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nubiola

Ultramarine Pigments: On the Road to Perfection
Masterbatch Asia
18-20 March 2013 Singapore

Alex Capuz
Global Marketing Manager

• 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 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

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Why are Ultramarines so popular? 1. 4. 6. 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. 5. 3. 7. 2. Good performance/cost ratio 4 .

Si)12]O24(Sy)2 Si/Al O Na S 5 .The Ultramarines chemical structure Na8-x[(Al.

The Ultramarines chemical structure Na8-x[(Al.Si)12]O24(Sy)2 Si/Al O Na S 6 .

The Ultramarines chemical structure PB 29 Ultramarine Blue PV 15 Ultramarine Violets and Pinks S4 Absorbance S3·- Absorbance S3·- S2·UV-Vis Spectrophotometer 7 .

5% PB 28 8 .07% PB 15:3 0.5% TiO2 0.5% UMB 0.07% PB 15:1 0.Ultramarine Blue vs other Blue pigments PS (Full shade) 0.05% PB 15:3 0.5% UMB 0.05% PB 15:1 0.5% PB 28 PS + 0.

Ultramarine Violets and Pinks . 1% UMV) PS + 1% UMV + 1% TiO2 More Bluish More Reddish + - Tinting Strength Manufacturing time + 9 .shades PS (Full shade.

03 % PV 19 10 .03 % PV 19 PP + 1% TiO2 1% Reddish UMV 0.Ultramarine Violets vs Organic Violets PP (Full shade) 1% Bluish UMV 0.006 % PV 23 1% Very Reddish UMV 0.006 % PV 23 1% Very Reddish UMV 0.

Barcelona.8 µm 1. UAB.5 µm +light +dark Scanning Electron Microscopy -SEM(Servei Microscopia Electrònica. Spain) 11 .4 µm 2.Average Particle Size Ultramarine Blues 0.

2% Conventional Phthalocyanine Blue 12 .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.

Weather Fastness Injection Molded HDPE + 1% Ultramarine Blue (*) (*) Source: E.2% LMW HALS + 0.the use of an acid resistant Ultramarine Blue is recommended 13 . Masterbatch Asia 2006 WOM wet (ISO 11341 A) Injection Molded PP + 0. Clariant Pigments & Additives.5 0.000 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.2% UV Absorber Blank 3.0 0.0 Outdoor exposure 1% UMB 1% UMB/TiO2 (1:5) dE 1.0 2. “Old and New Technologies for the improvement of plastic quality”.2% HMW HALS + 0.0 0 5 10 15 After 4.5 2.g. the case of PVC.Dongiovanni. Slide 7.5 1.

FDA §178. 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 14 .Regulations compliance • Nubiola is the REACH lead registrant of Ultramarine Blues. Regulation (EU) 10/2011. Violets and Pinks • Nubiola’s Ultramarines can be used in compliance with: – Food Contact Packaging: AP (89) I.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.

DIN CERTCO Gesellschaft für Konformitätsbewertung mbH (Berlin) Nubiola’s Ultramarines comply with all limit values of all Regulations 15 . Dipl.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”. Markus Weber.Ing.

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 .

the most recommended grades • Ease of dosage control • Stable performance at very low dosages • Good Performance/Cost ratio 17 .Making whites “whiter” Why Ultramarines? • Reddish undertone of Ultramarine Blues and Ultramarine Violets.

1 50 40 30 20 10 0 77 -0.1 79 78 Reflectance 460nm dL vs Blank 0 -0.6 -1.2 13.7 64.7 4.4 4.6 76 75 74 -1.4 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 18 .5 Yellowness Index 64.Making whites “whiter” PP + 1% TiO2 Whiteness Index 70 63.2 -0.7 6.0 60 52.9 65.8 -1 -1.8 -0.9 73 72 -1.4 5.

0 YI= 2.8 WI = 68.1 19 .3 YI = 2.8 WI = 69.6 WI= 63.2 +100 ppm Bluish UMV PP + 1% TiO2 Blank +0.6 ppm PV23 +200 ppm very Reddish UMV Blank +3 ppm PV19 WI = 70.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 = 3.8 WI= 63.8 WI = 67.

Masterbatch Asia 2007 20 .Ohleier. “The Effect of Pigment Concentration on Heat Stability”. Slide 2.Making whites “whiter” Organic Violets: Influence of pigment concentration on Heat fastness (*) Heat fastness (ºC) Pigment Concentration (%) (*) Source: H. Clariant Pigments&Additives.Wannemacher. S.

Making greys and blacks “bluer” 0.01% CB 1% TiO2 0.05% CB 1% TiO2 0.1% CB 1% TiO2 0.05% CB 1% TiO2 0.01% CB 1% TiO2 0.1% UMB S3·- 0.2% UMB Absorbance 0.1% CB 1% TiO2 0.02% UMB 21 .

