WO2015033850A1

WO2015033850A1 - Gas barrier film laminate and electronic component using same

Info

Publication number: WO2015033850A1
Application number: PCT/JP2014/072573
Authority: WO
Inventors: 正志橋本; 敦子藤田; 國信　隆史
Original assignee: Jnc株式会社
Priority date: 2013-09-03
Filing date: 2014-08-28
Publication date: 2015-03-12
Also published as: TW201511944A; JP2015047823A; JP6409258B2

Abstract

The present invention is capable of relaxing residual stress and reducing curling, while maintaining flexibility during the formation of a gas barrier film by a plasma CVD method, and enables achievement of a gas barrier film laminate that has sufficient gas barrier properties. A gas barrier film laminate according to the present invention is provided with: a resin film (11) that serves as a base; and at least one organic film layer (12) and at least one gas barrier film layer (13), that are arranged on at least one surface of the resin film (11). The gas barrier film layer (13) is a film which is formed by a plasma CVD method and which is mainly composed of a metal oxide, while containing an organic component.

Description

Gas barrier film laminate and electronic component using the same

The present invention relates to a gas barrier film laminate. In particular, the present invention relates to a gas barrier film laminate that can effectively suppress water vapor permeation to electronic components.

Conventionally, glass having a high barrier property has been used for substrates in organic electroluminescent elements (hereinafter also referred to as OLED elements), organic solar cell elements (hereinafter also referred to as OPV elements), liquid crystal elements, and the like. However, the glass substrate has the disadvantages that it is heavy, easily broken, and difficult to increase in area. Instead of such a glass substrate, a gas barrier film laminate in which a resin composition film in which an inorganic filler is mixed / dispersed on a plastic film or a metal oxide thin film is formed may be used as the substrate. As a method for forming a thin film such as a metal oxide on the surface of a plastic film, plasma chemical vapor deposition (CVD) is particularly known. However, the plasma CVD method has a problem of a rapid compressive stress generated during the formation of the gas barrier film and the occurrence of curling due to this.

As a technique for suppressing the occurrence of curling, Japanese Patent Application Laid-Open No. 2011-121347 (Patent Document 1) discloses that a gas barrier layer is an adhesive layer for a first film and a second film in which a gas barrier layer is formed on one surface of a substrate. Alternatively, a gas barrier film laminate having one or more units of a laminated structure formed by bonding with an adhesive layer made of an ultraviolet curable resin is disclosed. The technique of this document is a laminated structure in which a first film and a second film are symmetrically bonded to balance stress. However, there was a problem that the gas barrier film laminate would inevitably become thick.

JP 2011-121347 A

The present invention has been made in view of the above-described problems of the prior art. In the formation of a gas barrier film by a plasma CVD method using an organometallic compound as a raw material, the residual stress is relaxed while maintaining flexibility and curling is performed. An object of the present invention is to provide a gas barrier film laminate having a sufficient gas barrier property while being reduced.

As a result of intensive research to solve the above-mentioned problems, the inventors of the present invention formed a gas barrier film laminate having low curl and high gas barrier properties by combining a resin film, an organic film layer, and a gas barrier film layer. The present inventors have found that this can be done and have completed the present invention.

The gas barrier film laminate according to the first aspect of the present invention includes, for example, as shown in FIG. 1, a resin film 11 as a substrate; at least one organic film layer 12 and at least one on at least one surface of the resin film 11. Two gas barrier film layers 13 are provided; the gas barrier film layer 13 is a film formed by a plasma CVD method and containing an organic component mainly composed of a metal oxide.
The “main component” means that the composition constituting the gas barrier film layer contains 50% by weight or more of a portion corresponding to a metal oxide.

If comprised in this way, the unevenness | corrugation of the surface below an organic film layer can be planarized by providing an organic film layer. Further, the organic film layer can suppress the curling of the gas barrier film laminate due to the residual stress generated in the film formation process of the gas barrier film layer.
Since the gas barrier film layer is formed by a plasma CVD method, a dense and flexible film can be formed. Therefore, defects and peeling are hardly caused and high barrier properties can be imparted.

The gas barrier film laminate according to the second aspect of the present invention is obtained by photopolymerizing the photocurable resin composition in the gas barrier film laminate according to the first aspect of the present invention. Film.

If constituted in this way, since the photocurable resin composition is used, the production is easy and the production efficiency can be increased.

The gas barrier film laminate according to the third aspect of the present invention is the gas barrier film laminate according to the second aspect of the present invention, wherein the photocurable resin composition includes an acrylic resin.

With this configuration, an organic film layer having excellent transparency can be formed. Furthermore, an acrylic resin having photocurability is preferable because it has excellent curl prevention properties due to its hardness.

The gas barrier film laminate according to the fourth aspect of the present invention is the gas barrier film laminate according to any one of the first to third aspects of the present invention, wherein the organic film layer is a coating method. Are stacked.

With such a configuration, the organic film layer can be uniformly coated, and excellent smoothness can be obtained.

The gas barrier film laminate according to the fifth aspect of the present invention is the gas barrier film laminate according to any one of the first to fourth aspects of the present invention, wherein the plasma CVD method comprises a roll, Performed on a two-roll basis.

With this configuration, by combining the plasma CVD method and the roll-to-roll method, productivity can be improved and quality stability can be obtained.

The gas barrier film laminate according to the sixth aspect of the present invention is the gas barrier film laminate according to any one of the first to fifth aspects of the present invention, wherein the thickness of the organic film layer is: 1 to 20 μm.

With this configuration, when the thickness is 1 μm or more, sufficient smoothness can be ensured and curling can be suppressed. Moreover, by setting it as 20 micrometers or less, while being easy to prevent the crack by bending, it becomes easy to adjust the balance of the optical characteristic of a gas barrier film laminated body.

The gas barrier film laminate according to the seventh aspect of the present invention is the gas barrier film laminate according to any one of the first to sixth aspects of the present invention, wherein the thickness of the gas barrier film layer is: 0.2-2 μm.

With this configuration, by setting the thickness to 0.2 μm or more, the film thickness uniformity is improved and the gas barrier performance is improved. Moreover, generation | occurrence | production of the crack by bending can be suppressed by setting it as 2 micrometers or less.

