POLYMER-GLASS-POLYMER GAS BARRIER LAMINATE

Abstract

The invention provides a transparent gas barrier polymer-glass-polymer laminated film comprising a first polymeric film substrate; a silicate glass layer, comprising silica and a salt of a monovalent cation other than Lithium, in combination with at least one additive selected from organo-silanes or an epoxy silane precursor, laminated onto said first polymeric film substrate; and a second polymeric film laminated on said glass layer; wherein the oxygen transmission rate through the laminated polymer-glass-polymer film is lower than 0.2 cc/m.sup.2/day and methods for the production thereof.

Claims

1. A transparent gas barrier polymer-glass-polymer laminated film comprising; a. a first polymeric film substrate; b. a silicate glass layer, comprising silica and a salt of a monovalent cation other than Lithium, in combination with at least one additive selected from organo-silanes or an epoxy silane precursor, laminated onto said first polymeric film substrate; and c. a second polymeric film laminated on said glass layer; wherein the oxygen transmission rate through the laminated polymer-glass-polymer film is lower than 0.2 cc/m.sup.2/day.

2. A transparent gas barrier polymer-glass-polymer laminated film according to claim 1, wherein the haze of the laminated polymer-glass-polymer film is lower than 1%.

3. A transparent gas barrier polymer-glass-polymer laminated film according to claim 1, wherein said silicate glass layer is formed by printing and curing at least two layers of a silicate salt ink onto said first polymeric film substrate.

4. A transparent gas barrier polymer-glass--polymer laminated film according to claim 1 wherein said monovalent cation is selected from the group consisting of sodium, potassium, ammonium and any of a combinations thereof.

5. A transparent gas barrier polymer-glass-polymer laminated film according to claim 1, further comprising inorganic phosphate salts selected from monopotassium phosphate, monosodium phosphate, monoammonium phosphate, dipotassium phosphate, disodium phosphate, tripotassium phosphate, trisodium phosphate, Sodium Hexametaphosphate, sodium tripolyphosphate, ammonium tripolyphosphate, potassium tripolyphosphate, Sodium Pyrophosphate, Tricalcium Phosphate and combinations thereof.

6. The laminated film according to claim 1, wherein the transparency of the polymer-glass-polymer laminated film is higher than 60% in the visible spectral region of 390-700 nm.

7. The laminated film according to claim 1 wherein said salt of monovalent cation is selected from the group of carbonate, acetate, fumarate salts or any of a combination thereof.

8. The laminated film according to claim 1, wherein the second polymeric film comprises at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, polyolefins, polyurethanes, polyacrylics, polyamides, epoxides, silicons, polysulfides, chlorinated rubbers, phenolics, polyvinyls and copolymers thereof.

9. A method for producing a polymer-glass-polymer laminated gas barrier film comprising; printing and drying at least 2 layers of a glass ink formulation comprising a silicate salt comprising a monovalent cation other than Lithium, onto a first polymeric film substrate; curing said printed glass layers on the first polymeric film substrate to form a silicate glass coating on said first polymeric film substrate; and laminating the cured glass coated polymeric substrate with a second polymeric film to form said polymer-glass-polymer laminated gas barrier film; wherein the oxygen transmission rates through the polymer-glass-polymer laminated film is lower than 0.2 cc/m.sup.2/day.

10. The method according to claim 9, wherein the glass layer is directly printed.

11. The method according to claim 9 wherein said printing method is selected from screen printing, roller coating, spray coating, curtain coating, dip coating, gravure, inkjet printing or flexographic printing and combinations thereof.

12. The method according to claim 9, wherein the glass layer has a thickness of less than 30 micrometers.

13. The method according to claim 9, wherein the first polymeric film comprises at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, polyolefins, polyurethanes, polyacrylics, polyamides, epoxides, silicons, polysulfides, chlorinated rubbers, phenolics, polyvinyls and copolymers thereof.

14. The method according to claim 9, wherein the laminate is fabricated by depositing an adhesive resin layer on at least one of the glass layer and the second polymer film.

15. The method according to claim 9, wherein the second polymeric film comprises at least one thermoplastic polymer selected from polyesters, polyearbonates, polyarylates, polyolefins, polyurethanes, polyacrylics, polyamides, epoxides, silicons, polysulfides, chlorinated rubbers, phenolics, polyvinyls and copolymers thereof.

