JP6424671B2 - Gas barrier film laminate and electronic component using the same - Google Patents

Description

  The present invention relates to a gas barrier film laminate. In particular, the present invention relates to a gas barrier film laminate capable of effectively suppressing water vapor permeation to an electronic component.

In organic electroluminescent devices (hereinafter, also referred to as OLED devices), organic solar cell devices (hereinafter, also referred to as OPV devices), liquid crystal devices, etc., a gas barrier film laminate comprising a resin film and a thin film such as metal oxide It may be. In such a gas barrier film laminate, an organic film layer is coated on a resin film, and irregularities and foreign substances on the resin film that cause pinholes and the like are covered to planarize the surface, and the gas barrier film layer is formed thereon. There is known a method of obtaining a film having high gas barrier properties by forming a film.
Also, in the case of an OLED element susceptible to moisture, it has been conventionally dealt with that a film is formed on the surface using a sealing material to block contact with moisture, oxygen and the like. For example, the sealing material using photocurable resin for protecting the OLED element formed on the glass substrate of patent document 1 and its sealing method (solid sealing method) are known.

  However, it is known that the adhesion between an organic substance (organic film layer) and an inorganic substance (gas barrier film layer) is generally not good, and the gas barrier film laminate produced by the above method also has a long period of heat and humidity. There has been a problem that interfacial peeling of the organic film layer / gas barrier film layer occurs after storage or in the device manufacturing process.

Furthermore, when the thickness of the organic film layer is not sufficient, or when the surface free energy of the unevenness and foreign matter on the resin film is smaller than the surface free energy of the coating solution, the resin film does not get wet enough to cause repelling etc. There is a problem that a sufficiently flat surface can not be obtained. In order to solve this problem, Patent Document 2 discloses a technique for sufficiently reducing the surface free energy of a coating solution by using a fluorine-based surfactant as a surface control agent to obtain sufficient surface flatness. In patent document 2, the polyester base material surface is planarized with the acrylic resin layer containing a fluorine-type surface conditioner, a gas barrier film layer is formed into a film on it, and the gas barrier film is obtained.
Further, according to Patent Document 3, the surface free energy of the coating solution is reduced to 34 mN / m or less using a surface conditioner, so that the resin film can be used even if the film thickness of the organic film layer is as thin as 0.05 to 3 μm. It has been shown that surface irregularities and foreign matter can be coated. In order to reduce the surface free energy of the acrylic resin coating solution to 34 mN / m or less other than the fluorine-based surface conditioner, a silicone having a main chain as the surface conditioner is generally used. Also in Example 1 of Patent Document 3, as the surface control agent, one having silicone as a main chain is used.
However, the fluorine-based surface conditioning agent has a potential problem of decreasing the adhesion with the thin film formed on the surface, since the surface free energy of the cured organic film layer is significantly reduced. Furthermore, as a result of intensive investigations by the present inventors, a surface conditioner having a silicone main chain also has a problem of reducing the adhesion between the organic film layer and the gas barrier film layer. That is, both the fluorine-based surface conditioner and the surface conditioner having silicone as the main chain lower the adhesion between the organic film layer and the gas barrier film.

  In Patent Document 4, it is also pointed out that another problem occurs when the gas barrier film layer (silicon nitride) is formed on the organic film layer containing a fluorine-based surface conditioner using plasma CVD method ( Paragraphs [0051]-[0057]). That is, when fluorine is contained in the organic film layer, the fluorine in the organic film layer is etched by plasma to generate a large number of extremely fine pinholes in the gas barrier film layer. The pinholes become defects in the gas barrier film layer and cause deterioration of the gas barrier properties. In Patent Document 4, in place of the fluorine-based surface conditioner, a surface conditioner having silicone as a main chain is used.

JP 2004-139977 Patent No. 5239230 gazette JP, 2013-49019, A JP, 2013-166298, A

  The present invention has been made in view of the problems of the above-mentioned prior art, and is a gas barrier film laminate in which a gas barrier film layer is formed by plasma CVD method, and the adhesion between the organic film layer and the gas barrier film layer It is an object of the present invention to provide a gas barrier film laminate having excellent gas barrier properties.

  As a result of intensive studies to solve the above problems, the present inventors have found that compounds which do not contain fluorine having (meth) acrylate as the main chain, not surface conditioners having silicone as the main chain in the organic film layer. After adding the surface control agent to contain, the method of forming the gas barrier film layer by plasma CVD method was established. By this method, it is possible to form a gas barrier film laminate which has excellent adhesion between the organic film layer and the gas barrier film layer and also has high gas barrier properties and flexibility by obtaining a flat surface of the organic film layer. The present invention has been completed.

The gas barrier film laminate 10 according to the first aspect of the present invention is, for example, as shown in FIG. 1, a resin film 11 as a base material; and at least one organic film layer on at least one side of the resin film 11. 12 and at least one gas barrier film layer 13; the organic film layer 12 contains a surface control agent, and the surface control agent contains a fluorine-free compound having (meth) acrylate as a main chain, The film layer 13 is a film which contains a metal oxide as a main component, further contains an organic component, and is formed by plasma CVD.
The “compound containing no fluorine having (meth) acrylate as the main chain” in the present application includes not only low molecular weight compounds but also high molecular weight compounds, as long as the compounds function as surface regulators in the present invention. In the above example, the “one side” includes not only the case where the organic film layer is in contact with the resin film but also the case where the organic film layer is separated from the resin film via the other layer. The "main component" refers to containing 50% by weight or more of a metal oxide in the composition constituting the gas barrier film layer.
According to this structure, since the organic film layer contains a compound containing no fluorine having (meth) acrylate as a main chain as a surface conditioner, formation of extremely fine pinholes in the gas barrier film layer can be prevented. it can. Furthermore, since the organic film layer contains a fluorine-free compound having (meth) acrylate as a main chain as a surface conditioner, the adhesion between the organic film layer and the gas barrier film layer, and the flexibility of the gas barrier film laminate can be obtained. It can be improved. Furthermore, since the gas barrier film layer is formed by plasma CVD, a dense and flexible film can be formed. Therefore, defects and peeling do not easily occur, and high gas barrier properties can be provided.