The gas barrier film laminate according to the eighth aspect of the present invention is the gas barrier film laminate according to any one of the first to seventh aspects of the present invention, wherein the gas barrier film layer is the resin. Provide only on one side of the film.

With such a configuration, even if the gas barrier film layer is a gas barrier film laminate provided only on one side of the resin film, the gas barrier film layer has a sufficiently high barrier property and can be made thinner.

The gas barrier film laminate according to the ninth aspect of the present invention is the gas barrier film laminate according to any one of the first to eighth aspects of the present invention, wherein the resin film and the organic film are provided. And a curl height of 15 mm or less.

If constituted in this way, even if it is a gas barrier film laminate comprising three layers, the curl height is 15 mm or less, so that the gas barrier film laminate can exhibit good processability. In addition, since cracks and film peeling due to curling are suppressed, good gas barrier properties can be maintained.

The gas barrier film laminate according to the tenth aspect of the present invention is the gas barrier film laminate according to any one of the first to ninth aspects of the present invention, wherein the organic film layer is the resin film. And the gas barrier film layer.

With this configuration, the organic film layer can flatten the irregularities on the surface of the substrate.

The gas barrier film laminate according to the eleventh aspect of the present invention is the gas barrier film laminate according to any one of the first to tenth aspects of the present invention, wherein water vapor at 40 ° C. and 90% RH is used. The transmittance is 0.005 g / m ² / d or less.

If constituted in this way, it can be sufficiently utilized as a gas barrier film used for an electronic element such as an OLED element or an OPV element.

A gas barrier film laminate according to a twelfth aspect of the present invention is the gas barrier film laminate according to any one of the first to eleventh aspects of the present invention, wherein the resin film is a polyethylene phthalate. , Polyethylene naphthalate, cycloolefin polymer, polycarbonate, polyimide, or a mixture of these as a main component.

With this configuration, a resin film can be formed from a resin that is easily available, and a resin suitable for the application, such as being transparent, can be selected as appropriate.

An electronic component according to a thirteenth aspect of the present invention is, for example, as shown in FIG. 2B, an electronic element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes; And the gas barrier film laminate 10 according to any one of the first to twelfth aspects of the present invention.

If comprised in this way, since a gas barrier film laminated body is excellent in gas-barrier property, it can control that water vapor | steam and oxygen osmose | permeate the inside of an electronic device, the component which comprises an electronic device deteriorates, and a performance falls. it can.

An electronic component according to a fourteenth aspect of the present invention is the electronic component according to the thirteenth aspect of the present invention, wherein the gas barrier film laminate is transparent and the element is an OLED element or an OPV element.

When configured in this manner, when used in an OLED element, light emission from the element is not hindered, and the light emission efficiency is not deteriorated. Moreover, when it uses for a photoelectric element like an OPV element, it can comprise so that sunlight reception may be performed from the gas barrier film laminated body side.

According to the present invention, it is possible to provide a gas barrier film laminate having a sufficient gas barrier property while reducing the curl by relaxing the residual stress of the gas barrier film layer formed by the plasma CVD method. Furthermore, the gas barrier film laminate can be used to protect electronic elements such as OLED elements and OPV elements from intrusion of water vapor.

It is a figure which shows one Example of the gas barrier film laminated body of this invention. FIG. 2A is a cross-sectional view of an electronic component having an OLED element in a solid sealing method. FIG.2 (b) is sectional drawing of the electronic component using the gas barrier film laminated body of this invention as an alternative. It is sectional drawing of the other electronic component using the gas barrier film laminated body of this invention. FIG. 4A is a cross-sectional view of an electronic component having an OLED element with a conventional hollow structure. FIG.4 (b) is sectional drawing of the electronic component using the gas barrier film laminated body of this invention as an alternative. It is the schematic of a roll-to-roll system.

This application is based on Japanese Patent Application No. 2013-182610 filed on September 3, 2013 in Japan, the contents of which form part of the present application. The present invention will be more fully understood from the following detailed description. Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, the detailed description and specific examples are preferred embodiments of the present invention and are described for illustrative purposes only. From this detailed description, various changes and modifications will be apparent to those skilled in the art within the spirit and scope of the invention. The applicant does not intend to contribute any of the described embodiments to the public, and modifications and alternatives that may not be included in the scope of the claims within the scope of the claims are also subject to equivalence. As part of the invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same or similar reference numerals, and redundant description is omitted. Further, the present invention is not limited to the following embodiments.

1. Gas barrier film laminate The gas barrier film laminate according to the first embodiment of the present invention includes a resin film as a base material, and at least one organic film layer and at least one gas barrier film layer on at least one surface of the resin film. Prepare. Particularly preferably, for example, as shown in FIG. 1, the gas barrier film laminate 10 has an organic film layer 12 directly on the resin film 11, and further has a gas barrier film layer 13 directly on the organic film layer 12.
The gas barrier film layer is formed by a plasma CVD method, contains a metal oxide as a main component, and contains an organic component. The gas barrier film layer may be a single film or a composite film.

2. Organic film layer By providing an organic film layer on the gas barrier film laminate, unevenness on the surface of the substrate is flattened, and curling of the gas barrier film laminate is caused by residual stress generated during the film formation process of the gas barrier film layer. Can be suppressed.

The thickness of the organic film layer is preferably 1 to 20 μm, more preferably 1.2 to 10 μm, still more preferably 2 to 8 μm. By setting the thickness to 1 μm or more, sufficient smoothness can be ensured and curling can be suppressed. Moreover, by setting it as 20 micrometers or less, while being easy to prevent the crack by bending, it becomes easy to adjust the balance of the optical characteristic of a gas barrier film laminated body.

The surface roughness of the organic film layer is preferably an arithmetic average roughness Sa of 5 nm or less, more preferably 3 nm or less, and even more preferably 2 nm or less. By setting the thickness to 5 nm or less, a thin gas barrier film layer laminated on the organic film layer can be uniformly treated, and the barrier property of the gas barrier film laminate is improved.

The thermal expansion coefficient of the organic film layer is preferably 10 to 150 × 10 ⁻⁶ / ° C., more preferably 21 to 100 × 10 ⁻⁶ / ° C., and further preferably 21 to 80 × 10 ⁻⁶ / ° C. ° C. Although the reason is not clear, curling of the gas barrier film laminate that occurs during the production process of the gas barrier film laminate can be suppressed when it is in the above range.

