CA2312059A1

CA2312059A1 - Barrier-coated polyester

Info

Publication number: CA2312059A1
Application number: CA002312059A
Authority: CA
Inventors: Gerald A. Hutchinson; Robert A. Lee
Original assignee: Plastics Fabrication Technologies, Llc; Gerald A. Hutchinson; Robert A. Lee; Chemical Enterprises Limited; Advanced Plastics Technologies, Ltd.; Advanced Plastics Technologies Luxembourg S.A.; The Concentrate Manufacturing Company Of Ireland
Current assignee: Concentrate Manufacturing Company of Ireland
Priority date: 1997-10-17
Filing date: 1998-10-19
Publication date: 1999-04-29
Anticipated expiration: 2018-10-19
Also published as: NO325367B1; CN1170887C; RU2200667C2; CA2650806A1; US20080061476A1; WO1999020462A3; US6391408B1; CN1276816A; ES2293692T3; EP1023395B1; AU1100899A; BR9815227A; JP2001520135A; CA2312059C; US20030219555A1; NO20001915L; US6676883B2; TWI250934B; DE69838396D1; NO20001915D0

Abstract

This invention relates to articles made of polyester, preferably polyethylene terephthalate (PET), having coated directly to at least one of the surfaces thereof one or more layers of thermo-plastic material with good gas-barrier characteristics, and novel methods of making such articles. Preferably the barrier-coated articles take the form of preforms coated by at least one layer of barrier material and the containers blow-molded therefrom. Such barrier-coated containers are preferably of the type to hold beverages such as soft drinks, beer or juice. The preferred barrier materials have a lower permeability to oxygen and carbon dioxide than PET as well as key physical properties similar to PET.
The materials and methods provide that the barrier layers have good adherence to PET, even during and after the blow molding process to form containers from preforms. Preferred barrier coating materials include poly(hydroxyamino ethers). In one preferred method, preforms are injection molded then barrier-coated immediately thereafter.

Claims

1. A barrier-coated polyester article comprising at least one layer of polyester directly adhered to at least one layer of barrier material, wherein said barrier material:
a. comprises a copolyester of terephthalic acid, isophthalic acid, and at least one dial;
b. has a glass transition temperature between 55°C and 140°C;
and c. has a permeability to oxygen and carbon dioxide which is less than that of polyethylene terephthalate.

2. The barrier-coated polyester article of Claim 1 in the form of a preform.

3. The barrier-coated polyester article of Claim 1 in the form of a container.

4. The barrier-coated polyester article of Claim 1, wherein said layer of barrier material consists of a plurality of microlayers comprising barrier material.

5. The homer-coated polyester article of Claim 1, wherein said barrier material further comprises Nanoparticles.

6. The barrier-coated polyester article of Claim 1, wherein said layer of barrier material has a thickness of 0.01 - 5.0 mm.

7. The barrier-coated polyester article of Claim 1, wherein said polyester comprises polyethylene terephthalate.

8. The barrier-coated polyester article of Claim 1 in the form of a preform, wherein said polyester comprises polyethylene terephthalate.

9. The barrier-coated polyester article of Claim 1. wherein said copolyester is B-010.

10. The barrier-coated polyester article of Claim 1 in the form of a container, wherein said polyester comprises polyethylene terephthalate.

11. The barrier-coated polyester article of Claim 1, wherein said barrier material is not a homogeneous mixture of a Phenoxy-type Thermoplastic and said copolyester.

12. A method for making a barrier-coated container comprising the steps of:
providing the barrier-coated polyester of Claim 1 in the form of a preform;
and blow-molding said preform to form said barrier-coated container.

13. An injection molded preform comprising:
a first layer comprising a thermoplastic polyester; and a second layer comprising an amorphous thermoplastic material;
wherein said first layer is thinner in the end cap than in the wall portion and the second layer is thicker in the end cap than in the wall portion.

14. The injection molded preform of Claim 13, wherein at least one of said first and second layers comprises a barrier material.

15. The injection molded preform of Claim 13, further comprising a third layer comprising recycled polyester.

16. The injection molded preform of Claim 13, wherein said first layer is about 1/3 of the total thickness of the end cap and about 2/3 of the total thickness of the wall portion.

17. The injection molded preform of Claim 13, wherein said second layer consists of a plurality of microlayers comprising barrier material.