16. The method according to claim 9, wherein the adhesive is based on polyethylene, polyurethane, acrylic, methacrylic, epoxy, vinyl butyral (PVB), a ethylene vinyl acetate (EVA) or ethylene vinyl hydroxide (EVOH).

17. A glass ink used for preparing the laminated film of claims 9-16, wherein said silicate salt is selected from the group consisting of sodium silicate, potassium silicate, ammonium silicate and combinations thereof.

18. A glass ink according to claim 17, wherein the glass ink further comprises at least one additive selected from an inorganic phosphate salt, organo-silanes, epoxy silane precursor and combinations thereof.

19. A glass ink according to claim 17 wherein said organo silane or epoxy silane additive is thermally hydrolyzed prior or after being added to the ink formulation.

20. A glass ink according to claim 17 comprising at least 20% silicate salt by weight, wherein the surface tension of the ink is lower than 40 dynes/cm.

21. A glass ink according to claim 17 used for preparing the laminate of claim 1 further comprising inorganic phosphate salts selected from monopotassium phosphate, monosodium phosphate, monoammonium phosphate, dipotassium phosphate, disodium phosphate, tripotassium phosphate, trisodium phosphate, Sodium Hexametaphosphate, sodium tripolyphosphate, ammonium tripolyphosphate, potassium tripolyphosphate, Sodium Pyrophosphate, Tricalcium Phosphate and combinations thereof.

22. A glass ink according to claim 17, whereas the turbidity of the ink is lower than 0.2 at 600 nm (1 cm optical path).

Description

DETAILED DESCRIPTION OF EXAMPLES

[0074] Reference is now made to the following examples, which together with the above description illustrate the invention in a non-limiting fashion.

MATERIALS USED IN EXAMPLES

[0075] The following materials are used in exemplary formulations described in examples herein below: 36 micron (SH37), 45 micron (SP 18A), 50 micron (SG55C), 75 micron P.P.C. PET film and 100 microns P.P.C. PET films were supplied by SKC (Skyrol brand, SKC co. Ltd., Korea) and Jolybar ltd. (Israel). Silica sol was supplied as 30% colloidal dispersion in water, available from Alfa Aesar; SNOWTEX® ST-40 is colloidal silica particle dispersions available from Nissan Chemical, America Corporation, Houston, Tex. USA; PVA refers to Mowiol® 4-98 Mw˜27,000 available from Sigma Aldrich; epoxy silane refers to Z-6040 Silane Glycidoxypropyltrimethoxysilane available from Dow corning; Sodium phosphate is available from Sigma Aldrich ; PEI refers to Polyethylene imine, which is available from Bio lab Ltd, Israel; Ethylene glycol is available from Bio lab Ltd, Israel; hexadecyltrimethylammonium bromide; glycerol are both available from Sigma Aldrich; Potassium Silicate and Sodium silicate are available from Provetro gruppe,

[0076] Schlofβ Holte, Germany.

Comparative Example 1

[0077] A 75 micron PET film was laminated by POUCH LAMINATOR PDA3-330L using PE film (80 micron thick) at 150° C. Its OTR was 13.6 cc/m.sup.2/day.

Example 2

[0078] An ink formulation was prepared according to the following procedure; 10% epoxy silane was added to 90% sodium silicate (40% solid), it was applied on a PET film by an applicator bar at 24 micron wet thickness (Wire-wound Rod, BYK-Gardner, Germany). A continuous film was formed upon curing at 90° C. in a convection furnace. After 5 minutes in room temperature a second layer was applied and a 3.sup.rd layer as well. The resulting film was laminated by POUCH LAMINATOR PDA3-330L with PE film (80 micron thick) at 150° C. Its OTR was 0.038 cc/m.sup.2/day.

Example 3

[0079] An ink formulation was prepared according to the following procedure and with the following components; 4.1% epoxy silane, 32.7% sodium silicate, 2.0% Na5P3O10 and the remaining water. The ink was applied on a PET film by an applicator bar at 24 micron wet thickness (Wire-wound Rod, BYK-Gardner, Germany). A continuous film was formed upon curing at 90° C. in a convection furnace. After 5 minutes in room temperature a second layer was applied and a 3.sup.rd layer as well. The resulting film was laminated by POUCH LAMINATOR PDA3-330L with PE film (80 micron thick) at 150° C. Its OTR was 0.001 cc/m.sup.2/day.

