Laminate, laminate film and shaped article comprising inorganic laminar compound

• US 5,766,751 A
• Filed: 09/22/1995
• Issued: 06/16/1998
• Est. Priority Date: 01/24/1994
• Status: Expired due to Term

• Current Assignee: Sumitomo Chemical Company Limited
• Original Assignee: Sumitomo Chemical Company Limited
• Inventors: Sakaya, Taiichi, Kuroda, Toshiya, Kawakita, Toshio, Kotani, Kozo
• Primary Examiner(s): LE, HOA T
• Application Number:
  US08/522,425
• Time in Patent Office: 998 Days
• Field of Search: 428/323, 428/331, 428/325, 428/480, 428/910, 428/913, 428/328
• US Class Current: 428/323
• CPC Class Codes: B32B 15/08 of synthetic resin
• CPC Class Codes: B32B 2307/518 bi-axially
• CPC Class Codes: B32B 2307/7244 Oxygen barrier
• CPC Class Codes: B32B 27/06 as the main or only constituent of a layer, which is next to another layer of the same or of a different material next to a layer of a particular substance B32B9/045; next to a bituminous or tarry layer B32B11/046; next to a water setting substance layer B32B13/12; next to a metal layer B32B15/08; next to a glass layer B32B17/10; next to a layer formed of natural mineral fibres or particles B32B19/045; next to a wood layer B32B21/08; next to a cellulosic plastic layer B32B23/08; next to a natural or synthetic rubber layer B32B25/08
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/18 characterised by the use of special additives
• 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: B32B 27/36 comprising polyesters
• 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 7/048 Forming gas barrier coatings
• CPC Class Codes: C08J 7/052 Forming heat-sealable coatings
• CPC Class Codes: C08K 2201/008 Additives improving gas barrier properties
• CPC Class Codes: C08K 2201/016 Additives defined by their aspect ratio
• CPC Class Codes: C08K 3/346 Clay
• CPC Class Codes: Y10S 428/91 Product with molecular orientation
• CPC Class Codes: Y10S 428/913 Material designed to be responsive to temperature, light, moisture
• CPC Class Codes: Y10T 428/25 Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• CPC Class Codes: Y10T 428/252 : Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
• CPC Class Codes: Y10T 428/256 : Heavy metal or aluminum or compound thereof
• CPC Class Codes: Y10T 428/259 : Silicic material

Abstract

A laminate, laminate film or shaped article, which includes: a layer of a substance having a gas barrier property; and at least one layer or portion (1) disposed thereon comprising a resin composition comprising a resin and an inorganic laminar compound having an aspect ratio of not less than 50 and not more than 5000. As the gas barrier substance, a metal or oxide, ethylene-vinyl alcohol copolymer, or polyvinylidene chloride may preferably be used.

Such a laminate, laminate film or shaped article may exhibit a good gas barrier property which is much higher than that of a conventional plastic material.

Claims

1. A laminate comprising:

(a) a layer comprising a substance having a gas barrier property; and

(b) at least one layer which is disposed on the layer (a) wherein said layer (b) comprises a resin composition comprising a resin and an inorganic laminar compound having an aspect ratio of not less than 50 and not more than 5000, said inorganic laminar compound being such that it is swollen or cleft in a solvent, said inorganic laminar compound being selected from the group consisting of a graphite, a phosphoric acid salt derivative compound, a chalcogen compound, a kaolinite series clay mineral, an antigorite series clay mineral, a smectite series clay mineral, and a mica series clay mineral, said resin comprising one selected from the group consisting of polyvinyl alcohol (PVA), ethylenevinylalcohol copolymer (EVOH), polyacrylonitrile (PAN), polysaccharide, polyacrylic acid, and esters thereof.

2. A laminate according to claim 1, wherein the layer (a) comprising the gas barrier substance is disposed on another resin layer underlying the layer (a) substance.

