Graphic art films comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol

• US 20060287474A1
• Filed: 03/28/2006
• Published: 12/21/2006
• Est. Priority Date: 06/17/2005
• Status: Active Grant

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Chemical Company
• Inventors: Crawford, Emmett Dudley, McWilliams, Douglas Stephens, Porter, David Scott, Connell, Gary Wayne
• Granted Patent: US 7,902,320 B2
• Time in Patent Office: Days
• US Class Current: 528/272
• CPC Class Codes: A01G 9/1438 Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
• CPC Class Codes: A47F 5/00 Show stands, hangers, or shelves characterised by their constructional features
• CPC Class Codes: A61M 1/16 with membranes
• CPC Class Codes: B01D 61/30 Accessories; Auxiliary operation
• CPC Class Codes: B29C 49/00 Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
• CPC Class Codes: B29C 49/0005 characterised by the material
• CPC Class Codes: B29K 2067/00 Use of polyesters or derivatives thereof, as moulding material
• CPC Class Codes: B29L 2031/7542 Catheters
• CPC Class Codes: B32B 17/10018 comprising only one glass sheet
• CPC Class Codes: B32B 27/36 comprising polyesters
• CPC Class Codes: B65D 1/0207 characterised by material, e.g. composition, physical features
• CPC Class Codes: B65D 23/10 Handles
• CPC Class Codes: B65D 25/00 Details of other kinds or types of rigid or semi-rigid containers
• CPC Class Codes: B65D 43/00 Lids or covers for rigid or semi-rigid containers for cooking vessels A47J36/06; covers for pressure vessels in general F16J13/00
• CPC Class Codes: C08G 63/183 Terephthalic acids
• CPC Class Codes: C08G 63/199 Acids or hydroxy compounds containing cycloaliphatic rings
• CPC Class Codes: C08J 2367/00 Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
• CPC Class Codes: C08J 2367/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds; C08J2367/06 takes precedence
• CPC Class Codes: C08J 2483/00 Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08J 7/0427 : with only one layer of a composition containing a polymer binder with more layers C08J7/042
• CPC Class Codes: C08J 7/123 : Treatment by wave energy or particle radiation C08J7/18 takes precedence
• CPC Class Codes: C08K 2201/014 : Additives containing two or more different additives of the same subgroup in C08K
• CPC Class Codes: C08K 3/32 : Phosphorus-containing compounds
• CPC Class Codes: C08K 5/521 : Esters of phosphoric acids, e.g. of H3PO4
• CPC Class Codes: C08L 101/00 : Compositions of unspecified macromolecular compounds
• CPC Class Codes: C08L 2666/02 : Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/18 : Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
• CPC Class Codes: C08L 67/00 : Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 67/02 : Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence
• CPC Class Codes: C08L 69/00 : Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• CPC Class Codes: C09D 167/02 : Polyesters derived from dicarboxylic acids and dihydroxy compounds C09D167/06 takes precedence
• CPC Class Codes: E01F 8/0005 : used in a wall type arrangement
• CPC Class Codes: E04D 13/03 : Sky-lights; Domes; Ventilating sky-lights E04D13/14 takes precedence; structures therefor, e.g. dormer windows E04B7/18; saw-tooth roofs with light-transmission E04B7/12
• CPC Class Codes: G02B 1/10 : Optical coatings produced by application to, or surface treatment of, optical elements G02B1/08 takes precedence
• CPC Class Codes: G02B 1/105 : Protective coatings
• CPC Class Codes: G02B 1/14 : Protective coatings, e.g. hard coatings
• CPC Class Codes: G02B 5/3083 : Birefringent or phase retarding elements G02B5/3008, G02B5/3016 take precedence; systems for polarisation control G02B27/286; manufacturing phase modulating patterns by lithographic processes G03F7/001
• CPC Class Codes: G02F 1/133606 : including a specially adapted diffusing, scattering or light controlling members
• CPC Class Codes: Y02A 40/25 : Greenhouse technology, e.g. cooling systems therefor
• CPC Class Codes: Y10T 428/1352 : Polymer or resin containing [i.e., natural or synthetic]
• CPC Class Codes: Y10T 428/139 : Open-ended, self-supporting conduit, cylinder, or tube-type article
• CPC Class Codes: Y10T 428/1397 : Single layer [continuous layer]
• CPC Class Codes: Y10T 428/161 : with frame, casing, or perimeter structure
• CPC Class Codes: Y10T 428/162 : Transparent or translucent layer or section
• CPC Class Codes: Y10T 428/24107 : including mechanically interengaged strands, strand-portions or strand-like strips
• CPC Class Codes: Y10T 428/24479 : including variation in thickness
• CPC Class Codes: Y10T 428/24942 : including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/31504 : Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31507 : Of polycarbonate
• CPC Class Codes: Y10T 428/31663 : As siloxane, silicone or silane
• CPC Class Codes: Y10T 428/31786 : Of polyester [e.g., alkyd, etc.]

