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

• US 7,312,257 B2
• Filed: 01/23/2003
• Issued: 12/25/2007
• Est. Priority Date: 01/23/2003
• Status: Expired due to Term

• Current Assignee: SHPP Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: General Electric Company
• Inventors: Hobbs, Stanley Young, Seker, Fazila, Steiger, Daniel, Hartshorn, Christopher Mark, Acar, Ali Ersin, Colborn, Robert Edgar, van Hamersveld, Eelco Michiel Sebastiaan
• Primary Examiner(s): SHOSHO, CALLIE E
• Application Number:
  US10/351,386
• Publication Number:
  US 20040146641A1
• Time in Patent Office: 1,797 Days
• Field of Search: 523/200, 523/205, 523/212, 523/214, 524/420, 524/430, 524/439, 524/440, 524/441, 524/449, 524/494, 524/577, 524/560, 524/500
• 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 9/10 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 2200/405 : 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: Y10T 428/2982 : Particulate matter [e.g., sphere, flake, etc.]

Abstract

Embodiments of this invention comprise a pigment 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. Embodiments also comprise a resinous composition comprising said pigment. Yet further embodiments comprise a method of preparing said pigment via suspension polymerization.

Claims

1. A pigment comprising:

a substantially spherical-shaped bead comprising a high aspect ratio particle encapsulated within an encapsulating material,

wherein the substantially spherical-shaped bead has an average diameter of about 10 μ

m to about 300 μ

m, and

an amount of the high aspect ratio particle encapsulated within the encapsulating material is about 0.1 to about 25 weight percent, based on the weight of the substantially spherical-shaped bead.

2. The pigment of claim 1, wherein the high aspect ratio particle comprises at least one member selected from the group consisting 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, and colorants.

3. The pigment 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 pigment of claim 1, wherein the encapsulating material comprises at least one member selected from the group consisting of:

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

5. The pigment of claim 1, wherein the pigment further comprises an additive.

6. The pigment of claim 5, wherein the additive comprises at least one member selected from the group consisting 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, and a fire retardant.

7. The pigment of claim 6, wherein the colorant comprises at least one member selected from the group consisting of:

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

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

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

10. The pigment of claim 1, wherein the substantially spherical-shaped bead has an average aspect ratio of about 1:

1 to about 2;

1.

11. The pigment of claim 1, wherein the high aspect ratio particle has an average aspect ratio of greater than about 4:

1.

12. The pigment of claim 11, wherein the average aspect ratio is greater than about 8:

1.

13. The pigment of claim 1, wherein the high aspect ratio particles comprise about 2 to about 100 facets.

14. The pigment of claim 1, wherein the high aspect ratio particle comprises at least one member selected from the group consisting of:

gold, silver, copper, titanium, stainless steel, nickel sulfide, cobalt sulfide, manganese sulfide, metal oxides, mica coated with titanium dioxide, metal-coated glass flakes, and colorants.

15. The pigment of claim 1, wherein the amount is about 2 to about 15 weight percent.

16. The pigment of claim 1, wherein the average diameter is about 40 μ

m to about 250 μ

m.

17. The pigment of claim 16, wherein the average diameter is about 80 μ

m to about 200 μ

m.

18. The pigment of claim 1, wherein the average diameter is about 50 μ

m to about 150 μ

m.

19. A pigment comprising:

a substantially spherical-shaped bead comprising a high aspect ratio aluminum flake encapsulated within an encapsulating material comprising a polymer with structural units derived from styrene, wherein the substantially spherical-shaped bead has an average diameter of about 40 μ

to about 250 μ

m,

wherein the flake has an average aspect ratio of greater than about 4;

1, and

wherein an amount of the flake encapsulated in the encapsulating material is about 0.1 to about 25 weight percent, based on the weight of the substantially spherical-shaped bead.

20. A resinous composition comprising a plastic matrix material and a pigment, the pigment comprising a substantially spherical-shaped bead comprising a high aspect ratio particle encapsulated within an encapsulating material,

wherein the substantially spherical-shaped bead has an average diameter of about 10 μ

m to about 300 μ

m, and

an amount of the high aspect ratio particle encapsulated within the encapsulating material is about 0.1 to about 25 weight percent, based on the weight of the substantially spherical-shaped bead.

