Pvc Fact Book

5/22/2018 Pvc Fact Book

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CHAPTER 1:

INTRODUCTION TO

POLYVINYL CHLORIDE

Polyvinyl chloride (PVC) was rst manufacturedin Germany in 1931 as a robust and lightweight newplastic. This breakthrough material was broughtabout to substitute for metals, glass, wood, naturalbers, papers and fabrics. Over 30 million tonsof PVC is used around the globe today, both inindustrialized and developing countries, due to its costefciency, durability, self-extinguishing properties,processability, and resources saving features.

Owing to its safe, healthy, convenient andaesthetical advantages, PVC products supportdaily life in a wide variety of elds including urbaninfrastructures, electronic products, and consumer

goods.For example, PVC can be found in public lifelinessuch as water supply, sewage pipes, or power lines.It is also used in building materials such as sidings,furniture, spouts, window proles, ooring, deckingboards, and roong sheets. Agricultural and industrialapplications include green house sheets, semi-conductor cleansing facilities, exhaust ducts, andparts for automobile and home electrical appliances.Consumer products include food wraps, syntheticleather and stationery. As you can see, PVC, orpolyvinyl 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 aspectsof PVC; production, characteristics, safety andapplications.


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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 monomerAcrylonitrile/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 resin

Plastics are also called synthetic resins and are

broadly classied into two categories; thermosetting

resinsand 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

lms 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 rst landed Japan, where only rigid

thermosetting resins had been known, they left a very

strong impression among the population. This is how

bineelmistakenly became a synonym for all soft lms

including polyethylene lms.

A safe synthetic resin made fromvinyl 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 humanhealth 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 andsoil" - this of course, is a serious misunderstanding.

Resource saving and re resistantproperties

Only 40% of PVC's composition is petroleum-

1. What is PVC?


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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 re resistant plastic

with properties of chlorine containing substances.When PVC is set on re, the ames go out as the

re source is removed due to its self-extinguishing

properties.

One of four major plastics with the longest history

Plastics 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 around1948 in commonplace consumer applications, such

as air inated toys including oats and beach balls,

lms 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 ber

protective pipes, wallcovering, ooring, window

proles (PVC saches), and furniture.

Contributes to energy saving and reduces CO2emissions

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 CO2emissions occur from production

processes, thus contributing to the prevention of

global warming.

Furthermore, as PVC products have the requiredstrength, durability, and low thermal conductivity,

its heat-insulating efciency is three times as high as

that of metal such as aluminum when used as window

proles and siding boards. Therefore consumption of

fossil fuels such as petroleum can be cut back, which

contributes to further reduction of CO2emissions.

(1) Linkage of PVC related

industries

Upstream of the PVC industry (the basicpetrochemical 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 renery industry, which uses importedcrude 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 industry

The 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 rening at the renery toobtain heavy oil, light oil, kerosene, gasoline,

naphtha fractions, and LP gas. Naphtha istransferred to petrochemical plants, whereethylene, propylene, butylene etc. are obtainedby 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 HDPEand LDPE)

Total plastics

14.61million tons

Other

PVC

PP

PS (includingABS and AS)

Total of fourmajor plastics

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


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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 totalshipment 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 methodand 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

( 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 ( 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 ow chart of VCM

manufacturing processes shown in Fig.1-4.

PVC

Fig.1-4 VCM production method

Oxychlorination

Direct chlorination

Ethylene

Air (Oxygen)

Ethylene Chlorine

EDC

Hydrogen chlorideThermalcracking

Thermal cracking

PolymerizationVCM

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

Fig.1-3 Linkage of PVC related industries

Naphtha NaphthaPetroleum

Petroleum refiningindustry

Sea waterRock salt

Salt industry

(Installation,Assembly, Consumption)

End user industry,Consumer

Upstream

Basic petrochemicalindustry

EthyleneEthylene

(Electrolysis)

PVC industryIndustrialgrade salt

Industrial

grade salt

Causticsoda

Chlorine

Soda industry

EDC VCM PVC PVCindustries

Chlorine

(Processing Fabrication)

PVCPVC products

PVC converter industry

Downstream


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5

(3) PVC production processes

Generally, the suspension polymerization processis

adopted to manufacture PVC. First, the raw material

VCM is pressurized and liqueed, 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 isfed 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 m

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 rening, recycled as raw material for reuse in thisprocess (Fig.1-6). Emulsion polymerization process and

bulk polymerization process are also adopted.

