Coated bottle and method of coating

• US 4,171,056 A
• Filed: 10/25/1977
• Issued: 10/16/1979
• Est. Priority Date: 10/25/1977
• Status: Expired due to Term

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Celanese Corporation
• Inventors: Hannon, Martin J., Forschirm, Alex S., Greene, Richard K.
• Primary Examiner(s): Dixon, Jr., William R.
• Application Number:
  US05/844,820
• Time in Patent Office: 721 Days
• Field of Search: 428/35, 215/12 R, 427/189, 427/195, 427/201, 427/203, 427/222, 427/425
• US Class Current: 215/12.2
• CPC Class Codes: B65D 23/02 Linings or internal coatings
• CPC Class Codes: B65D 23/0814 characterised by the composition of the material
• CPC Class Codes: C03C 17/328 Polyolefins
• CPC Class Codes: C03C 17/3405 with at least two coatings of organic materials C03C17/36, C03C17/42 take precedence
• CPC Class Codes: C03C 17/42 at least one coating of an organic material and at least one non-metal coating
• CPC Class Codes: C03C 2217/42 consisting of particles only
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C09D 153/02 Vinyl aromatic monomers and conjugated dienes
• CPC Class Codes: Y10T 428/1321 Polymer or resin containing [i.e., natural or synthetic]

Abstract

A coated bottle comprising a bottle having an inner and an outer coating is disclosed. The inner coating applied to the external surface thereof is prepared from non-tacky composite powder particles which are made up of powder particles which have surface deposited thereon comparatively smaller solid particles which are hard and non-tacky. The tacky powder particles comprise a mixture of a thermoplatic elastomer, a specifically defined melt flow modifier, and an adhesion promoter. The smaller, hard particles comprise a specifically defined melt flow modifier which has a glass transition temperature of at least about 20° C. The first coating is applied to the bottle, preferably by electrostatic spraying techniques, and the bottle with the particles is baked to form a smooth coating. An outer coating comprising certain particularly defined synthetic resins, particularly acrylic polymers, is then applied and the coated bottle is again baked until a smooth second coat is formed. The coated bottle is fragment retentive and this coating is not substantially removed or destroyed during the cleaning and sterilization procedures commonly employed by carbonated beverage bottling companies.

Claims

1. A glass container coated on its outer surface to prevent the scattering of glass fragments which comprises

(A) a glass container,

(B) an inner smooth non-particulate coating initially applied to (A) as non-tacky composite powder particles intimately contacted on the external wall surface of said container said composite powder particles comprising

(a) tacky powder particles comprising a mixture of

(1) a block copolymer which is either unhydrogenated or selectively hydrogenated to at least some degree and having at least two kinds of polymer blocks wherein one polymer block is designated by A and a second polymer block is designated by B such that prior to hydrogenation,

(a) each A is a polymer end block of a monovinyl or alpha alkyl monovinyl arene having a number average molecular weight in the range of from about 5,000 to about 75,000, said blocks A comprising from about 5 to about 50% by weight of the total block copolymer, and

(b) each B is a polymer mid block having a number average molecular weight of from about 30,000 to about 300,000, and formed from a conjugated diene selected from homopolymers of at least one conjugated diene having 4 to 10 carbon atoms per molecule, said blocks B comprising from about 50 to about 95% by weight of the total block copolymer,

(2) at least one melt flow modifier selected from the group consisting of

(a) monovinyl arene homopolymers,

(b) alpha alkyl monovinyl arene homopolymers, and

(c) copolymers of monovinyl arenes and alpha alkyl monovinyl arenes, wherein the aromatic portions of the polymers described (2) (a), (b) and (c) are at least partially hydrogenated to remove the aromatic character thereof, and

(3) at least one adhesion promoter, and

(b) smaller solid particles, which are hard and non-tacky and which comprise at least one melt flow modifier of the group described in (a) (2) with the provision that the melt flow modifier have a glass transition temperature of at least about 20°

C., adhering to the tacky surface of said tacky particles of (a) in a non-continuous layer, said composite powder particles being rendered in the configuration of a smooth non-particulate inner coating of the external surface of the glass container by heat and,

(c) an outer top coat of a synthetic resin covering substantially the entire outer surface of said inner coat and a part of the external glass container surface and selected from the group consisting of epoxy resins, polyurethanes, polycarbonates, polyesters, polystyrenes, ethylene/vinyl acetate copolymers and acrylic homopolymers and copolymers wherein the outer film has high abrasion resistance, wet and dry scratch resistance, water resistance, chemical resistance, oil resistance, and weather resistance.

2. The glass container of claim 1, wherein said tacky powder particles of said non-tacky composite powder particles of (B) contain from about 25 to about 90% by weight of the block copolymer and from about 10 to about 75% by weight of the melt flow modifier.

3. The glass container of claim 1, wherein the block copolymer has a number average molecular weight of from about 15,000 to about 150,000.

4. The glass container of claim 1, wherein said tacky powder particles of said non-tacky composite powder particles of (B) contain from about 0.1 to about 8% by weight of an adhesion promoter selected from the group consisting of substituted silanes, the corresponding silanols, siloxanes, and mixtures thereof.