Abstract

Described are graphic art films comprising polyester compositions comprising polyesters which comprise (a) a dicarboxylicacidcomponent having terephthalic acid residues; optionally, aromatic dicarboxylic acid residues or aliphatic dicarboxylic acid residues or ester residues thereof; 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and 1,4-cyclohexanedimethanol residues.

Claims

1. A graphic art film comprising at least one polyester composition comprising at least one polyester, which comprises:

(a) a dicarboxylic acid component comprising;

i) 70 to 100 mole % of terephthalic acid residues;

ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b) a glycol component comprising;

i) 10 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii) 1 to 90 mole % of 1,4-cyclohexanedimethanol residues,

wherein the total mole % of the dicarboxylic acid component is 100 mole %, the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.1 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/00 ml at 25°

C.; and

wherein the polyester has a Tg of from 100 to 200°

C.

2. The graphic art film of claim 1, wherein the inherent viscosity of the polyester is from 0.35 to 1.2 dL/g.

3. The graphic art film of claim 1, wherein the inherent viscosity of the polyester is from 0.35 to 1.0 dL/g.

4. The graphic art film of claim 1, wherein the inherent viscosity of the polyester is from 0.35 to 0.75 dL/g.

5. The graphic art film of claim 1, wherein the inherent viscosity of the polyester is from 0.40 to 0.90 dL/g.

6. The graphic art film of claim 1, wherein the inherent viscosity of the polyester is from greater than 0.42 to 0.80 dL/g.

7. The graphic art film of claim 1, wherein the inherent viscosity of the polyester is from 0.45 to 0.75 dL/g.

8. The graphic art film of claim 1, wherein the inherent viscosity of the polyester is from 0.50 to 0.68 dL/g.

9. The graphic art film of claim 1, wherein the inherent viscosity of the polyester is from 0.60 to 0.75 dL/g.

10. The graphic art film of claim 1, wherein the polyester has a Tg of 100 to 180°

C.

11. The graphic art film of claim 1, wherein the polyester has a Tg of 100 to 160°

C.

12. The graphic art film of claim 1, wherein the polyester has a Tg of 105 to 140°

C.

13. The graphic art film of claim 1, wherein the polyester has a Tg of 100 to 120°

C.

14. The graphic art film of claim 9, wherein the polyester has a Tg of 100 to 120°

C.

15. The graphic art film of claim 1, wherein the polyester has a Tg of 120 to 140°

C.

16. The graphic art film of claim 9, wherein the polyester has a Tg of 120 to 140°

C.

17. The graphic art film of claim 1, wherein the glycol component of the polyester comprises 15 to 70 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 30 to 85 mole % 1,4-cyclohexanedimethanol residues.

18. The graphic art film of claim 1, wherein the glycol component of the polyester comprises 15 to 60 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 40 to 85 mole % 1,4-cyclohexanedimethanol residues.

19. The graphic art film of claim 1, wherein the glycol component of the polyester comprises 40 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 60 mole % 1,4-cyclohexanedimethanol residues.

20. The graphic art film of claim 1, wherein the glycol component of the polyester comprises 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 80 mole % 1,4-cyclohexanedimethanol residues.

21. The graphic art film of claim 15, wherein the glycol component of the polyester comprises 40 to 55 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 45 to 60 mole % 1,4-cyclohexanedimethanol residues.

22. The graphic art film of claim 13, wherein the glycol component of the polyester comprises 20 to 40 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 80 mole % 1,4-cyclohexanedimethanol residues.

23. The graphic art film of claim 1, wherein the dicarboxylic acid component comprises 80 to 100 mole % of terephthalic acid residues.

24. The graphic art film of claim 1, wherein the dicarboxylic acid component comprises 90 to 100 mole % of terephthalic acid residues.

25. The graphic art film of claim 1, wherein the dicarboxylic acid component comprises 95 to 100 mole % of terephthalic acid residues.

26. The graphic art film of claim 1, wherein the polyester comprises from 0.1 to 25 mole % of 1,3-propanediol residues, 1,4-butanediol residues, or a mixture thereof.

