nubiola

Ultramarine Pigments: On the Road to Perfection

Masterbatch Asia
18-20 March 2013 Singapore

Alex Capuz
Global Marketing Manager

 Worlds 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 Bismuth Vanadates 5 manufacturing plants and 5 Technical Service Labs all over the world 98 years experience making pigments R&D Investment/Sales = 2.5%
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Table of contents
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. 2. 3. 4. 5. 6. 7. Unique color Excellent dimensional stability Ease of dispersion High heat fastness Excellent light and weather fastness Excellent regulatory compliance Excellent ability to make whites whiter and greys and blacks bluer 8. Good performance/cost ratio

The Ultramarines chemical structure

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

Si/Al O Na S

The Ultramarines chemical structure

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

Si/Al O Na S

The Ultramarines chemical structure

PB 29 Ultramarine Blue PV 15 Ultramarine Violets and Pinks S4

Absorbance

S3-

Absorbance

S3-

S2UV-Vis Spectrophotometer 7

Ultramarine Blue vs other Blue pigments

PS (Full shade)
0.5% UMB 0.07% PB 15:1 0.07% PB 15:3 0.5% PB 28

PS + 0.5% TiO2

0.5% UMB

0.05% PB 15:1

0.05% PB 15:3

0.5% PB 28

Ultramarine Violets and Pinks - shades

PS (Full shade, 1% UMV)

PS + 1% UMV + 1% TiO2

More Bluish

More Reddish

+ -

Tinting Strength Manufacturing time

+
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Ultramarine Violets vs Organic Violets

PP (Full shade)
1% Bluish UMV 0.006 % PV 23 1% Very Reddish UMV 0.03 % PV 19

PP + 1% TiO2
1% Reddish UMV 0.006 % PV 23 1% Very Reddish UMV 0.03 % PV 19

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Average Particle Size

Ultramarine Blues
0.8 m 1.4 m 2.5 m

+light

+dark

Scanning Electron Microscopy -SEM(Servei Microscopia Electrnica, UAB, Barcelona, Spain)

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Dimensional stability

Warpage evaluation in Injection Molded HDPE

ISO 294-4:2001/ASTM D955
140

Warpage (% vs Blank)

120 100 80 60 40 20 0

+116%

Warpage (%) = hpart/dpart

+56 % +7%
1% Ultramarine Blue 0.2% Low Warping Phthalocyanine Blue 0.2% Conventional Phthalocyanine Blue

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Weather Fastness
Injection Molded HDPE + 1% Ultramarine Blue (*)
(*) Source: E.Dongiovanni, Clariant Pigments & Additives, Old and New Technologies for the improvement of plastic quality, Slide 7, Masterbatch Asia 2006

WOM wet (ISO 11341 A)

Injection Molded PP + 0.2% LMW HALS + 0.2% HMW HALS + 0.2% UV Absorber
Blank
3,0 2,5 2,0

Outdoor exposure

1% UMB

1% UMB/TiO2 (1:5)

dE

1,5 1,0 0,5 0,0 0 5 10 15

After 4,000 h:

Months

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 is recommended

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Regulations compliance
Nubiola is the REACH lead registrant of Ultramarine Blues, Violets and Pinks Nubiolas 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
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Use of UM in Biodegradable Plastics

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

(*) Source: Global review of Biodegradable Plastics testing and standards, Dipl.Ing. Markus Weber, DIN CERTCO Gesellschaft fr Konformittsbewertung mbH (Berlin)

Nubiolas Ultramarines comply with all limit values of all Regulations

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Making whites whiter

90

Absorbance

80

Reflectance (%)

70

60

50

40

30

Absorbance

400

450

500

550

600

650

700

h(

PP + 1% TiO2 PP + 1% TiO2 + 50 ppm Ultramarine Blue PP + 1% TiO2 + 100 ppm Ultramarine Violet
UV-Vis Spectrophotometer 16

Making whites whiter

Why Ultramarines?
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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Making whites whiter

PP + 1% TiO2
Whiteness Index 70 63,0 60 52,1 50 40 30 20 10 0 77 -0,6 76 75 74 -1,4 5,4 4,7 4,7 6,9 73 72 -1,6 -1,8 -0,8 -1 -1,2 13,9 65,5 Yellowness Index 64,7 64,1 79 78 Reflectance 460nm dL vs Blank 0 -0,2 -0,4

Blank

Reddish UMB

Medium UMB

Greenish UMB

Reddish UMV

Blank

Reddish UMB

Medium UMB

Greenish UMB

Reddish UMV

+ 50 ppm

+ 100 ppm

+ 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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Making whites whiter

ABS + 2% TiO2
+ 300 ppm Reddish UMV Blank + 100 ppm Reddish UMB Blank

PP
+ 50 ppm Reddish UMV + 100 ppm Reddish UMV

YI = 3.0

YI= 2.3

YI = 2.2

+100 ppm Bluish UMV

PP + 1% TiO2
Blank +0.6 ppm PV23 +200 ppm very Reddish UMV Blank +3 ppm PV19

WI = 70.6

WI= 63.8

WI = 69.8

WI = 67.8

WI= 63.8

WI = 68.1
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Making whites whiter

Organic Violets: Influence of pigment concentration on Heat fastness (*)

Heat fastness (C)

Pigment Concentration (%) (*) Source: H.Ohleier, S.Wannemacher, Clariant Pigments&Additives, The Effect of Pigment Concentration on Heat Stability, Slide 2, Masterbatch Asia 2007
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Making greys and blacks bluer