In the gas barrier film laminate according to the second aspect of the present invention, in the gas barrier film laminate according to the first aspect of the present invention, the content of the compound contained in the organic film layer is relative to the organic film layer. It is 0.01 to 2.5% by weight.
With this configuration, when the content is 0.01% by weight or more, the surface modification effect by the surface conditioner can be sufficiently obtained. Moreover, the deterioration of the surface flatness by the excessive orientation to the surface can be prevented as it is 2.5 weight% or less.

In the gas barrier film laminate according to the third aspect of the present invention, in the gas barrier film laminate according to the first aspect or the second aspect of the present invention, the water vapor transmission rate at 40 ° C., 90% RH is 0. It is less than 005 g / m ² / day.
With such a configuration, it can be sufficiently used as a gas barrier film used for an electronic device such as an OLED device or an OPV device.

In the gas barrier film laminate according to the fourth aspect of the present invention, in the gas barrier film laminate according to any one of the first aspect to the third aspect of the present invention, the thickness of the organic film layer is It is 0.1-20 micrometers, and the thickness of the said gas barrier film layer is 0.2-2 micrometers.
With this configuration, sufficient surface flatness and gas barrier properties can be ensured when the thickness is 0.1 μm or more. Moreover, while it becomes easy to prevent the crack by bending as it is 20 micrometers or less, the balance of the optical characteristic of a gas barrier film laminated body becomes easy to adjust. Furthermore, when the thickness of the gas barrier film layer is 0.2 μm or more, the film thickness uniformity becomes good and the gas barrier performance becomes excellent. When the thickness is 2 μm or less, coloring and curling of the gas barrier film laminate can be suppressed.

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 aspect to the fourth aspect of the present invention, wherein the organic film layer is photocured It is a film obtained by photopolymerizing the base resin composition.
According to this structure, since the photocurable resin composition is used, the production is easy and the production efficiency can be increased. Moreover, even if it is a resin film weak to heat, it can use for a base material.

The gas barrier film laminate according to a sixth aspect of the present invention is the gas barrier film laminate according to the fifth aspect of the present invention, wherein the photocurable resin composition contains an acrylic resin.
When configured in this manner, an organic film layer excellent in transparency can be formed. Furthermore, an acrylic resin having photo-curing property is preferable because it is excellent in anti-curling property and scratch resistance in a process due to its hardness.

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 aspect to the sixth aspect of the present invention, wherein the organic film layer is a coating method The gas barrier film layer is laminated by a roll-to-roll plasma CVD method.
According to this structure, the organic film layer can be uniformly coated by laminating the organic film layer by the application method, and excellent surface flatness can be obtained. Also, by combining the plasma CVD method for forming the gas barrier film layer and the roll-to-roll method, productivity can be improved and stability of quality can be obtained.

The gas barrier film laminate according to an eighth aspect of the present invention is the gas barrier film laminate according to any one of the first aspect to the seventh aspect of the present invention, wherein the resin film is polyethylene terephthalate, It is a film based on a resin that is polyethylene naphthalate, cycloolefin polymer, polycarbonate, polyimide, or a mixture thereof.
According to this configuration, the resin film can be formed of a resin that is easy to obtain, and, for example, a resin suitable for use such as transparency can be appropriately selected. Moreover, since the said film is excellent in heat resistance, it is preferable.

The electronic component according to the ninth aspect of the present invention is, for example, as shown in FIG. 2 (b), an electronic device 22 comprising a positive and negative electrode and an organic material sandwiched between the positive and negative electrodes; The gas barrier film laminate 10 according to any one of the first to eighth aspects of the present invention, which is protected from water vapor.
With this configuration, the gas barrier film laminate is excellent in gas barrier properties, so that water vapor and oxygen can penetrate into the inside of the electronic element to thereby deteriorate the components constituting the electronic element and prevent the performance from decreasing. it can.

An electronic component according to a tenth aspect of the present invention is the electronic component according to the ninth aspect of the present invention, wherein the gas barrier film laminate is transparent, and the electronic element is an OLED element or an OPV element. .
When configured in this way, when used in an OLED element, the light emission efficiency from the element is not impeded because the light emission from the element is not impeded. Moreover, when it uses for a photoelectric element like an OPV element, it can comprise so that sunlight reception may be performed from the side of a gas barrier film laminated body.

  According to the present invention, it is possible to provide a gas barrier film laminate having sufficient gas barrier properties, as well as improving the adhesion and flexibility of the gas barrier film layer formed by plasma CVD method to the organic film layer. The gas barrier film laminate can suppress peeling of the interface between the organic film layer and the gas barrier film layer after long-term storage in a moist and heat environment or in an element manufacturing process. Furthermore, the gas barrier film laminate can be used to protect an electronic device such as an OLED device or an OPV device from the penetration 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 conventional solid sealing method. FIG.2 (b) is sectional drawing of the electronic component using the gas barrier film laminated body of this invention. 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. It is the schematic of a roll-to-roll system.

  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 will be omitted. Further, the present invention is not limited to the following embodiments.

[Gas barrier film laminate]
FIG. 1 shows a gas barrier film laminate 10 according to a first embodiment of the present invention. The gas barrier film laminate 10 includes a resin film 11 as a base material, an organic film layer 12 on one side of the resin film 11, and a gas barrier film layer 13 on the organic film layer 12. The organic film layer 12 contains a surface conditioner. The surface conditioner includes a fluorine-free compound having a (meth) acrylate as a main chain. The gas barrier film layer 13 contains a metal oxide as a main component and further contains an organic component, and is formed on the organic film layer 12 by plasma CVD. The gas barrier film layer may be a single film or a composite film.
(Meth) acrylate represents acrylate or methacrylate. The surface conditioner may contain silicon in the side chain if the main chain is (meth) acrylate.
The gas barrier film laminate of the present invention may have a layer configuration other than that of the first embodiment. For example, another layer may be provided between the resin film 11 and the organic film layer 12. Moreover, the organic film layer 12 may be further provided on the gas barrier film layer 13, and the gas barrier film layer 13 may be further provided thereon. Thus, the organic film layer 12 and the gas barrier film layer 13 may alternately have a plurality of layers. In addition, the gas barrier film layer 13 may be provided on the back surface side of the resin film 11.

