Gas-barrier film and method of manufacturing the same

Abstract

The present application relates to gas barrier film having excellent adhesive strength and a method of manufacturing the same. Particularly, the present application is directed to providing a gas barrier film having excellent adhesion performance between an inorganic layer and a protective coating layer under harsh conditions by protective coating layer including inorganic nano particles surface-modified with organic silane on the inorganic layer.

Claims

1. A gas barrier film, comprising: an organic-inorganic hybrid coating layer comprising a cured product of a sol-type hydrolyzed composition containing tetraethoxy orthosilicate and 3-glycidoxypropyl-trimethoxysilane; an inorganic layer; and a protective coating layer including inorganic nanoparticles surface-modified with an organic silane, the layers being sequentially stacked on one surface or both surfaces of a base, wherein: the inorganic nanoparticles are at least one selected from the group consisting of alumina nanoparticles, zinc oxide nanoparticles, antimony oxide nanoparticles, titanium oxide nanoparticles, and zirconium oxide nanoparticles; the inorganic nanoparticles are spherical and have a diameter of 20 to 100 nm; and the organic silane is 3-glycidoxypropyltrimethoxysilane or a compound of Formula 1:
R.sup.1.sub.mSiX.sub.4-m[Formula 1] wherein: X is the same as or different from each other, and each independently is hydrogen, halogen, an alkoxy group having 1 to 12 carbon atoms, an acyloxy group, an alkylcarbonyl group, an alkoxycarbonyl group, or N(R.sup.2).sub.2 wherein R.sup.2 is hydrogen or an alkyl group having 1 to 12 carbon atoms; R.sup.1 is the same as or different from each other, and each independently represents an alkenyl group, an alkynyl group, an arylalkynyl group, an alkynylaryl group, or an alkylcarbonyl group, and has as a substituent an amino group, an amide group, an aldehyde group, a keto group, a carboxyl group, a mercapto group, a cyano group, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, a sulfonic acid, a phosphoric acid, an acryl group, a methacryl group, an epoxy group or a vinyl group; and m is an integer from 1 to 3.

2. The film according to claim 1, which satisfies Equation 1:
X48[Equation 1] wherein X represents a time (h) for which adhesive strength between the inorganic layer and the protective coating layer is maintained to be 90% or more at 85 C. and a relative humidity of 85% as verified by performing a cross hatch cut test.

3. The film according to claim 1, wherein the protective coating layer includes at 10 to 500 parts by weight of organic silane with respect to 100 parts by weight of the inorganic nanoparticles.

4. The film according to claim 1, wherein the base is a plastic film.

5. The film according to claim 4, wherein the plastic film is at least one selected from the group consisting of a homopolymer, at least one of polymer blends, and a polymer composite material containing an organic or inorganic additive.

6. The film according to claim 1, wherein the inorganic layer includes a metal oxide or nitride.

7. The film according to claim 6, wherein the metal is at least one selected from the group consisting of Al, Zr, Ti, Hf, Ta, In, Sn, Zn and Si.

8. The film according to claim 1, wherein the organic-inorganic hybrid coating layer has a thickness of 0.1 to 10 m.

9. The film according to claim 1, wherein the inorganic layer has a thickness of 5 to 1000 nm.

10. The film according to claim 1, wherein the protective coating layer has a thickness of 0.1 to 10 m.

11. A display device, comprising: the gas barrier film according to claim 1.

12. A photovoltaic cell according to claim 1, comprising: the gas barrier film according to claim 1.

13. A food packaging material, comprising: the gas barrier film according to claim 1.

14. The film according to claim 1, wherein the organic silane is 3-glycidoxy-propyltrimethoxysilane.

15. A method of manufacturing a gas barrier film, comprising: forming an organic-inorganic hybrid coating layer containing a reaction product obtained by curing a sol-type hydrolyzed coating composition comprising tetraethoxy orthosilicate and 3-glycidoxy-propyltrimethoxysilane on one or both surfaces of a base; forming an inorganic layer on the organic-inorganic hybrid coating layer; and forming a protective coating layer with a solution prepared by mixing a sol-type hydrolyzing solution and a solution including inorganic nanoparticles surface-modified with organic silane on the inorganic layer, wherein: the inorganic nanoparticles are spherical and have a diameter of 20 to 100 nm; and the inorganic nanoparticles are at least one selected from the group consisting of alumina nanoparticles, zinc oxide nanoparticles, antimony oxide nanoparticles, titanium oxide nanoparticles, and zirconium oxide nanoparticles.