5. The glass container of claim 4, wherein said tacky powder particles of said non-tacky composite powder particles of (B) additionally contain less than about 10% by weight of at least one member of the group consisting of stabilizers against oxidation and stabilizers against ultraviolet light.

6. The glass container of claim 5, wherein said monovinyl arene portion of said block copolymer is styrene and wherein said conjugated diene portion of said block copolymer is unsubstituted alpha, gamma butadiene.

7. The glass container of claim 1, wherein said melt flow modifier is a partially hydrogenated copolymer consisting essentially of styrene and alpha methyl styrene.

8. The glass container of claim 7, wherein said copolymer of styrene and alpha methyl styrene is a random copolymer which is at least about 20% hydrogenated.

9. The glass container of claim 8, wherein said random copolymer of styrene and alpha methyl styrene comprises from about 10 to about 50% by weight styrene and from about 50 to about 90% by weight alpha methyl styrene.

10. The glass container of claim 5, wherein said adhesion promoter is gamma-glycidoxypropyl-trimethoxy silane and said stabilizer against oxidation is tetra-bis methylene 3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate methane.

11. The glass container of claim 5, wherein said monovinyl arene is styrene, said conjugated diene is alpha, gamma butadiene, and said block copolymer is at least about 10% hydrogenated.

12. The glass container of claim 1, wherein the initial powder particle size of the composite powder particles of (B) is from about 50 to about 300 micrometers.

13. The glass container of claim 1 wherein said composite powder particles of (B) contain from about 3 to about 20% by weight of said small, hard, non-tacky particles.

14. The glass container of claim 13 wherein said small, hard, non-tacky particles may contain from about 0 to about 10% by weight of an adhesion promoter.

15. The glass container of claim 14 wherein said adhesion promoter is selected from the group consisting of substituted silanes, the corresponding silanols, siloxanes, and mixtures thereof.

16. The glass container of claim 1 wherein said block copolymer is selectively hydrogenated to at least some degree.

17. The glass container of claim 1 wherein said glass container is a pressurized glass bottle.

18. The glass container of claim 1 wherein said glass container has a glass fragment retention of at least about 50%.

19. The glass container of claim 1 wherein said outer coat comprises an acrylic homopolymer or copolymer.

42. The glass bottle of claim 1 wherein said outer coat comprises an acrylic homopolymer or copolymer.

20. A process for coating a glass container in order to prevent the scattering of glass fragments, said process comprising

(A) preheating said glass container,

(B) applying on the external wall surface of said container a non-tacky composite powder particle composition comprising

(1) tacky powder particles comprising a melt blend mixture of

(a) a block copolymer which is either unhydrogenated or selectively hydrogenated to at least some degree and having at least two kinds of polymer blocks wherein one polymer block is designated by A and a second polymer block is designated by B such that prior to hydrogenation,

(1) each A is a polymer end block of a monovinyl or alpha alkyl monovinyl arene having a number average molecular weight in the range of from about 5,000 to about 75,000, said blocks A comprising from about 5 to about 50% by weight of the total block copolymer, and

(2) each B is a polymer mid block having a number average molecular weight of from about 30,000 to about 300,000, and formed from a conjugated diene selected from homopolymers of at least one conjugated diene having 4 to 10 carbon atoms per molecule, said blocks B comprising from about 50 to about 95% by weight of the total block copolymer, and

(b) at least one melt flow modifier selected from the group consisting of

(1) monovinyl arene homopolymers,

(2) alpha alkyl monovinyl arene homopolymers, and

(3) copolymers of monovinyl arenes and alpha alkyl monovinyl arenes, wherein the aromatic portions of the polymers described in (b) (1), (2), and (3) are at least partially hydrogenated to remove the aromatic character thereof, and

adhering to the tacky surface of these tacky particles in a non-continuous layer,

(2) smaller solid particles which are hard and non-tacky and which comprise at least one melt flow modifier of the group described in (B) (1) (b) with the provision that the melt flow modifier have a glass transition temperature of at least about 20°

C.,

(c) baking the coated container until the composite powder particles become molten and form a smooth, molten coating on the external glass surface,

(D) applying to said coated container a synthetic resin selected from the group consisting of epoxy resins, polyurethanes, polycarbonates, polyesters, polystyrenes, ethylene/vinyl acetate copolymers and acrylic homopolymers and copolymers wherein the synthetic resin is applied to substantially the entire outer surface of the first coating and also to a part of the external glass container surface,

(E) baking said coated container until the synthetic resin forms a smooth coating, and

(F) cooling said coated container to substantially ambient temperature.