18. The injection molded preform of Claim 13, wherein said second layer comprises (i) a Phenoxy-type Thermoplastic or (ii) a copolyester of terephthalic acid, isophthalic acid and at least one diol.

19. The injection molded preform of Claim 13, wherein said first layer is the innermost layer.

20. The injection molded preform of Claim 13, wherein said preform is made by an overinjection process.

21. The injection molded preform of Claim 13, wherein said polyester is polyethylene terephthalate.

22. A multi-layer article comprising a wall portion comprising an inner multi-component layer and an outer layer, wherein:
a. said inner multi-component layer has at least two discrete sublayers having an interface surface between said sublayers and extends longitudinally of said article, one of said sublayers comprising polyester and another of said sublayers comprising a barrier material comprising a (i) a Phenoxy-type Thermoplastic or (ii) a copolyester of terephthalic acid, isophthalic acid, and at least one diol, said barrier material having a permeability to carbon dioxide of no mare than one-third of the permeability to carbon dioxide of polyethylene terephthalate;
b. said outer layer comprises recycled polyester; and c. said inner multi-component layer and said outer layer comprises materials with an absolute refractive index of 1.55-1.75.

23. The article of Claim 22, wherein said inner multi-component layer comprises at least three sublayers wherein the composition of said sublayers alternates between polyester and barrier material.

24. The article of Claim 23, wherein said inner multi-component layer comprises at least two sublayers of polyester in alternating configuration with at least two sublayers of said barrier material.

25. The article of Claim 22 in the form of a preform.

26. The article of Claim 22 in the form of a container.

27. The article of Claim 22, wherein said polyester comprises polyethylene terephthalate.

28. The article of Claim 22, wherein said sublayer of polyester forms the innermost layer of said multi-component layer.

29. The article of Claim 22, wherein said inner multi-component layer is no thicker than the thickness of said outer layer.

30. A multi-layer preform comprising a wall portion having an inner layer and an outer layer, wherein:
a. said inner layer comprises polyester, extends longitudinally of said preform terminating in a threaded neck finish section having externally upset threads to receive a closure member, has a support ring at the lower end of said threaded neck finish section, and has a thickness of at least two millimeters and an absolute refractive index of 1.55-1.85;

b. said outer layer co-extends with said inner layer to terminate below said support ring and comprises (i) a copolyester of terephthalic acid, isophthalic acid, and at least one diol or (ii) a Phenoxy-type Thermoplastic selected from the group consisting of poly(hydroxy ether), poly(hydroxy ester ether), and poly(hydroxyamino ether), wherein said outer layer has a permeability to oxygen less than that of said inner layer and a thickness of no more than one-fourth the thickness of said inner layer;
and c. said outer layer has an absolute refractive index of a value to provide a ratio of said refractive indices within the range of 1.0-1.2.

31. The preform of Claim 30, wherein said preform comprises a neck cylinder section immediately below said support ring and a transition section below said neck cylinder section which is tapered downwardly to a reduced diameter body portion of said preform and wherein said outer layer of said wall portion extends over said body portion, said transition section, and said neck cylinder section to terminate on the underside of said support ring.

32. A method for making a barrier coated polyester article comprising the steps of:
(1) providing a polyester article wherein at least one surface of said polyester article is at a temperature of at least 100°C; and (2) placing a barrier material on said heated surface of said polyester article to form a barrier coated polyester article, wherein said barrier material:
a. comprises (ii) a Phenoxy-type Thermoplastic or (ii) a copolyester of terephthalic acid, isophthalic acid and at least one diol;
b. has a glass transition temperature between 55°C and 140°C;
and c. has a permeability to oxygen and carbon dioxide which is less than that of polyethylene terephthalate.

33. The method of Claim 32, wherein said polyester article is in the form of a preform.

34. The method of Claim 32, wherein said polyester article is in the form of a preform, further comprising a step wherein said preform is blow molded to form a container.

35. The method of Claim 32, wherein said barrier material further comprises Nanoparticles.

36. The method of Claim 32, wherein said polyester is polyethylene terephthalate.

37. The method of Claim 36, wherein said barrier material comprises poly(hydroxyamino ether).

38. The method of Claim 36, wherein said barrier material comprises a copolyester of terephthalic acid, isophthalic acid and at least one diol.

