection molding temperature ℃

Injection molding pressure kg/cm2

Compression ratio

Molding shrinkage (linear shrinkage) cm/cm

Specific gravity

Specific volume cm3/g

Tensile break strength kg/cm2　　　　

Tensile elongation at break %

Tensile yield strength kg/cm2

Tensile modulus kg/cm2

Compressive strength kg/cm2

Bending strength kg/cm2

Young's modulus in flexure kg/cm2 (23℃)

Izod impact strength cm･kg/cm with notch

(3 mm thickness test piece)

Shore hardness

Thermal conductivity 10-4 cal･cm/sec/cm2/℃

Specific heat cal/℃/g

Coefficient of linear expansion 10-6cm/cm/℃

Heat distortion temperature ℃ (bending load 18.6 kg/cm2)

　　　　　　　　　　　 (bending load 4.6 kg/cm2)

Volume resistance Ω-cm

　　　　　　 (humidity50%、temperature23℃)

Voltage resistance (short time test)

　　　　　　 (thickness 3 mm, V/mil)

Dielectric constant 60 Hz

1 KHz

1 MHz

Power factor 60 Hz

1 KHz

1 MHz

Arc resistance sec

Refractive index nD

Light transmissibility %

Haze %

Water absorption (24 hour, 3 mm thickness) %

Sunlight influence　

Weak acid influence

Strong acid influence

Weak alkali influence

Strong alkali influence

Organic solvent influence

Fig. 5-10 Properties of PVC products

Source: Various annual editions of the Modern Plastics Encyclopedia

Test itemsASTM test

method

PVC polymer and (vinyl acetate) copolymer

Rigid Flexible(without filler)

Flexible(with filler)

Mo

ldab

ility

Mec

han

ical

pro

per

ties

Ther

mal

pro

pert

ies

Ele

ctri

cal p

rop

erti

esO

pti

cal

prop

ertie

sC

hem

ical

pro

per

ties

20

not soluble in alcohol, aliphatic hydrocarbon or oil/fat, either soluble or swells in ketone and ester, swells in aromatic hydrocarbons

Variable according to type and amount of plasticizer

(continued to next page)

68


(3) Advantages and disadvantages of PVC products

PVC is a general purpose plastic whose products strike an excellent cost-performance balance. The

advantages and disadvantages of PVC in terms of physical properties can be summarized as follows. Disadvantages can be improved by polymer alloy which will be mentioned at (5) Property modification of PVC products.

<Advantages>Superior mechanical propertiesSuperior creep resistanceFlexibility can be changed at ease using plasticizersSuperior chemical resistanceTransparenceSuperior adhesion properties and printabilityFire resistant propertiesGood electrical propertiesFor flexible PVC products, elastomer texture of rubber or leather-like texture can be obtained

<Disadvantages> Lack impact strength at low temperatures Slightly low heat distortion temperature (maximum temperature upon use)Leaching of plasticizers in the case of flexible PVC productsHigh viscoelasticity, not suitable for injection molding of large-sized products

―

―

―

―

―

―

―

D792

〃

D638

〃

〃

〃

D695

D790

〃

D256A

D2240/D2583

C177

―

D696

D648

〃

D257

D149

D150

〃

〃

〃

〃

〃

D492

D542

―

―

D570

―

D543

〃

〃

〃

〃

72～105

140～205

53～140

149～213

703～2,812

2.0～2.3

0.002～0.006

1.30～1.58

0.77～0.63

415～527

40～80

415～457

24,600～42,200

562～914

703～1,125

21,100～35,200

2.2～12

65～85

（Shore D）

3.5～5.0

0.25～0.35

50～100

60～76

57～82

＞1016

350～500

3.2～4.0

3.0～3.8

2.8～3.1

0.007～0.020

0.009～0.017

0.006～0.019

60～80

1.52～1.55

76～82

8～18

0.04～0.4

Generally changes

None

None-slight

None

None

75～105

140～176

35～140

160～196

562～1,758

2.0～2.3

0.010～0.050

1.16～1.35

0.86～0.74

105～246

200～450

―

―

63～120

―

―

50～100

（Shore A）

3～4

0.3～0.5

70～250

―

―

1011～1015

300～400

5.0～9.0

4.0～8.0

3.3～4.5

0.08～0.15

0.07～0.16

0.04～0.14

―

―

―

―

0.15～0.75

Changes according to stabilizer

None

None-slight

None

None

75～105

140～176

35～140

160～196

70～140

0.2～2.3

0.008～0.035

1.3～1.7

0.77～0.59

70～246

200～400

―

―

70～127

―

―

50～100

（Shore A）

3～4

0.3～0.5

―

―

―

1011～1014

250～300

5.0～6.0

4.0～5.0

3.5～4.5

0.10～1.05

0.09～0.16

0.09～0.10

―

―

―

―

0.50～1.0

None-slight

None

None-slight

None

None

Melting point ℃ Tg (amorphous)

Compression molding temperature ℃

Compression molding pressure kg/cm2

Injection molding temperature ℃

Injection molding pressure kg/cm2

Compression ratio

Molding shrinkage (linear shrinkage) cm/cm

Specific gravity

Specific volume cm3/g

Tensile break strength kg/cm2　　　　

Tensile elongation at break %

Tensile yield strength kg/cm2

Tensile modulus kg/cm2

Compressive strength kg/cm2

Bending strength kg/cm2

Young's modulus in flexure kg/cm2 (23℃)

Izod impact strength cm･kg/cm with notch

(3 mm thickness test piece)

Shore hardness

Thermal conductivity 10-4 cal･cm/sec/cm2/℃

Specific heat cal/℃/g

Coefficient of linear expansion 10-6cm/cm/℃

Heat distortion temperature ℃ (bending load 18.6 kg/cm2)

　　　　　　　　　　　 (bending load 4.6 kg/cm2)

Volume resistance Ω-cm

　　　　　　 (humidity50%、temperature23℃)

Voltage resistance (short time test)

　　　　　　 (thickness 3 mm, V/mil)

Dielectric constant 60 Hz

1 KHz

1 MHz

Power factor 60 Hz

1 KHz

1 MHz

Arc resistance sec

Refractive index nD

Light transmissibility %

Haze %

Water absorption (24 hour, 3 mm thickness) %

Sunlight influence　

Weak acid influence

Strong acid influence

Weak alkali influence

Strong alkali influence

Organic solvent influence

Fig. 5-10 Properties of PVC products

Source: Various annual editions of the Modern Plastics Encyclopedia

Test itemsASTM test

method

PVC polymer and (vinyl acetate) copolymer

Rigid Flexible(without filler)

Flexible(with filler)

Mo

ldab

ility

Mec

han

ical

pro

per

ties

Ther

mal

pro

pert

ies

Ele

ctri

cal p

rop

erti

esO

pti

cal

prop

ertie

sC

hem

ical

pro

per

ties

20

not soluble in alcohol, aliphatic hydrocarbon or oil/fat, either soluble or swells in ketone and ester, swells in aromatic hydrocarbons

Variable according to type and amount of plasticizer

69

(4) Physical properties of PVC products

① mechanical properties

PVC is a polar polymer and its mechanical properties are excellent due to strong interaction

among the molecular chains. Plastics can be categorized according to the tensile stress-strain curve (S-S curve) as one of the indexes for mechanical strength. As shown in Fig.5-11, rigid PVC products are hard and robust, while flexible PVC products are soft and tough.

Source: "Plastics" , 46 (5), 90 (1995)

Fig. 5-11 Classification of plastics by type of S-S curve

FeaturesTensile modulus

Type Tensile strength Elongation Others

A Soft and weak

B Hard and brittle

C Hard and robust

D Soft and resistant

E Hard and resistant

low

high

high

low

medium

high

low

medium~high

high

medium

medium~high

high

medium

low

medium

high

high

high

High-polymer soft gel

General purpose PS, phenol resin

Rigid PVC , AS resin

Flexible PVC , LDPE

HDPE, PP, ABSPolyamide, PC

Examples

Break below yielding point

Break around yielding point

Yielding point is low,

and the curve is flat

Yielding point is high

■ Specific mechanical properties

The mechanical properties of PVC product in specific are as follows:

0 20 6040 80 100

34～62

34～82

34～59

22～38

29～38

6.9～25

Fig. 5-12 Tensile strength of various plastics

PVC (rigid)）

PVC (flexible)

PS (general purpose)

ABS

PE (high density)

PP

Tensile strength (MPa)Source: “Plastic materials guidebook, new edition” by Kogyo Chosakai Publishing Co. Ltd (1993)

5

Fig. 5-13 Young's modulus of various plastics

0 1Modulus (103 MPa)

32 4

PVC (rigid)


PS (impact resistant)

ABS

HDPE

LDPE

PP

Polyamide (nylon 6)

PC

2.5～4.1

1.4～3.2

2.3～2.7

0.4～1.1

0.1～0.3

1.1～1.6

1.1～3.1

2.5

2.7～4.1

Source: Prepared from the "Dictionary of practical plastic terms" edited by Osaka City Industry Research Institute

Tensile strengthFig.5-12 shows the comparison

of tensile strength of PVC products with other plastics. The tensile strength is expressed in terms of the maximum stress per unit area of the cross section when the test piece breaks by applied loads to both ends of the test piece.

(an index to show the magnitude of force at break, when both ends of the test piece are pulled apart)

Tensile modulusFig.5-13 shows the comparison

of tensile modulus of PVC products with other plastics. The tensile modulus is also known as the Young's Modulus, which is expressed in terms of the ratio between the tensile stress per unit area of the cross section and the elongation in the direction of the tensile stress. Plastics possessing large tensile modulus have small stress-strain.

(an index to show the magnitude of elongation, when a test piece is pulled apart. It is like the equivalent of the spring constant)

70


Bending strengthFig.5-14 shows the bending

strength of PVC products in comparison with other plastics. It is expressed in terms of the maximum stress upon break of the test piece, where the test piece is supported at two points apart and a vertical stress load is applied at the center.

(an index to show the magnitude of force at break, when the test piece is bent)

Compressive strengthFig.5-15 shows the

compressive strength of PVC products in comparison with other plastics. It is expressed in terms of the maximum stress at break per unit area of the cross section, when a vertical stress is applied to the test piece sandwiched by two pieces of the test panel.

(an index to show the magnitude of force at break of a cubic test piece, i.e., resistance to crushing force)

PVC is used for municipal water supply/sewage pipes, spouts, frames, etc., since its mechanical properties such as tensile strength and tensile modulus are better than those of other general purpose olefin plastics, and are robust and durable.

When plasticizers are added, PVC shows rubber-like elasticity with high tensile strength and fatigue strength, and used for industrial hoses, gaskets, automobile parts, and electric cable covering in the place of natural synthetic rubber.

② Creep properties

Plastic products show creep phenomenon, where product is deformed in room temperature as time elapses when an external force is applied continuously. The phenomenon is also known as cold flow. When plastics are used for construction or industrial applications, cold flow is an especially important point to be considered. Under normal

Fig. 5-14 Bending strength of various plastics

0 50Bending strength (MPa)

100 150 200

Rigid PVC

PS

ABS

PE

PC

69～114

34～72

25～93

76～89

9.3

Source: "Plastic materials guidebook, new edition" by Kogyo Chosakai Publishing Co. Ltd.

