Barrier film and method for production thereof

• US 20030068534A1
• Filed: 05/31/2002
• Published: 04/10/2003
• Est. Priority Date: 10/13/2000
• Status: Active Grant

• Current Assignee: Dai Nippon Printing Company Limited
• Original Assignee: Dai Nippon Printing Company Limited
• Inventors: Yoshikata, Kuniaki, Ohkawa, Koujiro, Tsuzuki, Atsuo
• Granted Patent: US 6,720,097 B2
• Time in Patent Office: Days
• US Class Current: 428/701
• CPC Class Codes: C08J 7/048 Forming gas barrier coatings
• CPC Class Codes: C08J 7/052 Forming heat-sealable coatings
• CPC Class Codes: C08J 7/06 with compositions not containing macromolecular substances
• CPC Class Codes: C23C 14/081 of aluminium, magnesium or beryllium
• CPC Class Codes: C23C 14/10 Glass or silica
• CPC Class Codes: C23C 14/58 After-treatment
• CPC Class Codes: C23C 14/5806 Thermal treatment
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/407 of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: Y10T 428/24355 Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
• CPC Class Codes: Y10T 428/31725 Of polyamide
• CPC Class Codes: Y10T 428/31728 Next to second layer of polyamide
• CPC Class Codes: Y10T 428/31736 Next to polyester
• CPC Class Codes: Y10T 428/31765 Inorganic-containing or next to inorganic-containing
• CPC Class Codes: Y10T 428/31786 Of polyester [e.g., alkyd, etc.]

Abstract

The present invention provides a barrier-forming film (A) useful for manufacturing various packaging container, which has a higher barrier-formability to prevent permeation of oxygen gas or steam, and a manufacturing method thereof. The barrier-forming film of the invention comprises a substrate film (1) having a vapor-deposited film (2) of an inorganic oxide, and by applying an annealing treatment thereto to limit the steam permeability within a range of from 2.0 to 0.000001 g/m².day, and the oxygen permeability, within a range of from 2.0 to 0.000001 cc/m².day.

Claims

1. A barrier-forming film comprising a substrate film having a vapor-deposited inorganic oxide film, further subjected to an annealing treatment, wherein the steam permeability is within a range of from 2.0 to 0.000001 g/m².day and the oxygen permeability is within a range of from 2.0 to 0.000001 cc/m².day.atm.

13. A barrier-forming film according to any one of claims 1 to 12, wherein said vapor-deposited inorganic oxide film comprises a vapor-deposited silicon oxide film or a vapor-deposited aluminum oxide film.

14. A barrier-forming film according to any one of claims 1 to 13, wherein said substrate film comprises a polyester-based resin film, a polyamide-based resin film, or a polypropylene-based resin film.

15. A barrier-forming film according to any one of claims 1 to 14, wherein said annealing treatment comprises a heating treatment for a heating time of at least 60 minutes.

16. A barrier-forming film according to any one of claims 1 to 15, wherein said annealing treatment is carried out at a heating treatment temperature within a range of from room temperature to 200°

C.

17. A barrier-forming film according to any one of claims 1 to 16, wherein said annealing treatment is carried out for a heating treatment time within a range of from 30 minutes to five days.

2. A barrier-forming film comprising a substrate film having a vapor-deposited inorganic oxide film, further subjected to an annealing treatment, wherein the improvement ratio of the steam permeability is increased to a range of from 1/100 to 99/100, and that of the oxygen permeability to a range of from 1/100 to 99/100 as compared with those before the annealing treatment.

3. A barrier-forming film comprising a substrate film having a vapor-deposited inorganic oxide film. further subjected to an annealing treatment, wherein the amount of decrease in the steam permeability is improved to a range of from −

0.1 to −

30 g/m².day, and the amount of decrease in the oxygen permeability, to a range of from −

0. 1 to −

10 cc/m².day.atm.

4. A barrier-forming film comprising a substrate film having a vapor deposited inorganic oxide film, further subjected to an annealing treatment, wherein the degree of yellowing is improved to a range of from −

0.3 to −

2.0.

5. A barrier-forming film comprising a substrate film having a vapor-deposited inorganic oxide film, further subjected to an annealing treatment, wherein the amount of change in X-value of the inorganic oxide expressed by a formula MOx (where, M represents a metal element;

and the range of the value of X varies between metal elements) composing the vapor-deposited film of the inorganic oxide is increased to a range of from +0.01 to +0.50.

6. A barrier-forming film comprising a substrate film having a vapor-deposited inorganic oxide film, wherein the surface roughness of the vapor-deposited inorganic oxide film is adjusted within a range of from 3 to 30 nm.

7. A barrier-forming film comprising a substrate film having a vapor-deposited inorganic film, further subjected to an annealing treatment, wherein the surface roughness of said vapor-deposited inorganic oxide film is adjusted within a range of from 3 to 30 nm.

8. A barrier-forming film comprising a substrate film having a vapor-deposited inorganic oxide film, further subjected to an annealing treatment, wherein the standard deviation of surface irregularities Rms representing the surface roughness of said vapor-deposited inorganic oxide film is improved to a range of from 1.01 to 100 times as high as that before the annealing treatment.

