JPH0499165A - Transparent high barrier film - Google Patents

Abstract

PURPOSE:To improve the moisture-proof property, flexibility and printability of a transparent high barrier film based on a fluororesin film by laminating a thin film of a surface activating metal oxide on the high barrier film. CONSTITUTION:A layer of a metal oxide such as Al oxide (AlxOy) or Si oxide (SixOy) is formed in 200-1,000Angstrom thickness on at least one side of a transparent high barrier film of 12-25mum thickness based on a fluororesin film to activate the surface or to improve the moisture-proof property. The resulting film is made suitable for use as a material for sealing an electroluminescent substance which undergoes a remarkable change in the performance by the penetration of steam, a protective film for a solar cell and a moisture-proof film for packing food, pharmaceuticals, etc.

Description

[Detailed description of the invention] 【Technical field】

The present invention relates to a high-barrier transparent film with excellent transparency and gas barrier properties. More specifically, high-barrier materials are preferably applied to electroluminescent sealing materials whose performance changes significantly when water vapor permeates, protective films for solar cells, protective films for display displays, and moisture-proof packaging films for foods, beverages, and medical products. The present invention relates to a transparent film.

[Conventional technology]

The use of fluororesin films (e.g. trifluorochloroethylene) as a base material for high-barrier transparent films has been reported in Japanese Patent Application Laid-Open No. 2-141235 and Japanese Utility Model Publication No. 52
-454:18, is well known. However, in order to obtain a high degree of moisture resistance, the thickness of the fluororesin film itself was required to be 50 to 250 μs. Furthermore, since fluororesin films have low surface energy and are inert, adhesives, inks, etc. do not adhere to them, and they cannot be used as they are for applications that require printing or adhesion. On the other hand, in flexible amorphous silicon solar cells or thin-film electroluminescent displays using polymer films or sheets, it is necessary to seal the entire structure from the viewpoint of durability. In addition, it is necessary to completely seal the moisture-proof packaging for foods, drinks, medical products, etc., and a high-barrier transparent film with sufficient flexibility and adhesiveness is long-awaited, but there is still no satisfactory film. There wasn't.

[Purpose of the invention]

The present invention provides a high-barrier transparent film based on a fluororesin film, in which a metal oxide thin film is provided on at least one side of the film to activate the surface and to impart outstanding moisture resistance to the fluororesin film. Aluminum oxide is used to activate the surface of a high-barrier transparent film based on a fluororesin film or to activate the surface on at least one side of the fluororesin film, and to impart outstanding moisture resistance to the fluororesin film. (Al, 0.), the effect of activating the surface on at least one side of a high barrier transparent film based on a fluororesin film or by laminating a thin film of a metal oxide higher than silicon oxide. and silicon oxide (SiOy) to give the fluororesin film even more outstanding moisture resistance.The fluororesin film itself has a thickness of 12~25mm. In addition, the surface of the fluororesin film is modified with metal oxide to activate the surface and improve the adhesion of adhesives and inks, making it suitable for printing and contact. By making it possible to apply it to necessary applications, it can be used to seal flexible amorphous silicon solar cells using polymer films and sheets, thin-film electroluminescent displays, etc., as well as food and beverages and medical products. An object of the present invention is to provide a high-barrier transparent film that has sufficient flexibility, printability, and adhesiveness and can be used to seal moisture-proof packaging.

[Structure of the invention]