Measurement of thermal expansion coefficient The thermal expansion coefficient was measured with a tensile load of 5 g using a thermomechanical test apparatus TMA / SS6100 manufactured by SII Corporation as a measuring apparatus. The temperature range is 25 ° C. to 100 ° C. (temperature increase rate 5 ° C./min, measurement environment: 23 ° C.). The coefficient of thermal expansion was determined from the average value obtained by measuring two samples, approximating the temperature-elongation relationship in a straight line in the above temperature range on the apparatus.
Thermal expansion coefficient (linear expansion coefficient) α = ΔL / (L · ΔT)
(ΔL: sample elongation, L: sample length, ΔT: temperature rise)

The organic film layer of the present invention is preferably a film obtained by photopolymerizing a photocurable resin composition. The photocurable resin composition is preferably composed of a composition containing an acrylic resin. The “photocurable resin composition” may be a composition that is photocured as a whole, and the photocurable resin does not necessarily have to be a main component.

Examples of the photocurable resin that is a precursor of the organic film layer include acrylic resins that can be cured by light such as ultraviolet irradiation. Examples thereof include resins having an unsaturated bond capable of radical polymerization, such as (meth) acrylate monomers, unsaturated polyester resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, and urethane (meth) acrylate resins. . These acrylic resins can be used alone or in admixture of two or more. Among them, polyester (meth) acrylate resin, urethane (meth) acrylate resin, (meth) acrylate monomer and the like alone or a mixture thereof are preferable.

Examples of the (meth) acrylate monomer include compounds obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid. For example, polyalkylene glycol di (meth) acrylate, ethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, polyethylene polytrimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (Meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetra Methylolmethane tetra (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. Moreover, the compound which has a silsesquioxane skeleton and has a (meth) acrylate group in a functional group is also mentioned.

As said unsaturated polyester resin, the condensation product (unsaturated polyester) by esterification reaction of a polyhydric alcohol and unsaturated polybasic acid (and saturated polybasic acid as needed) was melt | dissolved in the polymerizable monomer. Things.
The unsaturated polyester can be produced by polycondensation of an unsaturated acid such as maleic anhydride and a diol such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, and itaconic acid or its anhydride is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2 -Butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane Polyhydric alcohols such as 1,4-dimethanol, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A are reacted as alcohol components, and phthalic acid, isophthalic acid, terephthalic acid, Such as tetrahydrophthalic acid, adipic acid, sebacic acid Polymerizable not have an unsaturated bond or a polybasic acid anhydrides may include those prepared by adding as an acid component.

As the polyester (meth) acrylate resin, (1) a terminal carboxyl group polyester obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol contains an α, β-unsaturated carboxylic ester group. (Meth) acrylate obtained by reacting an epoxy compound, (2) obtained by reacting a hydroxyl group-containing acrylate with a polyester having a terminal carboxyl group obtained from a saturated polybasic acid and / or unsaturated polybasic acid and a polyhydric alcohol (Meth) acrylates obtained, (3) (meth) acrylates obtained by reacting (meth) acrylic acid with polyesters of terminal hydroxyl groups obtained from saturated polybasic acids and / or unsaturated polybasic acids and polyhydric alcohols It is done.
Examples of the saturated polybasic acid used as a raw material for polyester (meth) acrylate include polybasic compounds having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Examples thereof include acids or anhydrides thereof and polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid and itaconic acid or anhydrides thereof. Further, the polyhydric alcohol component is the same as the unsaturated polyester.

The epoxy (meth) acrylate resin includes a polymerizable unsaturated bond formed by a ring-opening reaction between a compound having a glycidyl group (epoxy group) and a carboxyl group of a carboxyl compound having a polymerizable unsaturated bond such as acrylic acid. A compound having a compound (vinyl ester) dissolved in a polymerizable monomer.
The vinyl ester is produced by a known method, and includes an epoxy (meth) acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid.
Further, various epoxy resins may be reacted with bisphenol (for example, A type) or dibasic acid such as adipic acid, sebacic acid, dimer acid (Haridimer 270S: Harima Kasei Co., Ltd.) to impart flexibility.
Examples of the epoxy resin as a raw material include bisphenol A diglycidyl ether and its high molecular weight homologues, novolak glycidyl ethers, and the like.

As the urethane (meth) acrylate resin, for example, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, a hydroxyl group-containing (meth) acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound are reacted. And a radical-polymerizable unsaturated group-containing oligomer that can be obtained.
Specific examples of polyisocyanates include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenyl. Methane triisocyanate, Bannock D-750, Crisbon NK (trade name; manufactured by DIC Corporation), Desmodur L (trade name; manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate L (trade name; Nippon Polyurethane Industry Co., Ltd.) Manufactured), Takenate D102 (trade name; manufactured by Mitsui Takeda Chemical Co., Ltd.), Isonate 143L (trade name; manufactured by Mitsubishi Chemical Corporation), and the like.
Examples of the polyhydroxy compound include polyester polyol and polyether polyol. Specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, tri Methylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-ethylene oxide-propylene Examples include oxide adducts.
Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, and 1,3-butane. Diol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-butanediol, 1,2-cyclohexane glycol, 1,3- Examples include cyclohexane glycol, 1,4-cyclohexane glycol, paraxylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, and 2,7-decalin glycol.
The hydroxyl group-containing (meth) acrylic compound is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester is preferable, and specific examples thereof include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl. (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) An acrylate etc. are mentioned.

The photocurable resin composition contains a photopolymerization initiator. As a specific example of a photoinitiator, if it is a compound which generate | occur | produces a radical by irradiation of an ultraviolet-ray or visible light, it will not specifically limit. Compounds used as photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di (t-butylperoxycarbonyl) Benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichlorome ) -S-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2 , 6-Di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4 '-Methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7- Diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' Bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2 '-Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl- 2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η5-2,4-cyclope) Tajien-1-yl) - bis (2,6-difluoro-3-(1H-pyrrol-1-yl) - phenyl) titanium, and the like. These compounds may be used alone or in combination of two or more. 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxy) Carbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone is preferred.
The amount of the polymerization initiator used in the above addition polymerization is preferably about 0.01 to 10 mol% based on the total number of moles of monomers. These photopolymerization initiators can be used alone or in combination of two or more.