39. The method of Claim 38, wherein said at least one diol comprises ethylene glycol.

40. The method of Claim 32, wherein said article is in the form of a container.

41. The method of Claim 39, wherein the barrier material on said article has a thickness of 0.01 - 5.0 mm.

42. The method of Claim 32, wherein step (2) is done by dip coating the polyester article.

43. The method of Claim 32, wherein step (2) is done by spray coating the polyester article.

44. The method of Claim 32, wherein step (2) is done by flame spraying the polyester article.

45. The method of Claim 32, wherein step (2) is done by electrostatic spray coating the polyester article.

46. The method of Claim 32, wherein step (2) is done by dipping the polyester article in a fluidized bed of powdered barrier material.

47. The method of Claim 32, wherein step (2) is done by overmolding the polyester article with a melt of barrier material.

48. The method of Claim 32, further comprising the following step:
(3) overmolding said barrier coated polyester article with a layer comprising recycled polyester.

49. A method for making a barrier coated polyester article comprising the steps of:
a. injecting molten first material comprising polyester through a first gate into the space defined by a first mold half and a core mold half to form a polyester article comprising an inner surface and an outer surface, wherein said first mold half and said core mold half are cooled by circulating fluid, and said first mold half contacts the outer polyester surface and said core mold half contacts the inner polyester surface;
b. allowing said molten polyester to remain in contact with said mold halves until a skin forms on said inner and outer polyester surfaces, said skin surrounding a core of molten polyester in said polyester article;
c. removing said first mold half from said polyester article;
d. allowing the skin on said outer polyester surface to be softened by heat transfer from said core of molten polyester while said inner polyester surface is cooled by continued contact with said core mold half;
e. placing said polyester article into a second mold half, wherein said second mold half is cooled by circulating fluid;
f. injecting a molten second material comprising barrier material through a second gate into the space defined by said second mold half and said outer polyester surface to form a barrier coated polyester article comprising a barrier layer comprising barrier material on said outer polyester surface;
g. allowing said molten second material comprising barrier material to remain in contact with at least said second mold half;
h. removing said second mold half from said barrier coated polyester article;
and i. removing said barrier coated polyester article from said core mold half.

50. The method of Claim 49 wherein said barrier material comprises (i) a Phenoxy-type Thermoplastic or (i) a copolyester of terephthalic acid, isophthalic acid, and at least one diol.

51. The method of Claim 49 wherein said barrier material comprises poly(hydroxyamino ether).

52. The method of Claim 49 wherein said layer of barrier material consists of a plurality of microlayers comprising barrier material.

53. The method of Claim 49 wherein said barrier coated polyester article is a preform.

54. The method of Claim 53 further comprising a step of blow molding said preform to form a container.

55. The method of Claim 49 wherein said polyester article is thinnest in the region nearest said first gate and said barrier layer is thickest around the region nearest said second gate.

56. The method of Claim 49, wherein step (b) is performed in 5-15 seconds.

57. The method of Claim 49, wherein step (b) is performed in 8-12 seconds.

58. The method of Claim 49, wherein step (g) is performed in 5-15 seconds.

59. The method of Claim 49, wherein step (g) is performed in 8-12 seconds.

60. The method of Claim 49, wherein steps (c), (d), and (e) are performed in a total of 1-10 seconds.

61. The method of Claim 49, wherein steps (c) - (e) are performed in a total of 1-3 seconds.

62. The method of Claim 49, wherein steps (a) - (i) are performed in a total of 20-30 seconds.

63. The method of Claim 49, wherein steps (a) - (i) are performed in less than 25 seconds.

64. The method of Claim 49. wherein said core mold half is mounted on a rotatable plate, wherein rotation of said rotatable plate moves said core mold half from a position opposite said first mold half to a position opposite said second mold half.

65. The method of Claim 49, wherein said first and second mold halves are mounted in a single stationary block, wherein said block is divided to provide separate controls and conditions for each of said mold halves.