Fig. 5-15 Compressive strength of various plastics

0 50 100 150

Rigid PVC


ABS (general purpose )

HDPE (high density)

PP

PC

55～89

82～89

45～52

38～55

69～78

19～25

Source: "Plastics guidebook" by the Osaka Municipal Technical Research Institute and others

Compressive strength (MPa)

Fig. 5-16 Fatigue strength of various plastics

Source: "Plastics almanac" by Kogyo Chosakai Publishing Co. Ltd.

PlasticsFatigue strength at 107 timesapplication of external stress

kg/mm2 〔MPa〕

PVC

PS

PE

PPABS

1.7

1.02

1.12

1.12

1.2

〔17〕

〔10.0〕

〔11.0〕

〔11.0〕

〔11.8〕

7

6

5

4

3

2

1

1 2 3 4

10 20 30 40

Fig. 5-17 Creep properties of various thermoplastics

Stress (kg/mm2)

Cree

p st

rain

(%)

PE

PP

PVC

Source: "Plastics" 21(6), 24 (1970)

Fatigue strengthFig.5-16 shows the fatigue strength of PVC

products in comparison with other plastics. It is expressed in terms of the maximum stress at which the test piece would not break after applying repeated stress for 107 (10 million) times.

(the maximum stress, which the test piece can endure after repeated application of an external force).

71

environmental conditions, rigid PVC products show very little creep and are superior in comparison with other plastic products such as PE or PP, as shown in Fig.5-17. Therefore, PVC is used in various interior and exterior construction materials (e.g., ducts, panels, window frames and decks) and electric or machine parts.

③ Plasticizing effects

PVC is a polar polymer with strong intermolecular forces, therefore in room temperature it comes in a molded form. On the other hand, when plasticizer is added upon fabrication, flexible PVC products are obtainable. This is a major advantage of PVC.

PVC products without any plasticizers are called rigid PVC products, while PVC products that include plasticizers are called flexible PVC products. The softness of the flexible PVC products is obtained as a result of plasticizers coming between molecules to separate them, reducing intermolecular forces.

Fig.5-18 shows the correlation between plasticizer concentration and tensile strength and tensile elongation of the molded product. It can be seen that as the concentration of plasticizer increases, the softness of the flexible PVC products is enhanced, resulting in a soft state that is easier to stretch. Since rubber-like elasticity or pliable texture of leather is obtainable, flexible PVC is used for packaging, hoses, automobile parts, synthetic leather and surfaces.

④ Chemical resistance

Since the main chain of the polymer is comprised of single bonds of carbon atoms, PVC has excellent chemical resistance, as with other general-purpose olefin plastics such as PE, PP, or PS. Fig.5-19 shows the chemical resistance of PVC in comparison with other plastics. Some of the engineering plastics and specialty resins are susceptible to acid or alkali, and some plastics have excellent chemical resistance properties, such as polyfluorocarbons. PVC has excellent chemical resistance together with mechanical properties, therefore used for chemical storage tanks, plastic valves/flanges, drainage/sewage pipes, and plant piping.

Source: "Plastic almanac" by Kogyo Chosakai Publishing Co. Ltd.

NOTE : The 1~10 scale has been set by empirical means. Higher value shows higher effectiveness.

Fig. 5-19 Chemical resistance of various plastics and relative indexes

Nylon 66 PC

Polyester (chemical resistant) PE

Polyfluorocarbon Polymethyl methacrylate

PP PS PU

PVC (flexible) PVC (rigid)

ABS Epoxy resin

7665

1045284646

10101010101010101010101010

714

1010

71010

69

1087

377

1010

91010

61010

99

2668

1048446942

Relative resistance

Plastics

Orga

nic

solv

ents

Salts

Alka

lis

Acid

s

Oxidi

zing a

gents

800

600

400

200

0

400

200

00 10 20 30 40

0 10 20 30 40

32 1

1

3

2

（％）

（kg/cm2）1: Polyester adipate 2: DEHP 3: DEHA

Fig. 5-18 Effect of plasticizers (tensile strength, elongation)

Tens

ile s

treng

thEl

onga

tion

Plasticizer concentration (%)Source: Encyclopedia of PVC, 2nd edition Vol.1, p.494 Leonard I. Nass, Charles A. Heibergen (Marcel Dekker Inc.)

72


⑤ Transparency

PVC is an amorphous polymer; therefore its products are basically transparent. Non-transparent PVC products are thus since they are manufactured using compounding agents that are non-compatible. The haze value is used to measure the transparency of plastic products. This value is a percentage value calculated by dividing the diffused light transmittance of the test piece with the total light transmittance.

It is also possible to manufacture PVC products with superior gloss. Gloss is expressed in terms of gloss value, which usually shows the amount of reflected light from the test piece compared to amount of reflected light from glass (amount from glass defined as 100%). Fig.5-20 shows the haze value and gloss value of PVC films compared with other films made of generous purpose plastics. The smaller the haze value the higher the transparency, and higher gloss values indicate higher gloss.

Rigid PVC products which have high transparency are used in construction materials such as daylighting, transparent partitions for clean rooms, or industrial flat plates, corrugated panels, wrap films, and films for photo albums. Examples of flexible PVC products requiring transparency are wrap films, agro-films, and transparent bags.

⑥ Adhesion properties and printability

Adhesion properties and the printability of plastic are also due to the molecular structure of polymers. Generally, polar and amorphous structures offer better properties. In contrast, the non-polar and crystalline structure inherently causes difficulty in adhesion and printing, unless the product surface is treated and effectiveness of such surface treatment is comparatively low. Fig.5-21 shows the adhesion and printing properties of major plastics.

PVC has excellent adhesion properties and printability, and is used for the decoration or design-oriented products such as wall covering, flooring, synthetic leather, displays, and stone or wood grain printed films. PVC is also used as adhesive/paint by mixing with water or solvent.

Fig. 5-20 Haze value and gloss value of various films

Source: "Plastic films: processing and applications" by Gihodoh Shuppan Co., Ltd.

Films Haze value(%)

Gloss value (%)

High-pressure process PE (inflation molding)

High-pressure process PE(T-die extrusion)

Medium-low pressure process PE (inflation molding)

Medium-low pressure process PE (T-die extrusion)

Non-drawn PP(T-die extrusion)

Biaxial drawn PP

Rigid PVC

5～15

2～10

15～75

2～10

2～3

1.5～2

1～2

65

―

22

65

70～75

80

79.5

PVC

PS

Polycarbonate

Polymethyl methacrylate

Polyester (PET)

Polyamide (Nylon)

PUEpoxy resin

Good

Good

Good

Good

Good

Good

GoodGood

Pola

r/Am

orph

ous

HDPE

LDPE

PP

PolyimidSilicon resin

Poor

Poor

Poor

PoorPoor

Non

-pol

ar/A

mor

phou

s

Thermo-plastics

Thermo-plastics

Thermo-sets

Thermo-sets

Fig. 5-21 Adhesion property and printability of various plastics

Structure PropertiesAdhesion properties- Printability

Source: Prepared by VEC

73

⑦ Fire retarding property

One of the major drawbacks of plastics which are entirely derived from petroleum is their flammability. In contrast, PVC is a fire resistant plastic, the only exception among the general-purpose plastics, since more than 50% of its component is derived from salt. When PVC products are burned, hydrogen chloride gas resulting from thermal cracking stops the continuous combustion reaction and prevents burning progress by warding off the PVC product surface from oxygen in the air.

There may be many ways of evaluating the fire retarding properties, but the oxygen index can be used for the evaluation with a comparatively high precision and reproducibility of the results. It represents the minimum oxygen concentration required for the test piece to continue burning in mixed gas of oxygen and nitrogen. When the value is higher, the fire retarding property is higher. Since the oxygen concentration in the air is 21%, a plastic with an oxygen index greater than 22 has self-extinguishing property, while a plastic with oxygen index smaller than 21 is flammable. Since PVC is highly

fire resistant, it is widely used in exterior construction materials such as window profiles, siding boards, or interior housing materials, such as wallcovering and flooring. It is also used in industrial facilities such as tanks, ducts, parting strips, or for sign boards, corrugated boards, and cable coverings.

Fig. 5-22 Oxygen index of various plastics

Source: M.M. Hirschier "Macromol. Chem." Macromol. Symp. Vol.29, p.133~153, 1989

Materials Oxygen index

Polytetrafluoroetylene

PVC

PC

Nylon 66

PET

PS

PP PE

95.0

45～49

26～28

24～29

20.0

17.6～18.3

17.4

17.4

Self-

extin

guish

ing pl

astic

s

0 10 20 30 40 50 60

Fig. 5-24 Dielectric strength of various materials

Rubber Ceramics

Thermoplastics Thermosets

PVC PP PS PE

Source: "Plastic utilization: 3rd edition", "Introduction to plastics: fully revised edition" by Kogyo Chosakai Publishing Co., Ltd

(flex

ible

)

(rigi

d)

Dielectric strength (kV/mm)

Fig. 5-23 Volume resistivity of various materials

Source: "Plastics almanac" by Kogyo Chosakai Publishing Co. Ltd., p.422, 1976

MaterialsValue

(Ω-cm)

PEPPPS

TetrafluoroethylenePVC

MethacrylatePU

NylonPolyesterNeoprene

Epoxy resin

1016～1020

1016～1020

1017～1019

1015～1019

1014～1016

1014～1015

1013～1015

1013～1014

1012～1014

1011～1013

108～1014

Materials

Various plastics

⑧ Electrical characteristics

The electrical characteristics of PVC such as electrical insulating properties or dielectric constant are excellent. To express electrical insulating properties, volume resistivity or dielectric strength is widely used as an index. The volume resistivity is expressed in terms of electrical resistance calculated per unit volume of the test piece. The dielectric strength is expressed in terms of the magnitude of voltage withstood without destruction of the test piece when a specified amount of voltage is charged for a specified period of time. In both cases, greater value means better electrical characteristics. As shown in Fig.5-23,24, the volume resistivity of PVC products is slightly lower than those of olefin resin products, but

since higher fire resistant properties are required for electrical components, PVC is used widely in a variety of applications such as electric cables for residential buildings, vehicles, household electrical appliances, cable coverings, insulating tapes, switch boxes, wire coverings, and protecting tubes for power and telecommunications cables.

Fire resistant properties can also be given to olefin plastics such as PE and PP by crosslinking treatment or by adding large quantities of fire retardants, but it would be difficult for these plastics to compete with the versatility of flexible PVC whose softness can be controlled with ease and can be easily material-recycled.

Apart from its excellent electrical insulating

74


properties, PVC also features large dielectric losses. Due to this feature, high frequency welding (gluing) is possible, making secondary processing easier. Fig.5-23 shows the dielectric constant (which correlates to dielectric losses) of PVC in comparison to those of other plastics.

Production of wide films/sheets as well as bags, covers, files, and pouches of various size and shape would be easier by such welding process. For example, welded PVC products are used for bags for medical applications, air inflated toys and flexible containers.

⑨ Specific gravity (density)

The true specific gravity of PVC is about 1.4, which is comparatively heavy among plastics, as with PET. This could be a disadvantage depending on the application. By taking advantage of the fact that PVC does not float in water, it is used in water sealing sheets for agricultural water reservoir or swimming pools, or revetment materials for rivers and gulfs.

As for flexible PVC products, the specific gravity falls within the 1.1~1.3 range depending on the amount of plasticizer used, which is slightly lower than that of rigid PVC.