Recovered VCM storage tank

RecoveredVCM

storage tank

VCM tank

Volumeter

Catalyst

Polymerizationreactor

Additives

Gasholder

Crude VCMstorage tank

VCM purification column

Vacuumpump

Compressor

Purified water StrippingTank

Centrifuge

Slurry tank

Fluidized-bed dryer

Screen

PVCstorage 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

chlorinationreactor Air

(oxygen)

Ethylene

Oxychlorinationreactor

Direct Caustic soda

Quench column

Caustic sodawashing column

Decanter

Dehydratingcolumn

Low boilingpoint fractioncollectioncolumn

High boiling

point fractioncollection column

Recovery column

Cracking furnace

Quenchcolumn

Hydrochloricacid removalcolumn

Monomerrecovery column

CausticsodawashingcolumnVCM

Source: Prepared from material by the JPI


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6


(4) PVC as petrochemicalproduct

A petrochemical product manufactured from ethylene

PVC is a petrochemical product, since its

intermediate raw material, EDC, is manufacturedfrom 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 complexesThe petroleum rening 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

58,403thousand kl(25%)


22,630 thousand kl(10%)



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

Causticsoda

Industrialgrade 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

EthylenediaminePP

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

1.25EDC(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 JapanPetrochemical 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


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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

reneries, ethylene centers and the petrochemical

plants are connected by pipelines. Likewise, the soda

industry is located together with petrochemicalcomplexes 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 ow of ethylene

which is one of ve 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 totalchlorine 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 soda

Chlorine 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 sodawas 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


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8


Dependency of VCM production on imported EDC

Especially 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 decit 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 patternwhen the substance is in solid form and stable.

PVC has a dominant amorphous molecularstructure, with only 5~10% of crystallinecomponents.

Polarity :Tendency within parts of the molecule to beslightly charged positively and negatively. Parts

within the molecule that are charged are calledpolar parts, as opposed to nonpolar parts wherethere is very little electrical charge.

Imported EDC

PVC production

VCM production

VCM production (EDC requirement)*EDC dependency ratio (%)**

(1,000 tons)

1,000 tonsImported EDC EDC dependency ratio VCM production (EDC requirement)

100VCM production (EDC requirement)

** EDC Dependency Ratio

* VCM production (EDC requirement) VCM production x 0.838

Imported 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


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3. Characteristics ofPVC

9

PVC, PE, PP and PS are called general-

purpose plastics. The features of the plastic

are determined by the chemical compositionand type of molecular structure (molecular

formation: crystalline/amorphous

structure)(Fig.1-12).

PVC has a unique amorphous structure

withpolarchlorine 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 olen plastics which have only carbon

and hydrogen atoms in their molecularstructures.

(1) Chemical stability

Chemical stability is a common feature

among substances, containing halogens

such as chlorine and uorine. This applies to

PVC resins also, which furthermore possess

re retarding properties, durability, and oil/

chemical resistance.

Fire retarding properties

PVC has an inherently superior re

retarding property due to its chlorine atom

components, and do not require addition of

re retardants to its products. For example,

the ignition temperature of PVC is as high

as 455 , and is a material with less risk for

re 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 re to nearby materials even

while burning (Fig.1-14). Therefore, PVC

is the most suitable plastic to be used in

products requiring re retarding properties

such as housing materials.