16. The method according to claim 15, wherein the organic silane is 3-glycidoxypropyltrimethoxysilane or a compound of Formula 1:
R.sup.1.sub.mSiX.sub.4-m[Formula 1] where X is the same as or different from each other, and each independently is hydrogen, halogen, an alkoxy group having 1 to 12 carbon atoms, an acyloxy group, an alkylcarbonyl group, an alkoxycarbonyl group, or N(R.sup.2).sub.2 wherein R.sup.2 is hydrogen or an alkyl group having 1 to 12 carbon atoms; R.sup.1 is the same as or different from each other, and each independently is an alkenyl group, an alkynyl group, an arylalkyl group, an alkylaryl group, an arylalkenyl group, an alkenylaryl group, an arylalkynyl group, an alkynylaryl group, or an alkylcarbonyl group, and has as a substituent an amino group, an amide group, an aldehyde group, a keto group, a carboxyl group, a mercapto group, a cyano group, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, a sulfonic acid, a phosphoric acid, an acryl group, a methacryl group, an epoxy group or a vinyl group; and m is an integer from 1 to 3.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The above and other objects, features, and advantages of the present application will become more apparent to those of ordinary skill in the art by describing in detail exemplary embodiments thereof with reference to the adhered drawings, in which:

(2) FIG. 1 is a cross-sectional view of a gas barrier film according to one embodiment of the present application.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

(3) Hereinafter, the present application will be described in detail with reference to Examples, but the scope of the present application is not limited to the following Examples.

Example 1

(4) As a base, a PET film having a thickness of 100 m (A4300, produced by Toyobo) was used.

(5) A sol-type coating composition solution prepared by diluting 50 g of tetraethoxy orthosilicate and 50 g of 3-glycidoxypropyltrimethoxysilane in 150 g of ethanol, and adding 56.4 g of water and 1.6 g of 0.1N HCl to react at room temperature for 1 day, was coated on one surface of the PET film and cured at 120 C. for 10 minutes, thereby forming an organic-inorganic hybrid coating layer having a thickness of approximately 0.6 m.

(6) An inorganic layer formed of SiOx was deposited on the organic-inorganic hybrid coating layer to have a thickness of 34 nm using a sputtering technique while a mixed gas of argon and oxygen was provided to a deposition apparatus.

(7) Separately, 10 g of 3-glycidoxypropyltrimethoxysilane and 10 g of tetraethoxy orthosilicate were diluted in 30 g of ethanol, 9.5 g of distilled water and 0.5 g of 0.1N HCl were added, and the resulting solution was hydrolyzed at room temperature for 24 hours, thereby preparing a sol-type solution (a).

(8) 10 g of MA ST produced by Nissan Chemical (silica nano particles, particle diameter: 1015 nm, solid content: 30 wt %) was diluted in 10 g of methanol, 3.1 g of 3-glycidoxypropyltrimethoxysilane which is an organic silane having excellent adhesive strength, 6.8 g of distilled water and 0.1 g of 0.1N HCl were added, and the resulting solution was stirred at 60 C. for 4 hours and then cooled at room temperature, thereby preparing a solution (b) including silica nano particles surface-modified with organic silane.

(9) 7.2 g of the solution (a) was diluted with 14.6 g of ethanol and stirred at room temperature for 30 minutes, and 8.2 g of the solution (b) was added, thereby completing a protective coating solution. The protective coating solution was coated on the inorganic layer (SiOx layer) by bar coating and cured at 120 C. for 10 minutes, thereby forming a protective coating layer (thickness: 0.6 m). As a result, a gas barrier film was manufactured.

Example 2

(10) 8 g of MA ST produced by Nissan Chemical (silica nano particles, particle diameter: 1015 nm, solid content: 30 wt %) was diluted in 8 g of methanol, 3.7 g of 3-glycidoxypropyltrimethoxysilane, 8.2 g of distilled water and 0.1 g of 0.1N HCl were added, and the resulting solution was stirred at 60 C. for 4 hours and then cooled at room temperature, thereby preparing a solution (c) including the silica nano particles surface-modified with organic silane, instead of the solution (b) of Example 1.

(11) A gas barrier film was manufactured as described in Example 1, except that 7.2 g of the solution (a) of Example 1 was diluted with 15 g of ethanol and stirred at room temperature for 30 minutes, and 7.2 g of the solution (c) was added, thereby completing a protective coating solution to be used in manufacturing a protective coating layer.

Example 3

(12) A gas barrier film was manufactured by forming a protective coating layer (thickness: 0.6 m) as described in Example 1, except that, in preparation of a solution (b), 8 g of alumina nano particles (average particle diameter: 20 nm, solid content: 30 wt %) were used instead of the silica nano particles.