⑩ Heat distortion temperature (softening temperature)

The molecular structure of PVC is comprised of continuous carbon - carbon single bonds in the main chain. As this main chain is highly flexible, PVC products have the disadvantage of having low heat distortion temperature (softening temperature) compared with other plastics of the similar molecular structure. Fig.5-27 and Fig.5-28 show the thermal deformation temperature and the softening temperature (called the“Vicat softening temperature”) of major plastics. The heat distortion temperature is the temperature when the test piece placed in the heat medium with bending load applied reaches specified deflection as temperature rises. Vicat softening temperature is defined as the temperature where the needle shaped penetrator sinks into the test piece to a specified depth as temperature of the heating medium rises and specified vertical load is set to the test piece.

Source: "Polymeric Materials Encyclopedia" by J.S. Salamone. p.8949, CRC Press (1996)

Fig. 5-25 Dielectric constant of various plastics

Plastics ℃

PEPVCPSPE

-12 252525

1×103

2.374.55

2.54～2.563.22～4.3

1×106

Frequency (Hz)

2.353.3

2.54～2.563.12～4.0

1×108

2.33－

2.552.94～2.98

Fig. 5-26 Specific gravity of various plastics

Source: "Polymer dictionary" by Taiseisha Co., Ltd (1970)

Plastics Specific gravity

LDPEHDPE

PPPS

PVCABS

PolyesterPC

Nylon 66Teflon

0.91～0.930.94～0.970.90～0.911.04～1.071.35～1.450.99～1.101.38～1.39

1.21.13～1.15

2.1～2.2

Fig. 5-27 Heat distortion temperature of various plastics

PlasticsHeat distortion temp.　　　(℃)

(Load 18.6 kg/cm2)

PVCPS (general purpose) PS (impact resistant)

ABS HDPE LDPE

PP PC

54～80＜104＜99

104～10643～4932～4157～64

130～138

Source: "Practical dictionary of plastic terminology" edited by the Osaka Municipal Technical Research Institute

Fig. 5-28 Vicat softening temperature of various plastics

Plastics Measured value 　　(℃)

(1 kg load)

PS ABS PVC PC PE PP

102.5102.392.0156.2127.3152.2

Source: report by Japan Society for Testing Plastics, 1972

75

⑪ Impact strength

The glass transition temperature (second order transition point) of PVC is over 70℃ , which is higher than room temperature, representing low impact strength. Having poor impact resistance especially at low temperature range is one of the disadvantages of PVC. There are many ways to measure impact strength. Fig.5-29 shows the results of energies

absorbed by test pieces when they are fixed and hammered to break (impact failure). Higher values show higher impact strength.

Fig.5-30 shows the relation between the temperature and the impact strength of major plastics.

Fig.5-29 Impact strength of various plastics

Notched impact strength αk (kg・cm/cm2 ≒ kJ/m2)

High pressure PE

Low pressure PE

PP

Rigid PVC

PS

ABSPC

not broken

Source: K. Oberbach: Z.f. Werkstofftechnik, 2.281 (1971)

0 5 10 2015 3025

(kg ・

cm/c

m2 ≒

kJ/m

2 )

140

120

100

80

60

40

20

0-50 -30 -10 0 10 20 40 60 80

Fig. 5-30 Impact strength and temperature for various plastics

Char

py im

pact

(kg・

cm/c

m2 ≒

kJ/

m2 )

HDPELDPE

Rigid PVC

PS

Temperature (℃)Source: "Plastics" 22(5), 28 (1971)

15 60 135 2400

5

10

15

20

Fig. 5-31 Volatilization of phthalate plasticizers

Wei

ght l

oss

of te

st s

heet

upo

n he

atin

g (w

t.%)

Heating time (hrs) Oven temp. 165℃Source: "Revised practical manual for plastics and rubber additives" by Kagaku Kogyosha

DHP DOP(DEHP)

DnOP

DIDP

⑫ Bleeding and volatilization of plasticizers

Plasticizers may sometimes bleed or be volatilized from the surface of the PVC product after years of use. Plasticizers may also migrate to other materials which come in contact with PVC products. Such cases can be seen when plasticizers of low-molecular weights or low compatibility (low miscibility) are used, or when large amounts of plasticizers are used, and these are disadvantages of flexible PVC products. Fig.5-31 shows the result of accelerated tests on the volatilization of plasticizers. Test sheets using plasticizers are heated in an oven. Heat loss (weight loss) due to volatilization of plasticizers is shown on the graph.

76


(5) Property modification of PVC products

Since PVC has high polarity and high compatibility with a variety of other high-performance plastics, it is possible to mix these to form polymer alloys with ease. By polymer alloy techniques, the disadvantages

of rigid PVC products can be modified. Fig.5-32 shows the outline of property modification through polymer alloy.

Other than the polymer alloy technique, modifications on heat resistance etc. can be made possible by selecting plasticizers with high molecular weight.

Fig. 5-32 Property modification of PVC by polymer alloy

Source: “ Polymer alloy utilization”, edited by Takashi Inoue, Kogyo Chosakai (1992)

PVC ABSTPU

EVA

Acrylic resin

CPE

MBS

NBR

TPEE

High fluidity, Heat resistance, Impact resistance

Fire retardance

High elasticity, Abrasion resistance, Flexibility

Processability, CostIm

pact

resi

stan

ceFr

eeze

resi

stan

ce

Proc

essa

bilit

yAn

ti m

igra

tion

Heat

resi

stan

ceIm

pact

resi

stan

ce

Proc

essa

bilit

y

Acrylonitrile butadiene rubber

Thermoplastic polyester elastomer

Chlorinated polyethylene

Thermoplastic polyurethane

Methacrylate butadiene styrene

Acrylonitrile-butadiene-styrene

Ethylene-vinyl acetate copolymer

Weatherability,

Cost, Processability

Freeze resistance, Elasticity,

Oil resistance

High elasticity, Flexibility

Freeze resistance,

Abrasion resistance

Impact resistance,

Processability

Impact resistance

Processability

① Impact resistance

Generally, in order to improve the impact resistance of PVC products, impact modifiers (toughening agents) which have rubber-like properties such as ABS, MBS, acrylic rubber, chlorinated polyethylene or EVA, are mixed with PVC. Sufficient impact resistance for practical use can be obtained by blending 5~20 weight parts of these impact modifiers to 100 weight parts of PVC. The impact modifier in the form of micro particles is dispersed within the molecular structure of PVC. When the PVC products receive impact, these micro particles in the molecular structure absorb the impact energy and prevent damages to the PVC product.

PVC whose impact resistance is modified is used in a wide range of applications including exterior construction materials (window frames, siding), industrial boards, impact resistant water pipes, rigid PVC packaging (blister packs, caps, casings), surface protecting films, or electrical parts (connectors).

Fig. 5-33 Effect of blending impact modifiers

Source: “ PVC and polymers” by Mitsui Polychemical, 19(12), 26 (1979)

EVA

ABS

MBS

CPE

(kg･c

m･cm

-1)

Amount of impact modifier (phr)5 100 15 20 25

0

50

100

150（20℃）

EVA (Ethylene-vinyl acetate copolymer)ABS (Acrylonitrile-butadiene-styrene)MBS (Methacrylate butadiene styrene)CPE (Chlorinated polyethylene)Izo

d imp

act s

treng

th

77

② Heat distortion temperature (softening temperature)

In order to enhance the heat resistance, heat distortion temperature or softening temperature of PVC products, heat resistant resins such as ABS resins, α -methylstyrene copolymers, or after-chlorinated PVC is usually blended. Fig.5-34 and Fig.5-35 show the improvement of the softening temperature by blending ABS as an example, and the improvement of thermal deformation temperature by blending after-

chlorinated PVC, respectively.PVC with enhanced heat resistance is used for

heat resistant rigid PVC pipes, such as hot water supply pipes or electric cable protecting tubes, and instrument panels of vehicles.

On the other hand, soft PVC products with modified heat resistance are used for heat resistant cable covering and others, by blending the high-polymer plasticizer.

1000

HAPVC

5050

0100

60

70

90

100

80

Fig. 5-35 Effects of blending after-chlorinated PVC

Heat

dist

ortio

n te

mp.

(℃ a

t 18.5

kg/c

m2 )

Sekisui PVC-HA 31K

Blending ratio (%)

Source: Extracted from a catalogue by Sekisui Chemical Co., Ltd.

③ Prevention of plasticizer bleed and volatilization

In order to prevent bleeding, volatilization or migration of plasticizers to other materials from soft PVC products, plasticizers with high molecular weight or high compatibility with PVC is adopted. Fig.5-36 shows an example where a polyester plasticizer with the molecular weight of 1,500 is used to replace DOP, which is a general-purpose plasticizer with the molecular weight of 390. Test pieces are placed in an oven of 160℃ and rates of weight loss are measured to represent volatilization of plasticizers as time elapses.

On the other hand, plasticizer free flexible PVC products are manufactured as in the case of graft polymerized EVA (ethylene vinyl-acetate copolymer) and PVC, or a terpolymer composed of ethylene-vinyl acetate-carbon monoxide.

PVC including non-migrating or non-bleeding plasticizers at high temperatures is used for electric/electronic parts and heat resistant cables. Some of the non-migrating type plasticizers are used for medical bags/tubes or industrial hoses. Artificial leather and gaskets manufactured with volatilization preventive

After-chlorinated PVC :It is a thermoplastic manufactured by further reacting PVC with chlorine, also known as chlorinated PVC or CPVC. The chlorine content of regular PVC is 56.8%, but that of CPVC is 60~70%. As a result, the heat distortion resistance, fire resistance, electrical insulating properties and chemical resistance are further improved.

Vica

t（℃）

8020

1000

6040

4060

2080

80

90

110

120

100

Fig. 5-34 Effect of blending heat resistant ABS

Condition for vicat softening temperature: 1 kg load

"Ther-alloy" A-15

PVC "Ther-alloy"

PVC/ "Ther-alloy" (phr)

Source: Extracted from a technical document by Kaneka Corporation

200 40 60 800

2

6

10（％）

8

4

Fig. 5-36 Effect of polyester plasticizer for prevention of volatile loss

Vola

tile

loss

Heating time (min)* PVC 100 parts, plasticizer 50 parts, 160℃ geer oven

Source: "Revised practical manual for plastic and rubber additives" by Kagaku Kogyosha

DOP 50 parts

DOP 37.5 p

arts +

Polyeste

r 12.5

parts

DOP 25 parts +

Polyester 25 parts

DOP 12.5 parts +

Polyester 37.5 parts

Polyester 50 parts

78


This chapter introduces a brief history of PVC, which has the longest history among general purpose plastics, dating back to the postwar period (initial phase) and its growth thereafter to mark 2.5 million tons of production per year. Related information such as the transition of production and shipment, the growth of the PVC industry in the world, the position of the Japanese PVC market, and the unique features of the PVC industries and markets in Japan, the U.S. and EU will also be explained though comparison of data per application.

The excellent physical properties of PVC are highly regarded globally. PVC will sustain its broad applications and would further expand in construction materials such as window profiles and sidings.

CHAPTER 6: BRIEF HISTORY AND DATA REGARDING THE JAPANESE PVC INDUSTRY

80

CHAPTER 6 : BRIEF HISTORY AND REGARDING THE JAPANESE PVC INDUSTRY


(1) Initial phase (1937~1951)

In 1941, Nippon Chisso Hiryo K.K. produced the first PVC in Japan via emulsion polymerization using VCM made of acetylene synthesis method, and marketed with the trade name "Nipolit". However, the production was terminated in the post World War II period. In 1946, the Yokohama Rubber Co., Ltd and Tokyo Shibaura Electric Co., Ltd (today’s Toshiba) restarted the test production of PVC for electric cable covering, and 18 companies subsequently started commercial production of PVC by 1952. Industrial production of PVC applications was achieved in succession, such as general purpose films in 1947, synthetic leather in 1949, agro-films and rigid PVC pipes in 1951.