Durability

Under normal conditions of use, the factor

most strongly inuencing the durability of

a material is resistance to oxidation within

the air. PVC, having the molecular structure

where chlorine atom is bound to every othercarbon chains, is very resistant to oxidative

reactions, and maintains its performance

Vinylidene chloride

Low flammability FluoroplasticPS

Hard to ignite

Cellulose acetate

PVCNylon

PU

PE

Nylon

PVC

PEPU

Methacrylicresin

Pine woodPine wood

CottonPaperPaper

WoolHigh 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 releasekW/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)

Molecular form Amorphouspart

Crystallinepart

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


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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 measurementson 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 (exible 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 Resistance

PVC 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.

2000

1500

1000

500

0

25

20

15

10

5

0

120

100

80

60

40

20

0

2

0

-2

-4

-6

-8

-10

13 years later

400

300

200

100

0

250

200

150

100

50

0

400

300

200

100

0

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)

MPa

Tensilestrength

Number of years in use

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

Source: Japan PVC Pipe & Fittings Association


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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 itsyield

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. Specically, 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 andelasticity. Distortion occurs as soon as externalforce is applied and thereby absorbing the force(elasticity), but when the force is continuouslyapplied, deformation occurs to a certain extent

(viscosity).

Yield point :When external force is applied to a material, elasticdeformation (strain) takes place up to the yieldpoint, and the strain disappears as soon as theexternal force is removed. When the external stressis greater than the yield point, plastic deformation

(permanent set) takes place and the material wouldnot recover its original shape even after removal ofexterior 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 proling

(e.g., housing materials), as well as calenderingof wide lms and sheets (e.g., agricultural lms

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 ooring, wall

covering, automobile sealants and undercoating.

Interior decoration lms

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

Circumferentialst

ress(MPa)

Elapsed time (hrs) 50 years

Source: Japan PVC Pipe & Fittings Association


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4. Safety of PVC

12


(4) Others (versatility in designingthrough 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.,

exibility, elasticity, impact resistance, anti-fouling,anti-bacteria, anti-mist, re retarding) can be freely

designed through formulation with plasticizers and

various additives, modiers, 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 exibility, elasticity, and impact

resistance, by adding plasticizers,

additives, and modiers.

Since the physical properties of

end products are adjustable through

compounding, it requires only a

few types of resin to cover all theapplications of high-polymer materials

(ber, rigid and exible plastic, rubber,

paint, and adhesive). This controllability

is also extremely benecial 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 oorings, housingmaterials, 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 ash 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 re 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.

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

Fire retardance

Oil resistance

Abrasion resistance

Scratch resistance

Adhesion

Gloss

Compression Set

Exterior appearance

Moldability

Tensile strength

PVC materials

Polyolefin materials

Improved polyolefin materials

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


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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 identied 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.110Disclaimer

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 designation

Distinction of single/mixed material

Chemical name

Chemical formula

Structural formula

Classification # in official gazette

CAS No.

Classification of hazardousness

Title of classification

Danger

Hazardousness

First aid

If in contact with eye

If in contact with skin

If swallowed

Measures in case of fire

Extinguish method

Extinguishing Agent

Others

Measures upon leakage

Cautions upon handling

Handling

Storage

(CH2CHCl)n

Polyvinyl chloride

Single material

Polyvinyl 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 mins

and consult a physicianRinse with water

Consult 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

VolatilityTrue specific gravity

Solubility

Info on danger (Stability/Reactivity)

Ignition temperature

Flash ignition temperature

Combustibility

Oxidative property

Dust explosiveness

Stability/Reactivity

Info 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 applicable

Not applicable

Not applicable1.4 (20)

Not soluble in water

391 1

454 2

Stable in room temperature

Stable in terms of dust explosiveness

Stable under normal handling conditions

None specifically

Use the following protective gearswhen necessaryRespirators (dust masks in operation, andair breathing apparatus mask in case of fire)Protective spectacles(dustproof spectacles)

Protective glovesProtective clothes(not required generally)

Self-extinguishing resin withoxygen index of approx. 45

Avoid damage to containersand collapse of cargo

Unclear, but no case knownto show hazardousness

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


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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 wasestablished 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), classied VCM

as substance belonging

to Group 1 (Carcinogenic

to humans) in June, 2001

(Fig.1-20). On the other

hand, PVC was classied as

Group 3 (Not-classiable 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 safetymeasures; therefore the following specications have

been established.