[Resin film as base material]
The substrate is not particularly limited as long as it is formed of a resin film and is a film formed of an organic material capable of holding the organic film layer and the 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, polyetheretherketone, polysulfone, polyethersulfone, acrylic acid ester polymer, methacrylic acid ester polymer, resin film such as polyimide, polyetherimide, sill having organic-inorganic hybrid structure Heat-resistant transparent film (product name Sila-DEC, manufactured by JNC Co., Ltd.) having sesquioxane as a basic skeleton, and a resin film formed by laminating two or more layers of the above-mentioned plastic And composite films of resin-impregnated glass cloth and the like. From the viewpoint of cost and ease of availability, a film composed mainly of a resin such as polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, polycarbonate or polyimide can be preferably used.

  Although the thickness of the resin film is not particularly limited, the thickness is preferably 20 to 500 μm, more preferably 30 to 300 μm. When the thickness is 20 μm or more, the rigidity of the substrate is insufficient, and the stability does not decrease in the roll-to-roll film formation. Moreover, it can avoid that a flexibility increases and it becomes expensive that it is 500 micrometers or less.

  When the resin film is transparent, the organic film layer and the gas barrier film layer formed on the resin film are also transparent, whereby 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.

[Organic layer]
By providing the organic film layer on the gas barrier film laminate, the unevenness and foreign matter on the surface of the substrate are flattened, and further, the curling of the gas barrier film laminate caused by the residual stress generated in the film formation process of the gas barrier film layer is suppressed. be able to.

The thickness of the organic film layer is preferably 0.1 to 20 μm, more preferably 1 to 10 μm, and still more preferably 3.5 to 8 μm. When the thickness is 0.1 μm or more, it is possible to flatten the unevenness of the substrate surface. While it becomes easy to prevent the crack by bending as it is 20 micrometers or less, the balance of the optical characteristic of a gas barrier film laminated body becomes easy to adjust.
Furthermore, by setting the thickness to 1 μm or more, larger foreign particles can be embedded, and the quality stability of the gas barrier film laminate is improved. In particular, when the thickness is 3.5 μm or more, the peeling durability (adhesion) of the organic film layer and the resin film is extremely excellent.

  The surface roughness of the organic film layer is preferably such that the arithmetic mean roughness Sa is 5 nm or less, more preferably 3 nm or less, and still more preferably 2 nm or less. It becomes possible to process uniformly the gas barrier film layer of the thin film laminated | stacked on an organic film layer as it is 5 nm or less, and the gas barrier property of a gas barrier film laminated body improves.

  The organic film layer of the present invention is preferably a film obtained by photopolymerization of a photocurable resin composition. It is preferable that a photocurable resin composition consists of a composition containing acrylic resin. The "photocurable resin composition" may be any composition that is photocurable as a whole, and the photocurable resin does not necessarily have to be the main component.

  As a photocurable resin, the acrylic resin which can be hardened | cured by light, such as ultraviolet irradiation, is mentioned. For example, mention may be made of resins having unsaturated bonds capable of radical polymerization such as (meth) acrylate monomers, unsaturated polyester resins, polyester (meth) acrylate resins, epoxy (meth) acrylate resins, urethane (meth) acrylate resins, etc. it can. These acrylic resins may be used alone or in combination 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 is preferable. The photocurable resin may be dissolved or dispersed in a solvent and used as a coating solution.

  As said (meth) acrylate monomer, the compound obtained by making an (alpha), (beta)-unsaturated carboxylic acid react with a polyhydric alcohol is mentioned. For example, polyalkylene glycol di (meth) acrylate, ethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, polyethylenepolytrimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytriol (Meth) acrylate, trimethylolpropane diethoxy tri (meth) acrylate, trimethylolpropane triethoxy tri (meth) acrylate, trimethylolpropane tetraethoxy tri (meth) acrylate, trimethylolpropane pentaethoxy tri (meth) acrylate, tetra Methylolmethane tetra (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythrito Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. Moreover, it is a compound which has silsesquioxane frame | skeleton and the compound which has a (meth) acrylate group in a functional group is also mentioned.

As said unsaturated polyester resin, the condensation product (unsaturated polyester) by the esterification reaction of polyhydric alcohol and unsaturated polybasic acid (and saturated polybasic acid if necessary) was melt | dissolved in the polymerizable monomer The thing is mentioned.
Unsaturated polyester can be produced by polycondensation of unsaturated acid such as maleic anhydride and diol such as ethylene glycol. Specifically, a polybasic acid having a polymerizable unsaturated bond such as fumaric acid, maleic acid, itaconic acid or the anhydride thereof is used as an acid component, and this together with 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 an alcohol component, and, if necessary, phthalic acid, isophthalic acid, terephthalic acid, 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) polyester of terminal carboxyl group obtained from saturated polybasic acid and / or unsaturated polybasic acid and polyhydric alcohol contains α, β-unsaturated carboxylic acid ester group (Meth) acrylate obtained by reacting an epoxy compound to be reacted, (2) a polyester of a terminal carboxyl group obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol, obtained by reacting a hydroxyl group-containing acrylate (Meth) acrylates obtained by reacting (meth) acrylic acid with polyesters of terminal hydroxyl groups obtained from (meth) acrylates, (3) saturated polybasic acids and / or unsaturated polybasic acids and / or polyhydric alcohols Be
As a saturated polybasic acid used as a raw material of polyester (meth) acrylate, for example, poly acids having no polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid and the like Examples thereof include basic acids or their anhydrides, and polymerizable unsaturated polybasic acids or their anhydrides such as fumaric acid, maleic acid and itaconic acid. Furthermore, as a polyhydric alcohol component, it is the same as that of the said unsaturated polyester.

As said epoxy (meth) acrylate resin, the polymerizable unsaturated bond produced | generated by the ring-opening reaction of the compound which has a glycidyl group (epoxy group), and the carboxyl group of the carboxyl compound which has polymeric unsaturated bonds, such as acrylic acid What melt | dissolved the compound (vinyl ester) which had these in the polymerizable monomer is mentioned.
The vinyl ester is produced by a known method, and includes epoxy (meth) acrylate obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid.
Furthermore, flexibility may be imparted by reacting various epoxy resins with a dibasic acid such as bisphenol (for example, type A) or adipic acid, sebacic acid, dimer acid (Haridimer 270S: Harima Chemicals, Inc.) .
As an epoxy resin as a raw material, bisphenol A diglycidyl ether, its high molecular weight homologue, novolak-type glycidyl ethers, etc. are mentioned.