(2) Development phase (1952~1965)

In 1952, Zeon Corporation (former Geon) imported the suspension polymerization process from B.F. Goodrich Chemicals Co. of the U.S. and started commercial production. In 1953, the PVC Association of Japan was established. Suspension polymerization process replaced the emulsion polymerization process as the mainstream production method, which initiated the full-fledged industrial production of PVC in Japan. In those days, VCM, which is the raw material of PVC, was produced from acetylene produced by carbide, and chlorine produced as by-product from electrolysis upon caustic soda production, or as by-product from potassium chloride production.

PVC products were highlighted as epoch making

0

500

1,000

1,500

2,000

2,500

3,000Thousand tons

'46 '47 '48 '49 '50 '51 '52 '53 '54 '55 '56 '57 '58 '59 '60 '61 '62 '63 '64 '65 66 '67 '68 '69 '70 '71 '72 '73 '74 '75 '76 '77 '78 '79 '80 '81 '82 '83 '84 '85 '86 '87 '88 '89 '90 '91 '92 '93 '94 '95 '96 '97 '98 '99 '00 '01 '02 '03 '04 '05 '06 '07

Fig. 6-1 Transition of PVC production in Japan (calendar year)

Initial phase (domestic technology)

PVC Association of Japan the PVC Industry Association the PVC Industry Association VEC

Development phase (technology introduction) Boom phase (upsizing

(Active exports of PVCproduction technologies)

Structural reform phase (intensive production, new application development) Restructuring and counter-environmental issues phase

Com

mer

cial

izat

ion

Switc

h fr

om e

mul

sion

to s

uspe

nsio

n po

lym

eriz

atio

n

2nd

larg

est p

rodu

ctio

n in

the

wor

ld

Intr

oduc

tion

of th

e ED

C pr

oces

s

Intr

oduc

tion

of o

xych

lorin

atio

n pr

oces

s

Firs

t VCM

cen

ter b

y ox

ychl

orin

atio

n pr

oces

sPr

oduc

tion

brok

e1

mill

ion

ton

mar

k

The

Nix

on S

hock

Coun

term

easu

res

for p

last

ic w

aste

s

The

2nd

oil c

risis

The

1st o

il cr

isis

Measures for structural reform

Esta

blis

hmen

t of f

our

join

t sal

es c

ompa

nies

Mea

sure

s fo

r ca

rcin

ogen

icity

by

VCM

Production facilityclosedown

(450 thousandtons : 22%)

Recessioncaused bythe strong

yen

Coun

term

easu

res

for d

ioxi

ns is

sues

Prod

uctio

n br

oke

2 m

illio

n to

n m

ark

Inno

vatio

n to

poly

mer

izat

ion

proc

esse

sEs

tabl

ishm

ent o

f Jap

an P

VC R

ecyc

le P

rom

otin

g Co

unci

l

Brea

k up

of t

he jo

int s

ales

com

pani

es a

nd re

orga

niza

tion

Prom

ulga

tion

of C

onta

iner

and

Pac

kagi

ng R

ecyc

ling

Law

Pilo

t stu

dy o

n fe

edst

ock

for b

last

furn

aces

The Heiseirecession

Hollowing outof the industry

Esta

blis

hmen

t of J

apan

PVC

Env

ironm

enta

l Affa

irs C

ounc

il (J

PEC)

81


innovations previously unheard of, and a series of exhibitions were held from 1954 at major commercial facilities such as Nihonbashi Shirokiya department store, Kintetsu department store, and Ohtemachi Sangyo Kaikan. In addition to consumer products such as synthetic leather shoes, watchstraps and handbags, industrial products such as water pipes, cable coverings and agro-films drew the attention of citizens and industries alike.

Subsequently, construction material applications expanded to include corrugated boards, flooring tiles etc. In 1959, Japan became the second largest PVC producer country in the world with 179,000 tons/year, exceeding production in the UK. As a result, securing chlorine and hydrocarbon sources became an impending issue in Japan, and the Japanese PVC

industry started to study on possible raw material switchovers and dispatched survey teams to Europe.

In 1963, Kaneka Corporation imported the "EDC process" for VCM manufacturing from UCC of the U.S. In 1965, Mitsubishi Monsanto Kasei Co., imported the "oxychlorination VCM production process" from Monsanto, U.S. Subsequently, several manufacturers started to use this production process, forming mass production systems for PVC as a petrochemical product. As a result of increased PVC production, the demand for chlorine exceeded that for caustic soda in 1965, and this trend continues today.

0

500

1,000

1,500

2,000

2,500

3,000Thousand tons

'46 '47 '48 '49 '50 '51 '52 '53 '54 '55 '56 '57 '58 '59 '60 '61 '62 '63 '64 '65 66 '67 '68 '69 '70 '71 '72 '73 '74 '75 '76 '77 '78 '79 '80 '81 '82 '83 '84 '85 '86 '87 '88 '89 '90 '91 '92 '93 '94 '95 '96 '97 '98 '99 '00 '01 '02 '03 '04 '05 '06 '07

Fig. 6-1 Transition of PVC production in Japan (calendar year)

Initial phase (domestic technology)

PVC Association of Japan the PVC Industry Association the PVC Industry Association VEC

Development phase (technology introduction) Boom phase (upsizing

(Active exports of PVCproduction technologies)

Structural reform phase (intensive production, new application development) Restructuring and counter-environmental issues phase

Com

mer

cial

izat

ion

Switc

h fr

om e

mul

sion

to s

uspe

nsio

n po

lym

eriz

atio

n

2nd

larg

est p

rodu

ctio

n in

the

wor

ld

Intr

oduc

tion

of th

e ED

C pr

oces

s

Intr

oduc

tion

of o

xych

lorin

atio

n pr

oces

s

Firs

t VCM

cen

ter b

y ox

ychl

orin

atio

n pr

oces

sPr

oduc

tion

brok

e1

mill

ion

ton

mar

k

The

Nix

on S

hock

Coun

term

easu

res

for p

last

ic w

aste

s

The

2nd

oil c

risis

The

1st o

il cr

isis

Measures for structural reform

Esta

blis

hmen

t of f

our

join

t sal

es c

ompa

nies

Mea

sure

s fo

r ca

rcin

ogen

icity

by

VCM

Production facilityclosedown

(450 thousandtons : 22%)

Recessioncaused bythe strong

yen

Coun

term

easu

res

for d

ioxi

ns is

sues

Prod

uctio

n br

oke

2 m

illio

n to

n m

ark

Inno

vatio

n to

poly

mer

izat

ion

proc

esse

sEs

tabl

ishm

ent o

f Jap

an P

VC R

ecyc

le P

rom

otin

g Co

unci

l

Brea

k up

of t

he jo

int s

ales

com

pani

es a

nd re

orga

niza

tion

Prom

ulga

tion

of C

onta

iner

and

Pac

kagi

ng R

ecyc

ling

Law

Pilo

t stu

dy o

n fe

edst

ock

for b

last

furn

aces

The Heiseirecession

Hollowing outof the industry

Esta

blis

hmen

t of J

apan

PVC

Env

ironm

enta

l Affa

irs C

ounc

il (J

PEC)

82


(3) Boom phase (1966~1974)

In 1966, the Ministry of International Trade and Industry (MITI, METI at present) announced its VCM center plan. Two years later, Kashima VCM center which was jointly established by Shin-Etsu Chemical Co. and Kaneka Corporation etc. started up in 1968, accelerating the establishment of large-scale production facilities. In 1969, PVC production in Japan exceeded one million tons for the first time.

In November 1970, disposal issues of PVC waste were taken up at the regular Diet session (“Pollution Diet”). The Japanese PVC industry had jointly established a "PVC waste disposal measures conference" with related PVC converting industries in April 1970, establishing systems to cope with the situation by the industry as a whole. In 1971, "situation and measures to deal with plastic waste issues" was

prepared and distributed to appeal to various public and private sector organizations. In the same year, the PVC Industry established the "plastic waste disposal research association" (the present Plastic Waste Management Institute, PWMI) jointly with the Japan Petrochemical Industry Association and the Japan Plastic Industry Federation, to cope with waste disposal issues.

In 1972, "Japan PVC Industry Association" was formed, and "VCM conference" was merged to it. Along with the Japanese economic boom, demands for PVC and VCM grew largely, and MITI made a request to the industry to secure supply at the time of the First Oil Crisis in 1973.

In 1974, carcinogenicity of VCM was reported in the U.S. Our association established voluntary standards for the working environment of VCM production plants.

1937～1944

1945

1946

1947

1948

1949

1950

1951

0

0.5

5

3

190

1,493

5,085

1952

1953

1954

1955

1956

1957

1958

1959

1960

1961

1962

1963

1964

1965

9,667

16,203

21,960

32,210

55,852

108,905

91,160

179,247

257,561

307,526

303,144

348,061

473,376

482,992

1966

1967

1968

1969

1970

1971

1972

1973

1974

489,664

711,099

941,778

1,047,078

1,162,058

1,019,269

1,079,248

1,313,098

1,459,230

1975

1976

1977

1978

1979

1980

1981

1982

1983

1984

1985

1986

1987

1988

1989

1990

1,106,126

1,022,588

1,026,622

1,200,322

1,581,477

1,413,191

1,105,981

1,191,828

1,400,436

1,487,011

1,529,943

1,511,625

1,634,701

1,809,378

1,940,746

2,015,782

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

2,024,386

1,952,020

1,940,401

2,077,418

2,223,763

2,473,235

2,607,172

2,470,391

2,466,007

2,397,963

2,195,220

2,212,337

2,147,923

2,131,270

2,122,210

2,105,097

2,121,766

Fig. 6-2 Transition of PVC production (1945~2007, calendar year)

Initial phase Development phase Boom phase Structural reform phase

Restructuring andcounter-environmental

issues phase

small-scaleproduction

(NOTE) Figures for 1946~1951 are fiscal year (Apr-Mar) based, while the figures after 1952 are calendar year (Jan-Dec) based.

Source: VEC

Unit : Tons

(4) Structural reform phase (1975~1990)

After 1975, a depression cartel was formed under guidance of MITI in order to adjust the demand-supply discrepancies due to excessive competitions and imports. At the same time, production and sales was rationalized as part of structural reform, in order to meet the requirements of sustainable growth phase

and to enhance international competitive edge. In 1982, four joint sales companies were established

prior to the enactment of the Law Concerning Special Measures for the Stabilization of Specified Industries.

On the other hand, the production technology of the Japanese PVC Industry has been clearly established to be the highest level in the world, since PVC production processes and plants were exported, and establishment of overseas production

83

subsidiaries were actively deployed in the U.S., Europe and other Asian countries by Shin-Etsu Chemical Co., Tosoh Corporation, Kaneka Corporation, Tokuyama Corporation, Mitsubishi Monsanto Chemical Co. (V-Tech Corporation at present), etc.

In 1983, a professor of Ehime University announced that dioxins were detected from municipal waste incinerators, which triggered the issue to become a matter of public concern. The Japanese PVC industry promptly established a "subcommittee for measures against dioxins", and in 1981 confirmed that there was no correlation between dioxins emission and the

volume of PVC wastes generated. The Japanese PVC industry successfully overcame

the business recession due to the strong yen which started from 1985. Partially due to joint efforts with the PVC converter industries for quality improvement, domestic PVC demand increased further in housing construction materials, automobiles and electronic products, and in 1990, the domestic PVC production exceeded 2 million tons for the first time. Prior to that, "PVC Association of Japan" changed its designation to "Japan PVC Industry Association" in May 1987.