Example 4

(13) A gas barrier film was manufactured by forming a protective coating layer (thickness: 0.6 m) as described in Example 1, except that, in preparation of a solution (b), 8 g of zinc oxide nano particles (average particle diameter: 30 nm, solid content: 30 wt %) were used instead of the silica nano particles.

Example 5

(14) 30 g of zinc oxide nano particles (average particle diameter: 5 nm, solid content: 10 wt %) were added to 3.1 g of 3-glycidoxypropyltrimethoxysilane, which is an organic silane for reinforcing adhesive strength, 6.8 g of distilled water and 0.1 g of 0.1N HCl, and the resulting solution was stirred at 60 C. for 4 hours and cooled at room temperature, thereby preparing a solution (d) including silica nano particles surface-modified with organic silane.

(15) A gas barrier film was manufactured as described in Example 1, except that 7.2 g of the solution (a) of Example 1 was diluted in 12 g of ethanol and stirred at room temperature for 30 minutes, and 10.8 g of the solution (d) was added, thereby completing a protective coating solution to be used in manufacturing a protective coating layer.

Example 6

(16) A gas barrier film was manufactured by forming a protective coating layer (thickness: 0.6 m) as described in Example 1, except that, in preparation of a solution (b), 8 g of antimony oxide nano particles (average particle diameter: 30 nm, solid content: 30 wt %) were used instead of the silica nano particles.

Example 7

(17) A gas barrier film was manufactured as described in Example 1, except that an inorganic layer formed of AlOx was deposited on an organic-inorganic hybrid coating layer to have a thickness of 35 nm using a sputtering technique while a mixed gas of argon and oxygen was provided to a deposition apparatus.

Comparative Example 1

When Inorganic Nano Particles Were Not Surface-Treated With Organic Silane

(18) A gas barrier film was manufactured as described in Example 1, except that a protective coating solution composed of 10 parts by weight of non-surface-treated silica nano particles (average particle diameter: 1015 nm) and 90 parts by weight of the solution (a) of Example 1 was prepared to be used in manufacturing a protective coating layer, instead of the solution (b) of Example 1.

Comparative Example 2

When a Hydrolyzing Solution Including no Silane Was Used

(19) 20 g of tetraethoxy orthosilicate was diluted in 35 g of ethanol, 11.4 g of distilled water and 0.5 g of 0.1N HCl were added, and the resulting solution was hydrolyzed at room temperature for 24 hours, thereby preparing a sol-type solution (f).

(20) 11.3 g of the solution (f) was diluted with 10.3 g of ethanol and stirred at room temperature for 30 minutes, and 8.2 g of the solution (b) of Example 1 was added, thereby preparing a protective coating solution. The protective coating solution was coated on the inorganic barrier layer (SiOx layer) of the Example 1 and cured at 120 C. for 10 minutes, thereby forming a protective coating layer (thickness: 0.6 m).

Experimental Example 1

Confirmation of Adhesive Strength

(21) Adhesive strengths of the plastic films of Examples 1 to 6 and Comparative Examples 1 to 3 were measured according to the following criteria of the cross hatch cut test.

(22) The cross hatch cut test was performed according to ASTM D 3002/D3359.

(23) A sample film was cut horizontally and vertically into 11 rows and columns at intervals of 1 mm using a knife to create a grid of 100 squares each having a size of 1 mm1 mm (width x length). A CT-24 adhesive tape produced by Nichiban was attached to a test surface and detached to measure adhesive strength between the inorganic barrier layer and the protective coating.

(24) In addition, the plastic film was left for 2, 5 and 7 days under harsh conditions (85 C./relative humidity: 85%), and then the cross hatch cut test was performed by the same method as described above.

(25) [Evaluation Criteria]

(26) : 90% or more of the grids were attached to the surface

(27) : 50 to 90% of the grids were attached to the surface

(28) X: less than 50% of the grids were attached to the surface

(29) TABLE-US-00001 Comparative Comparative Example Example Example Example Example Example Example Example Example Condition 1 2 3 4 5 6 7 1 2 RT* (5 days) HC** (2 days) HC X (5 days) HC X X (7 days) *RT: room temperature **HC: harsh conditions

(30) A gas barrier film can be used in all fields to which a conventional plastic film can be applied, for example, a display device, a photovoltaic cell, a packing material, a container, etc., by enhancing adhesive strength between an inorganic layer and a protective coating layer under harsh conditions.

(31) While the invention has been shown and described with reference to certain exemplary embodiments thereof, it will be understood by those skilled in the related art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.