In the addition polymerization, a chain transfer agent may be used. The molecular weight can be appropriately controlled by using the chain transfer agent. Examples of chain transfer agents include thio-β-naphthol, thiophenol, butyl mercaptan, ethyl thioglycolate, mercaptoethanol, mercaptoacetic acid, isopropyl mercaptan, t-butyl mercaptan, dodecanethiol, thiomalic acid, pentaerythritol tetra (3 -Mercaptans such as mercaptopropionate) and pentaerythritol tetra (3-mercaptoacetate); disulfides such as diphenyl disulfide, diethyl dithioglycolate and diethyl disulfide; and the like, toluene, methyl isobutyrate, Carbon tetrachloride, isopropylbenzene, diethyl ketone, chloroform, ethylbenzene, butyl chloride, sec-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, chloride Pyrene, methyl chloroform, t- butyl benzene, butyl alcohol, isobutyl alcohol, acetic acid, ethyl acetate, acetone, dioxane, tetrachloroethane, chlorobenzene, cyclohexane, t- butyl alcohol, benzene and the like. In particular, mercaptoacetic acid can lower the molecular weight of the polymer and make the molecular weight distribution uniform. These chain transfer agents can be used alone or in admixture of two or more.

Solvents used when preparing a coating solution in which a photocurable resin is dissolved or dispersed in a solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, α- or β- Terpenes such as terpineol, etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, aroma such as toluene, xylene, tetramethylbenzene Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether Ter, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and other glycol ethers, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carb Acetic esters such as tall acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate Diethylene glycol dialkyl ether, dipropy Glycol dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide. These solvents can be used alone or in admixture of two or more.

In addition, a coating solution in which a photocurable resin is dissolved or dispersed in a solvent improves the surface fluidity and leveling properties of the coating solution applied at the time of coating, and prevents pinholes and defects in the coating film due to poor wetting and repellency. A surface conditioner (leveling agent, wettability improving agent, interfacial slipping agent, etc.) for preventing generation may be contained. Examples of the surface conditioner include polysiloxane, polyacrylate and wax.
In addition, an additive such as an antifoaming agent for preventing the generation of bubbles in the coating solution may be used. Examples of antifoaming agents include mineral oil compounds and polysiloxane compounds.
Furthermore, you may contain additives, such as a plasticizer, a ultraviolet absorber, antioxidant, and a silane coupling agent, as needed.

The method for forming the organic film layer is not particularly limited, but it is preferable to use a wet coating method (coating method) in order to uniformly coat the photocurable resin composition. By using the coating method, excellent surface smoothness can be obtained. Among the coating methods, when a small amount is prepared, a spin coating method capable of simple and uniform film formation is preferable. In the case of roll-to-roll, where productivity is important, gravure coating method, die coating method, reverse coating method, roll coating method, slit coating method, dipping method, spray coating method, kiss coating method, reverse kiss coating method, air A knife coating method, a curtain coating method, a rod coating method and the like are preferable. The coating method can be appropriately selected from these methods according to the required film thickness, viscosity, curing conditions, and the like.

The applied coating solution can be dried with hot air or the like in an environment of room temperature to about 200 ° C. After the coating and drying, a photoactive energy beam or an electron beam is irradiated and cured by an active energy beam source. Although there is no particular limitation as a photoactive energy ray source, depending on the nature of the photopolymerization initiator used, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, a gas laser, a solid laser, An electron beam irradiation apparatus etc. are mentioned.
The drying furnace passage time for drying differs depending on the line speed, the type of coating liquid, the coating thickness, and the apparatus capacity (air volume, area, etc.). For example, 1 to 105 minutes can be mentioned. Similarly, the amount of irradiation for curing varies depending on the material and thickness. For example, when a high-pressure mercury lamp is used, about 200 to 700 mJ / cm ² can be mentioned.

3. Gas Barrier Film Layer The gas barrier film layer included in the gas barrier film laminate is a film containing metal oxide as a main component, formed by a plasma CVD method, and is a single film or a composite film.
Note that a film mainly containing a metal nitride or a mixture of a metal oxide and a metal nitride may be used instead of the metal oxide.

The thickness of the gas barrier film layer is preferably 0.2 to 2 μm, more preferably 0.3 to 1.5 μm, still more preferably 0.5 to 1.5 μm. When the thickness is 0.2 μm or more, the film thickness uniformity is good and the gas barrier performance is excellent. If it is 2 μm or less, cracks due to bending are less likely to occur.

As a method of forming a metal oxide thin film on the surface of a plastic substrate, physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, thermochemical vapor deposition, plasma, etc. There is chemical vapor deposition (CVD) such as chemical vapor deposition. However, the vacuum deposition method is widely used as a highly productive process, but the gas barrier performance is inferior. Although a dense film can be formed by sputtering, the film formation rate is low and sufficient productivity cannot be obtained. Furthermore, since the film formed by the PVD method is inorganic and brittle, defects and peeling are likely to occur, and high barrier properties cannot be imparted.
On the other hand, the plasma CVD method has an advantage in terms of productivity as compared with the sputtering method, and further has a good gas barrier performance as compared with the vacuum evaporation method and the sputtering method.

As described above, the plasma CVD method can be preferably used as the method for forming the gas barrier film layer. More preferably, a roll-to-roll type plasma CVD method can be used in terms of productivity and quality stability.
In CVD (Chemical Vapor Deposition), one or more source gases of a compound containing a constituent element of a thin film material to be manufactured are supplied onto a film formation target (for example, a substrate), and the gas phase or the surface of the substrate is supplied. The plasma CVD method is a method in which a reactive gas is brought into a plasma state, active radicals and ions are generated, and a chemical reaction is performed in an active environment. In addition, as shown in FIG. 5, the roll-to-roll means that a film-forming object wound in a roll shape is sent out from a feed roll 31, and a target substance is formed on a surface and printed, and another roll (winding is wound again). This is a production method in which a take-up reel 32) is wound up and collected.