3. A laminate according to claim 1, wherein the gas barrier substance comprises a metal or metal oxide.

4. A laminate according to claim 1, wherein the layer comprising the gas barrier substance comprises a layer comprising an ethylene-vinyl alcohol copolymer as a main component.

5. A laminate according to claim 1, wherein the layer comprising the gas barrier substance comprises a layer comprising a polyvinylidene chloride as a main component.

6. A laminate according to claim 1, wherein the inorganic laminar compound is an inorganic laminar compound having a particle size of 5 μ

m or smaller.

7. A laminate according to claim 1, wherein the inorganic laminar compound comprises a clay mineral having a swelling property.

8. A laminate according to claim 1, wherein the inorganic laminar compound is an inorganic laminar compound having an aspect ratio of 200 to 3000.

9. A laminate according to claim 1, wherein the inorganic laminar compound and the resin constituting the resin composition have a volume ratio (inorganic laminar compound/resin) in the range of (5/95) to (90/10).

10. A laminate according to claim 1, wherein the resin constituting the resin composition is a highly hydrogen-bonding resin.

11. A laminate according to claim 10, wherein the highly hydrogen-bonding resin is a resin such that the wt. percent of a hydrogen-bonding group or ionic group per unit weight of the resin is not less than 30% and not more than 50%.

12. A laminate according to claim 10, wherein the highly hydrogen-bonding resin is polyvinyl alcohol or polysaccharide.

13. A laminate according to claim 10, wherein the resin composition further comprises a crosslinking agent for hydrogen-bonding group.

14. A laminate according to claim 13, wherein the crosslinking agent for hydrogen-bonding group is a zirconia compound.

15. A laminate according to claim 1, which has an oxygen permeability of not more than 0.2 cc/m² ·

day·

atm under the conditions of 30°

C. and 60% RH.

16. A laminate according to claim 1, which has a shape in the form of a laminate film.

17. A laminate film, comprising:

a base material, and at least one layer disposed thereon comprising a laminate according to claim 1.

18. A laminate film according to claim 17, which has an oxygen permeability of not more than 0.2 cc/m² ·

day·

atm under the conditions of 30°

C. and 60% RH.

19. A shaped article, comprising a laminate according to claim 1 as at least a portion thereof.

20. A shaped article according to claim 19, which has an oxygen permeability of not more than 02 cc/m² ·

day·

atm under the conditions of 30°

C. and 60% RH.

21. A laminate, comprising:

at least one layer comprising a resin selected from biaxially oriented polypropylene, biaxially oriented nylon and biaxially oriented polyethylene terephthalate; and

at least one layer comprising a laminate according to claim 1.

22. A laminate according to claim 21, which has a shape in the form of a laminate film.

23. A laminate according to claim 1, wherein the inorganic laminar compound is at least one selected from the group consisting of a graphite, a phosphoric acid salt derivative compound and a chalcogen compound.

24. A laminate according to claim 23, wherein the inorganic laminate compound is a chalcogen compound represented by the formula MX₂, wherein M denotes an element selected from the group consisting of Group IV, Group V and Group VI, and X is S, Se, Te.

25. A laminate according to claim 24, wherein said chalcogen compound M is at least one member selected from the group consisting of Ti, Zr, Hf, V, Mb, Ta, Mo and W.

26. A laminate according to claim 1, wherein the inorganic laminar compound is at least one selected from the group consisting of a salt, a kaolinite series clay mineral, antigorite series clay mineral, smectite series clay mineral, and mica series clay minerals, said inorganic compound being at least one of (i) a clay having a two-layer structure, which comprises a silica tetrahedral layer, and an octahedral layer disposed thereon and comprising a central metal;

or a three-layer structure, which comprises an octahedral layer comprising a central metal, and a silica tetrahedral layer disposed on the both sides of the octahedral layer so as to sandwich the octahedral layer.

27. A laminate according to claim 26, wherein the clay mineral comprises at least one selected from the group consisting of:

kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilylic mica, sodium taeniolite, muscovite, margarite, talc, phlogopite, xanthophyllite, and chlorite.