Barrier composite films and a method for producing the same

• US 5,770,301 A
• Filed: 10/25/1996
• Issued: 06/23/1998
• Est. Priority Date: 03/14/1995
• Status: Expired due to Term

• Current Assignee: Daicel Chemical Industries Limited (Daicel Corporation)
• Original Assignee: Daicel Chemical Industries Limited (Daicel Corporation)
• Inventors: Murai, Takaaki, Miyake, Ryuta
• Primary Examiner(s): Nakarani, D. S.
• Application Number:
  US08/732,226
• Time in Patent Office: 606 Days
• Field of Search: 428/35.3, 428/35.4, 428/35.8, 428/36.6, 428/36.7, 428/213, 428/215, 428/216, 428/446, 428/448, 428/447, 428/451, 427/387
• US Class Current: 428/213
• CPC Class Codes: B32B 2307/31 Heat sealable
• CPC Class Codes: B32B 2307/7242 Non-permeable
• CPC Class Codes: B32B 2309/105 Thickness
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/16 specially treated, e.g. irradiated
• CPC Class Codes: B32B 27/304 comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• CPC Class Codes: B32B 27/306 comprising vinyl acetate or vinyl alcohol (co)polymers
• CPC Class Codes: B32B 27/32 comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/34 comprising polyamides
• CPC Class Codes: C08J 7/0423 with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
• CPC Class Codes: C08J 7/043 Improving the adhesiveness of the coatings per se, e.g. forming primers adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50
• CPC Class Codes: C08J 7/048 Forming gas barrier coatings
• CPC Class Codes: Y10T 428/2495 Thickness [relative or absolute]
• CPC Class Codes: Y10T 428/24967 Absolute thicknesses specified
• CPC Class Codes: Y10T 428/24975 No layer or component greater than 5 mils thick
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane
• CPC Class Codes: Y10T 428/31667 Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product

Abstract

At least one side of a polyester or other base film is successively covered with an inorganic layer composed of a silicon oxide or the like and a coating layer comprising a silane coupling agent and a barrier resin (e.g. vinylidene chloride-based copolymer, ethylene-vinyl alcohol copolymer) to provide a barrier composite film. The amount of the silane coupling agent is about 0.05 to 10 parts by weight relative to 100 parts by weight of the barrier resin. A heat-sealing layer is optionally formed on the surface of the barrier resin coating layer or on the other side of the base film. Such barrier composite film has excellent transparency and retains high barrier properties and adhesive properties of covering layer despite its thin covering layer.

Claims

1. A barrier composite film which comprises a base film layer, an inorganic thin layer having a thickness of 100 to 5,000 Å

formed on at least one side of said base film layer, and a gas barrier resin coating layer containing a silane coupling agent formed on said inorganic thin layer.

2. A barrier composite film according to claim 1, wherein said base film layer is formed with a polypropylene, a polyalkylene terephthalate or a polyamide.

3. A barrier composite film according to claim 1, wherein said inorganic thin layer is transparent to visible light.

4. A barrier composite film according to claim 1, wherein said inorganic layer is formed with at least one oxide of a metal selected from the group consisting of Group 2A elements, transitional metal elements, Group 2B elements, Group 3B elements, Group 4B elements and Group 6B elements of Periodic Table of the Elements.

5. A barrier composite film according to claim 1, wherein said inorganic layer is formed with an oxide of a Group 3B element or Group 4B element of Periodic Table of the Elements.

6. A barrier composite film according to claim 1, wherein said inorganic layer is formed with a silicon oxide.

7. A barrier composite film according to claim 1, wherein said gas barrier resin coating layer comprises a copolymer of vinylidene chloride with other copolymerizable monomers or an ethylene-vinyl alcohol copolymer.

8. A barrier composite film according to claim 7, wherein said gas barrier resin coating layer comprises at least one barrier resin selected from the group consisting of a vinylidene chloride-acrylonitrile copolymer, a vinylidene chloride-methacrylic acid copolymer,a vinylidene chloride-alkyl acrylate copolymer, a vinylidene chloride-acrylic acid copolymer, a vinylidene chloride-alkyl methacrylate copolymer, a vinylidene chloride-vinyl acetate copolymer and a solvent-soluble or dispersible ethylene-vinyl alcohol copolymer with an ethylene content of 5 to 50 mol %.

