Polymer encapsulation of high aspect ratio materials and methods of making same

• US 7,488,764 B2
• Filed: 10/20/2004
• Issued: 02/10/2009
• Est. Priority Date: 01/23/2003
• Status: Expired due to Fees

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: Sabic Innovative Plastics IP BV (Government of Saudi Arabia)
• Inventors: Acar, Ali Ersin, Hobbs, Stanley Young, Colborn, Robert Edgar, Steiger, Daniel, Seker, Fazila, Hartshorn, Chris, van Hamersveld, Eelco M. S.
• Primary Examiner(s): McClendon; Sanza L.
• Application Number:
  US10/970,507
• Publication Number:
  US 20050154083A1
• Time in Patent Office: 1,574 Days
• Field of Search: 523/212, 523/214, 523/200, 523/205, 524/420, 524/440, 524/430, 524/441, 524/449, 524/494, 524/577, 524/560, 524/500, 428/402, 428/430, 428/404, 428/406, 428/407
• US Class Current: 523/200
• CPC Class Codes: B01J 13/14 Polymerisation; cross-linking
• CPC Class Codes: C01P 2002/88 by thermal analysis data, e.g. TGA, DTA, DSC
• CPC Class Codes: C01P 2004/02 obtained by optical microscopy
• CPC Class Codes: C01P 2004/20 extending in two dimensions, e.g. plate-like
• CPC Class Codes: C01P 2004/32 Spheres
• CPC Class Codes: C01P 2004/54 Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
• CPC Class Codes: C08K 9/04 Ingredients treated with organic substances treated with macromolecular compounds C08K9/08
• CPC Class Codes: C08K 9/10 Encapsulated ingredients
• CPC Class Codes: C09B 67/0097 Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
• CPC Class Codes: C09C 1/00 Treatment of specific inorganic materials other than fibrous fillers tenebrescent materials C09K9/00; luminescent materials C09K11/00; Preparation of carbon black
• CPC Class Codes: C09C 1/0015 Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
• CPC Class Codes: C09C 1/0018 uncoated and unlayered plate-like particles
• CPC Class Codes: C09C 1/0021 comprising a core coated with only one layer having a high or low refractive index
• CPC Class Codes: C09C 1/28 Compounds of silicon C09C1/0009, C09C1/0015, C09C1/0078 take precedence
• CPC Class Codes: C09C 1/3063 Treatment with low-molecular organic compounds
• CPC Class Codes: C09C 1/62 Metallic pigments or fillers C09C1/0015 takes precedence
• CPC Class Codes: C09C 1/627 Copper
• CPC Class Codes: C09C 1/64 Aluminium
• CPC Class Codes: C09C 1/644 treated with organic compounds, e.g. polymers
• CPC Class Codes: C09C 2200/1004 the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
• CPC Class Codes: C09C 2200/102 : the core consisting of glass or silicate material like mica or clays, e.g. kaolin
• CPC Class Codes: C09C 2200/1025 : comprising at least one metal layer adjacent to core material, e.g. core-M or M-core-M
• CPC Class Codes: C09C 2200/403 : Low molecular weight materials, e.g. fatty acids
• CPC Class Codes: C09C 2200/404 : comprising additional functional groups, e.g. -NH2, -C=C- or -SO3
• CPC Class Codes: C09C 2200/405 : High molecular weight materials, e.g. polymers
• CPC Class Codes: C09C 3/08 : Treatment with low-molecular-weight non-polymer organic compounds C09C3/006, C09C3/048 take precedence
• CPC Class Codes: C09C 3/10 : Treatment with macromolecular organic compounds C09C3/006 takes precedence
• CPC Class Codes: Y10T 428/2982 : Particulate matter [e.g., sphere, flake, etc.]
• CPC Class Codes: Y10T 428/2989 : Microcapsule with solid core [includes liposome]
• CPC Class Codes: Y10T 428/2991 : Coated
• CPC Class Codes: Y10T 428/2993 : Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
• CPC Class Codes: Y10T 428/2995 : Silane, siloxane or silicone coating
• CPC Class Codes: Y10T 428/2996 : Glass particles or spheres
• CPC Class Codes: Y10T 428/2998 : including synthetic resin or polymer

Abstract

A pigment contains one or more substantially spherical-shaped beads. Each substantially spherical-shaped bead includes one or more high aspect ratio particles encapsulated within an encapsulating material. Resinous compositions containing this pigment and a plastic, for example a polycarbonate, have a flowline-free colored, sparkling and/or metallescent appearance.