As the urethane (meth) acrylate resin, for example, after reacting polyisocyanate and a polyhydroxy compound or polyhydric alcohol, further reacting a hydroxyl group-containing (meth) acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound And radically polymerizable unsaturated group-containing oligomers which can be obtained by
Specific examples of the polyisocyanate include 2,4-tolylene diisocyanate and isomers thereof, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenyl Methane triisocyanate, Bannock D-750, Klisson NK (trade name; manufactured by DIC Corporation), Desmodur L (trade name; Sumitomo Bayer Urethane Co., Ltd.), Coronate L (trade name; Nippon Polyurethane Industry Co., Ltd.) And Takenate D102 (trade name; manufactured by Mitsui Takeda Chemical Co., Ltd.) and Isonate 143L (trade name; manufactured by Mitsubishi Chemical Corp.).
As a polyhydroxy compound, polyester polyol, polyether polyol, etc. are mentioned. 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 Oxide adducts and the like can be mentioned.
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. Diols, adducts of bisphenol A with propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-butanediol, 1,2-cyclohexane glycol, 1,3- Cyclohexane glycol, 1,4-cyclohexane glycol, paraxylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, 2,7-decalin glycol and the like can be mentioned.
The hydroxyl group-containing (meth) acrylic compound is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester is preferable. Specifically, for example, 2-hydroxyethyl (meth) acrylate, 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. It will not specifically limit, if it is a compound which generate | occur | produces a radical by irradiation of an ultraviolet-ray or visible light as a specific example of a photoinitiator. Compounds used as a photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy -2-Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropylbenzoin ether, isobutylbenzoin 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-dimethylaminoethyl benzoate, 4-dimethylaminobenzoate isoamyl, 4,4'-di (t-butylperoxycarbonyl) Benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethyl benzoyl diphenyl phosphine 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 (trichloro) -Yl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, 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-cyclo) Ntajien-1-yl) - bis (2,6-difluoro-3-(1H-pyrrol-1-yl) - phenyl) titanium, and the like. These compounds may be used alone, and it is also effective to use two or more in combination. 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) Preferred is carbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone and the like.
The amount of the polymerization initiator used in the above-mentioned addition polymerization is preferably about 0.01 to 10 mol% with respect to the total number of moles of the monomers. These photopolymerization initiators may be used alone or in combination of two or more.

  A chain transfer agent may be used in the addition polymerization. The molecular weight can be appropriately controlled by using a chain transfer agent. Examples of chain transfer agents include thio-β-naphthol, thiophenol, butyl mercaptan, ethyl thioglycollate, mercaptoethanol, mercaptoacetic acid, isopropyl mercaptan, t-butyl mercaptan, dodecanethiol, thiomalic acid, pentaerythritol tetra (3 -Mercaptans such as mercapto propionate) and pentaerythritol tetra (3-mercapto acetate); Disulfides such as diphenyl disulfide, diethyl dithioglycolate and diethyl disulfide; toluene, methyl isobutyrate, etc. Carbon tetrachloride, isopropyl benzene, diethyl ketone, chloroform, ethyl benzene, butyl chloride, s-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, chloride 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 to make the molecular weight distribution uniform. These chain transfer agents can be used alone or in combination of two or more.

  As a solvent used when preparing a coating liquid (photocurable resin composition) in which a photocurable resin is dissolved or dispersed in a solvent, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, etc. Alcohols, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, ketones such as 2-heptanone, 4-heptanone, toluene, Aromatic hydrocarbons such as xylene and tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, pro Glycol ethers such as pyrene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, Butyl cellosolve acetate, carbitol 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 Acetate esters such as diethylene glycol Lumpur dialkyl ethers, dipropylene glycol dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, etc. N- dimethylformamide and the like. These solvents may be used alone or in combination of two or more.

In addition, additives such as antifoaming agents for preventing the generation of air bubbles may be used in the coating solution in which the photocurable resin is dissolved or dispersed in a solvent. As an antifoamer, a mineral oil type compound etc. are illustrated.
Furthermore, additives such as a plasticizer, a UV absorber, an antioxidant, and a silane coupling agent may be contained, if necessary.

  The method for forming the organic film layer is not particularly limited, but in order to uniformly coat the photocurable resin composition, it is preferable to use a wet coating method (coating method). By using the coating method, excellent surface flatness can be obtained. Among the coating methods, in the case of producing a small amount, a spin coating method which is simple and enables uniform film formation is preferable. In the case of roll-to-roll where productivity is important, the 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 The knife coating method, the curtain coating method, the rod coating method and the like are preferable. The coating method can be appropriately selected from among these methods in accordance with the film thickness, viscosity, curing conditions and the like required.

Drying of the applied coating solution can be performed by hot air or the like in an environment of room temperature to about 200 ° C. After the application and drying, a photoactive energy ray or an electron beam is irradiated and cured by an active energy ray source. The light active energy source is not particularly limited, but depending on the nature of the photopolymerization initiator used, for example, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, carbon arc, xenon arc, gas laser, solid state laser And electron beam irradiation devices.
The drying furnace passing time for drying differs depending on the line speed, the type and thickness of the coating solution, and the apparatus capacity (air volume, area, etc.). For example, 1 minute to 105 minutes can be mentioned. The dose for curing also varies depending on the material and thickness. For example, when using a high pressure mercury lamp, about 200-700 mJ / cm < ² > can be mentioned.

[Surface modifier]
The surface conditioner to be added to the organic film layer is a fluorine-free compound having a (meth) acrylate as a main chain. When such a compound is used as a surface control agent, the adhesion between the organic film layer and the gas barrier film layer can be improved. Therefore, it is possible to suppress peeling of the gas barrier film layer in the manufacturing process of a photoelectric device, an OLED device, an OPV device or the like using the gas barrier film laminate of the present invention. In addition, the gas barrier film layer is not easily peeled off even after long-term storage or in a high temperature and high humidity environment, and the gas barrier film laminate can be used as a durable gas barrier film laminate.