(5) Restructuring and counter- environmental issues phase (1991~2007)

From 1987 to 1992, attempts were made to find ways to realize a recycle oriented society, such as "The Limits to Growth" by the Club of Rome and propositions at the Rio Summit to prevent global warming. Our association established the "Japan PVC Recycle Promoting Council" jointly with PVC processor industries under the guidance from MITI in order to effectively utilize used PVC products. The council deployed various model recycling activities for rigid PVC products such as PVC bottles and egg packaging, jointly with soy sauce manufacturers and consumer’s cooperative, prior to the enactment of the Container and Packaging Recycling Law in 1995.

Around 1997 when PVC production in Japan peaked, PVC was suspected to cause dioxins generations upon combustion, and coupled with the endocrine disrupter issue related to phthalate plasticizers, the trend moved further towards PVC avoidance. In 1997, "Japan PVC Recycle Promoting Council" was reorganized and renamed to "Japan PVC Environmental Affairs Council (JPEC)", and besides PVC recycling they started to cover environmental issues comprehensively.

Recycling of used PVC pipes initiated by Japan PVC Pipe and Fittings Association in this period showed significant progress, and sewage pipes manufactured from regenerated PVC were approved as specified items for green procurement in March 2003. Along with pipes, flooring, wallcovering, spouts and window profiles were also specified to be labeled under the "Law for Promotion of Effective Utilization of Resources". The Japanese PVC industry actively backed up the efforts of these industries.

In January 1998, the Japanese PVC industry established the "PVC Environmental Association" as a succeeding organization to the “special committee for measures to deal with environmental issues”, as measures for the PVC de-selection trend which had become critical and to bear responsibilities not only as the PVC resin industry, but also as the PVC related industries as a whole. During May of the same year, "Japan PVC Industry Association" and "PVC Environmental Association" merged to form the present "Vinyl Environmental Council (VEC)".

In 1999, mass media reports on dioxins pollution in Tokorozawa, Saitama Prefecture, brought back attention on waste incineration issues, and a "campaign to ban PVC products to prevent mixing into waste streams" was launched widely, and the society’s view on PVC industries as a whole became tougher.

As a result of actions by the Japanese government such as legal regulations including the "Law Concerning Special Measures against Dioxins" and the "PRTR Law" in 1999, the level of dioxins emission was cut drastically. As of today, there are almost no sensational mass media reports or attacks on PVC. VEC has been promoting activities to establish the PVC industry that contributes to health and safety, having self awareness of responsibilities for safe management through "Responsible Care" and "HPV" (high production volume chemicals) by the OECD.

Simultaneously, amount of export increased largely, mainly to China. In 1997, the production of PVC in Japan peaked at 2.6 million tons. On the other hand, some companies withdrew from the business due to sluggish domestic demands which reflected the long term economic recession. As of April 2008 there are 10 member companies within VEC.

84


(6) Our stride towards future developments

In May 2003, JFE Steel Corp. started its recycling tests using agro-films, pipes etc. at a 3,000 tons/year facility, to prepare for its full fledged industrial operation of blast furnace feedstock preparation from used PVC products. It is a new recycling system jointly developed by JFE Steel, PWMI, and VEC, with financial support from NEDO (the New Energy and Industrial Technology Development Organization). This system provides future directions to take for appropriate treatment of industrial PVC waste other than incineration.

Due to concerns and misunderstandings on additives such as lead stabilizers and plasticizers used for PVC products, an increased number of companies are heading for PVC de-selection, from the health and safety standpoint.

However, there are many conventional application fields where PVC is irreplaceable such as construction/

civil work materials, electrical cables, films and sheets etc. There are also new useful applications such as heat insulating window profiles, which are highly effective for reduction of CO2 emissions. The present growth of PVC in the world is proof.

We firmly believe that our efforts to protect these application fields from ungrounded rumors and to make the usefulness of PVC widely known will meet the benefits of citizens and the national economy, enabling coexistence of the environment and the economy.

We will have to win trust for PVC and PVC products, and cooperate with the PVC converter industries, the end users, governments and citizens to develop the appropriate waste disposal systems.

Currently, three specific programs, i.e. the development of new applications to prove the serviceability of PVC, safe management and informational disclosure, and recycling systems to deal with the waste disposal issues are being implemented.

Some estimate that the world PVC demand in 2020 would be double the present level, reaching 50 million tons. The Japanese PVC industry will have to reposition itself to be understood and loved by the citizens, and further develop the PVC industries as a whole, so as to not let Japan be left behind in the global progress.

85

2. PVC Related Data

1965

1966

1967

1968

1969

1970

1971

1972

1973

1974

1975

1976

1977

1978

1979

1980

1981

1982

1983

1984

1985

1986

1987

1988

1989

1990

1991

1992

1993

1994

1995

1996

1997

1998

1999

2000

2001

2002

2003

2004

2005

2006

2007

445,486

533,906

791,503

961,473

1,066,899

1,127,265

1,050,049

1,127,436

1,379,621

1,344,678

1,091,169

1,041,854

1,024,438

1,308,890

1,631,623

1,304,340

1,062,252

1,250,280

1,470,547

1,481,683

1,515,145

1,541,899

1,673,764

1,852,502

1,951,745

2,052,759

1,969,985

1,951,089

1,958,761

2,134,201

2,260,181

2,546,325

2,558,881

2,433,901

2,526,407

2,340,802

2,153,514

2,215,159

2,152,537

2,119,885

2,108,142

2,117,666

2,059,892

87.7

67.5

82.3

90.1

94.6

107.4

93.1

107.4

122.4

97.5

81.1

95.5

98.3

127.8

124.7

79.9

81.4

117.7

117.6

100.8

102.3

101.8

108.6

110.7

105.4

105.2

96.0

99.0

100.4

109.0

105.9

112.7

100.5

95.1

103.8

92.7

92.0

102.9

97.2

98.5

99.4

100.5

97.3

176,877

250,298

395,783

485,243

523,718

543,696

534,341

596,203

770,847

665,917

601,244

533,560

553,850

688,740

852,530

638,857

593,595

635,159

722,148

754,425

749,401

748,459

870,819

961,607

1,018,394

1,044,039

953,439

936,462

920,819

981,100

982,724

1,102,481

1,051,151

938,564

942,732

899,236

782,213

777,587

820,557

824,421

785,439

763,463

708,437

75.5

63.2

81.6

92.7

96.3

101.8

89.6

111.6

129.3

86.4

90.3

88.7

103.8

124.4

123.8

74.9

92.9

107.0

113.7

104.5

99.3

99.9

116.3

110.4

105.9

102.5

91.3

98.2

98.3

106.5

100.2

112.2

95.3

89.3

100.4

95.4

87.0

99.4

105.5

100.5

95.3

97.2

92.8

140,079

167,927

242,674

272,839

299,923

301,972

291,582

302,850

359,111

325,063

326,321

294,413

319,346

392,721

487,744

405,432

362,155

394,377

446,635

474,821

476,484

465,071

489,179

522,102

557,412

597,303

559,022

545,982

532,720

548,757

548,707

587,792

545,951

463,192

473,931

465,058

420,687

418,161

375,875

377,875

363,437

347,365

318,217

92.1

69.2

88.9

91.0

99.3

103.6

96.3

103.9

118.6

90.5

100.4

90.2

108.5

123.0

124.2

83.1

89.3

108.9

113.3

106.3

100.4

97.6

105.2

106.7

106.8

107.2

93.6

97.7

97.6

103.0

100.0

107.1

92.9

84.8

102.3

98.1

90.5

99.4

89.9

100.4

96.3

95.6

91.6

62,666

74,527

102,434

117,527

131,525

133,688

111,784

113,489

133,830

116,701

121,690

117,154

121,367

147,403

214,028

173,999

160,446

182,892

202,627

202,824

207,743

206,162

254,182

294,096

300,379

326,928

317,501

310,948

299,905

309,043

326,693

364,062

346,965

293,511

296,393

304,400

270,987

265,826

248,984

240,508

241,410

246,611

237,167

84.6

72.8

87.2

89.4

98.4

119.6

98.4

101.5

117.9

87.2

104.3

96.3

103.6

121.5

145.2

81.3

92.2

114.0

110.8

100.1

102.4

99.2

123.3

115.7

102.1

108.8

97.1

97.9

96.4

103.0

105.7

111.4

95.3

84.6

101.0

102.7

89.0

98.1

93.7

96.6

100.4

102.2

96.2

379,622

492,752

740,891

875,609

955,166

979,356

937,707

1,012,542

1,263,788

1,107,681

1,049,255

945,127

994,563

1,228,864

1,554,302

1,218,288

1,116,196

1,212,428

1,371,410

1,432,070

1,433,628

1,419,692

1,614,180

1,777,805

1,876,185

1,968,270

1,829,962

1,793,392

1,753,444

1,838,900

1,858,124

2,054,335

1,944,067

1,695,267

1,713,056

1,668,694

1,473,887

1,461,574

1,445,416

1,442,465

1,390,286

1,357,439

1,263,821

82.4

66.5

84.6

91.7

97.5

104.4

92.6

108.0

124.8

87.6

94.7

90.1

105.2

123.6

126.5

78.4

91.6

108.6

113.1

104.4

100.1

99.0

113.7

110.1

105.5

104.9

93.0

98.0

97.8

104.9

101.0

110.6

94.6

87.2

101.0

97.4

88.3

99.2

98.9

99.8

96.4

97.6

93.1

66,579

46,984

47,551

82,743

117,272

143,361

146,509

142,619

110,141

98,380

122,624

103,207

75,914

53,966

89,868

40,144

14,639

22,231

65,399

59,377

75,853

125,145

67,246

58,754

65,465

61,679

121,243

201,264

230,777

302,514

383,377

480,006

628,256

727,207

776,955

717,846

694,564

742,519

723,558

660,619

723,989

767,486

779,090

177.2

98.8

57.5

70.6

81.8

97.9

102.7

97.3

77.2

89.3

124.6

84.2

73.6

71.1

166.5

44.7

36.5

151.9

294.2

90.8

127.7

165.0

53.7

87.4

111.4

94.2

196.6

166.0

114.7

131.1

126.7

125.2

130.9

115.8

106.8

92.4

96.8

106.9

97.4

91.3

109.6

106.0

101.5

446,201

539,736

788,442

958,352

1,072,438

1,122,717

1,084,216

1,155,161

1,373,929

1,206,061

1,171,879

1,048,334

1,070,477

1,282,830

1,644,170

1,258,432

1,130,835

1,234,659

1,436,809

1,491,447

1,509,481

1,544,837

1,681,426

1,836,559

1,941,650

2,029,949

1,951,205

1,994,656

1,984,221

2,141,414

2,241,501

2,534,341

2,572,323

2,422,474

2,490,011

2,386,540

2,168,451

2,204,093

2,168,974

2,103,084

2,114,275

2,124,925

2,042,911

89.6

68.5

82.3

89.4

95.5

103.6

93.9

106.5

118.9

87.8

97.2

89.5

102.1

119.8

128.2

76.5

89.9

109.2

116.4

103.8

101.2

102.3

108.8

109.2

105.7

104.5

96.1

102.2

99.5

107.9

104.7

113.1

101.5

94.2

102.8

95.8

90.9

101.6

98.4

97.0

100.5

100.5

96.1

16,049

10,471

18,135

25,127

19,588

38,736

73,166

45,610

60,488

199,105

118,395

114,527

68,488

94,548

81,994

127,902

59,319

74,940

108,678

98,914

104,578

101,640

93,978

109,921

120,016

142,826

161,606

118,039

92,579

85,366

104,046

116,030

102,588

119,861

156,257

110,520

95,583

106,649

90,212

107,013

101,846

94,587

111,567

95.7

57.7

72.2

128.3

50.6

52.9

160.4

62.3

132.6

329.2

59.5

96.7

59.8

138.1

86.7

156.0

46.4

126.3

145.0

91.0

105.7

97.2

92.5

117.0

109.2

119.0

113.1

73.0

78.4

92.2

121.9

111.5

88.4

116.8

130.4

70.7

86.5

111.6

84.6

118.6

95.2

92.9

118.0

Fig. 6-3 PVC production & shipment statistics, Japan (fiscal year)