(1) In a high-barrier transparent film based on a fluororesin film, metal oxidation is performed on at least one side of the film to activate the surface and to impart outstanding moisture resistance to the fluororesin film. (2) In a high-barrier transparent film based on a fluororesin film, the effect of activating the surface on at least one side of the fluororesin film and further outstanding moisture resistance are imparted to the fluororesin film. (3) By laminating thin films of one or more metal oxides selected from the group consisting of aluminum oxide (AlOy) and silicon oxide (Sixty) to In a high-barrier transparent film based on a fluororesin film, silicon oxide (S
This is a high-barrier transparent film characterized by laminating thin films of metal oxides having a thickness of 200 to 200 mm. That is, the present invention provides a high-barrier transparent film based on a fluororesin film, which has a metal oxide thin film on at least one side of the film for activating the surface and for imparting outstanding moisture resistance to the fluororesin film. In high-barrier transparent films based on fluororesin films,
One type selected from the group consisting of aluminum oxide (A1.Oy) and silicon oxide (SixOv) for activating the surface on at least one side and imparting excellent moisture resistance to the fluororesin film. Or, by laminating thin films of two or more metal oxides, or in a high-barrier transparent film based on a fluororesin film, the effect of activating the surface on at least one side and the effect of activating the surface and the fluororesin film are even more outstanding. The fluororesin film itself has a thickness of 12 to 25 mm, which provides sufficient moisture resistance. In addition, the surface of fluororesin film can be modified with metal oxides to activate the surface and improve adhesion of adhesives, inks, etc., and can be applied to applications such as printing and adhesion. What I tried to do was
It has sufficient adhesive capacity to seal flexible amorphous silicon solar cells using polymer films and sheets, thin-film electroluminescent displays, and moisture-proof packaging for foods, drinks, and medical products. flexibility, printability,
This makes it possible to provide a high-barrier transparent film with adhesive properties. Examples of the fluororesin film constituting the base material of the high-barrier transparent film of the present invention include homopolymers such as tetrafluoroethylene resin, trifluorochloroethylene resin, polyvinylidene fluorolite, and polyvinyl fluoride; A film made of a copolymer such as ethylene-perfluorovinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, or tetrafluoroethylene-ethylene copolymer may be used as appropriate. Is there any particular limit to the thickness? The thickness of the resin film is 12 to 25 mm.
It is preferable to use a film on the order of microseconds or from the viewpoint of continuous mass production of a high-barrier transparent film without wrinkles or cracks. Further, the fluororesin film may be -axially stretched or biaxially stretched, and from the viewpoint of gloss, strength, etc., biaxially stretched is preferably used. Further, the surface of the fluororesin film may be subjected to surface treatment such as corona discharge treatment or low temperature plasma treatment. Furthermore, the fluororesin film may have an undercoat layer provided on its surface if necessary, and resins for forming the undercoat layer include, for example, thermoplastic resins, thermosetting resins, Either electron beam curable resin or ultraviolet ray curable resin can be used, such as acrylic resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polycarbonate, nitrocellulose, cellulose acetate, urethane resin, urea resin, Preferably used are melamine resins, urea-melamine resins, epoxy resins, alkyd resins, aminoalkyd resins, rosin-modified maleic acid resins, etc. alone or in mixtures, and silane coupling agents. To form the undercoat layer, an organic solvent solution or aqueous solution of the resin or a coupling agent for forming the undercoat layer is applied using a conventional method such as a roll coating method, a gravure coach ink method, a reverse coating method, a spray coach ink method, etc. This is done by applying the coating using the coating method described above and drying (curing in the case of thermosetting resin, electron beam curable resin, ultraviolet ray curable resin, etc.). The undercoat layer may be colored with a coloring agent such as a general-purpose dye or pigment. A colorant such as a dye or a pigment is appropriately selected from a range of about 3 to 30% based on the resin for forming the undercoat layer. Silicon oxide or aluminum oxide is used as the evaporation raw material for forming the transparent metal oxide thin film in the high-barrier transparent film of the present invention. It is formed by vapor deposition using a vacuum evaporation method. In the present invention, there is no particular limit to the thickness of the transparent metal oxide thin film, or it may be selected and determined as appropriate depending on the product's use and desired performance, or it may be normally determined in consideration of transparency and adhesion. is selected from a range of about 200 to 1000 people, preferably from about 300 to 800 people. In addition to the metal oxides mentioned above, the evaporation raw materials for forming the metal oxide vapor deposition film in the high-barrier transparent film of the present invention include -silicon oxide alone, for example, when forming a thin film of silicon oxide; For example, a mixture consisting of approximately equimolar % silicon and silicon dioxide, or a mixture consisting of approximately equimolar % silicon and silicon dioxide, and 1 mol% or more and less than 30 mol% silicon monoxide, for example, It is formed by vapor deposition using a known vacuum deposition method such as a beam heating method or a high frequency heating method. The high-barrier transparent film of the present invention can also be used for the purpose of obtaining an excellent transparent film with better moisture permeability and low oxygen permeability, or by combining two or more high-barrier transparent films of the present invention with each other according to the purpose. It can also be bonded to a base material using an adhesive. There are no particular restrictions on the adhesive and bonding method in this case, and ordinary lamination methods and adhesives can be used. As the adhesion method, for example, an extrusion lamination method, a dry lamination method, a solvent-free lamination method, etc. are used as appropriate. Examples of adhesives include acrylic-vinyl chloride-vinyl acetate, acrylic,
Ethylene-vinyl acetate system, epoxy system, styrene-tutadiene system, phthalic acid ponaryester system, polyester-isocyanate system, polyethylene system, vinyl chloride-vinyl acetate system, vinyl chloride system, vinyl acetate system, chlorinated polypropylene system, polyurethane system, etc. These adhesives can be used alone or in an appropriate blend. The thickness of the adhesive layer is usually selected from a range of 1-10M, preferably from a range of 2-5M. Adhesive layer thickness: 113
If it is less than that, sufficient adhesive strength cannot be obtained, which is not preferable. On the other hand, even if it exceeds 10 μs, no change is observed to the extent that it contributes to the adhesive strength. In addition, in addition to a protective coating film, a protective film, a heat seal layer, etc., a printing layer such as a character design may be provided on the plastic film surface and the metal oxide vapor deposited film surface by a conventional method, expanding the application. Something comes up. Next, the present invention will be explained with reference to Examples.