There are various types of film forming apparatuses using the plasma CVD method, but the film forming apparatus is not limited as long as the object of the present invention is not impaired.
For example, Japanese Patent Publication No. 2005-504880 includes a pair of film forming rolls that wind and convey a film to be formed, forms a magnetic field across the rolls, and the two film forming rolls are the same. It is connected to a high-frequency power source so as to be polar, and simultaneously, high-frequency power of several tens to several hundreds of kHz is supplied, and Benning discharge is generated in the opposing space (discharge region) between the rolls to confine plasma and oxygen in the opposing space And a material gas such as hexamethyldisiloxane (HMDSO) is supplied to form a film on a film on a film forming roll on both sides of the discharge region at the same time.

Japanese Patent No. 2587507 discloses a pair of film forming rolls (metal drums) arranged facing each other in a vacuum chamber, an AC power source in which one and the other electrode are connected to one and the other film forming rolls, respectively. A plasma CVD film forming apparatus having a discharge chamber disposed in an opposing space between film forming rolls and having a surface facing the film forming roll opened, and a monomer (raw material) gas supply means connected to the discharge chamber is described. Has been.

Further, in Japanese Patent No. 4268195, a pulse voltage accompanied by alternating current or polarity reversal is applied to the film forming rolls arranged to face each other under reduced pressure, and a facing space (film forming zone) between the film forming rolls arranged opposite to each other. ) Describes a device for generating a film by plasma CVD on a belt-like base material wound around facing a facing space of a film forming roll.
As an example, a plasma CVD apparatus (Roll coater W35) manufactured by Kobe Steel, Ltd. can be preferably used.

Examples of the metal oxide that is the main component of the gas barrier film layer include silicon oxide, aluminum oxide, and titanium oxide. In applications where transparency is required for the gas barrier film laminate, silicon oxide is more preferable.

The source gas used for forming the gas barrier film layer is preferably an organometallic compound. For example, an organosilicon compound containing silicon, an organoaluminum compound containing aluminum, or the like can be used. Among these raw material gases, it is more preferable to use an organosilicon compound from the viewpoints of handling of the compound and imparting flexibility and high gas barrier properties to the resulting gas barrier film layer.
Examples of organosilicon compounds include HMDSO, 1.1.3.3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethoxysilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyl Examples include triethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and octamethylcyclotetrasiloxane.
Among these organosilicon compounds, HMDSO, 1.1.3.3-tetramethyldisiloxane, and tetraethoxysilane are particularly preferable from the viewpoints of properties such as compound handling properties and gas barrier properties of the obtained thin film layer.
These raw materials such as organosilicon compounds can be used singly or in combination of two or more.
Examples of the organoaluminum compound include trimethylaluminum.

In addition to the raw material gas, a reactive gas can be used. As the reaction gas, a gas that reacts with the raw material gas and its radical to become a compound such as an oxide or a nitride can be used. As the reaction gas, for example, oxygen, nitrogen, ammonia, ozone, or the like can be used. These reaction gases can be used alone or in combination of two or more.

In order to supply the raw material gas into the vacuum chamber as a film forming gas, a carrier gas may be used as necessary. Furthermore, as a gas for film formation, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, and for example, rare gases such as helium, argon, neon, xenon, and the like can be used.

Such gases for film formation (gases used during film formation such as source gas, reaction gas, carrier gas, discharge gas) are collectively referred to as “film formation gas”. The mixing ratio of the reaction gas to the raw material gas is such that the molar amount of the reaction gas used is A × when the molar ratio of the reaction gas that is theoretically necessary for complete reaction with 1 mol of the raw material gas is A. A range of (0.2 to 1.5) is preferable, and a range of A × (0.3 to 1.25) is more preferable.
For example, when a gas barrier film layer is formed by reacting a film forming gas containing HMDSO as a source gas and oxygen (O ₂ ) as a reaction gas by plasma CVD, the reaction is described in the following reaction formula (1). The following reaction occurs.
_{_{_{(CH 3) 6 Si 2 O}}} + 12O 2 → 2SiO 2 + 6CO 2 + 9H 2 O (1)
The theoretical amount of oxygen which is a reaction gas with respect to 1 mol of HMDSO which is a raw material gas is 12 mol. Therefore, in this case, a preferable molar ratio of oxygen to 1 mol of HMDSO is 12 × (0.2 to 1.5) = 2.4 to 18 mol, and a more preferable molar ratio is 3.6 to 15 mol. .
If the ratio of the reaction gas is too low, an organic component derived from the source gas in the formed barrier film (for example, when HMDSO is used as the source gas, a component containing carbon due to the methyl group contained in the source material) ) And a high barrier property cannot be obtained, and if the ratio of the reaction gas is too high, the reaction proceeds too much and the barrier film becomes brittle and the flexibility and durability are poor.

The pressure (degree of vacuum) in the vacuum chamber of the plasma CVD apparatus can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.1 Pa to 50 Pa.

The electric power applied for discharging can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.2 to 10 kW. When the applied power is equal to or higher than the lower limit, the reaction of the raw material gas is not insufficient and the barrier property is not lowered. As a result, wrinkles are not generated on the object of film formation, and irregularities are generated on the film surface and the appearance is not impaired.

The conveyance speed of the film forming target can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.1 to 50 m / min, preferably 0.3 to 20 m. / Min is more preferable. When the line speed is equal to or higher than the lower limit, wrinkles due to heat tend not to occur in the resin film being conveyed. When the line speed is equal to or lower than the upper limit, the thickness of the formed thin film layer does not become too thin.

The gas barrier film layer contains an organic component. For example, when a thin film is formed by a plasma CVD method from a film forming gas (mixed gas of HMDSO as a source gas and oxygen gas as a reaction gas (also functioning as a discharge gas)) and a gas barrier film layer is formed, the following reaction formula is obtained. As described in (2), the formed film contains Cy (a trace amount of carbon component) as an organic component.
(CH ₃ ) ₃ Si—O—Si (CH ₃ ) ₃ + O ₂ → SiOxCy (2)

4). Resin film The resin film used as a base material of a gas barrier film laminated body will not be specifically limited if it is formed with the organic material which can hold | maintain a gas barrier film layer.

For example, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), cycloolefin polymer, aromatic polyamide, polyether ether ketone, polysulfone, polyether sulfone, acrylic ester polymer, methacrylic ester polymer, polyimide, polyetherimide, etc. Heat-resistant transparent film based on sesquioxane (product name Sila-DEC, manufactured by JNC Co., Ltd.), resin films made by laminating two or more layers of the above plastics, The composite film of resin-impregnated glass cloth and the like. From the viewpoint of cost and availability, a film mainly composed of polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, polycarbonate, or polyimide resin can be preferably used.