When the compound having (meth) acrylate as the main chain does not contain fluorine, the surface free energy of the cured organic film layer is prevented from being excessively reduced, and sufficient adhesion between the organic film layer and the gas barrier film layer is achieved. Can be secured.
Furthermore, the compound having (meth) acrylate as the main chain may be a compound not containing halogen other than fluorine, or may be a compound not containing silicon.

  The weight percent concentration of the surface conditioner contained in the organic film layer after curing is preferably 0.01 to 2.5% by weight, more preferably 0.05 to 1.5% by weight, and still more preferably 0.1 to 0.1% by weight. It is 1.0% by weight. The surface modification effect can fully be exhibited as it is 0.01 weight% or more. Moreover, the deterioration of the surface flatness by the excessive orientation to the surface can be prevented as it is 2.5 weight% or less.

  Since the surface conditioner is oriented on the surface of the organic film layer, the effect of the surface conditioner becomes greater as the thickness of the organic film layer becomes thinner, even if the concentration by weight contained in the organic film layer is the same. Further, the proportion of the surface conditioner to be oriented on the surface differs depending on the compatibility of the resin used for the organic film layer and the surface conditioner. Therefore, the optimum concentration can be appropriately selected in consideration of the film thickness and the compatibility between the resin and the surface control agent.

As a compound which does not contain the fluorine which has a (meth) acrylate as a principal chain used for a surface conditioner, BYK-350, BYK-352, BYK-354, BYK-354, BYK-355, BYK-356, made by Big Chemie Japan KK BYK-358N, BYK-361N, BYK-392, BYK-394, BYK-3550, polyflow No. 1 manufactured by Kyoeisha Chemical Co., Ltd. 36, polyflow no. 56, Polyflow No. 85HF, polyflow no. 99C, etc. Particularly preferably, BYK-354 and BYK-3550 manufactured by Big Chemie Japan Ltd. can be mentioned. In addition, as long as it is a compound which has (meth) acrylate as a principal chain, you may contain silicon in a side chain.
The “compound containing no fluorine having (meth) acrylate as the main chain” includes not only low molecular weight compounds but also high molecular weight compounds, as long as the compounds function as surface regulators in the present invention. The molecular weight of the compound is appropriately selected depending on the degassing property and the leveling property.

[Gas barrier layer]
The gas barrier film layer included in the gas barrier film laminate is a film mainly formed of a metal oxide, which is formed by plasma CVD, and is a single film or a composite film.
In addition, metal nitride may be contained in the said gas barrier film layer in the range which does not inhibit the effect of this invention.

  The thickness of the gas barrier film layer is preferably 0.2 to 2 μm, more preferably 0.3 to 1.5 μm, and still more preferably 0.5 to 1.5 μm. While the film thickness uniformity becomes favorable as it is 0.2 micrometer or more, the diffusion process of a gas molecule becomes long and it is excellent in gas barrier performance. While being able to suppress the curl and coloring of a gas barrier film laminated body as it is 2 micrometers or less, while becoming a more transparent gas barrier film, the crack by bending becomes difficult to generate | occur | produce.

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

Thus, as a film formation method of a gas barrier film layer, plasma CVD method can be used preferably. More preferably, a roll-to-roll plasma CVD method can be used in terms of productivity and stability of quality.
Note that CVD (Chemical Vapor Deposition, chemical vapor deposition) supplies one or more source gases of a compound containing the constituent elements of a thin film material to be produced onto a film formation target (for example, a base material), Plasma CVD is a method of forming a reactive gas into a plasma state, generating active radicals and ions, and performing a chemical reaction in an active environment. Further, as shown in FIG. 5, with roll-to-roll, a film-forming target wound in a roll is sent out from the delivery roll 31, and the target substance is formed on the surface and printed. It is a production method of winding and collecting on the take-up roll 32).

There are various types of film forming apparatuses by the plasma CVD method, but there is no limitation as long as the object of the present invention is not impaired.
For example, JP 2005-504880 A comprises a pair of film forming rolls for winding and transporting a film to be formed, forming a magnetic field so as to straddle 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 supplies high frequency power of several tens to several hundreds kHz, generates a penning discharge in an opposing space (discharge area) between rolls and confines plasma and oxygen in the opposing space It is described that a source gas such as H.D. and hexamethyldisiloxane (HMDSO) is supplied to simultaneously form a film on a film forming roll on both sides of a discharge region.

  Further, in Japanese Patent No. 2587507, a pair of film forming rolls (metal drums) disposed opposite to each other in a vacuum chamber, and an AC power supply in which one electrode and the other electrode are connected to one film forming roll and the other. A plasma CVD film forming apparatus is described which is disposed in an opposing space between the film forming rolls and has a discharge chamber whose surface facing the film forming roll is released and a monomer (raw material) gas supply means connected to the discharge chamber. It is done.

Furthermore, according to Japanese Patent No. 4268195, a pulse voltage accompanied by alternating current or polarity reversal is applied to the film forming rolls disposed opposite to each other under reduced pressure, and an opposing space (film forming zone) is disposed between the oppositely disposed film forming rolls. An apparatus is disclosed which generates glow discharge and forms a film by plasma CVD on a band-like base material which is wound facing the 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.

  As a metal oxide used as a main component of a gas barrier film layer, silicon oxide, aluminum oxide, titanium oxide etc. are mentioned, for example. In applications where transparency is required for the gas barrier film laminate, silicon oxide is more preferred.

As a raw material gas used for formation of a gas barrier film layer, an organic metal compound is preferable, for example, an organic silicon compound containing silicon, an organic aluminum compound containing aluminum, etc. can be used. Among these raw material gases, it is more preferable to use an organic silicon compound from the viewpoints of the handleability of the compound and the ability to impart flexibility and high gas barrier properties to the obtained gas barrier film layer.
Examples of organic silicon compounds include HMDSO, 1.1.3.3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethoxysilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyl Triethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, octamethylcyclotetrasiloxane and the like.
Among these organic silicon compounds, HMDSO, 1.1.3.3-tetramethyldisiloxane, and tetraethoxysilane are particularly preferable from the viewpoints of the handleability of the compound and the properties such as gas barrier properties of the obtained thin film layer. The raw materials such as these organosilicon compounds can be used singly or in combination of two or more.
As an organic aluminum compound, trimethyl aluminum etc. are mentioned, for example.