Production

(%)* (%)* (%)* (%)* (%)* (%)* (%)* (%)*For rigidPVC

For flexiblePVC

Breakdown of shipment Total shipment Year-endinventory

For cable/others

Domesticshipment Export

Source: VEC

Unit : Tons

* against the previous year

86


0

500

1,000

1,500

2,000

2,500

3,000

'05'00'95'90'85'80'75'70'65

Fig. 6-5 Domestic shipment and exports of PVC (fiscal year)

Total shipment

Domestic

Export

The domestic shipment of PVC has the following four major peaks: 1973: About 1.26 million tons affected by the first oil crisis 1979: About 1.55 million tons affected by the second oil crisis 1990: About 1.97 million tons by general growth of the domestic economy 1996: About 2.05 million tons due to increased public works Declines of domestic shipment after fiscal 1990 was caused by decreased public works, collapse of the bubble economy and decreased demands in the packaging/wrapping application fields. In contrast, the export started increasing due to the sharp increased of the demand in China and others. The declines of the domestic shipment after 1997 were caused by the combined effects of the extended slump in the domestic economy, end-user industries moving abroad, and PVC de-selection trend in the packaging field.

Source: VEC

MEMO

thousand tons

PVC was the first general purpose plastic produced in Japan in 1950, and full scale commercial production started soon thereafter.

During the 1960s, the PVC applications were extended to construction and industrial fields, and the production volume exceeded one million tons in 1969, and 2 million tons in 1991.

The present production level is around 2.2 million tons, which is the third largest production next to PE and PP. PVC production in Japan is declining as with other general-purpose plastics.

Comparison with other general-purpose plastic productions.

The ratio of PVC production among general-purpose plastics was 31.3% in 1970, and 25% during the 1980s when other general-purpose plastics became well established and 21.2% in 2006.

0

2,000

4,000

6,000

8,000

10,000

12,000

'05'00 '06'03 '04'90 '02'70

18.0

21.1

23.3

21.6

32.2 31.8

25.9

19.318.6 18.2 18.0 17.0 17.3

26.7 27.8 28.7 30.1 30.2

32.1 32.0 32.0 31.8 31.317.3

34.8

31.3

26.7

22.8

23.0 22.5 21.9 21.3 21.1 21.2

15.6

35.1

'80'60

1950

1

5

11

17

1960

41

258

22

16

217

554

1970

1,305

581

1,161

668

14

239

1,160

5,128

1980

1,860

927

1,429

1,129

32

508

1,633

7,518

1990

2,888

1,942

2,049

2,092

455

114

1,047

2,043

12,630

2002

3,176

2,641

2,225

1,837

697

386

1,376

1,271

13,609

2003

3,165

2,751

2,164

1,801

603

409

1,470

1,261

13,624

2004

3,238

2,908

2,153

1,825

720

411

1,528

1,301

14,084

2005

3,240

3,063

2,151

1,734

684

431

1,556

1,286

14,145

2000

3,342

2,721

2,410

2,024

699

354

1,440

1,746

14,736

2006

3,166

3,049

2,146

1,746

686

413

1,568

1,276

14,050

● Production ratio of general-purpose plastics

● Transition of plastics production

thousand tons

Fig. 6-4 Transition of raw material plastics production & ratio of general purpose plastics production

MEMO<Transition of plastics production> Unit : 1,000 tons

PE (total of HD & LD)

PE(total of HD & LD)

PP

PP

PVC

PVC

PS (incl. ABS & AS)

PS(incl. ABS& AS)

PC

PET

Other thermoplastics

Thermosets

Total

<Production ratio of general-purpose plastics>

Source: Plastic raw-materials production statistics, the Japan Plastics Industry Federation

87

0

5

10

15

20

25

30

9.8

26.8

27.4

24.9

11.1

9.3

25.5

27.5

26.5

11.2

8.3

25.0

27.2

29.3

10.2

8.1

24.9

27.1

29.9

9.9

7.7

24.1

26.3

32.2

9.8

7.1

23.6

25.6

33.8

9.9

6.9

21.8

24.4

37.1

9.8

6.5

20.3

24.1

39.8

9.3

2006

2.15

6.70

7.94

13.11

3.06

32.95

1999

2.46

6.76

6.91

6.09

2.80

25.02

2000

2.41

6.55

7.07

6.56

2.89

25.49

2001

2.20

6.63

7.22

7.49

2.72

26.25

2002

2.23

6.80

7.41

7.94

2.70

27.07

2003

2.16

6.80

7.41

8.90

2.77

28.04

2004

2.15

7.13

7.73

9.96

2.98

29.95

2005

2.15

6.52

7.61

11.29

2.99

30.87

20061999 2000 2001 2002 2003 2004 2005

Fig. 6-6 World PVC production (calendar year)Million tons

Others

Asia

Europe

NorthAme-rica

Japan

Unit : %

Year


PVC production in Japan decreased about 0.3 million tons during the 7 years from 1999 to 2006. North America's production roughly levelled off, while Europe's increase was 1 million.

The increase in the Asian region was the most remarkable with about 7 million tons, which was approximately a twofold increase during the same 7 years. Especially in China, further enhancement of PVC production capacity is expected with active capital investments.

MEMO

Japan

North America (U.S. & Canada)

Europe (incl. CIS & East Europe)

Asia (except Japan)

Others

Total

Unit : Million tons

6.9

26.3

27.0

27.7

12.1

6.9

25.6

26.3

28.6

12.6

5.9

23.7

25.5

32.9

12.0

Asia has shown the greatest growth with an annual average of about 9.2%.

Among the Asian countries, China has shown a sharp increase in consumption, and there are wide varieties of applications from infrastructure related such as watersupply/ sewage pipes or electric cables, to construction materials for housing, parts for household electrical appliances, decoration films, and consumer products.

The outstanding characteristic of PVC demand in Asia is window profiles.

About one million tons of PVC is estimated to be used for production of window profiles in China, while about 0.2 million tons are estimated for the same purpose in South Korea.

PVC is drawing attention as a construction material that substitutes for wood.

MEMO

5.4

24.0

25.6

33.1

11.9

5.1 4.6 4.14.9

23.5 23.1 21.5 19.4

25.2 24.9 25.7 26.5

35.136.2 37.2

38.7

11.111.1 11.1

11.2

Fig. 6-7 World PVC consumption (calendar year)


0

5

10

15

20

25

30

35

2006

1.38

6.46

8.81

12.84

3.73

33.22

1999

1.73

6.60

6.78

6.93

3.02

25.06

2000

1.74

6.47

6.66

7.23

3.18

25.28

2001

1.55

6.26

6.74

8.70

3.16

26.40

2002

1.48

6.53

6.99

9.01

3.25

27.25

2003

1.43

6.51

6.98

9.74

3.07

27.72

2004

1.47

6.92

7.45

10.84

3.29

29.98

2005

1.44

6.69

7.99

11.58

3.44

31.14

20061999 2000 2001 2002 2003 2004 2005

Million tons

Others

Asia

Europe

NorthAme-rica

Japan

Unit : %

Year

Japan

North America (U.S. & Canada)

Europe (incl. CIS & East Europe)

Asia (except Japan)

Others

Total

Unit : Million tons

88


'00 year

year

'98 '99'95 '96 '97'93 '94'91 '92

1992110 381 491 76 42 23 11

152 1,691

187 442 182 89 24

139 2,754

87 104 42

233 90

155 41

3,916 625

4,541

1991100 355 455 61 33 34 9

137 1,411

163 361 155 128

132 2,350

92 98

105 295 102

33 3,372

679 4,051

1993103 396 499 89 44 24 12

169 1,775

179 536 101 129 25

175 2,920

81 109 49

239 95

178 46

4,146 521

4,667

1994105 425 530 96 54 25 12

187 2,091

195 669 133 150 26

222 3,486

86 127 47

260 104 208 55

4,830 521

5,351

199599

412 511 94 49 24 12

179 2,063

189 654 147 165 27

224 3,469

78 115 48

241 98

233 61

4,792 672

5,464

1996104 454 558 102 51 27 11

191 2,433

204 790 161 156 35

255 4,034

76 125 54

255 97

264 73

5,472 606

6,078

1997109 426 535 100 46 30 11

187 2,630

209 846 232 125 50

291 4,383

68 132 59

259 306 96 46

5,812 580

6,392

1998

547

201 2,668

216 953 224

194 327

4,583 73

145 60

278 73

340 6,022

642 6,664

1999

534

202 2,887

269 988 254

227 682

5,307 75

148 67

289 65

70 6,466

371 6,837

2000

556

198 2,851

304 970 257

208 691

5,281 71

141 81

292 65

54 6,447

177 6,624

0

1,000

2,000

3,000

4,000

5,000

6,000

7,000

8,000 thousand tons

Fig. 6-8 PVC consumption in the U.S. and Canada (calendar year)

Calendering

Coating

Extrusion

(films, sheets)

Injection molding

Paste resin converting Compounds Others Total domestic consumption Export Total shipment

Flooring Others Total Flooring Wallcovering/Fabrics Paint Others Total Pipes Wires/Cables Siding Window profiles/Doors Wrapping Non-wrapping Others Total Bottles Fittings Others Total

NOTE: Data for the 1991~1997 period covers only the U.S., while the data after 1998 represent the total for the U.S. and Canada.NOTE: The result for 2000 is tentative.

Source: Modern Plastics International

unit : thousand tons

Calendering

Coating

Extrusion (films, sheets)

Injection molding

Paste resin converting

Compounds

Others

Export

Extruded PVC products doubled in ten years from 1991 to 2000 in North America.

This is probably due to the fact that PVC's durability had gained credit in the construction field and demands grew for pipes, sidings, window profiles, and cable coverings.

In contrast, injection molded products such as bottles and fittings, and resin for exports have both decreased.

PVC consumption in North America has grown 1.6 times during the same ten years.