The thickness of the resin film is not particularly limited, but is preferably 20 to 500 μm, more preferably 30 to 300 μm. When the thickness is 20 μm or more, the rigidity as a base material is insufficient, and stability does not decrease during film formation on a roll-to-roll basis. Moreover, if it is 500 micrometers or less, it can avoid that a flexibility falls and it becomes cost up.

Furthermore, when the resin film is transparent, the organic film layer and the gas barrier film layer formed on the resin film are also transparent, so that a transparent gas barrier film laminate can be obtained. Therefore, a transparent substrate such as an OLED element or an OPV element can be used, which is more preferable.

In addition, the surface (resin film surface, organic film layer surface, gas barrier film layer surface) of the gas barrier film laminate according to the present invention is subjected to surface modification treatment such as corona treatment or plasma treatment for the purpose of improving adhesion. Also good.

The gas barrier film laminate of the present invention has at least one organic film layer and at least one gas barrier film layer on at least one side of the resin film, and the resin film and the organic film layer are preferably in contact with each other. More preferably, as shown in FIG. 1, a gas barrier film laminate 10 having a structure in which an organic film layer 12 and a gas barrier film layer 13 are laminated only on one side of a resin film 11.
By stacking the organic film layer and the gas barrier film layer on the resin film in the order of resin film / organic film layer / gas barrier film layer, compared to the case of stacking in the order of resin film / gas barrier film layer / organic film layer, The adhesion between the organic film layer and the gas barrier film layer can be improved, which is more preferable.
In addition, the gas barrier film layer has a structure that is laminated only on one side of the resin film, so that the weight of the gas barrier film laminate is improved, the light transmittance is improved, and the manufacturing process is simplified compared to the case where it is laminated on both sides. It is possible to achieve the above and more preferable.

The gas barrier film laminate formed by the configuration of the present invention has a high gas barrier with a water vapor transmission rate (temperature: 40 ± 0.5 ° C., relative humidity: 90 ± 5% RH) of 0.005 g / m ² / d or less. Expresses sex. By optimizing the film formation conditions, 0.001 g / m ² / d or less can be developed, and by optimizing the thickness of the organic film layer and gas barrier film layer, 0.0001 g / m ² / d or less Is achieved.

The gas barrier film laminate of the present invention is preferably composed of only a transparent material when used for applications such as a photoelectric element, an OLED element, or an OPV element, and has a total light transmission measured according to the JIS 7105 method. The rate is preferably 80% or more, more preferably 85% or more, and particularly preferably 88% or more.
However, when it is desired to block transmission of visible light or ultraviolet light, or when transparency is not so required, an opaque gas barrier film laminate may be produced.

The gas barrier film laminate of the present invention suppresses the internal stress that tends to curl in the use environment as much as possible, and exhibits good curl prevention properties. Thereby, after manufacturing the said gas barrier film laminated body, when passing through other processes, such as an assembly process to a device, favorable workability is exhibited. Further, there is no crack or film peeling due to curling, and good gas barrier properties can be maintained.
For example, the gas barrier film laminate of the present invention laminated on a 125 μm-thick PET film is cut to 100 mm × 100 mm and placed on a surface plate, and from a surface plate surface using a height measuring instrument such as a ruler. When the average value of the height (distance from the surface of the platen) of the curled and warped portion is the curl height, the curl height is preferably 15 mm or less, more preferably 10 mm or less, and particularly preferably 5 mm or less. The “curl height” is an average of the heights of the four corners of a square film.

5. Applications The gas barrier film laminate of the present invention can be used for applications that require blocking of various gases such as water vapor and oxygen. Particularly preferably, it can be usefully used for blocking various gases such as OLED elements or OPV elements. Moreover, when a gas barrier film laminated body is transparent, when it uses for a photoelectric element like an OPV element, it can comprise so that sunlight reception may be performed from the gas barrier film laminated body side. Further, when used in an OLED element, light emission from the element is not hindered, so that the light emission efficiency is not deteriorated.

FIG. 2A shows a schematic diagram of an electronic component having an OLED element in a solid sealing system. An OLED element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes is disposed on a glass substrate 21, and the OLED element 22 is entirely covered with a solid sealing agent 23. In the electronic component having such a configuration, the gas barrier film laminate 10 of the present application can be used instead of the glass substrate 21 as shown in FIG.
Or as shown in FIG. 3, it is good also as a sandwich structure which pinched | interposed OLED element 22 with the gas barrier film laminated body 10 of this application. In that case, the gas barrier film laminate 10 may be adhered by the adhesive 25.

FIG. 4A shows a schematic diagram of an electronic component having an OLED element with a conventional hollow structure. An OLED element 22 having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes is disposed on the glass substrate 21 and covered with a glass sealing material 28 that is present at a distance. The glass substrate 21 and the glass sealing material 28 are bonded (sealed) with an adhesive 25 on both sides. A getter 26 that adsorbs moisture is disposed inside the hollow and is filled with N ₂ gas 27. In the conventional electronic component having such a configuration, the gas barrier film laminate 10 of the present application can be used as an alternative to the glass base material 21 and the glass sealing material 28 as shown in FIG.

Also in an OPV element having positive and negative electrodes and a semiconductor material sandwiched between the positive and negative electrodes, the gas barrier film laminate of the present application can be similarly used as an alternative to a glass substrate.

As described above, when the gas barrier film laminate of the present invention is used as a transparent substrate for OLED elements, OPV elements, liquid crystal elements, etc., it is possible to meet the demands for weight reduction and size increase. Furthermore, roll-to-roll (feeding a substrate such as a resin film wound in a roll shape, processing the target substance on the surface of the substrate, etc., and then winding it up again to collect it In place of glass substrates that are heavy, easy to break, and difficult to increase in area. Can be satisfied.
Conventionally, film base materials such as transparent plastics have a problem that gas barrier properties are inferior to glass, but when the gas barrier film laminate of the present invention is used, for example, electronic components such as OLED elements and OPV elements When used as a material, the substrate having excellent gas barrier properties can prevent water (water vapor) or oxygen from permeating and degrading components constituting the device, thereby reducing performance.