27. The graphic art film of claim 1, wherein the polyester comprises from 0.1 to 10 mole % of 1,3-propanediol residues, 1,4-butanediol residues, or a mixture thereof.

28. The graphic art film of claim 1, wherein the polyester comprises from 0.01 to 15 mole % of ethylene glycol residues.

29. The graphic art film of claim 1, wherein the 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues is a mixture comprising greater than 50 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and less than 50 mole % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

30. The graphic art film of claim 1, wherein the 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues is a mixture comprising greater than 55 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and less than 45 mole % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

31. The graphic art film of claim 1, wherein the 2,2,4,4-tetramethyl-1,3-cyclobutanediol is a mixture comprising greater than 50 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and less than 50 mole % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, and wherein the dicarboxylic acid component comprises 80 to 100 mole % of terephthalic acid residues.

32. The graphic art film of claim 1, wherein the polyester composition comprises at least one polymer chosen from poly(etherimides), polyphenylene oxides, poly(phenylene oxide)/polystyrene blends, polystyrene resins, polyphenylene sulfides, polyphenylene sulfide/sulfones, poly(ester-carbonates), polycarbonates, polysulfones;

polysulfone ethers, poly(ether-ketones), polyamides, polystyrene, polystyrene copolymers, styrene acrylonitrile copolymers, acrylonitrile butadiene styrene copolymers, poly(methylmethacrylate), and acrylic copolymers.

33. The graphic art film of claim 1, wherein the polyester composition comprises at least one polycarbonate.

34. The graphic art film of claim 1, wherein the polyester comprises residues at least one branching agent an amount of 0.01 to 10 weight % based on the total weight of the polyester.

35. The graphic art film of claim 1, wherein the melt viscosity of the polyester is less than 30,000 poise as measured at 1 radian/second on a rotary melt rheometer at 290°

C.

36. The graphic art film of claim 1, wherein the polyester has a crystallization half-time of greater than 100 minutes at 170°

C.

37. The graphic art film of claim 1, wherein the polyester has a crystallization half-time of greater than 1,000 minutes at 170°

C.

38. The graphic art film of claim 1, wherein the polyester composition has a density of less than 1.3 g/ml at 23°

C.

39. The graphic art film of claim 1, wherein the polyester composition comprises at least one thermal stabilizer or a reaction product thereof.

40. The graphic art film of claim 1, wherein the yellowness index of the polyester according to ASTM D-1925 is less than 50.

41. The graphic art film of claim 1, wherein the polyester has a notched Izod impact strength of at least 3 ft-lbs/in at 23°

C. according to ASTM D256 with a 10-mil notch in a ⅛

-inch thick bar.

42. The graphic art film of claim 1, wherein the polyester has a notched Izod impact strength of at least 10 ft-lbs/in at 23°

C. according to ASTM D256 with a 10-mil notch in a ¼

-inch thick bar.

43. The graphic art film of claim 1, wherein the polyester comprises the residue of at least one catalyst comprising a tin compound or a reaction product thereof.

44. The graphic art film of claim 1, wherein the graphic art film is thermoformed.

45. The graphic art film of claim 1, further comprising at least one ink chosen from a thermally-cured ink and an ultra-violet cured ink.

46. The graphic art film of claim 1, wherein the graphic art film is chosen from:

nameplates;

membrane switch overlays;

point-of-purchase displays;

flat and in-mold decorative panels on washing machines;

flat touch panels on refrigerators;

flat panel on ovens;

decorative interior trim for automobiles;

instrument clusters for automobiles;

cell phone covers;

heating and ventilation control displays;

automotive console panels;

automotive gear shift panels;

control displays and warning signals for automotive instrument panels;

facings, dials and displays on household appliances;

facings, dials, and displays on washing machines;

facings, dials, and displays on dishwashers;

keypads for electronic devices;

keypads for mobile phones, personal digital assistants, and remote controls;

displays for electronic devices;

panels and housings for phones;

logos on electronic devices; and

logos for hand-held phones.