MEMO

89

0

1,000

2,000

3,000

4,000

5,000

6,000

Sources: Modern Plastics International

'00 year'98 '99'95 '96 '97'93 '94'91 '92

1992420 554 28

1,395 827 138

3,362 222 370 263 214 437 248

1,754 9

5,125 1.8%

1991438 557 27

1,307 782 159

3,270 219 384 241 199 426 283

1,752 10

5,032 -2.1%

1993421 515 40

1,390 903 124

3,393 205 357 252 210 432 240

1,696 8

5,097 -0.5%

1994436 570 40

1,415 1,017

150 3,628

225 309 239 226 409 299

1,707 8

5,343 4.8%

1995420 520 38

1,440 1,044

120 3,582

210 363 260 215 448 255

1,751 7

5,340 -0.1%

1996385 585 45

1,430 1,100

120 3,665

220 375 280 205 430 275

1,785 10

5,460 2.2%

1997315 615 45

1,473 1,135

65 3,648

224 425 300 180 454 279

1,862 10

5,520 1.1%

1998260 614 72

1,449 1,231

108 3,735

225 435 306 190 443 285

1,884 22

5,641 2.2%

1999185 690 148

1,460 1,204

102 3,789

229 443 285 195 460 294

1,906 12

5,707 1.2%

2000165 696 143

1,530 1,292

98 3,924

217 417 305 185 472 285

1,881 12

5,817 1.9%

Total

Fig. 6-9 PVC Consumption in Western Europe (calendar year)

for R

igid

pro

duct

sfo

r Fle

xibl

e pr

oduc

ts

BottlesFilms/Sheets

Films/Sheets

Injection moldingPipes/Conduit tubesProfile extrusion

Synthetic leather

FlooringTubes & other extruded productsWires/CablesOthers

Bottles

Films/Sheets

Films/Sheets

InjectionmoldingPipes/Conduit tubesProfileextrusionRigid products& othersSyntheticleather

Flooring

Tubes & otherextruded products

Wires/Cables

Flexible &others

Others

Examples of application calendar year

Total for flexible products Others (Adhesives, Paper coating)

Growth (%) against the previous year

OthersTotal for rigid products

"Profiles" in construction applications, mainly window profiles, have grown largely.

Apart from profiles, consumption for flooring, films/sheets, pipes and conduit tubes have steadily increased.

Thus, PVC consumption in Western Europe is growing steadily.

MEMOthousand tons

unit : thousand tons

90


0 2,000 4,000 6,000 8,000

The world PVC consumption amounted to more than 33 million tons in 2006.

Some predict that "the world PVC consumption may reach 50 million tons per year in 2020".

This forecast is based on steady growth in major countries, mainly construction materials, and steep growth in Asia, especially in China, and also the African region.

The forecast is also based on important roles expected of PVC products in various application fields, such as water supply and sewage systems; agricultural water supplies which are indispensable for the improvement of agricultural productivity through soil modification; and general industrial water supply systems, to enhance the standard of living and to protect people's health.

MEMOFig. 6-10 PVC consumption in major countries (2006)

Japan

U.S.Canada

West Europe(incl. Turkey)CIS/East Europe

Middle East

ChinaKorea

TaiwanIndia

ThailandIndonesia

VietnamMalaysia

Hong KongPakistan

the PhilippinesSingapore

Other Latin AmericaBrazil

MexicoAustralia

New ZealandAfrica

Source: Future demand trends for global prtrochemical products 2007, METI

10,000 Thousand tons

1,376

5,709750

6,5892,219

714

8,582854755

1,121472

220222

1871741189642

926752

484210

40603

1999

1.73

6.60

6.78

6.93

3.02

25.06

2006

1.36

6.46

8.81

12.84

3.73

33.22

2009

1.30

6.94

9.43

16.83

3.44

37.95

2010

1.30

7.08

9.66

18.06

4.66

40.79

2011

1.30

7.22

9.84

19.39

4.91

42.66

2012

1.30

7.30

10.02

20.74

5.19

44.55

- 3.2

- 0.3

3.8

9.2

3.0

- 0.9

2.1

2.2

8.3

5.7

Japan

Japan

20

15

10

5

0

North America

North America

Europe (including CIS)

Europe (including CIS)

Asia (excluding Japan)

Asia (excluding Japan)

Others (Latin America, Middle East, Oceania)

Others (Latin America, Middle East, Oceania)

Total demand

Unit : Million tons

Million tons

'99 '06 '09 '10 '11 '12'99 '06 '09 '10 '11 '12 '99 '06 '09 '10 '11 '12 '99 '06 '09 '10 '11 '12'99 '06 '09 '10 '11 '12

forecast forecast forecast forecast

4.1 % / yr 5.0 % / yr

Av. annualgrowth rate

('99 / '06)

Av. annualgrowth rate

('06 / '12)

Fig. 6-11 World PVC resin demand forecast (2009 - 2012)

According to METI, the world annual average growth rate of PVC demand is projected to be 4.1% between 2006 and 2012. Growth in Asia is expected to be as high as 8.3% with particular leverage from China, where the growth potential for urban infrastructure products such as pipes, electric cables and PVC sashes are high. Growth in North America and Europe is expected to be about 2% respectively. Negative growth is expected in Japan affected by investment cuts in public projects and overseas transfer of PVC user industry plants.

MEMO

Source: Future demand trends for global prtrochemical products 2007, METI

91

Outline of the Vinyl Environmental Councilin Japan

OUTLINEOF THE VINYLENVIRONMENTALCOUNCIL

92

■ Designation : Vinyl Environmental Council (Abbreviation: VEC)■ Date of Establishment : May 26, 1998■ Address : 8th Floor, Rokko Building, 1-4-1 Shinkawa, Chuo-ku, Tokyo, Japan Telephone Number: 81-3-3297-5601 Facsimile Number: 81-3-3297-5783■ Objective : (1) Promote correct understanding of PVC through survey and research on the environment and safety related issues surrounding the PVC industry (2) Contribution to the development of the PVC industry through research on production, technology, distribution and consumption facets of the industry■ Activities : VEC shall perform the following activities to achieve the above: (1) Survey and research on the environment, security and safety related issues within the PVC industry, and promote countermeasures. (2) Survey and research on PVC recycling related issues, and promote countermeasures. (3) Propagation and education for the correct understanding of PVC. (4) Survey and research on production, technology, distribution and consumption of PVC. (5) Interaction and cooperation with other domestic or foreign PVC related organizations. (6) Other activities for attainment of the above mentioned objective■ Members : 10 PVC and VCM manufacturers and 4 associates■ Board : Chairman Vice-chairman Vice-chairman Executive director

Outline of the Vinyl Environmental Council

Itochu CorporationMitsui & Co., Ltd.

Marubeni CorporationMitsubishi Corporation

V-Tech CorporationKashima VCM Co., Ltd.Kaneka Corporation

Keiyo Monomer Co., Ltd.Shin-Etsu Chemical Co., Ltd.

Shin Dai-ichi Vinyl CorporationTaiyo Vinyl Corporation

Tosoh CorporationTokuyama Corporation

Tokuyama Sekisui Co., Ltd.

MEMBER COMPANIES OF VEC

ASSOCIATE MEMBER COMPANIES OF VEC

Kimikazu SugawaraShigeaki NakaharaYukio NakamuraShigetaka Seki

93

tel. 81-3-6414-4710

tel. 81-299-96-3415

tel. 81-6-6226-5355

tel. 81-436-24-8535

tel. 81-3-3246-5071 tel. 81-3-3595-0721

tel. 81-3-5427-5441

tel. 81-3-5427-5100

tel. 81-3-3499-1030

tel. 81-6-6365-3410

4-14-1, Shiba, Minato-ku, Tokyo, 108-0014

2, Higashi wada, Kamisu-shi, Ibaragi, 314-0102

3-2-4, Nakanoshima, Kita-ku, Osaka, 530-0005

11-6, Goiminamikaigan, Ichihara-city, Chiba, 290-0045

2-6-1, Ohtemachi, Chiyoda-ku, Tokyo, 100-0004

1-4-5, Nishishinbashi, Minato-ku, Tokyo, 105-0003



3-3-1, Shibuya, Shibuya-ku, Tokyo, 150-8383

2-4-4, Nishi Temma, Kita-ku, Osaka City, Osaka, 530-0047

V-Tech Corporation

Kashima VCM Co., Ltd.

Kaneka Corporation

Keiyo Monomer Co., Ltd.

Shin-Etsu Chemical Co., Ltd.

Shin Dai-ichi Vinyl Corporation

Taiyo Vinyl Corporation

Tosoh Corporation

Tokuyama Corporation

Tokuyama Sekisui Co., Ltd.

LIST OF VEC MEMBER COMPANIES

Kashima VCM

Kaneka

Keiyo Monomer

Tokuyama

Tosoh

V-Tech

Total

Kaneka

Shin-Etsu

Shin Dai-ichi Vinyl

Taiyo Vinyl

Tokuyama Sekisui

Tosoh

V-Tech

Total

466

550

292

564

116

28

334

2,351

466

550

292

558

115

28

304

2,314

▲37

600

540

200

330

1,454

391

3,515

600

540

200

330

1,454

391

3,515

0

VCM Production capacity by manufacturers PVC Production capacity by manufacturers

Unit: 1,000 tons/year Unit: 1,000 tons/year

Manufacturers As of December, 2006

As of December, 2007

Manufacturers As of December, 2006

As of December, 2007

Source: Chemical division of the METI

Source: Chemical division of the METI

(B) － (A)

(B) － (A)

(A)

(A) (B)

(B)

94

Vinyl Environmental Council(VEC)

Japan PVC Environmental Affairs Council(JPEC)

Japan PVC Pipe and FittingsAssociation

Japan Plastic Sheet Association

Japan Vinyl Goods ManufacturersAssociation

Interior Floor Industrial Association

Japan Carpet Manufacturers Association(Carpet Tiles Committee)

Noubi Recycle Acceleration Council

The Japanese Electric Wire &Cable Makers' Association

Japan Plasticizer Industry Association

Japan Inorganic Chemical IndustryAssociation (PVC stabilizers committee)

Japan Hygienic PVC Association

Japan Hygienic Association of Vinylidene Chloride

Japan Chemical Industry Association

Japan Petrochemical Industry Association

Japan Soda Industry Association

Plastic Waste Management Institute

The Japan Plastic Industry Federation

Japan Chemical Industry Ecology-Toxicology and Information Center (JETOC)

Plastic Sash Industries Association

Plastic Windows Promotion Committee(JMADO)

PVC Siding Promotion Committee

Survey, research, and measures for the environment, safety, production, distribution and consumption relating to the PVC industry

Information of PVC and PVC products, technical development and research for solving environmental issues

Rigid PVC pipes and fittings and their recycling

Rigid PVC sheets, polycarbonate sheets

Compounds, films, wallcovering, synthetic leather, stretched films, agro-films

Floor tiles, floor sheets and their recycling

Tile (modular) carpet products

Recycling of used agro-films

Electric cables in general

Plasticizers for PVC and others (DEHP, DINP, etc.).

Stabilizers for PVC, etc.