9. A barrier-forming film comprising a substrate film having a vapor-deposited inorganic oxide film, further subjected to an annealing treatment, wherein the shrinkage factor of said substrate film is reduced to a range of from −

0.001 to −

1.0% in at least any one of the flow direction and the width direction upon forming the film, and the thickness of said vapor-deposited inorganic oxide film is adjusted within a range of from 50 to 1,000 Å

(5 to 100 nm) as compared with those before the annealing treatment.

10. A barrier-forming film comprising a substrate film having a vapor-deposited inorganic oxide film, further subjected to an annealing treatment, wherein the standard deviation of surface irregularities Rms representing the surface roughness of said vapor-deposited inorganic oxide film is improved to a range of from 1.01 to 100 times as high;

the steam permeability thereof is adjusted within a range of from 2.0 to 0.000001 g/m².day; and

the oxygen permeability, within a range of from 2.0 to 0.000001 cc/m².day.atm, as compared with those before the annealing treatment.

11. A barrier-forming film comprising a substrate film having a vapor-deposited inorganic oxide film, further subjected to an annealing treatment, wherein the shrinkage factor of said substrate film is reduced to a range of from −

0.001 to −

1.0% in at least any one of the flow direction and the width direction upon forming the film;

the steam permeability thereof is adjusted within a range of from 2.0 to 0.000001 g/m².day; and

the oxygen permeability, within a range of from 2.0 to 0.000001 cc/m².day.atm, as compared with those before the annealing treatment.

12. A barrier-forming film comprising a substrate film having a vapor-deposited inorganic oxide film, further subjected to an annealing treatment, wherein the steam permeability thereof is improved to a range of from 2.0 to 0.000001 g/m².day;

the oxygen permeability thereof, to a range of from 2.0 to 0.000001 cc/m².day.atm;

the degree of yellowing, to a range of from −

0.3 to −

2.0;

the amount of change in X-value of the inorganic oxide expressed by a formula MOx (where, M represents a metal element;

the range of the value of X varies between metal elements) composing the vapor-deposited film of the inorganic oxide is increased to a range of from +0.01 to +0.50; and

the surface roughness of the vapor-deposited inorganic oxide film is adjusted within a range of from 3 to 30 nm.

18. A manufacturing method of a barrier-forming film comprising the steps of providing a vapor-deposited inorganic oxides film on a side of a substrate film, and applying an annealing treatment to the substrate film having said vapor-deposited inorganic film.

20. A manufacturing method of a barrier-forming film according to any one of claims 18 and 19, wherein said vapor-deposited inorganic oxide film comprises a vapor-deposited silicon oxide film or a vapor-deposited aluminum oxide film.

21. A manufacturing method of a barrier-forming film according to any one of claims 18 to 20, wherein said annealing treatment comprises a heating treatment carried out at a heating treatment temperature of at least room temperature for a heating treatment time of at least 30 minutes.

22. A manufacturing method of a barrier-forming film according to any one of claims 18 to 21, wherein said annealing treatment is carried out at a heating treatment temperature within a range of from room temperature to 200°

C.

23. A manufacturing method of a barrier-forming film according to any one of claims 18 to 22, wherein said annealing treatment is carried out for a heating treatment time within a range of from 30 minutes to five days.

19. A manufacturing method of a barrier-forming film comprising the steps of providing a vapor-deposited inorganic oxides film on a side of a substrate film, and applying an annealing treatment to the substrate film having said vapor-deposited inorganic film, to cause thermal shrinkage of the substrate film composing the substrate film having the vapor-deposited inorganic oxide film, and to increase density of the vapor-deposited inorganic oxide film.

24. A barrier-forming film comprising a substrate film having a vapor-deposited silicon oxide film formed on one side of the substrate film, wherein said substrate film having said vapor-deposited silicon oxide film is heat-treated at a heat treatment temperature of at least room temperature for a heat treatment time of at least one hour;

the steam permeability thereof is within a range of from 2.0 to 0.000001 g/m².day;

the oxygen permeability is within a range of from 2.0 to 0.000001 cc/m².day.atm;

the degree of yellowing is improved to a range of from −

0.3 to −

2.0; and

the amount of change in X-value of silicon oxide as expressed by a formula building the vapor-deposited film SiOx is increased to a range of from +0.01 to +0.50.

25. A barrier-forming film comprising a substrate film having a vapor-deposited silicon oxide film formed on one side of the substitute film, wherein the steam permeability thereof is within a range of from 2.0 to 0.000001 g/m².day;

and the oxygen permeability thereof is within a range of from 2.0 to 0.000001 cc/m².day.atm.

26. A barrier-forming film comprising a substrate film having a vapor-deposited silicon oxide film formed on one side of the substrate film, wherein said substrate film is heat-treated at a heat treatment temperature of at least room temperature for a heat treatment time of at least one hour to improve the degree of yellowing to a range of from −

0.3 to −

2.0.

27. A barrier-forming film comprising a substrate film having a vapor-deposited silicon oxide film formed on one side of the substrate film, wherein said substrate film is heat-treated at a heat treatment temperature of at least room temperature for a heat treatment time of at least one hour to increase the amount of change in X-value of silicon oxide as expressed by a formula SiO2 composing the deposited film to a range of from +0.01 to +0.50.

28. A manufacturing method of a barrier-forming film, comprising the steps of providing a vapor-deposited silicon oxide film on one side of a substrate film, and heat-treating the substrate film having said vapor-deposited silicon oxide film at a heat treatment temperature of at least room temperature for a heat treatment time of at least one hour.