[Examples and comparative examples]

Example 1 50% silicon monoxide was applied to one side of a 12 μs thick trifluorochloroethylene film under a vacuum of 5×10-'Torr.
A silicon oxide thin film was formed by vacuum evaporation to a thickness of 0.0 mm to obtain a high barrier transparent film of the present invention. The moisture permeability and oxygen permeability of the obtained high-barrier transparent film were 0.5 g/2.24 Hrs and 0.5 cc/2.24 Hrs, respectively, and the following values were stably obtained. Example 2 Thickness: 5 on one side of a 2-layer trifluorochloroethylene film
500% silicon monoxide under a vacuum of 10-' Torr
A high-barrier transparent film of the present invention was obtained by forming a thin film of silicon oxide by vacuum deposition to a thickness of about 100 yen. Polyester polyol resin (manufactured by Dainippon Ink & Chemicals Co., Ltd., LX-901, solid content 50%) was applied on the silicon oxide thin film.
90 parts (by weight, the same applies hereinafter) and 10 parts of a polyisocyanate curing agent (manufactured by Dainippon Ink & Chemicals Co., Ltd., KG-75, solid content 75%) were mixed into ethyl acetate:toluene=1:
A two-ply type high barrier transparent film of the present invention was prepared by applying an adhesive diluted in 100 parts of IR mixing solution to a solid content thickness of 2 Ja and laminating it with a 60-thick polyethylene film. When we made a product and forcibly peeled it into two films, we found that the polyethylene film was torn and it was impossible to peel it off. The contents of the product packaged using this film could be confirmed without opening the package, and the product had the ability to sufficiently maintain its quality. Example 3 5 on one side of a 12-thick trifluorochloroethylene film
X, 50% of silicon monoxide under a vacuum of 10-' Torr
A silicon oxide thin film was formed by vacuum evaporation to a thickness of 0.0 mm to obtain a high barrier transparent film of the present invention. Polyester polyol resin (manufactured by Dainippon Ink & Chemicals Co., Ltd., L
X-, 901, solid content 50%) and a polyisocyanate curing agent (manufactured by Dainippon Ink & Chemicals Co., Ltd., KG-
75, solid content 75%) 10 parts ethyl acetate, toluene =
1.1 A polyethylene terephthalate film with a thickness of 60 mm was bonded by applying an adhesive diluted in 100 parts of a mixed solution to a solid content thickness of 2 ta (A
film) was made. On the other hand, silicon monoxide was vacuum-deposited to a thickness of 500 mm on one side of a 12 μs thick trifluorochloroethylene film under a vacuum of 5 x 1 G-'Torr to form a silicon oxide thin film. A high barrier transparent film was obtained. Next, 90 parts of polyester polyol resin (manufactured by Dainippon Ink & Chemicals Co., Ltd., LX-901, solid content 50%) and a polyisocyanate curing agent (Dainippon Ink & Chemicals Co., Ltd.) were placed on the other side of the trifluorochloroethylene film. Manufactured by K
G-75, solid content 75%) diluted in 100 parts of ethyl acetate toluene = 11 mixed solution, the adhesive was applied to a solid content thickness of 2 μs to a thickness of 60. A film (B film) was made by laminating the following polyethylene films together. After that, film A and film B are coated with polyester resin (
100 parts of Atcoat 810-A (manufactured by Toyo Morton Co., Ltd., solid content 50%) and a polyisocyanate curing agent (manufactured by Toyo Morton Co., Ltd., Atcoat 810-B, solid content 7)
5%) diluted in 50 parts of ethyl acetate solvent to a solid content thickness of 21%. When we made a 4-ply type film and forcibly peeled it into two films, the polyethylene terephthalate film was torn and it was impossible to peel it off. The contents of the product packaged using this film could be confirmed without opening the package, and the product had the ability to sufficiently maintain its quality. Example 4 5 on one side of a 12-thick trifluorochloroethylene film