Claims

1. An encapsulated pigment composition comprising one or more substantially spherical-shaped beads, wherein each substantially spherical-shaped bead comprises one or more high aspect ratio particles encapsulated within an encapsulating material and wherein the substantially spherical-shaped beads have an average diameter of 10 μ

m to 300 μ

m.

2. The encapsulated pigment composition of claim 1, wherein the high aspect ratio particles comprise at least one of:

aluminum, gold, silver, copper, nickel, titanium, stainless steel, nickel sulfide, cobalt sulfide, manganese sulfide, metal oxides, white mica, black mica, synthetic mica, mica coated with titanium dioxide, metal-coated glass flakes, or colorants.

3. The encapsulated pigment composition of claim 1, wherein the encapsulating material comprises a polymer with structural units derived from at least one monomer selected from the group consisting of styrene, alpha-methyl styrene, para-methyl styrene, acrylonitrile, alkyl acrylate, alkyl methacrylate, methyl methacrylate, divinyl benzene, and mixtures thereof.

4. The encapsulated pigment composition of claim 1, wherein the encapsulating material comprises at least one of:

polystyrene, polymethyl methacrylate, styrene acrylonitrile copolymer, methyl methacrylate styrene acrylonitrile copolymer, or an acrylonitrile-styrene-acrylate resin.

5. The encapsulated pigment composition of claim 1, wherein the encapsulated pigment composition further comprises at least one additive.

6. The encapsulated pigment composition of claim 5, wherein the at least one additive comprises at least one of:

a colorant, a thermal stabilizer, an oxidation inhibitor, butylated hydroxytoluene, a radical scavenger, a vinyl-based monomer, a filler, an impact modifier, a UV absorber, or a fire retardant.

7. The encapsulated pigment composition of claim 6, wherein the colorant comprises at least one of:

Solvent Blue 35, Solvent Blue 36, Disperse Violet 26, Solvent Green 3, Anaplast Orange LFP, Morplas Red 36, or Perylene Red.

8. The encapsulated pigment composition of claim 1, wherein the encapsulating material is transparent.

9. The encapsulated pigment composition of claim 1, wherein the encapsulating material is translucent.

10. The encapsulated pigment composition of claim 1, wherein the substantially spherical-shaped beads have an average aspect ratio of 1:

1 to 2;

1.

11. The encapsulated pigment composition of claim 1, wherein the high aspect ratio particles have an average aspect ratio of greater than 1.5:

1.

12. The encapsulated pigment composition of claim 1, wherein the high aspect ratio particles have an average aspect ratio of 1.5:

1 to 40;

1.

13. The encapsulated pigment composition of claim 1, wherein the substantially spherical-shaped beads have an average diameter of 75 to 125 microns.

14. The encapsulated pigment composition of claim 1, wherein the substantially spherical-shaped beads have a maximum diameter of 150 microns.

15. The encapsulated pigment composition of claim 14, wherein an average weight percent of high aspect ratio particles encapsulated within an encapsulating material comprises 0.1 to 25 weight percent, based on the weight of the pigment composition bead.

16. The encapsulated pigment composition of claim 1, wherein the high aspect ratio particles comprise 2 to 100 facets.

17. An encapsulated pigment composition comprising one or more substantially spherical-shaped beads, wherein each substantially spherical-shaped bead comprises one or more high aspect ratio particles encapsulated within an encapsulating material and wherein the substantially spherical-shaped beads have an average diameter of 10 μ

m to 300 μ

m, wherein the encaspulating material is cross-linked.

18. The encapsulated pigment composition of claim 17, wherein the cross-link density is from 0.175 to 0.25 parts per hundred parts of cross-linking agent.