21. The resinous composition of claim 20, 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 synthetic rubber, copolymers or modifications of any of the these substances, and combinations of two or more of these substances.

22. The resinous composition of claim 20, wherein the high aspect ratio particles comprise at least one member selected from the group consisting 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, and colorants.

23. The resinous composition of claim 20, 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.

24. The resinous composition of claim 20, wherein the encapsulating material comprises at least one member selected from the group consisting of:

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

25. The resinous composition of claim 20, wherein the encapsulating material is transparent.

26. The resinous composition of claim 20, wherein the encapsulating material is translucent.

27. The resinous composition of claim 20, wherein a refractive index difference between the plastic matrix and the encapsulating material of the pigment is less than about 0.01.

28. The resinous composition of claim 20, wherein a refractive index difference between the plastic matrix and the encapsulating material of the pigment is in the range of between about 0.01 and about 0.05.

29. The resinous composition of claim 20, wherein the substantially spherical-shaped bead has an average aspect ratio of about 1:

1 to about 2;

1.

30. The resinous composition of claim 20, wherein the high aspect ratio particle has an average aspect ratio of greater than about 4:

1.

31. The resinous composition of claim 30, wherein the average aspect ratio is greater about 8:

1.

32. The resinous composition of claim 20, wherein the high aspect ratio particle comprises about 2 to about 100 facets.

33. The resinous composition of claim 20, wherein unencapsulated high aspect ratio particles comprise no more than 1 weight percent of the composition.

34. The resinous composition of claim 20, wherein the substantially spherical-shaped bead is colored.

35. The resinous composition of claim 20, formed by a process which comprises an extrusion compounding step in an extruder.

36. The resinous composition of claim 35, wherein at least a portion of pigment is fed to the extruder at a down-stream feed inlet.

37. A molded article made from the composition of claim 20.

38. The molded article of claim 37 formed by a process which comprises compounding the composition during molding.

39. The resinous composition of claim 20, wherein the amount is about 2 to about 15 weight percent.

40. The resinous composition of claim 20, wherein the average diameter is about 40 μ

m to about 250 μ

m.

41. The resinous composition of claim 40, wherein the average diameter is about 80 μ

m to about 200 μ

m.

42. A resinous composition, comprising:

a plastic matrix material and a pigment, wherein the pigment comprises an additive and a substantially spherical-shaped bead comprising a high aspect ratio particle encapsulated within an encapsulating material wherein the substantially spherical-shaped bead has an average diameter of about 40 μ

m to about 250 μ

m.

43. The resinous composition of claim 42, wherein the additive comprises at least one additive member selected from the group consisting 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, and a fire retardant.

44. The resinous composition of claim 43, wherein the colorant comprises at least one colorant member selected from the group consisting of:

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

45. A resinous composition comprising an acrylonitrile-styrene-butadiene matrix material and a pigment comprising a substantially spherical-shaped bead comprising a high aspect ratio aluminum flake encapsulated within an encapsulating material comprising a polymer with structural units derived from styrene, wherein the flake has an average aspect ratio of greater than about 4:

1, and wherein an amount of the flake encapsulated in the encapsulating material is about 0.1 to about 25 weight percent, based on the weight of the substantially spherical-shaped bead.

46. The resinous composition of claim 45, wherein the matrix material further comprises polycarbonate.

47. A molded article made from the composition of claim 45.

48. A molded article made from the composition of claim 46.

49. A pigment, comprising:

a substantially spherical-shaped bead comprising a high aspect ratio particle encapsulated within a cross-linked encapsulating material wherein the substantially spherical-shaped bead has an average diameter of about 40 μ

m to about 250 μ

m.

50. The pigment of claim 49, wherein the substantially spherical-shaped bead has an average diameter of about 50 μ

m to about 150 μ

m.

51. The pigment of claim 49, wherein the average diameter is about 80 μ

m to about 200 μ

m.

52. The pigment of claim 49, wherein an amount of the high aspect ratio particle encapsulated in the encapsulating material is about 0.1 to about 25 weight percent, based on the weight of the substantially spherical-shaped bead.

53. The pigment of claim 49, wherein the substantially spherical-shaped bead is a sphere.