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: ¾ High jetness ¾ High impact strength ¾ Good surface appearance ¾ High weatherability ¾ High gloss 22 .

high reddish undertone & high dispersibility UMB •Color measurements of injection molded plaques •Iluminant: D-65 •10º observer •Specular component excluded .1.) ABS-Compounds Evaluation 23 .0. 2 % UMB . 2 .40% Nubiperf H-56 in ABS Nubiola •Nubiperf H56 is a high color strength.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.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. high dispersibility & medium blue undertone CB Direct Injection Molding in ABS ABS Compounds with various pigment loadings .Color : CIE lab coordinates . 3 % UMB Nubiola and Cabot Blue Masterbatch preparation using a Leistritz Extruder at Nubiola . 1 .5% CB with 0.0% CB with 1 .35% E570 in GPPS .Making blacks “bluer” Technical Procedure Black Masterbatch preparation using a Banbury mixer at Cabot .25mm.5 .

8 1% E570 + x% H56 -1.0 3. the modified sample ‹ if dL<0.L L (CB) (CB) ‹ if dL<0.4 0.0 2.5% BP4840 + x% H56 0. the modified sample is is bluer bluer 1% BP4840 + x% H56 The blue undertone is clearly increased by the addition of UMB.2 -1.Making blacks “bluer” Blue undertone (b value) -0.b b (CB) (CB) ‹ if db<0.0 0 0.5 -2.5 2.5 3.0 ‹ ‹ dL dL = =L L (( CB+UMB CB+UMB )) -.2 -0.5 2.5 1. the modified sample ‹ if db<0.0 -1.0 2.5 1.5 3.5 24 Nubiperf H-56 (%) .5 1% BP4840 + x% H56 The jetness of the finished samples is practically unaffected (within measurement error) by the incorporation of UMB dL 0 0.6 2. This effect is more noticeable at lower loadings of Carbon Black db -0.0 Jetness (L value) 1.5 1.6 -0.5% E570 + x% H56 0.0 3.5% E570 + x% H56 1% E570 + x% H56 -0.5 ‹ ‹ db db = =b b (( CB+UMB CB+UMB )) -.0 -1.5% BP4840 + x% H56 -1.0 1. the modified sample is is jetter jetter 0.5 -1.0 1.4 Nubiperf H-56 (%) 0 0.

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 • • 25 .

Enhanced Tinting Strength Reddish formula Reddish+ formula Greenish formula Milling time Average Particle Size larger + smaller 26 .

Enhanced Organoleptics < 1 ppm 27 .

12% PB28 (Food Packaging grade) 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 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 28 . 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) 1.75% Nubiperf FCP-R in HDPE 0.Enhanced Organoleptics • • Tests carried out at Certech (Belgium) Caps made by Ineos.

46 5.06 TASTE TESTING Average 26% Weak 29% S1 (Blank) S2 (PB28) S3 (FCP‐R) S4 (PB15:3) Conclusion: there are no significant differences among samples (including the blank) 29 .62 5. the more intense the odor/taste Very weak 27% Strong 18% Taste rate (*) Sample Average 35 panellists 3.51 ODOR TESTING Average 17% Weak 29% (*) The higher the rate.37 6.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 (FCP‐R) S4 (PB15:3) Average 35 panellists 2.58 6.87 4.63 3.

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 30 .

New Silica Encapsulation Technology Conventional Silica Encapsulation Technology New Silica Encapsulation Technology Conventional Acid Resistant Ultramarine Blue Nubiperf AR 31 .

New Silica Encapsulation Technology Non-encapsulated UMB Nubiperf AR 1µ Conventional Silica Encapsulation Technology • More efficient silica encapsulation • Smaller average particle size • Narrower particle size distribution Scanning Electron Microscopy -SEM(Servei Microscopia Electrònica. Barcelona. UAB. Spain) 32 1µ .

I20 0 5 Color Stability in Process ( dE after 3 reprocessing cycles) 5 Weatherability in acid conditions 0 ( dE after 3 Years outdoor exposure in industrial area) 0 33 .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 .

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 • • 34 .

a new Super-Reddish UMB Reddish UMB Commercial version of Prototype SR-1 available in Q4’13 Darker Calendered LDPE (0.5% TiO2) 35 .5% Blue pigments + 0.Prototype SR-1.

New Shades & High Tinting Strength UMV Commercial versions of Prototypes XM-1 and XP-1 available in Q4’13 36 .

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 • • 37 .

High Tinting Strength Ultramarine Violet Prototypes XM1 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 38 .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.

Andreu) Thanks for your attention.March. J.Villasante. Operations (P.Monllonch). Marketing (E. J.Fernández).Acknowledgements: Applications (D.Ruiz). F. R. R&D (Dr. Dr. Do you have any questions? 39 .Lladó.