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

  A carrier gas may be used as necessary for supplying the source gas into the vacuum chamber as a film forming gas. Furthermore, as a gas for film formation, a discharge gas may be used as necessary to generate plasma discharge. As such carrier gas and discharge gas, known ones can be appropriately used, and for example, rare gases such as helium, argon, neon, xenon and the like can be used.

Gases for such film formation (gases used for film formation, such as source gas, reaction gas, carrier gas, and discharge gas) are collectively referred to as “film formation gas”. The mixing ratio of the reaction gas to the raw material gas is the molar amount of the reaction gas used when the molar ratio of the reaction gas theoretically required for completely reacting with 1 mol of the raw material gas is A. The range of (0.2 to 1.5) is preferable, and the range of A × (0.3 to 1.25) is more preferable.
For example, in the case where a film forming gas containing HMDSO as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to form a gas barrier film layer, it is described in the following reaction formula (1) A reaction like that occurs.
(CH ₃ ) ₆ Si ₂ O + 12 O ₂ → ₂ SiO ₂ + 6 CO ₂ + 9 H ₂ O (1)
The theoretical amount of oxygen, which is a reaction gas, is 12 moles with respect to 1 mol of HMDSO, which is a source gas. Therefore, in this case, the molar ratio of oxygen is preferably 12 × (0.2 to 1.5) = 2.4 to 18 moles, more preferably 3.6 to 15 moles per mole of HMDSO. .
If the proportion of the reaction gas is too low, an organic component derived from the source gas (for example, when HMDSO is used as the source gas), carbon formed by the methyl group contained in the source is contained in the formed gas barrier film If the ratio of the reaction gas is too high, the reaction proceeds too much, the gas barrier film becomes brittle and the flexibility and durability deteriorate.

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

  The electric power applied for discharging 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 0.2 to 10 kW. If the applied power is not less than the lower limit, the reaction of the raw material gas is insufficient and the gas barrier property is not lowered, and if it is not more than the upper limit, the temperature of the surface of the film formation target (for example, substrate) Is not raised, and wrinkles are not generated on the film formation target, and irregularities are not generated on the film surface to impair the appearance.

  The transport speed of the film formation 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. It is more preferable to set it in the range of / min. If the line speed is at least the lower limit, wrinkles due to heat are less likely to be generated in the resin film being transported, and if it is at the upper limit or less, the thickness of the thin film layer formed may be too thin. Absent.

The gas barrier film layer contains an organic component. For example, when a thin film is formed by plasma CVD from a deposition gas (a mixed gas of HMDSO as a source gas and an oxygen gas (also functioning as a discharge gas) as a reaction gas) to form a gas barrier film layer, the following reaction formula 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 → SiO x Cy (2)

  The surface (resin film surface, organic film layer surface, gas barrier film layer surface) of the gas barrier film laminate of the present invention may be subjected to surface modification treatment such as corona treatment or plasma treatment for the purpose of improving adhesion.

The gas barrier film laminate of the present invention comprises an organic film layer containing, as a surface control agent, at least one kind of compound containing no fluorine having (meth) acrylate as a main chain on at least one surface of the resin film. It has a gas barrier film layer, and preferably the gas barrier film layer is in contact with the organic film layer.
Compared with the case where resin film / gas barrier film layer / organic film layer is laminated in the order of resin film / organic film layer / gas barrier film layer, the organic film layer and the gas barrier film layer are laminated in the order of resin film / organic film layer / gas barrier film layer. It is more preferable because a gas barrier film laminate having high gas barrier properties can be obtained by suppressing pinholes caused by unevenness or foreign matter to be formed into a film.

The gas barrier film laminate formed by the constitution of the present invention has a high water vapor permeability (temperature: 40 ± 0.5 ° C., relative humidity: 90 ± 5% RH), and a high gas barrier of 0.005 g / m ² / day or less. Express sex. 0.001 g / m ² / day or less can be expressed by optimizing the film forming conditions etc. Furthermore, 0.0001 g / m ² / day or less can be obtained by optimizing the thickness of the organic film layer and the gas barrier film layer. Is achieved.

The gas barrier film laminate of the present invention is preferably made of only a transparent material when used for applications such as photoelectric devices, OLED devices, or OPV devices, and is measured according to the JIS K-7361-1 method. The total light transmittance is preferably 80% or more, more preferably 85% or more, and particularly preferably 88% or more.
However, when it is desired to block the transmission of visible light or ultraviolet light, or when the transparency is not required so much, it may be produced as an opaque gas barrier film laminate.

[Use]
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. In particular, it can be usefully used for blocking various gases such as an OLED element or an OPV element, and is preferable. Moreover, when a gas barrier film laminated body is transparent, when it uses for a photoelectric device like an OPV element, it can comprise so that sunlight reception may be performed from the side of a gas barrier film laminated body. In addition, when used in an OLED element, the light emission efficiency is not deteriorated because the light emission from the element is not hindered.

  FIG. 2A shows a schematic view of an electronic component having an OLED element in a conventional solid sealing method. An OLED element 22 having a positive and negative electrode and an organic material sandwiched between the positive and negative electrodes is disposed on a glass substrate 21, and the entire OLED element 22 is covered with a solid sealant 23. In the electronic component of such a configuration, as shown in FIG. 2B, the gas barrier film laminate 10 of the present invention can be used in place of the glass substrate 21.

  Moreover, as shown in FIG. 3, it is good also as a sandwich structure which pinched | interposed the OLED element 22 by the gas barrier film laminated body 10 of this application. In that case, the gas barrier film laminate 10 may be adhered with the adhesive 25.

