4. Nubiola.pdf

nubiolaUltramarine Pigments:On the Road toPerfection

Alex CapuzGlobal Marketing Manager

Masterbatch Asia

18-20 March 2013

Singapore

• World’s largest producer of Ultramarines• Specialized producer of high performance

Iron Oxides and Zinc Ferrites• Other key product ranges for Plastics:

Chrome Oxide Greens, Chrome Yellows, Molybdate Oranges and BismuthVanadates

• 5 manufacturing plants and 5 TechnicalService Labs all over the world

• 98 years experience making pigments• R&D Investment/Sales = 2.5%

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Table of contents

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• Why are Ultramarines so popular?

• What has been done to overcome some of Ultramarines’ “natural” limitations?

• What is coming up in the near future?

• Conclusions

Why are Ultramarines so popular?

1. Unique color2. Excellent dimensional stability3. Ease of dispersion4. High heat fastness5. Excellent light and weather fastness6. Excellent regulatory compliance7. Excellent ability to make whites “whiter”

and greys and blacks “bluer”8. Good performance/cost ratio

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The Ultramarines chemical structure

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Na8-x[(Al,Si)12]O24(Sy)2

Si/Al

O

Na

S


6

Na8-x[(Al,Si)12]O24(Sy)2

Si/Al

O

Na

S


7

S3·-

Ab

sorb

an

ce

PB 29Ultramarine Blue

S3·-

S4

Ab

sorb

an

ce

S2·-

PV 15Ultramarine Violets

and Pinks

UV-Vis Spectrophotometer

Ultramarine Blue vs other Blue pigments

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0.5%UMB

0.07%PB 15:1

0.07%PB 15:3

0.05% PB 15:1

0.05%PB 15:3

PS (Full shade)

PS + 0.5% TiO2

0.5%PB 28

0.5%PB 28

0.5%UMB

Ultramarine Violets and Pinks - shades

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Manufacturing time- +

Tinting Strength+ -

More ReddishMore Bluish

PS (Full shade, 1% UMV)

PS + 1% UMV+ 1% TiO2

Ultramarine Violets vs Organic Violets

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PP (Full shade)

1%Bluish UMV

0.006 %PV 23

1% VeryReddish UMV

0.03 %PV 19

PP + 1% TiO2

1%Reddish UMV

0.006 %PV 23

1% VeryReddish UMV

0.03 %PV 19

Average Particle Size

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Scanning Electron Microscopy -SEM-

(Servei Microscopia Electrònica, UAB, Barcelona, Spain)

+dark

0.8 µm 1.4 µm 2.5 µm

+light

Ultramarine Blues

Dimensional stability

12

0

20

40

60

80

100

120

140

1% Ultramarine Blue 0.2% Low Warping Phthalocyanine Blue

0.2% Conventional Phthalocyanine Blue

Warp

ag

e(%

vs

Bla

nk)

Warpage evaluation in Injection Molded HDPE

ISO 294-4:2001/ASTM D955

+7%

+116%

+56 %

Warpage (%) = hpart/dpart

Weather Fastness

• Excellent weather fastness… but polymer stabilization to UV light is a must

• The use of UV Absorbers is recommended• If the polymer degradation can produce acid traces/radicals -e.g.

the case of PVC- the use of an acid resistant Ultramarine Blue isrecommended 13

0,0

0,5

1,0

1,5

2,0

2,5

3,0

0 5 10 15

Blank 1% UMB 1% UMB/TiO2 (1:5)

Months

dE

Outdoor exposureInjection Molded PP + 0.2% LMW HALS +

0.2% HMW HALS + 0.2% UV Absorber

WOM wet (ISO 11341 A)Injection Molded HDPE + 1% Ultramarine

Blue (*)

(*) Source: E.Dongiovanni, ClariantPigments & Additives, “Oldand New Technologies for theimprovementof plasticquality”, Slide7, MasterbatchAsia 2006

After4,000 h:

Regulations compliance

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• Nubiola is the REACH lead registrant of Ultramarine Blues, Violets and Pinks