47. The graphic art film of claim 1, wherein the graphic art film is formed by extrusion.

48. The graphic art film of claim 1, wherein the graphic art film is produced by calendering.

49. The graphic art film of claim 1, wherein the graphic art film is produced by compression molding.

50. The graphic art film of claim 1, wherein the graphic art film is produced by solution casting.

51. An in-mold decorated article comprising the graphic art film of claim 1.

52. An embossed article comprising the graphic art film of claim 1.

53. A hard-coated article comprising the graphic art film of claim 1.

54. The graphic art film of claim 1, wherein the graphic art film is textured.

55. A graphic art film comprising at least one polyester composition comprising at least one polyester, which comprises:

(a) a dicarboxylic acid component comprising;

i) 70 to 100 mole % of terephthalic acid residues;

ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b) a glycol component comprising;

i) 15 to 70 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii) 30 to 85 mole % of 1,4-cyclohexanedimethanol residues,

wherein the total mole % of the dicarboxylic acid component is 100 mole %, the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.35 to 1.2 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°

C.; and

wherein the polyester has a Tg of from 100 to 160°

C.

56. The graphic art film of claim 55, wherein the inherent viscosity of the polyester is from 0.35 to 0.75 dL/g.

57. The graphic art film of claim 55, wherein the inherent viscosity of the polyester is from 0.45 to 0.75 dL/g.

58. The graphic art film of claim 55, wherein the inherent viscosity of the polyester is from 0.50 to 0.68 dL/g.

59. The graphic art film of claim 55, wherein the inherent viscosity of the polyester is from 0.60 to 0.75 dL/g.

60. The graphic art film of claim 55, wherein the polyester has a Tg of 105 to 140°

C.

61. The graphic art film of claim 55, wherein the polyester has a Tg of 100 to 120°

C.

62. The graphic art film of claim 55, wherein the polyester has a Tg of 120 to 140°

C.

63. The graphic art film of claim 60, wherein the glycol component of the polyester comprises 25 to 50 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 50 to 75 mole % 1,4-cyclohexanedimethanol residues.

64. The graphic art film of claim 55, wherein the graphic art film is thermoformed.

65. The graphic art film of claim 55, further comprising at least one ink chosen from a thermally-cured ink and an ultra-violet cured ink.

66. The graphic art film of claim 55, wherein the graphic art film is chosen from:

nameplates;

membrane switch overlays;

point-of-purchase displays;

flat and in-mold decorative panels on washing machines;

flat touch panels on refrigerators;

flat panel on ovens;

decorative interior trim for automobiles;

instrument clusters for automobiles;

cell phone covers;

heating and ventilation control displays;

automotive console panels;

automotive gear shift panels;

control displays and warning signals for automotive instrument panels;

facings, dials and displays on household appliances;

facings, dials, and displays on washing machines;

facings, dials, and displays on dishwashers;

keypads for electronic devices;

keypads for mobile phones, personal digital assistants, and remote controls;

displays for electronic devices;

panels and housings for phones;

logos on electronic devices; and

logos for hand-held phones.

67. An in-mold decorated article comprising the graphic art film of claim 55.

68. An embossed article comprising the graphic art film of claim 55.

69. A hard-coated article comprising the graphic art film of claim 55.

70. The graphic art film of claim 55, wherein the graphic art film is textured.

71. A graphic art film comprising at least one polyester composition comprising at least one polyester, which comprises:

(a) a dicarboxylic acid component comprising;

i) 70 to 100 mole % of terephthalic acid residues;

ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b) a glycol component comprising;

i) 20 to 40 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii) 60 to 80 mole % of 1,4-cyclohexanedimethanol residues,

wherein the total mole % of the dicarboxylic acid component is 100 mole %, the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.60 to 0.75 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°

C.; and

wherein the polyester has a Tg of from 100 to 120°

C.

72. An in-mold decorated article comprising the graphic art film of claim 71.

73. An embossed article comprising the graphic art film of claim 71.

74. A hard-coated article comprising the graphic art film of claim 71.

75. The graphic art film of claim 71, wherein the graphic art film is textured.

76. A graphic art film comprising at least one polyester composition comprising at least one polyester, which comprises:

(a) a dicarboxylic acid component comprising;

i) 70 to 100 mole % of terephthalic acid residues;

ii) 0 to 30 mole % of aromatic dicarboxylic acid residues having up to 20 carbon atoms; and

iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbon atoms; and

(b) a glycol component comprising;

i) 40 to 55 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

ii) 45 to 60 mole % of 1,4-cyclohexanedimethanol residues,

wherein the total mole % of the dicarboxylic acid component is 100 mole %, the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity of the polyester is from 0.60 to 0.75 dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25°

C.; and

wherein the polyester has a Tg of from 120 to 140°

C.

77. An in-mold decorated article comprising the graphic art film of claim 76.

78. An embossed article comprising the graphic art film of claim 76.

79. A hard-coated article comprising the graphic art film of claim 76.

80. The graphic art film of claim 76, wherein the graphic art film is textured.