As described above, the present invention mainly includes display elements typified by organic electroluminescence elements (OLED elements) and liquid crystal elements, photoelectric elements typified by organic solar cell elements (OPV elements), illumination using OLED elements, and the like. It is a gas barrier film laminated body which can be used for the product. The gas barrier film laminate of the present invention is characterized by good productivity, low curl, and good gas barrier properties.

Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to the contents described in the following examples.

<Measurement of film thickness of gas barrier layer and organic film layer>
Using a scanning electron microscope (SEM), the tomographic plane of the gas barrier film laminate was observed under the following conditions, and the film thickness was measured.
・ SEM observation equipment: SU-70 manufactured by Hitachi, Ltd.
Acceleration voltage: 10 kV

<Flexibility>
The produced gas barrier film laminate was evaluated for bending resistance based on JIS K5600-5-1 (cylindrical mandrel method).

<Adhesion>
The prepared gas barrier film laminate was evaluated for adhesion based on JIS K5600-5-6 (adhesiveness [cross-cut method]).
Cutting interval: 1mm
Number of cuts: 10 × 10 Judgment: ○: Peeling area ≦ 5%
Δ: 5% <peeling area ≦ 30%
×: 30% <peeling area

<Curl test>
The produced gas barrier film laminate was allowed to stand for 1 day or longer in an environment of 23 ± 2 ° C. and 50 ± 10% RH while being wound into a roll. Then, it cut | judged to 100 mm x 100 mm, mounted on the surface plate in the environment of 23 +/- 2 degreeC and 50 +/- 10% RH, and left to stand for 24 hours. Then, the height (distance from the surface of the surface plate) of the part curled and warped from the surface of the surface plate was measured using a length measuring device (JIS 1 grade metal ruler). That is, the curl height was measured for each of the four corners of the sample, and the average value thereof was taken as the curl height.

<Measurement of water vapor transmission rate (WVTR)>
The method for measuring the water vapor transmission rate is not particularly limited, but in the present invention, evaluation was performed by the method described in ISO 15106-3 or the Ca corrosion method described below.
Measurement method 1 (ISO 15106-3 method)
Evaluation apparatus: Illinois water vapor permeability measuring apparatus Model 7002
Temperature and humidity: 40 ° C, 90% RH
・ Measurement method 2 (Ca corrosion method)
When the measurement method 1 was below the measurement limit, the measurement was performed by the following method. A method that utilizes the phenomenon that metal calcium is vapor-deposited on one side of a gas barrier film laminate, Ca is sealed with Al and wax, and the metal Ca is corroded by moisture that has passed through the film. The water vapor transmission rate is calculated from the corrosion area and the time to reach the corrosion area. In the present invention, the evaluation was performed by the method described in Japanese Patent No. 3958235 and the following conditions.
-Ca method used for evaluation of the present invention Vapor deposition apparatus: Electron beam vacuum deposition apparatus SVC-700LEB manufactured by Sanyu Electronics Co., Ltd.
Constant temperature and humidity chamber: Espec Co., Ltd. constant temperature and humidity chamber LHL-113
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor impermeable metal for Ca sealing: Aluminum (φ3-5mm, granular)
Sealing material: mixture of paraffin (melting point 60-62 ° C) / beeswax (melting point 61-65 ° C) in a weight ratio of 1: 1 Observation device: Calcium corrosion observation device MFB-1000 manufactured by Mitsuwa Frontec Co., Ltd.

<Example 1>
-Base material As the base material, use is made of polyethylene terephthalate (PET) film (trade name "COSMO SHINE A4300", manufactured by Toyobo Co., Ltd.) wound in a roll shape with a thickness of 125 μm and a width of 550 mm that is easily bonded on both sides. It was.

-Preparation of coating solution of photo-curable resin composition Unidic V-4000BA (trade name, urethane acrylate / butyl acetate = 75 to 85 parts by weight / 15 to 25 parts by weight, DIC Corporation UV curable resin) 36 parts by weight butyl acetate (solvent manufactured by Wako Pure Chemical Industries) 63 parts by weight IC184 (trade name, photopolymerization initiator manufactured by BASF) 1 part by weight was prepared.

-Formation of an organic film layer Using a roll-to-roll gravure coater, the coating solution was applied on the substrate so that the average film thickness after drying was 5 µm, and then the temperature was 85 ° C and the air volume was 20 m. / Sec., Drying time in the drying furnace was 50 seconds. Thereafter, photocuring was performed at a dose of 300 mJ / cm ² using a high-pressure mercury lamp in a nitrogen atmosphere to form an organic film layer.

・ Formation of gas barrier film layer Using the plasma CVD apparatus (model number W35 type) PE-CVD manufactured by Kobe Steel Co., Ltd., capable of forming a film roll-to-roll on the surface of the base material treated with the organic film layer. Thus, a gas barrier film layer was formed.
Under the conditions shown below, plasma is generated between the discharge electrodes, and a film forming gas (mixed gas of HMDSO as a source gas and oxygen gas (which also functions as a discharge gas) as a reaction gas) is formed in this discharge region. Then, a thin film was formed by plasma CVD using the method described in JP 2012-81632 A, and a gas barrier film laminate having a gas barrier film layer having the thickness shown in Table 1 was obtained.
Source gas: HMDSO (trade name “SIH6115.0” manufactured by Asmax Co., Ltd.)
Reaction gas: oxygen gas (manufactured by Suzuki Shokan Co., Ltd., high-purity oxygen, purity ≧ 99.999%)

<Example 2>
Preparation of coating solution for photocurable resin composition Unidic V-6841 (trade name, (meth) acrylate polymer / acrylate monomer / methyl isobutyl ketone = 25 to 35 parts by weight / 25 to 35 parts by weight / 35 to 45 parts by weight of mixture, DIC Corporation UV curable coating agent) 55 parts by weight Methyl isobutyl ketone (solvent made by Wako Pure Chemical Industries) 43 parts by weight IC184 (trade name, photopolymerization initiator manufactured by BASF) 2 parts by weight did.
A gas barrier film laminate was prepared in the same manner as in Example 1 except that the coating liquid for the photocurable resin composition was prepared.

<Example 3>
A gas barrier film laminate was prepared in the same manner as in Example 2 except that the gas barrier film layer formed by plasma CVD was processed to have the thickness shown in Table 1.