Specications 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 notication No.17. The notication

continues to be effective to date.

Voluntary Standard by Japan Hygienic PVCAssociation (JHP Standard):

In 1970, prior to the abovementioned public

notication, 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 notication

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 othersMaterial 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 to

humans

Probably

carcinogenic to

humans

Possibly

carcinogenic to

humans

Not classifiable as

to its carcinogenicityin 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,

PVC

Caprolactam

(raw material for nylon)

Mixtures

Alcoholic 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


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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 ofcial regulations,

and following the revision of the Food Sanitation

Law, the 1ppm limit of residual VCM was immediately

adopted (Fig.1-21).

Standards for medical equipment

Another example of measures against residual VCM

is the case in medical PVC products including blood

bags, liquid/blood transfusion sets, articial heart

lung apparatus and articial kidneys. PVC has been

used safely for more than 40 years both at home and

abroad, in accordance with the Pharmacopoeia of

Japan, voluntary standardsestablished 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 eld as well.

(1) The Japanese IndustrialStandard (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 PVCproducts. 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 ofmedical products

Transparency/Externalappearance

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 1g (1 ppm) (others: omitted)

(others: omitted)

PH, KMnO4reducing substance,UV absorption spectrum

Acute toxicity tests, Intracutaneous reaction

Tests on eluates

Biological tests

Blood set, Disposable set for artificialheart/lung equipment, Blood tube forhemodialysis, 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 compound

Materials 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- 12K 6737K 7117-2K 7365K 7367-2K 7380K 7381K 7382K 7383K 6723

K 6740K 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.


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16


PVC has superior features in one, and is used in

various elds 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, exible, 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 andservice life of PVC - 1 Long ShortService life

Long term (several years50 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

Flatplates

Rigid

products

Films/Sheets

Constructionmaterials

Corrugatedsheets

corrugated sheet

Agriculturalapplications

name plates, construction materials

terrace roofing

displays

displays

separated trays

separated trays

blister packsNon food

packaging

dimpled sheets

packaging

(for eggs,

tofu, fruits)caps,

food trays

Foodpackaging

Others cooling towers,toys,

electronic equipment accessories,

stationeries,cards,

FDJ

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

accessories

cards

temporary structuressnow fences

casing,

lightweight packaging

clean rooms


17/20

17

agricultural water system



Rigid

products

Water supply

Agricultural water

Sewege

Industrial, facility drainage

Cable protection

Pipes

Fittings

Spouts

Other applications

power tube

Specialpurposes 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 pipelines

industrial waterworks, marine structures, components

water discharge facility buildings,

roadworks, railroad sathletic fields,

air conditioning, gray waterworks

water 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 pipeline

irrigation for farmland

waterworks

exclusive water works

simplified water works

public sewage system

farm village sewage system

development of housing premises

Sewage system

waterworks

Y shaped fitting

rainspout


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18




Rigid

products

Profileextrusion

Construction materials

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

Vehicleapplications

vehicle interior

interior of JR sleeper express trains

For foodpackaging

soy sauce, Worcester sauce,vinegar, seaweed

For non foodapplications

cosmetics, shampoo, detergents

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

sumps valves/flanges

various rigid PVCextrusion molded products

various bottlesBlowm

olde

dproducts

penholder


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19



non woven fabric

Flexibleprod

ucts

Generalfilms/Sheets

Laminatedproducts

printed plywood, PVC laminated steel plates

printed 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

Vehicleapplications

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

Consumerproducts

furniture, accessories

Agricultural filmsgreen 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

agriculturalPVC films

footwear


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20




Flexibleproducts

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 hoseshousingmaterial 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 cartbumpers

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 constructionworks (low-voltage )

power cords

interfacing cables flat-shaped cablestape/ribbon cables

Electriccab

lesandothers

Flooring homogeneous tiles, composite tiles, cushion flooring,

long sheet flooring, tile carpet, laminated tileflooring for stores such asdepartment 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

Pvc Fact Book

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