Example 4

[0080] An ink formulation was prepared according to the following procedure and with the following components: 1.9% glucose, 32.8% sodium silicate, 4.1% epoxy silane and the remain water, The composition was applied on a PET sheet, at 24 micron wet thickness by an applicator bar (Wire-wound Rod, BYK-Gardner, Germany) in 3 layers. Each layer was cured at 90° C. in a convection furnace forming a continuous film. The resulting film was laminated by POUCH LAMINATOR PDA3-330L with PE film (80 micron thick) at 150° C. OTR=0.06 cc/m.sup.2/day.

Example 5-8

[0081] Ink formulations were prepared using various compositions (as listed in table 1) of sodium silicate and epoxy silane. compositions were applied on PET film by an applicator bar, 24 micron wet thickness (Wire-wound Rod, BYK-Gardner, Germany) in 3 layers. A continuous film was formed upon curing at 90° C. in a convection furnace. The resulting film was laminated by POUCH LAMINATOR PDA3-330L with PE film (80 micron thick) at 150° C.

TABLE-US-00001 TABLE 1 Examples 5-8 Sodium silicate, Epoxy silane, wt % wt % H.sub.2O OTR Example 5 39.6 0.5 59.9 0.039 Example 6 37.9 2.6 59.5 0.014 Example 7 36.4 4.5 59.1 0.13 Example 8 32 10 58 0.06

Example 9-11

[0082] An ink formulation was prepared using various compositions (as listed in table 2) of sodium silicate, epoxy silane and sodium triphosphate, compositions were applied on PET film by an applicator bar, 24 micron wet thickness (Wire-wound Rod, BYK-Gardner, Germany) in 3 layers. A continuous film was formed upon curing at 90° C. in a convection furnace. The resulting film was laminated by POUCH LAMINATOR PDA3-330L with PE film (80 micron thick) at 150° C.

TABLE-US-00002 TABLE 2 Examples 9-11 Sodium Epoxy silicate, silane, sodium wt % wt % H.sub.2O triphosphate OTR Example 9 34.5 4.3 60.1 1.0 0.285 Example 10 29.1 3.6 63.3 4.0 0.06 Example 11 32.7 4.1 61.2 2.0 0.001

Example 12-16

[0083] An ink formulation was prepared using compositions of sodium silicate, epoxy silane and sodium triphosphate. The mol ratio of the sodium silicate achieved by mixing different liquid glass with 3.2 and 1.6 mol ratio. compositions were applied on PET film by an applicator bar, 24 micron wet thickness (Wire-wound Rod, BYK-Gardner, Germany) in 3 layers. A continuous film was formed upon curing at 90° C. in a convection furnace. The resulting film was laminated by POUCH LAMINATOR PDA3-330L with PE film (80 micron thick) at 150° C.

TABLE-US-00003 TABLE 3 Examples 12-16 Sodium Epoxy silicate, silane, Mol wt % wt % H.sub.2O ratio OTR Example 12 40 4.5 55.5 1.6 0.039 Example 13 37 4.5 58.4 2.4 0.16 Example 14 35.6 4.5 59.9 2.8 0.061 Example 15 33.6 4.5 61.8 3.2 0.1

Example 16

[0084] An ink formulation was prepared using the compositions listed in table 4 of sodium silicate, epoxy silane and sodium triphosphate. Ink was applied on a PET film by an applicator bar, 24 micron wet thickness (Wire-wound Rod, BYK-Gardner, Germany) in 3 layers. A continuous film was formed upon curing at 90° C. in a convection furnace. The resulting film was laminated by POUCH LAMINATOR PDA3-330L with PE film (80 micron thick) at 150° C.

TABLE-US-00004 TABLE 4 Example 16 Sodium, Potassium Epoxy silicate, silicate, silane, wt % wt % H.sub.2O wt % OTR Example 16 27.9 20.3 46.8 5 0.029

[0085] It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is therefore desired that the present embodiments and examples be considered in all respects as illustrative and not restrictive, reference being made to the appended claims, rather than to the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.