<Example 4>
A gas barrier film laminate was prepared in the same manner as in Example 2 except that the organic film layer by the gravure coater was processed so that the thickness after drying was as shown in Table 1.

<Example 5>
Example 2 except that a polyethylene naphthalate (PEN) film (trade name “Teonex Q65FA” manufactured by Teijin DuPont Films Ltd.) wound in a roll shape with a thickness of 125 μm and a width of 550 mm was used as the substrate. Similarly, a gas barrier film laminate was prepared.

<Comparative Example 1>
A gas barrier film laminate was produced in the same manner as in Example 1 except that the photocurable resin composition was not applied.

<Comparative example 2>
・ Preparation of coating solution for photocurable resin composition PMMA (Polymethylmethacrylate / Toluene / Methylethylketone = 9-11 parts by weight / 40-50 parts by weight / 40-50 parts by weight) "ATOM BOND MA-830-M50" Thermosetting coating agent) 60 parts by weight Methyl ethyl ketone (Wako Pure Chemicals solvent) 20 parts by weight Toluene (Wako Pure Chemicals solvent) 20 parts by weight Photo-curable resin composition coating solution A gas barrier film laminate was prepared in the same manner as in Example 1 except that the drying temperature after preparation and application was 110 ° C., and that irradiation (photocuring) of a high-pressure mercury lamp was not performed.
The obtained gas barrier film laminate had poor adhesion between the gas barrier film layer and the organic film layer, and peeling occurred between the layers.

<Comparative example 3>-When the thickness of a gas barrier film layer is thin Except having processed the gas barrier film layer by plasma CVD so that it might become thickness shown in Table 2, the gas barrier film laminated body was created like Example 2. FIG.

<Comparative example 4> When the thickness of the gas barrier film layer is thick A gas barrier film laminate was prepared in the same manner as in Example 2 except that the gas barrier film layer formed by plasma CVD was processed to have the thickness shown in Table 2.
After film formation, cracking of the gas barrier film layer was confirmed during sampling from the roll state.

<Comparative Example 5> When the thickness of the organic film layer is thin A gas barrier film laminate is prepared in the same manner as in Example 2 except that the organic film layer by the gravure coater is processed as shown in Table 2 after the thickness is dried. did.

<Comparative Example 6> When the thickness of the organic film layer is thick A gas barrier film laminate is prepared in the same manner as in Example 2 except that the organic film layer by the gravure coater is processed as shown in Table 2 after the thickness is dried. did.

As is clear from Table 1, it can be seen that the gas barrier film laminate of the present invention has high barrier properties while curling is reduced.

The present invention mainly relates to a gas barrier film laminate used for an electronic component having an OLED element, an OPV element, a liquid crystal element, and the like, and an electronic component including the gas barrier film laminate.

All publications, including publications, patent applications and patents cited herein are specifically incorporated by reference with reference to each reference individually, and the entire contents thereof are described herein. To the same extent, reference here is incorporated.

The use of nouns and similar directives used in connection with the description of the invention (especially in connection with the claims below) is not specifically pointed out herein or clearly contradicted by context. , And construed to cover both singular and plural. The phrases “comprising”, “having”, “including” and “including” are to be interpreted as open-ended terms (ie, including but not limited to) unless otherwise specified. The use of numerical ranges in this specification is intended only to serve as a shorthand for referring individually to each value falling within that range, unless otherwise indicated herein. Each value is incorporated into the specification as if it were individually listed herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. Any examples or exemplary phrases used herein (eg, “etc.”) are intended only to better describe the invention, unless otherwise stated, and to limit the scope of the invention. is not. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

In this specification, preferred embodiments of the present invention are described, including the best mode known to the inventors for carrying out the invention. Variations of these preferred embodiments will become apparent to those skilled in the art after reading the above description. The present inventor expects skilled workers to apply such modifications as appropriate, and intends to implement the present invention in a manner other than that specifically described herein. . Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

10 Gas barrier film laminate 11 resin film 12 organic film layer 13 barrier layer 21 of glass substrate 22 OLED element 23 solid sealing material 25 adhesive 26 getter 27 _{N 2} gas 28 glass sealing material 31 feed roll 32 winding roll 33 roller

Claims

A resin film as a substrate;
Comprising at least one organic film layer and at least one gas barrier film layer on at least one surface of the resin film;
The gas barrier film layer is a film formed by a plasma CVD method, containing a metal oxide as a main component and containing an organic component.
Gas barrier film laminate.
The organic film layer is a film obtained by photopolymerizing a photocurable resin composition.
The gas barrier film laminate according to claim 1.
The photocurable resin composition is a composition containing an acrylic resin.
The gas barrier film laminate according to claim 2.
The organic film layer was laminated by a coating method,
The gas barrier film laminate according to any one of claims 1 to 3.
The plasma CVD method was performed in a roll-to-roll manner,
The gas barrier film laminate according to any one of claims 1 to 4.
The organic film layer has a thickness of 1 to 20 μm.
The gas barrier film laminate according to any one of claims 1 to 5.
The gas barrier film layer has a thickness of 0.2 to 2 μm.
The gas barrier film laminate according to any one of claims 1 to 6.
The gas barrier film layer is provided only on one side of the resin film,
The gas barrier film laminate according to any one of claims 1 to 7.
It consists of three layers of the resin film, the organic film layer, and the gas barrier film layer, and the curl height is 15 mm or less.
The gas barrier film laminate according to any one of claims 1 to 8.
The organic film layer is provided between the resin film and the gas barrier film layer,
The gas barrier film laminate according to any one of claims 1 to 9.
The water vapor transmission rate at 40 ° C. and 90% RH is 0.005 g / m 2 / d or less,
The gas barrier film laminate according to any one of claims 1 to 10.
The resin film is a film mainly composed of a resin that is polyethylene phthalate, polyethylene naphthalate, cycloolefin polymer, polycarbonate, polyimide, or a mixture thereof.
The gas barrier film laminate according to any one of claims 1 to 11.
An electronic device having positive and negative electrodes and an organic material sandwiched between the positive and negative electrodes;
The gas barrier film laminate according to any one of claims 1 to 12, which protects the electronic device from water vapor;
Electronic components.
The gas barrier film laminate is transparent,
The electronic element is an OLED element or an OPV element;
The electronic component according to claim 13.