19. The encapsulated pigment composition of claim 18, wherein the cross-link density is 0.2 parts per hundred parts of cross-linking agent.

20. The encapsulated pigment composition of claim 18, wherein the substantially spherical-shaped beads have an average diameter of 75 to 125 microns.

21. The encapsulated pigment composition of claim 20, wherein the substantially spherical-shaped beads have a maximum diameter of 150 microns.

22. The encapsulated pigment composition of claim 21, wherein the cross-link density is 0.2 parts per hundred parts of cross-linking agent.

23. An encapsulated pigment composition comprising one or more substantially spherical-shaped beads having an average diameter of 10 μ

m to 300 μ

m, wherein each substantially spherical-shaped bead comprises one or more high aspect ratio aluminum flakes encapsulated within an encapsulating material comprising a polymer with structural units derived from at least one monomer which is styrene, wherein the flakes have an average aspect ratio of 1.5;

1 to 40;

1 and wherein the encapsulated pigment composition comprises 0.1 to 25 weight percent of the flakes.

24. A resinous composition comprising a plastic matrix material and an encapsulated pigment composition, the encapsulated pigment composition comprising one or more substantially spherical-shaped beads, wherein each substantially spherical-shaped bead comprises one or more high aspect ratio particles encapsulated within an encapsulating material, and wherein the substantially spherical-shaped beads have an average diameter of 10 μ

m to 300 μ

m.

25. The resinous composition of claim 24, wherein the plastic matrix material comprises at least one member selected from the group consisting of thermoplastics, polyesters, polyolefins, polyethylene, polypropylene, polybutylene, polymethylpentene;

resins comprising structural units derived from styrene monomer, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-styrene-butadiene, acrylonitrile-styrene-acrylate;

polyamide;

polycarbonate;

bisphenol A polycarbonate;

polyphenylene ether;

polyimide;

polyamide imide;

polyetherimide;

polysulfone;

polyether sulfone;

polyketone;

polyether ketone;

polyether ether ketone;

polyarylate;

phenoxy resins;

fluorocarbon resins;

thermoplastic elastomers;

thermoplastic elastomers derived from polystyrene, from polyolefin, from polyurethane, from polyester, from polyamide, from polybutadiene, from polyisoprene, from fluorine-containing monomer;

a natural rubber, a synthelic rubber, copolymers or modifications of any of the these substances that introduce crosslinking sites, and combinations of two or more of these substances.

26. The resinous composition of claim 24, wherein the high aspect ratio particles comprise at least one of:

aluminum, gold, silver, copper, nickel, titanium, stainless steel, nickel sulfide, cobalt sulfide, manganese sulfide, metal oxides, white mica, black mica, synthetic mica, mica coated with titanium dioxide, metal-coated glass flakes, or colorants.

27. The resinous composilion of claim 24, wherein the encapsulating material comprises a polymer with structural units derived from at least one monomer selected from the group consisting of styrene, alpha-methyl styrene, para-methyl styrene, acrylonitrile, alkyl acrylate, alkyl methacrylate, methyl methacrylate, divinyl benzene, and mixtures thereof.

28. The resinous composition of claim 24, wherein the encapsulating material comprises at least one of:

polystyrene, polymethyl methacrylate, styrene acrylonitrile copolymer, methyl methacrylate styrene acrylonitrile copolymer, or an acrylonitrile-styrene-acrylate resin.

29. The resinous composition of claim 24, wherein the pigment further comprises at least one additive.

30. The resinous composition of claim 29, wherein the at least one additive comprises at least one of:

a colorant, a thermal stabilizer, an oxidation inhibitor, butylated hydroxytoluene, a radical scavenger, a vinyl-based monomer, a filler, an impact modifier, a UV absorber, or a fire retardant.

31. The resinous composition of claim 30, wherein the additive is a colorant and the colorant comprises at least one of:

Solvent Blue 35, Solvent Blue 36, Disperse Violet 26, Solvent Green 3, Anaplast Orange LFP, Morplas Red 36, or Perylene Red.