Voluntary standards for safety of PVC food packaging

Vinylidene chloride stretched films

Chemical products in general, Responsible Care

Petrochemical products in general

Caustic soda, chlorine, and hydrogen

Survey, research, and promotion of proper disposal for plastic wastes

Standards for PVC and PVC products (ISO, JIS) and measures for national/social policies e.g. the Container and Packaging Recycling Law

Survey and tests on safety of chemical substances

Promotion of PVC windows

Promotion of PVC windows, and aluminum & PVC combined windows

Promotion of PVC siding

8th Floor, Rokko Building, 1-4-1 Shinkawa, Chuo-ku, Tokyo, 104-0033 8th Floor, Rokko Building, 1-4-1 Shinkawa, Chuo-ku, Tokyo, 104-0033

Tobu Building, 1-5-26 Moto-Akasaka, Minoto-ku, Tokyo, 107-0051



Uchiyama Building, 3-9-3 Nishi-Shinbashi, Minato-ku, Tokyo, 105-0003

Osaka Shoko-Kaikan Building, 4-3-6 Minami-Honmachi, Chuo-ku, Osaka, 541-0054


Konwa Building, 1-12-22 Tsukiji, Chuo-ku, Tokyo, 104-0045


3rd Floor, Taisei Building, 2-4-10 Nihonbashikayabacho, Chuo-ku, Tokyo, 103-0025

6th Floor, Rokko Building, 1-4-1 Shinkawa, Chuo-ku, Tokyo, 104-0033

3rd Floor, Marutomo Daiichi Building, 2-10-16, Higashikanda, Chuo-ku, Tokyo, 101-0031





Kaseihin-Kaikan Building, 5-18-17 Roppongi, Minato-ku, Tokyo, 106-0032

2nd Floor, Rokko Building, 1-4-1 Shinkawa, Chuo-ku, Tokyo, 104-0033

Tokuyama Building, 1-4-5 Nishi-Shimbashi, Minato-ku, Tokyo, 105-8249 (c/o Shanon Corp)



TEL.81-3-3297-5601

TEL.81-3-3297-5601

TEL.81-3-3470-2251

TEL.81-3-3408-4342

TEL.81-3-5413-1311

TEL.81-3-3578-1260

TEL.81-6-4704-2150

TEL.81-3-5775-2051

TEL.81-3-3542-6035

TEL.81-3-3404-4603

TEL.81-3-3663-1235

TEL.81-3-5541-6901

TEL.81-3-3864-8030

TEL.81-3-3297-2550

TEL.81-3-3501-7041

TEL.81-3-3297-0311

TEL.81-3-3297-7511

TEL.81-3-3586-9761

TEL. 81-3-3297-8051

TEL.81-3-3597-5133

TEL.81-3-3297-5781

TEL.81-3-3297-5782

/ FAX.81-3-3297-5783

/ FAX.81-3-3297-5783

/ FAX.81-3-3470-4407

/ FAX.81-3-3403-6990

/ FAX.81-3-3401-9351

/ FAX.81-3-3578-1250

/ FAX.81-6-5545-1648

/ FAX.81-3-5775-2053

/ FAX.81-3-3542-6037

/ FAX.81-3-3403-4604

/ FAX.81-3-3663-1237

/ FAX.81-3-5543-6902

/ FAX.81-3-3864-8031

/ FAX.81-3-3297-2610

/ FAX.81-3-3501-3895

/ FAX.81-3-3297-0315

/ FAX.81-3-3297-7501

/ FAX.81-3-3586-9760

/ FAX. 81-3-3297-8055

/ FAX.81-3-3597-5133

/ FAX.81-3-3297-5783

/ FAX.81-3-3297-5783

http://www.vec.gr.jp

http://www.pvc.or.jp

http://www.ppfa.gr.jp

http://www.p-bankyo.com

http://www.vinyl-ass.gr.jp

http:www.ifa-yukazai.com

http://www.carpet.or.jp

http://www.noubi-rc.jp

http://www.jcma.jp

http://www.kasozai.gr.jp

http://www.mukiyakukyo.gr.jp

http://www.jhpa.jp

http://vdkyo.jp

http://www.nikkakyo.org

http://www.jpca.or.jp

http://www.jsia.gr.jp

http://www.pwmi.or.jp/ei/index.htm

http://www.jpif.gr.jp

http://www.jetoc.or.jp

http://www.p-sash.jp

http://www.jmado.jp

http://www.psiding.jp

Designation Assignments/Products Address Contact (phone / fax. and website)

■ LIST OF PVC RELATED INDUSTRIAL ORGANIZATIONS

95

Vinyl Environmental Council(VEC)

Japan PVC Environmental Affairs Council(JPEC)

Japan PVC Pipe and FittingsAssociation

Japan Plastic Sheet Association

Japan Vinyl Goods ManufacturersAssociation

Interior Floor Industrial Association

Japan Carpet Manufacturers Association(Carpet Tiles Committee)

Noubi Recycle Acceleration Council

The Japanese Electric Wire &Cable Makers' Association

Japan Plasticizer Industry Association

Japan Inorganic Chemical IndustryAssociation (PVC stabilizers committee)

Japan Hygienic PVC Association

Japan Hygienic Association of Vinylidene Chloride

Japan Chemical Industry Association

Japan Petrochemical Industry Association

Japan Soda Industry Association

Plastic Waste Management Institute

The Japan Plastic Industry Federation

Japan Chemical Industry Ecology-Toxicology and Information Center (JETOC)

Plastic Sash Industries Association

Plastic Windows Promotion Committee(JMADO)

PVC Siding Promotion Committee

Survey, research, and measures for the environment, safety, production, distribution and consumption relating to the PVC industry

Information of PVC and PVC products, technical development and research for solving environmental issues

Rigid PVC pipes and fittings and their recycling

Rigid PVC sheets, polycarbonate sheets

Compounds, films, wallcovering, synthetic leather, stretched films, agro-films

Floor tiles, floor sheets and their recycling

Tile (modular) carpet products

Recycling of used agro-films

Electric cables in general

Plasticizers for PVC and others (DEHP, DINP, etc.).

Stabilizers for PVC, etc.

Voluntary standards for safety of PVC food packaging

Vinylidene chloride stretched films

Chemical products in general, Responsible Care

Petrochemical products in general

Caustic soda, chlorine, and hydrogen

Survey, research, and promotion of proper disposal for plastic wastes

Standards for PVC and PVC products (ISO, JIS) and measures for national/social policies e.g. the Container and Packaging Recycling Law

Survey and tests on safety of chemical substances

Promotion of PVC windows

Promotion of PVC windows, and aluminum & PVC combined windows

Promotion of PVC siding

8th Floor, Rokko Building, 1-4-1 Shinkawa, Chuo-ku, Tokyo, 104-0033 8th Floor, Rokko Building, 1-4-1 Shinkawa, Chuo-ku, Tokyo, 104-0033




Uchiyama Building, 3-9-3 Nishi-Shinbashi, Minato-ku, Tokyo, 105-0003

Osaka Shoko-Kaikan Building, 4-3-6 Minami-Honmachi, Chuo-ku, Osaka, 541-0054


Konwa Building, 1-12-22 Tsukiji, Chuo-ku, Tokyo, 104-0045


3rd Floor, Taisei Building, 2-4-10 Nihonbashikayabacho, Chuo-ku, Tokyo, 103-0025


3rd Floor, Marutomo Daiichi Building, 2-10-16, Higashikanda, Chuo-ku, Tokyo, 101-0031





Kaseihin-Kaikan Building, 5-18-17 Roppongi, Minato-ku, Tokyo, 106-0032

2nd Floor, Rokko Building, 1-4-1 Shinkawa, Chuo-ku, Tokyo, 104-0033

Tokuyama Building, 1-4-5 Nishi-Shimbashi, Minato-ku, Tokyo, 105-8249 (c/o Shanon Corp)



TEL.81-3-3297-5601

TEL.81-3-3297-5601

TEL.81-3-3470-2251

TEL.81-3-3408-4342

TEL.81-3-5413-1311

TEL.81-3-3578-1260

TEL.81-6-4704-2150

TEL.81-3-5775-2051

TEL.81-3-3542-6035

TEL.81-3-3404-4603

TEL.81-3-3663-1235

TEL.81-3-5541-6901

TEL.81-3-3864-8030

TEL.81-3-3297-2550

TEL.81-3-3501-7041

TEL.81-3-3297-0311

TEL.81-3-3297-7511

TEL.81-3-3586-9761

TEL. 81-3-3297-8051

TEL.81-3-3597-5133

TEL.81-3-3297-5781

TEL.81-3-3297-5782

/ FAX.81-3-3297-5783

/ FAX.81-3-3297-5783

/ FAX.81-3-3470-4407

/ FAX.81-3-3403-6990

/ FAX.81-3-3401-9351

/ FAX.81-3-3578-1250

/ FAX.81-6-5545-1648

/ FAX.81-3-5775-2053

/ FAX.81-3-3542-6037

/ FAX.81-3-3403-4604

/ FAX.81-3-3663-1237

/ FAX.81-3-5543-6902

/ FAX.81-3-3864-8031

/ FAX.81-3-3297-2610

/ FAX.81-3-3501-3895

/ FAX.81-3-3297-0315

/ FAX.81-3-3297-7501

/ FAX.81-3-3586-9760

/ FAX. 81-3-3297-8055

/ FAX.81-3-3597-5133

/ FAX.81-3-3297-5783

/ FAX.81-3-3297-5783

http://www.vec.gr.jp

http://www.pvc.or.jp

http://www.ppfa.gr.jp

http://www.p-bankyo.com

http://www.vinyl-ass.gr.jp

http:www.ifa-yukazai.com

http://www.carpet.or.jp

http://www.noubi-rc.jp

http://www.jcma.jp

http://www.kasozai.gr.jp

http://www.mukiyakukyo.gr.jp

http://www.jhpa.jp

http://vdkyo.jp

http://www.nikkakyo.org

http://www.jpca.or.jp

http://www.jsia.gr.jp

http://www.pwmi.or.jp/ei/index.htm

http://www.jpif.gr.jp

http://www.jetoc.or.jp

http://www.p-sash.jp

http://www.jmado.jp

http://www.psiding.jp

Designation Assignments/Products Address Contact (phone / fax. and website)

■ LIST OF PVC RELATED INDUSTRIAL ORGANIZATIONS

No part of this publication may be reproduced or transmitted in any form or by any means without first obtaining written approval from VEC.

8th Floor, Rokko Building, 1-4-1 Shinkawa, Chuo-ku, Tokyo, JapanTelephone Number: 81-3-3297-5601 / Facsimile Number: 81-3-3297-5783

First print of the second edition, August 2008Vinyl Environmental Council (VEC), Japan

Musashino create Co., Ltd.

Published by VINYL ENVIRONMENTAL COUNCIL (VEC), JAPAN

Edition :Research & Text :Production :

Designed by GL Design worksKazuo Terao

10 -310 -610 -910 -12

g (one thousandth of a gram)g (one millionth of a gram)g (one billionth of a gram)g (one trillionth of a gram)

＝＝＝＝

kgg

mgμgngpg

(kilogram) (gram)(milligram)(microgram)(nanogram)(picogram)

Reference : Units for trace quantities

Weight units :

IARCJHPAJICIAJPIJPIAJPPFAJSIAMETIMHLWMITIMoEPWMIVECWACOAWHO

ABSDBPDEHADEHPEDCHDPELDPEPCPEPETPPPSPUPVCSMVCM

International Agency for Research on CancerJapan Hygienic PVC AssociationJapan Inorganic Chemical Industry Associationthe Japan Petroleum InstitueJapan Plasticizer Industry AssociationJapan PVC Pipe & Fittings AssociationJapan Soda Industry AssociationMinistry of Economy, Trade and IndustryMinistry of Health, Labour and WelfareMinistry of International Trade and Industry (now METI)Ministry of EnvironmentPlastic Waste Management InstituteVinyl Environmental CouncilWallcoverings Association of JapanWorld Health Organaization

Acrylonitrile-Butadiene-StyreneDibutyl phthalateDi-2-ethylhexyl adipateDi-2-ethylhexyl phthalateEthylene dichlorideHigh-density polyethyleneLow-density polyethylenePolycarbonatePolyethylenePolyethylene terephthalatePolypropylenePolystyrenePolyurethanePolyvinyl chloride Styrene monomerVinyl chloride, Vinyl chloride monomer

Abbreviation:

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