FIG. 4A shows a schematic view of an electronic component having an OLED element in a conventional hollow structure. An OLED element 22 having a positive electrode and a negative electrode and an organic material sandwiched between the positive electrode and the negative electrode is disposed on the glass substrate 21 and covered with a glass sealing material 28 which exists separately. The glass substrate 21 and the glass sealing material 28 are bonded (sealed) by an adhesive 25 on both sides. A getter 26 for adsorbing water is disposed inside the hollow and filled with N ₂ gas 27. In the conventional electronic component having such a configuration, as shown in FIG. 4B, the gas barrier film laminate 10 of the present application can also be used as a substitute for the glass substrate 21 and the glass sealing material 28.
Also in the OPV element having the positive and negative electrodes and the semiconductor material sandwiched between the positive and negative electrodes, the gas barrier film laminate of the present invention can be used as a substitute for the glass substrate 21 as well.

As described above, when the gas barrier film laminate of the present invention is used as a transparent substrate for an OLED element, an OPV element, a liquid crystal element, etc., it is possible to meet the demands for weight reduction and enlargement. Furthermore, after a substrate such as a roll-to-roll (rolled resin film or the like is sent out and the target substance is formed into a film on the surface of the substrate, etc., it is wound up again in a roll shape and recovered. Method), high degree of freedom of shape, curved surface display, etc. are replaced with glass substrates that are heavy and fragile and difficult to be enlarged. , Can meet.
Although a film base such as a transparent plastic has conventionally had a problem that the gas barrier property is inferior to that of glass, when the gas barrier film laminate of the present invention is used, for example, an electronic component such as an OLED element or an OPV element When used as a material of the above, it is possible to suppress degradation of performance as a substrate having excellent gas barrier properties due to penetration of water (water vapor) or oxygen and deterioration of components constituting the device.

  As described above, the present invention mainly relates to a display element represented by an organic electroluminescent element (OLED element) or a liquid crystal element, a photoelectric element represented by an organic solar cell element (OPV element), illumination using an OLED element, etc. It is a gas barrier film laminate which can be used for the product of The gas barrier film laminate of the present invention is characterized by high durability, excellent productivity, little curl, and good gas barrier properties since the adhesion and flexibility of the gas barrier film layer and the organic film layer are excellent. .

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

<Film thickness>
The fault plane of the gas barrier film laminate was observed under the following conditions using a scanning electron microscope (SEM), and the film thicknesses of the gas barrier film layer and the organic film layer were measured.
-SEM observation device: SU-70 manufactured by Hitachi, Ltd.
Acceleration voltage: 7kV

<Adhesiveness>
The adhesion of the produced gas barrier film laminate was evaluated based on JIS K5600-5-6 (adhesion [cross cut method]). The adhesion was evaluated after treatment (accelerated deterioration test) for 500 hours in a room temperature environment of 23 ± 2 ° C. and 50 ± 10% RH and a moist heat environment of 85 ° C. and 85% RH. The moist heat environment was realized by the following thermo-hygrostat.
Constant temperature and humidity chamber: ESPEC Co., Ltd. constant temperature and humidity chamber LHL-113
・ Crosscut method Cutting interval: 2 mm
Number of cuts: 5 × 5 judgment: ○: Peeling area ≦ 5%
Δ: 5% <peeled area ≦ 30%
X: 30% <peeled area

<Water vapor permeability (WVTR)>
Although the method of measuring the water vapor transmission rate is not particularly limited, in the present invention, evaluation was carried out by the method described in ISO15106-3 or the Ca corrosion method described below.
・ Measurement method 1 (ISO15106-3 method)
Evaluation device: manufactured by Illinois Water Vapor Permeability Measurement Device Model 7002 (ISO 15106-3), measurement limit value 2 × 10 ⁻³ (gm ⁻² day ⁻¹ )
Temperature and humidity: 40 ° C, 90% RH
・ Measurement method 2 (Ca corrosion method)
When it became below the measurement limit value by the said measurement method 1, water vapor transmission rate was measured by the Ca corrosion method. The Ca corrosion method is a method in which metallic calcium is vapor-deposited on one surface of a gas barrier film laminate, Ca is sealed with Al and wax, and the phenomenon that metallic Ca is corroded by moisture transmitted through the film is used. The water vapor permeability is calculated from the corrosion area and the time to reach it. In the present invention, evaluation was carried out under the method described in Japanese Patent No. 3958235 and the conditions shown below.
・ Ca corrosion method used in the evaluation of the present invention Deposition apparatus: Sanyu Electronics Co., Ltd. electron beam vacuum deposition apparatus SVC-700LEB
Constant temperature and humidity chamber: ESPEC Co., Ltd. constant temperature and humidity chamber LHL-113
Metals that react with moisture and corrode: Calcium (granular)
Water-impermeable metal for Ca sealing: Aluminum (φ3 to 5 mm, granular)
Sealing material: Weight ratio 1: 1 mixture of paraffin (melting point 60-62 ° C.) / Beeswax (melting point 61-65 ° C.) Observation device: Calcium corrosion observation device MFB-1000 made by Three Tsuwa Frontech Co., Ltd.

Flexibility
The flexibility of the produced gas barrier film laminate was evaluated based on JIS K5600-5-1 (cylindrical mandrel method).

Example 1
Base material A polyethylene terephthalate (PET) film (made by Toyobo Co., Ltd., trade name "Cosmo Shine A4300"), which is 125 μm thick and 550 mm wide and is easily adhered on both sides. Using.

Preparation of photocurable resin composition (coating solution) (A) Unidic 17-806 (trade name, urethane acrylate / acrylate monomer / normal butyl acetate / toluene = 35 to 40 parts by weight / 35 to 40 parts by weight / 15 -25 parts by weight / 1 to 5 parts by weight of a mixture, UV-curable coating agent manufactured by DIC Corporation 42 parts by weight (B) methyl ethyl ketone (Wako Pure Chemical Industries, Ltd. solvent) 56.2 parts by weight (C) IC 184 (trade name, a photopolymerization initiator manufactured by BASF Japan Ltd.) 1.8 parts by weight (D) BYK-354 (trade name, a product manufactured by Bick Chemie Japan Ltd.) A compound having (meth) acrylate as a main chain Surface control agent) 0.1 parts by weight (parts by weight based on 100 parts by weight of the total of (A), (B) and (C))
Was prepared.