21. A glass bottle coated on its outer surface to prevent the scattering of glass fragments which comprises

(A) a glass bottle

(B) an inner smooth non-particulate coating initially applied to (A) as non-tacky composite powder particles intimately contacted on the external wall surface of said bottle, said composite powder particles comprising

(a) tacky powder particles comprising a melt blend mixture of

(1) from about 25 to about 90% by weight of a block copolymer which is either unhydrogenated to at least about 10% and having at least two kinds of polymer blocks wherein one block is designated by A and a second polymer block is designated by B such that prior to hydrogenation,

(a) each A is a polymer end block of a monovinyl or alpha alkyl monovinyl arene having a number average molecular weight in the range of from about 5,000 to about 75,000, said blocks A comprising from about 10 to about 40% by weight of the total block copolymer, and

(b) each B is a polymer mid block having a number average molecular weight of from about 30,000 to about 300,000, and formed from a conjugated diene selected from homopolymers of at least one conjugated diene having 4 to 10 carbon atoms per molecule, said blocks B comprising from about 60 to about 90% by weight of the total block copolymer,

(2) from about 10 to about 75% by weight of at least one melt flow modifier selected from the group consisting of

(a) monovinyl arene homopolymers,

(b) alpha alkyl monovinyl arene homopolymers, and

(c) copolymers of monovinyl arenes and alpha alkyl monovinyl arenes

wherein the aromatic portions of the polymers described in (2) (a), (b) and (c) are at least partially hydrogenated to remove the aromatic character thereof,

(3) from about 0.1 to about 8% by weight of at least one adhesion promoter, and

(4) less than about 10% by weight of at least one member of the group consisting of stabilizers against oxidation and stabilizers against ultraviolet light, and

(b) smaller solid particles, which are hard and non-tacky and which comprise at least one melt flow modifier of the group described in (a) (2) with the provision that the melt flow modifier have a glass transition temperature of at least about 20°

C., adhering to the tacky surface of said tacky particles of (a) in a non-continuous layer, said composite powder particles being rendered in the configuration of a smooth non-particulate inner coating of the external surface of the glass container by heat and

(C) an outer top coat of a synthetic resin covering substantially the entire outer surface of said inner coat and a part of the external glass bottle surface and selected from the group consisting of epoxy resins, polyurethanes, polycarbonates, polyesters, polystyrenes, ethylene/vinyl acetate copolymers and acrylic homopolymers and copolymers wherein the outer film has high abrasion resistance, wet and dry scratch resistance, water resistance, chemical resistance, oil resistance, and weather resistance.

22. The glass bottle of claim 21, wherein said tacky powder particles of said non-tacky composite powder particles of (B) contain from about 45 to about 75% by weight of the block copolymer and from about 25 to about 55% by weight of the melt flow modifier.

23. The glass bottle of claim 21, wherein the block copolymer has a number average molecular weight of from about 30,000 to about 300,000.

24. The glass bottle of claim 21, wherein said adhesion promoter is selected from the group consisting of substituted silanes, the corresponding silanols, siloxanes, and mixtures thereof.

25. The glass bottle of claim 24, wherein said stabilizer is tetra-bis methylene 3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate methane.

26. The glass bottle of claim 25, wherein said monovinyl arene portion of said block copolymer is styrene and wherein said conjugated diene portion of said block copolymer is unsubstituted alpha, gamma butadiene.

27. The glass bottle of claim 21, wherein said melt flow modifier is a partially hydrogenated copolymer consisting essentially of styrene and alpha methyl styrene.

28. The glass bottle of claim 27, wherein said copolymer of styrene and alpha methyl styrene is a random copolymer which is at least about 25% hydrogenated.

29. The glass bottle of claim 28, wherein said random copolymer of styrene and alpha methyl styrene comprises from about 15 to about 35% by weight styrene and from about 65 to about 85% by weight alpha methyl styrene.

30. The glass bottle of claim 25, wherein said adhesion promoter is gamma-glycidoxyproply-trimethoxy silane.

31. The glass bottle of claim 25, wherein said monovinyl arene is styrene, said conjugated diene is alpha, gamma butadiene, and said block copolymer is at least about 50% hydrogenated.

32. The glass bottle of claim 21, wherein the block copolymer is a radial block copolymer.

33. The glass bottle of claim 21, wherein said conjugated diene portion of said block copolymer is at least about 50% hydrogenated.

34. The glass bottle of claim 21, wherein said composition contains from about 1 to about 6% by weight of at least one adhesion promoter and from about 0.5 to about 5% by weight of at least one stabilizer.

35. The glass bottle of claim 21, wherein the initial powder particle size of the composite powder particles of (B) is from about 75 to about 250 micrometers.

36. The glass bottle of claim 21 wherein said composite powder particles of (B) contain from about 5 to about 15% by weight of said small, hard, non-tacky particles.

37. The glass bottle of claim 36 wherein said small, hard, non-tacky particles may contain from about 2 to about 6% by weight of an adhesion promoter.

38. The glass bottle of claim 37 wherein said adhesion promoter is selected from the group consisting of substituted silanes, the corresponding silanols, siloxanes, and mixtures thereof.

39. The glass bottle of claim 21 wherein said block copolymer is selectively hydrogenated to at least some degree.

40. The glass bottle of claim 21 wherein said glass bottle is pressurized.

41. The glass bottle of claim 21 wherein said glass bottle has a glass fragment retention of at least about 85%.