0.1% CB 1% TiO2 0.1% CB 1% TiO2 0.2% UMB

Absorbance

0.05% CB 1% TiO2

0.05% CB 1% TiO2 0.1% UMB

S3-

0.01% CB 1% TiO2

0.01% CB 1% TiO2 0.02% UMB

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Making blacks bluer

Cabot-Nubiola: Project Goal
Blue

Target Black

Bluish undertone (b value)

BP 120 E570 BP 4840

Yellow

Light

Jetness (L value)

Dark

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 jetness High impact strength Good surface appearance High weatherability High gloss
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Making blacks bluer

Technical Procedure
Black Masterbatch preparation using a Banbury mixer at Cabot - 35% E570 in GPPS - 30% BP4840 in GPPS
Cabot
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

Direct Injection Molding in ABS

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

Blue Masterbatch preparation using a Leistritz Extruder at Nubiola - 40% Nubiperf H-56 in ABS
Nubiola
Nubiperf H56 is a high color strength, high reddish undertone & high dispersibility UMB

Color measurements of injection molded plaques Iluminant: D-65 10 observer Specular component excluded

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

Nubiola and Cabot
Samples taken from injection molding multipurpose test specimen (ISO 3167 type A) ISO 180/1A Hammer Energy: 2J Notch type A (radii 0.25mm.)

ABS-Compounds Evaluation

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Making blacks bluer

Blue undertone (b value)
-0,2 -0,4

Nubiperf H-56 (%)

0 0,5 1,0 1,5 2,0 2,5 3,0 3,5
db db = =b b (( CB+UMB CB+UMB )) -- b b (CB) (CB) if db<0, the modified sample if db<0, the modified sample is is bluer bluer

1% BP4840 + x% H56

The blue undertone is clearly increased by the addition of UMB. This effect is more noticeable at lower loadings of Carbon Black

db

-0,6 -0,8
1% E570 + x% H56

-1,0 -1,2 -1,4

0,5% E570 + x% H56 0,5% BP4840 + x% H56

-1,6
2,0

Jetness (L value)

1,5 1,0

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

0,5% BP4840 + x% H56

0,5

1% BP4840 + x% H56

The jetness of the finished samples is practically unaffected (within measurement error) by the incorporation of UMB

dL

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

-0,5 -1,0 -1,5 -2,0 0 0,5 1,0

1,5

2,0

2,5

3,0

3,5
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Nubiperf H-56 (%)

Table of contents
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

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Enhanced Tinting Strength

Reddish formula

Reddish+ formula

Greenish formula
Milling time

Average Particle Size larger

+
smaller
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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 S2 S3 S4 100% HDPE (Blank) 1.12% PB28 (Food Packaging grade) in HDPE 0.75% Nubiperf FCP-R in HDPE 0.15% PB15:3 (Food Packaging grade) in HDPE

Methodology: Organoleptic testing of water in contact with caps

4 caps per liter of water totally immersed for 10 days at 40C (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
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Enhanced Organoleptics
Differences between the least and the most intense sample
Strong 8% Very strong 9% Very weak 37%

Odor rate (*)

Sample S1 (Blank) S2 (PB28) S3 (FCPR) S4 (PB15:3) Average 35 panellists 2.58 6.63 3.87 4.51

ODOR TESTING

Average 17%

Weak 29%

(*) The higher the rate, the more intense the odor/taste
Very weak 27%

Strong 18%

Taste rate (*)

Sample Average 35 panellists 3.37 6.62 5.46 5.06

TASTE TESTING

Average 26%

Weak 29%

S1 (Blank) S2 (PB28) S3 (FCPR) S4 (PB15:3)

Conclusion: there are no significant differences among samples (including the blank)
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Enhanced Acid Resistance

1-Pigment + Water 2-Dispersion in Water

Non-encapsulated UMB

Non-encapsulated UMB

3- Add HCl (aq)

4-Acid attack

Non-encapsulated UMB

Non-encapsulated UMB

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New Silica Encapsulation Technology

Conventional Silica Encapsulation Technology New Silica Encapsulation Technology

Conventional Acid Resistant Ultramarine Blue

Nubiperf AR
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New Silica Encapsulation Technology

Non-encapsulated UMB Nubiperf AR

Conventional Silica Encapsulation Technology

More efficient silica encapsulation Smaller average particle size Narrower particle size distribution
Scanning Electron Microscopy -SEM(Servei Microscopia Electrnica, UAB, Barcelona, Spain) 32

Nubiperf AR vs Conventional Acid Resistant UMB

Nubiperf AR Conventional Acid Resistant UMB

Tinting Strength
250 200 150 100 Low 10 10 5

Acid Resistance in Use

High Medium

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

0

Color Stability in Process

( dE after 3 reprocessing cycles)

Weatherability in acid conditions

0
( dE after 3 Years outdoor exposure in industrial area)

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Table of contents
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

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Prototype SR-1, a new Super-Reddish UMB

Reddish UMB

Commercial version of Prototype SR-1 available in Q413

Darker

Calendered LDPE
(0.5% Blue pigments + 0.5% TiO2)
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New Shades & High Tinting Strength UMV

Commercial versions of Prototypes XM-1 and XP-1 available in Q413

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Table of contents
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

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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 XM1 and XP-1 will be available in Q413 Focus on continuous improvement is a key success factor to keep on providing high added value to the Plastics industry
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Acknowledgements: Applications (D.Llad, J.Monllonch), R&D (Dr. R.March, Dr. J.Fernndez), Operations (P.Villasante, F.Ruiz), Marketing (E. Andreu)

Thanks for your attention. Do you have any questions?

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