32. The resinous composition of claim 24, wherein the encapsulating material is transparent.

33. The resinous composition of claim 24, wherein the encapsulating material is translucent.

34. The resinous composition of claim 24, wherein the refractive index difference between the plastic matrix and the encapsulating material of the pigment is less than 0.01.

35. The resinous composition of claim 24, wherein the refractive index difference between the plastic matrix and the encapsulating material of the pigment is in the range of between 0.01 and 0.05.

36. The resinous composition of claim 24, wherein ihe substantially spherical-shaped beads have an average aspect ratio of 1:

1 to 2;

1.

37. The resinous composition of claim 24, wherein the high aspect ratio particles have an average aspect ratio of greater than about 1.5:

1.

38. The resinous composition of claim 24, wherein the high aspect ratio particles have an average aspect ratio of 1.5:

1 to 40;

1.

39. The resinous composition of claim 24, wherein the substantially spherical-shaped beads have an average diameter of 75 to 125 microns.

40. The resinous composition of claim 39, wherein the substantially spherical-shaped beads have a maximum diameter of 150 microns.

41. The resinous composition of claim 40, wherein an average weight percent of high aspect ratio particles encapsulated within an encapsulating material comprises 0.1 to 25 weight percent, based on the weight of the pigment bead.

42. The resinous composition of claim 24, wherein the high aspect ratio particles comprise 2 to 100 facets.

43. The resinous composition of claim 24, wherein unencapsulated high aspect ratio particles comprise no more than 1 weight percent of the composition.

46. The resinous composition of claim 24, wherein the encaspulating material is cross-linked.

47. The resinous composition of claim 46, wherein the cross-link density is from 0.175 to 0.25 parts per hundred parts of cross-linking agent.

48. The resinous composition of claim 47, wherein the cross-link density is 0.2 parts per hundred parts of cross-linking agent.

49. The resinous composition of claim 48, wherein the substantially spherical-shaped beads have an average diameter of 75 to 125 microns.

50. The encapsulated pigment composition of claim 49, wherein the substantially spherical-shaped beads have a maximum diameter of 150 microns.

51. The encapsulated pigment composition of claim 50, wherein the cross-link density is 0.2 parts per hundred pails of cross-linking agent.

52. A molded article made from the composition of claim 24.

58. The composition of claim 24, wherein the encapsulated pigment composition is loaded in the plastic matrix at a level of from 0.05 to 10% by weight.

44. A resinous composition comprising a plastic matrix material and an encapsulated pigment composition, the encapsulated pigment composition comprising one or more substantially spherical-shaped beads, wherein each substantially spherical-shaped bead comprises one or more high aspect ratio particles encapsulated within an encapsulating material, and wherein the substantially spherical-shaped beads have an average diameter of 10 μ

m to 300 μ

m, formed by a process which comprises at least one extrusion compounding step.

45. The resinous composition of claim 44, wherein at least a portion of pigment is kd to the extruder at a down-stream feed inlet.

53. A molded article formed from a resinous composition comprising a plastic matrix material and an encapsulated pigment composition, the encapsulated pigment composition comprising one or more substantially spherical-shaped beads, wherein each substantially spherical-shaped bead comprises one or more high aspect ratio particles encapsulated within an encapsulating material, and wherein the substantially spherical-shaped beads have an average diameter of 10 μ

m to 300 μ

m by a process which comprises compounding the composition during molding.

54. A resinous composition comprising an acrylonitrile-styrene-butadiene matrix material and a pigment comprising one or more substantially spherical-shaped beads, wherein each substantially spherical-shaped bead comprises one or more high aspect ratio aluminum flakes encapsulated within an encapsulating material comprising a polymer with structural units derived from styrene, optionally with at least one other monomer, wherein the flakes have an average aspect ratio of 1.5:

1 to 40;

1 and comprise 0.1 to 25 weight percent of the pigment bead.

55. The resinous composition of claim 54, wherein the matrix material further comprises at least one polycarbonate.

56. A molded artidle made from the composition of claim 54.

57. A molded article made from the composition of claim 55.