• Nubiola’s Ultramarines can be used in compliance with:– Food Contact Packaging: AP (89) I, Regulation (EU)

10/2011, FDA §178.3297 (Colorants for Polymers)– Cosmetics and Personal Care products packaging– Electric and Electronic Equipment: RoHS legislation

(Directive 2011/65/EU) and WEEE (Directive 2002/96/EC)– Automotive: GADSL and Directive 2000/53/EC. Included

in the IMDS (Automotive International Material Data System)

– Toys: EN 71 Part 3, ASTM F 963-11 and Directive 2009/48/EC

– Industrial applications: non classified substances according to GHS, Regulation (EC) 1272/2008)

– General Packaging: CONEG and Directive 94/62/EC– Textile: Oeko-Tex standards

Use of UM in Biodegradable Plastics

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Limit values (in the final Plastic part)for Hazardous Substances (*)

(*) Source: “Global review of Biodegradable Plasticstesting and standards”, Dipl.Ing. MarkusWeber, DIN CERTCO Gesellschaft fürKonformitätsbewertungmbH (Berlin)

Nubiola’s Ultramarines comply with all limitvalues of all Regulations

Making whites “whiter”

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Ab

sorb

an

ceA

bso

rban

ce

30

40

50

60

70

80

90

h ( )400 450 500 550 600 650 700

Refl

ect

an

ce(%

)

PP + 1% TiO2

PP + 1% TiO2 + 50 ppm Ultramarine Blue

PP + 1% TiO2 + 100 ppm Ultramarine Violet

UV-Vis Spectrophotometer


• Reddish undertone of Ultramarine Blues and Ultramarine Violets, the most recommended grades

• Ease of dosage control• Stable performance at very low dosages • Good Performance/Cost ratio

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Why Ultramarines?


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52,1

63,0 65,5 64,7 64,1

13,9

5,4 4,7 4,7 6,9

0

10

20

30

40

50

60

70

Blank Reddish UMB

Medium UMB

Greenish UMB

Reddish UMV

Whiteness Index Yellowness Index

PP + 1% TiO2

+ 50 ppm + 100 ppm

-1,8

-1,6

-1,4

-1,2

-1

-0,8

-0,6

-0,4

-0,2

0

72

73

74

75

76

77

78

79

Blank Reddish UMB

Medium UMB

Greenish UMB

Reddish UMV

Reflectance 460nm dL vs Blank

+ 50 ppm + 100 ppm

Reddish Ultramarine Blues and Reddish Ultramarine Violets are the most suitable products to obtain the most

neutral white correction effect


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PP + 1% TiO2 Blank +0.6 ppm

PV23

+100 ppm Bluish UMV

+3 ppmPV19

+200 ppm very Reddish

UMV

Blank

WI = 70.6 WI= 63.8 WI = 69.8 WI = 67.8 WI= 63.8 WI = 68.1

ABS + 2% TiO2Blank+ 300 ppm

Reddish UMV+ 100 ppm

Reddish UMB

PP+ 50 ppm

Reddish UMVBlank+ 100 ppm

Reddish UMV

YI = 3.0 YI= 2.3 YI = 2.2


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(*) Source: H.Ohleier, S.Wannemacher, Clariant Pigments&Additives, “The Effectof Pigment Concentration on Heat Stability”, Slide 2, Masterbatch Asia 2007

Heat

fast

ness

(ºC

)

Pigment Concentration (%)

Organic Violets: Influence of pigmentconcentration on Heat fastness (*)

Making greys and blacks “bluer”

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0.1% CB1% TiO2

0.1% CB1% TiO2

0.2% UMB

0.05% CB1% TiO2

0.05% CB1% TiO2

0.1% UMB

0.01% CB1% TiO2

0.01% CB1% TiO2

0.02% UMB

S3·-

Ab

sorb

an

ce

Making blacks “bluer”

To demonstrate that by formulating a BLACK color ABS injection-molded plastic part for the Automotive industry with:

– either Black Pearls 4840 or Elftex 570 from Cabot, and– the right Ultramarine Blue

a high bluish undertone can be reached whilst maintaining:High jetnessHigh impact strengthGood surface appearanceHigh weatherabilityHigh gloss

Jetness (L value) DarkLight

Blu

ish

unde

rton

e (b

val

ue)

Yellow

Blue

BP 120

BP4840

E570

Target BlackCabot-Nubiola: Project Goal

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ABS Compounds with various pigment loadings- 0,5% CB with 0,5 ; 1 ; 2 % UMB- 1,0% CB with 1 ; 2 ; 3 % UMB

Direct Injection -

Molding in ABS

Nubiola and CabotNubiola and Cabot

ABS-CompoundsEvaluation

- Color : CIE lab coordinates- Mechanical : Notched Izod Impact Strength

Nubiola and Cabot

Nubiola and Cabot

•Color measurements of injection molded plaques

•Iluminant: D-65

•10º observer

•Specular component excluded

•Samples taken from injection molding multipurpose test specimen (ISO 3167 type A)

•ISO 180/1A

•Hammer Energy: 2J

•Notch type A (radii 0.25mm.)

Black Masterbatch preparation using a Banbury mixer at Cabot

- 35% E570 in GPPS- 30% BP4840 in GPPS

CabotCabot •BP4840 (Black Pearls 4840) is a high color strength, medium dispersibility & low blue undertone CB)

•E570 (Elftex 570) is a medium color strength, high dispersibility & medium blue undertone CB

Blue Masterbatch preparation using a Leistritz Extruder at Nubiola

- 40% Nubiperf H-56 in ABSNubiolaNubiola •Nubiperf H56 is a high color

strength, high reddish undertone & high dispersibility UMB

Making blacks “bluer”Technical Procedure

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The blue undertone is clearly increased by the

addition of UMB. This effect is more noticeable

at lower loadings of Carbon Black

Making blacks “bluer”Blue undertone

(b value)

Jetness (L value)

The jetness of the finished samples is practically

unaffected (within measurement error) by

the incorporation of UMB

db

-0,2

-0,4

-0,6

-0,8

-1,0

-1,2

-1,4

-1,6

-0,2

-0,4

-0,6

-0,8

-1,0

-1,2

-1,4

-1,60,5% E570 + x% H560,5% E570 + x% H56

0 0,5 1,0 1,5 2,0 2,5 3,0 3,50 0,5 1,0 1,5 2,0 2,5 3,0 3,5

0,5% BP4840 + x% H560,5% BP4840 + x% H56

1% E570 + x% H561% E570 + x% H561% E570 + x% H56

1% BP4840 + x% H561% BP4840 + x% H561% BP4840 + x% H56 db = b ( CB+UMB ) - b (CB)if db<0, the modified sample is bluer

db = b ( CB+UMB ) - b (CB)if db<0, the modified sample is bluer

Nubiperf H-56 (%)

0 0,5 1,0 1,5 2,0 2,5 3,0 3,50 0,5 1,0 1,5 2,0 2,5 3,0 3,5

1,5

1,0

0,5

0

-0,5

-1,0

-1,5

-2,0

2,0

1,5

1,0

0,5

0

-0,5

-1,0

-1,5

-2,0

2,0

0,5% E570 + x% H560,5% E570 + x% H56 1% E570 + x% H561% E570 + x% H56

0,5% BP4840 + x% H560,5% BP4840 + x% H56

1% BP4840 + x% H561% BP4840 + x% H56

dL = L ( CB+UMB ) - L (CB)if dL<0, the modified sample is jetter

dL = L ( CB+UMB ) - L (CB)if dL<0, the modified sample is jetter

dL

Nubiperf H-56 (%) 24

Table of contents

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• Conclusions

Reddish+ formula

Enhanced Tinting Strength

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Milling time

- +Average Particle Size

larger smaller

Reddishformula

Greenishformula

Enhanced Organoleptics

< 1 ppm

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Enhanced Organoleptics• Tests carried out at Certech (Belgium)• Caps made by Ineos, using:

– Ineos’ HDPE (Organoleptic grade) for let-down– Masterbatches made by Nubiola with Ineos’ carrier (Organoleptic grade)

• 4 types of caps were prepared:– S1 100% HDPE (Blank)– S2 1.12% PB28 (Food Packaging grade) in HDPE– S3 0.75% Nubiperf FCP-R in HDPE– S4 0.15% PB15:3 (Food Packaging grade) in HDPE

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• Methodology: “Organoleptic testing of water in contact with caps”– 4 caps per liter of water totally immersed for 10 days at 40ºC (according to

XP ENV 13130-1:1999)– Used water: Chaudfontaine (stored in glass bottles)– Water presented in drinking cups labelled with “blind” codes– 35 panellists

Enhanced Organoleptics

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Very weak37%

Weak29%

Average17%

Strong8%

Very strong

9%

OD

OR

TE

STIN

G

Differences between the least and the most intense sample

TA

STE

TE

STIN

G

Very weak27%

Weak29%

Average26%

Strong18%

Conclusion: there are no significant differences amongsamples (including the blank)

SampleAverage 35 panellists

S1 (Blank) 2.58S2 (PB28) 6.63S3 (FCP‐R) 3.87

S4 (PB15:3) 4.51

Odor rate (*)

SampleAverage 35 panellists

S1 (Blank) 3.37S2 (PB28) 6.62S3 (FCP‐R) 5.46

S4 (PB15:3) 5.06

Taste rate (*)

(*) The higher the rate, the more intense the odor/taste

Enhanced Acid Resistance

Non-encapsulated UMB

1-Pigment + Water 2-Dispersion in Water

4-Acid attack3- Add HCl (aq)


Non-encapsulated UMB Non-encapsulated UMB

30

Conventional Acid ResistantUltramarine Blue

Conventional Silica Encapsulation Technology

Nubiperf AR

New Silica Encapsulation Technology


31

Conventional SilicaEncapsulation Technology

Nubiperf AR


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• More efficient silica encapsulation

• Smaller average particle size

• Narrower particle size distribution

1 µ

1 µ

Scanning Electron Microscopy -SEM-

(Servei Microscopia Electrònica, UAB, Barcelona, Spain)

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Nubiperf AR vs Conventional Acid Resistant UMB

Nubiperf AR

Conventional Acid Resistant UMB

Tinting Strength

Acid Resistancein Use

100

200

150

250

Low

Medium

High

Dispersibility(Filter Test - I20 (bar/g)-)

0

10

5

Color Stabilityin Process( dE after 3

reprocessing cycles)

Weatherabilityin acid conditions

( dE after 3Years outdoor exposure

in industrial area)0

5

10

0

5

Table of contents

34




• Conclusions

Prototype SR-1, a new Super-Reddish UMB

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Reddish UMB

Commercial version of Prototype SR-1

available in Q4’13

Calendered LDPE(0.5% Blue pigments + 0.5% TiO2)

Dar

ker

New Shades & High Tinting Strength UMV

36

Commercial versions of Prototypes XM-1 and

XP-1 available in Q4’13

Table of contents

37




• Conclusions

Conclusions• The physicochemical characteristics of Ultramarines

make them excellent pigments to be used in a wide range of coloristic options in Plastics

• Some of the Ultramarines’ “natural” limitations have partly or totally been overcome with new technical developments carried out in recent years… but there is room for improvement yet

• Commercial versions of the New Super-Reddish Ultramarine Blue Prototype SR-1 and the New Shade, High Tinting Strength Ultramarine Violet Prototypes XM-1 and XP-1 will be available in Q4’13

• Focus on continuous improvement is a key success factor to keep on providing high added value to the Plastics industry

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Thanks for your attention.

Do you have any questions?

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Acknowledgements:Applications (D.Lladó, J.Monllonch),R&D (Dr. R.March, Dr. J.Fernández),

Operations (P.Villasante, F.Ruiz), Marketing (E. Andreu)

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