500% silicon monoxide under a vacuum of X 1O-5 Torr
A high-barrier transparent film of the present invention was obtained by forming a thin film of silicon oxide by vacuum deposition to a thickness of about 100 yen. Then, on the other side of the trifluorochloroethylene film, 100 parts of a polyester resin (Atocoat 810-A, manufactured by Toyo Morton Co., Ltd., solid content 50%) and a polyisocyanate curing agent (Atcoat 810-B, manufactured by Toyo Morton Co., Ltd., An adhesive prepared by diluting 10 parts (solid content 75%) in 50 parts ethyl acetate solvent was applied to a solid content thickness of 2-2, and a polyethylene terephthalate film with a thickness of 60 mm was laminated (A film). I made two. A 601-thick polypropylene film was placed on the surface of one polyethylene terephthalate film of the A film and cured with 90 parts of polyester polyol resin (LX-901, manufactured by Dainippon Ink & Chemicals Co., Ltd., solid content 50%) and polyisocyanate. Adhesive (manufactured by Dainippon Ink & Chemicals Co., Ltd., KG-75, solid content 75%): 10 parts of ethyl acetate, toluene = 1; 1. Apply the adhesive diluted in 100 parts of a mixed solution to a solid content thickness of 21. Formed and laminated with a 60 μs thick polypropylene film (
B film) was made. After that, film A and film B are coated with polyester resin (
100 parts of Atcoat 810-A (manufactured by Toyo Morton Co., Ltd., solid content 50%) and a polyisocyanate curing agent (manufactured by Toyo Senton Co., Ltd., Atcoat 810-B, solid content 7)
5%) diluted in 50 parts of ethyl acetate solvent and bonded through an adhesive layer formed by applying an adhesive to a solid content thickness of 2 μs to form a high-barrier transparent film of the present invention. When I made a 4-ply type and forcibly peeled it into two films, I found that the polyethylene terephthalate film was torn and it was impossible to peel it off. The contents of the product packaged using this film could be checked without opening the package, and it had the ability to sufficiently maintain quality. Comparative Example 1 A silicon oxide thin film was not formed on one side of a trifluorochloroethylene film having a thickness of 121 cm. Comparative Example 2 Polyester polyol resin (Dainippon Ink & Chemicals Co., Ltd. Manufactured by LX-9
01, solid content 50%) and 90 parts of a polyisocyanate curing agent (manufactured by Dainippon Ink & Chemicals Co., Ltd., KG-75, solid content 75%) were diluted into 10 parts of an ethyl acetate toluene = ll mixed solution. A 2-ply transparent film was made by applying adhesive to a solid content of 2 μs and laminating a 60 μs thick polyethylene film, and then forcefully peeling this into two films.
Moreover, it was possible to easily peel off the layered ethylene film from the fluororesin film base material to the layered ethylene film, which greatly improved the adhesion strength between the polyethylene film and each layer provided on the trifluoride salt. You can do good.

[Patent applicant] Oike Kogyo Co., Ltd. ■ Moisture permeability: JIS Z-0280 cup method Oxygen permeability: JIS K-7126B method (equivalent notes) Peel strength: JIS K-68547 type peeling * indicates film or breakage cannot be measured

【Effect of the invention】

Claims (1)

[Scope of Claims] 1. In a high-barrier transparent film based on a fluororesin film, metal oxidation is applied to at least one side of the film to activate the surface and to impart outstanding moisture resistance to the fluororesin film. A high-barrier transparent film characterized by laminating thin films. 2 The metal oxide is aluminum oxide (Al_x
2. The high-barrier transparent film according to claim 1, wherein the film comprises one or more metal oxides selected from the group consisting of O_y), silicon oxide (Si_xO_y). 3. The high barrier transparent film according to claim 1, wherein the metal oxide thin film is made of silicon oxide and has a thickness of 200 to 1000 Å.