9. A barrier composite film according to claim 1, wherein said silane coupling agent has at least one functional group selected from the group consisting of a halogen atom, an epoxy group, an amino group, a hydroxyl group, a mercapto group, a vinyl group and a (meth)-acryloyl group, and an alkoxy group.

10. A barrier composite film according to claim 1, wherein said silane coupling agent is a compound shown by the following formula

11. A barrier composite film according to claim 10, wherein the hydrocarbon group represented by R is a C_1-4 alkylene group, or C_5-8 cycloalkene-C_1-4 alkyl residue, the double bond of said cycloalkene being epoxidated, and X is the same or different methoxy group or ethoxy group.

12. A barrier composite film according to claim 10, wherein n is 0 with a proviso that Y is a vinyl group.

13. A barrier composite film according to claim 1, wherein the proportion of the silane coupling agent is 0.05 to 10 parts by weight relative to 100 parts by weight of the gas barrier resin.

14. A barrier composite film according to claim 1, wherein the proportion of the silane coupling agent is 0.1 to 7 parts by weight relative to 100 parts by weight of the gas barrier resin.

15. A barrier composite film according to claim 1, wherein the thickness of the gas barrier resin coating layer is 0.05 to 15 μ

m.

16. A barrier composite film according to claim 1, wherein the ratio of the thickness T μ

m of said gas barrier resin coating layer relative to the thickness t μ

m of said inorganic layer is T/t =0.1 to 1,500.

17. A barrier composite film according to claim 1, wherein the ratio of the thickness T μ

m of said gas barrier resin coating layer relative to the thickness t μ

m of said inorganic layer is T/t =0.5 to 500.

18. A barrier composite film according to claim 1, wherein said film comprises a polypropylene, polyalkylene terephthalate or polyamide base film layer, an inorganic layer formed from a silicon oxide of the composition formula SiOx wherein x is defined by 0 <

x ≦

2 and having a thickness of 100 to 5,000 Å and

a gas barried resin coating layer comprising a silane coupling agent and a copolymer of vinylidene chloride with other copolymerizable monomers or ethylene-vinyl alcohol copolymer, said inorganic layer and barrier resin coating layer being formed in the order mentioned on at least one surface of said base film layer and the ratio of the thickness T μ

m of said barrier resin coating layer relative to the thickness t μ

m of said inorganic layer being in the range of 1 to 200.

19. A barrier composite film according to claim 1, wherein at least one surface of a polypropylene, polyalkylene terephthalate or polyamide base film layer is successively covered with an inorganic layer formed from an electrically nonconductive inorganic substance in a thickness of 200 to 3,000 Å

, and a gas barrier resin coating layer formed in a thickness of 0.1 to 10 μ

m in that order.

20. A barrier composite film according to claim 1, wherein the peeling strength of the coating layer relative to the base film layer after storage at a temperature of 40°

C. and relative humidity of 90% for 1 week is not less than 100 g/15 mm.

21. A barrier composite film according to claim 1, wherein the composite film shows an oxygen gas permeability of not greater than 5 cc/M² 19 24 hr. at 25°

C., and a water vapor permeability of not greater than 5 g/m² ·

24 hr. at 40°

C. and relative humidity of 90% as determined with a base film layer thickness of 10 to 30 μ

m and a thickness of a covering layer comprising the inorganic layer and the coating layer of 0.5 to 5 μ

m.

22. A barrier composite film according to claim 1, wherein the other side of said base film or the surface of said gas barrier resin coating layer is covered with a heat-sealing layer.

23. A process for producing a barrier composite film which comprises depositing an inorganic thin layer having a thickness of 100 to 5,000 Å

on at least one side of a base film and coating the deposited side of said base film with a coating composition containing a silane coupling agent and a gas barrier resin.

24. A process for producing a barrier composite film according to claim 23, wherein a heat-sealing layer is formed in a thickness of 3 to 100 μ

m on said coating layer or on the other side of said base film.