66. A process for the production of a multi-layer plastic container comprising the steps of:
a. providing a first polymer comprising a polyester and a second polymer comprising a copolyester of terephthalic acid, isophthalic acid and at least one diol;
b. injecting said first and second polymers through a lamellar injection system to provide a composite multi-lamellae stream having at least one discrete lamella of polyester and at least another discrete lamella of said copolyester;
c. supplying said composite stream to a mold to form an initial preform having inner and outer sublayers comprising polyester and said copolyester, said sublayer comprising said copolyester having a permeability to air which is less than the permeability to air of said sublayer comprising polyester;
d. supplying recycled polyester over said initial preform to form an outer layer around said initial preform to form a final preform; and e. subjecting said final preform to a blow molding operation to form a multi-layer plastic container.

67. The process of Claim 68, wherein said recycled polyester is applied over said preform in an amount to provide an outer layer which is thicker than at least one of the inner and outer sublayers provided in step (c).

68. The process of Claim 66, wherein said first and second polymers are injected through said lamellar injection system in relative amounts to provide a thickness of said discrete lamella of said copolyester which is less than the discrete lamella of polyester.

69. The process of Claim 66, wherein said at least one diol comprises ethylene glycol.

70. The process of Claim 66, wherein said composite stream is supplied to said mold such that the polyester forms an inner sublayer of said initial preform and said copolyester forms an outer sublayer of said initial preform wherein said outer sublayer covers said inner sublayer.

71. The process of Claim 70, wherein said first and second polymers are coinjected through said lamellar injection system in relative amounts to provide a thickness of said outer sublayer of said copolyester which is less than the thickness of said inner layer of polyester.

72. The process of Claim 66, wherein said first and second polymers are coinjected through said lamellar injection system having at least one layer multiplication step to provide a composite multi-lamella stream having a plurality of discrete lamella of polyester and a plurality of discrete lamella of said copolyester and said multi-lamella composite stream is supplied to said mold to form an initial preform having a plurality of sublayers of polyester and a plurality of sublayers of said copolyester in a multi-layer sandwich configuration.

73. A process for the production of a multi-layer plastic container, comprising the steps of:
a. supplying polyester to a mold to form an initial preform comprising polyester of a thickness sufficient to form a self-supporting structure when removed from said mold;
b. providing a first body of a thermoplastic polymer comprising recycled polyester and a second body of thermoplastic barrier polymer comprising (i) a copolyester of terephthalic acid, isophthalic acid, and at least one diol or (ii) a Phenoxy-type Thermoplastic;
c. injecting said thermoplastic polymer and said thermoplastic barrier polymer through a lamellar injection system having a coextrusion feed block unit to provide a composite multi-lamella stream having at least one discrete lamella of recycled polyester and at least one discrete lamella of said thermoplastic barrier polymer;
d. supplying said composite stream over said initial preform to form a final preform wherein said composite stream comprising sublayers of recycled polyester and said thermoplastic barrier material overlays said initial preform of polyester, and e. subjecting said final preform to a blow molding operation to form a multi-layer plastic container.

74. The process of Claim 73 wherein:
said initial preform comprises a neck portion at the upper end thereof and a body portion at the lower end thereof, wherein said neck portion comprises a support ring at the lower end of said neck portion and said neck portion has a threaded finish; and said composite stream is supplied over said body portion of said initial preform and terminates on the underside of said support ring.

75. The process of Claim 73, wherein said recycled polyester is recycled polyester or post-consumer polyethylene terephthalate.

76. The process of Claim 73, wherein said thermoplastic barrier polymer is poly(hydroxyamino ether).

77. The process of Claim 73, wherein said at least one diol comprises ethylene glycol.

78. A method of making and coating preforms, comprising the following steps:
closing a mold comprising a stationary half and a movable half, wherein said stationary mold half comprises at least one preform molding cavity and at least one preform coating cavity and said movable mold half comprises a rotatable plate having mounted thereon a number of mandrels equal to the sum of the number of preform molding cavities and preform coating cavities;
injecting a first material into the space defined by a mandrel and a preform molding cavity to form a preform having an inner surface and an outer surface;
opening said mold;
rotating said rotatable plate;
closing said mold;
injecting a second material into the space defined by said outer surface of said preform and said preform coating cavity to form a coated preform;
opening said mold;
removing said coated preform.

79. The method of Claim 78, wherein said preform molding cavities and said preform coating cavities occupy separate halves of said stationary mold half.

80. The method of Claim 78, wherein said preform is not solid ar cured prior to injection of said second material.