-Formation of an organic film layer After applying the coating solution to a dry thickness of 5 μm on the substrate using a die coater in a roll-to-roll precision coating apparatus, The drying was performed at a temperature of 85 ° C., an air flow of 20 m / sec, and a residence time in a drying oven of 50 seconds. Thereafter, photocuring was performed at a dose of 300 mJ / cm ² using a high pressure mercury lamp under a nitrogen atmosphere to form an organic film layer.

-Formation of a gas barrier film layer It is possible to form a film by roll-to-roll on the surface of the base material treated with the organic film layer, using a plasma CVD apparatus (Model No. W35 type) PE-CVD made by Kobe Steel. , And a gas barrier film layer was formed.
Plasma is generated between the discharge electrodes under the conditions shown below, a film forming gas comprising the following components is supplied to the discharge region, and a thin film is formed by the plasma CVD method according to the method described in JP 2012-81632A. To obtain a gas barrier film laminate having a gas barrier film layer having a thickness shown in Table 1.
Components of film forming gas Source gas: HMDSO (made by Asmax Co., Ltd., trade name "SIH 6115.0")
Reactive gas: Oxygen gas (Suzuki Shokan Co., Ltd. High purity oxygen, purity ≧ 99.999%)

Example 2
Preparation of Photocurable Resin Composition (Coating Liquid) (A) Unidic V-6841 (trade name, (meth) acrylic acid ester polymer / acrylate monomer / methyl isobutyl ketone = 25 to 35 parts by weight / 25 to 35 parts by weight Part: 35 to 45 parts by weight of a mixture, DIC Corporation UV curable coating agent 55 parts by weight (B) Methyl ethyl ketone (Wako Pure Chemical Industries, Ltd. solvent) 43.2 parts by weight (C) IC 184 (merchandise Name, BASF Japan Ltd. product photopolymerization initiator 1.8 parts by weight (D) BYK-3550 (trade name, product of Big Chemie Japan Co., Ltd.) surface conditioner which is a compound having (meth) acrylate as a main chain 0.1 parts by weight (parts by weight relative to 100 parts by weight of the total of (A), (B) and (C))
A gas barrier film laminate was produced in the same manner as in Example 1 except for the preparation of the coating solution of the photocurable resin composition.

Comparative Example 1
A gas barrier film laminate was produced in the same manner as in Example 1 except that the surface conditioner was changed to the following.
BYK-315 (trade name, a surface conditioner which is a compound having a silicone main chain, manufactured by Bick Chemie Japan KK) 0.1 parts by weight

Comparative Example 2
A gas barrier film laminate was produced in the same manner as in Example 1 except that the surface control agent was not used.

Comparative Example 3
A gas barrier film laminate was produced in the same manner as in Example 2 except that the surface conditioner was changed to the following.
BYK-UV 3510 (trade name, a surface conditioner which is a compound having a silicone main chain manufactured by Big Chemie Japan KK) 0.2 parts by weight (the above-mentioned (A), (B) and (C) in Example 2) Parts by weight based on a total of 100 parts by weight)

Comparative Example 4
A gas barrier film laminate was produced in the same manner as in Example 2 except that the surface control agent was not used.

  As shown in Table 1, when a compound having (meth) acrylate as the main chain is used as a surface conditioner (Examples 1 and 2), the gas barrier film layer is an organic film even in a room temperature environment or after an accelerated deterioration test. It has good adhesion to the layer. However, when a compound having a silicone main chain is used as a surface conditioner (Comparative Examples 1 and 3), adhesion is insufficient even at room temperature, and adhesion after accelerated deterioration test is very poor. . When no surface conditioner is used (comparative examples 2 and 4), the adhesive property is sufficient at room temperature, but the adhesive property after the accelerated deterioration test is very bad. In addition, when a compound having (meth) acrylate as the main chain is used as a surface conditioner, it is compared with the case where a surface conditioner is not used or a compound having a silicone as a main chain is used as a surface conditioner. And the flexibility is improved. Furthermore, the gas barrier film laminate of the examples has extremely high gas barrier properties.

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

DESCRIPTION OF SYMBOLS 10 Gas barrier film laminated body 11 Resin film 12 Organic film layer 13 Gas barrier film layer 21 Glass base material 22 OLED element 23 Solid sealing material 25 Adhesive 26 Getter 27 N ₂ gas 28 Glass sealing material 31 Delivery roll 32 Winding roll 33 roller

Claims (10)

A resin film as a base material;
At least one organic layer and at least one gas barrier layer on at least one side of the resin film;
The organic film layer contains a surface conditioning agent, and the surface conditioning agent contains a fluorine-free polymer compound having (meth) acrylate as a main chain,
The surface conditioner is oriented on the surface of the organic film layer,
The content of the fluorine-free polymer compound having the (meth) acrylate as a main chain is 0.01 to 2.5% by weight with respect to the organic film layer,
The gas barrier film layer contains a metal oxide as a main component, further contains an organic component, and is deposited by plasma CVD method.
Gas barrier film laminate. The surface roughness of the organic film layer is such that the arithmetic average roughness Sa is 5 nm or less.
The gas barrier film laminate according to claim 1. The water vapor transmission rate at 40 ° C., 90% RH is 0.005 g / m ² / day or less,
The gas barrier film laminated body of Claim 1 or Claim 2. The thickness of the organic film layer is 0.1 to 20 μm,
The thickness of the gas barrier film layer is 0.2 to 2 μm.
The gas barrier film laminated body of any one of Claims 1-3. The organic film layer is a film obtained by photopolymerizing a photocurable resin composition.
The gas barrier film laminated body of any one of Claims 1-4. The photocurable resin composition contains an acrylic resin as a photocurable resin ,
The gas barrier film laminate according to claim 5. The organic film layer is laminated by a coating method,
The gas barrier layer is laminated by a roll-to-roll plasma CVD method.
The gas barrier film laminated body of any one of Claims 1-6. The resin film is a film based on a resin which is polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, polycarbonate, polyimide, or a mixture thereof.
The gas barrier film laminated body of any one of Claims 1-7. An electronic device having a positive and negative electrode, and an organic material sandwiched between the positive and negative electrodes;
The gas barrier film laminate according to any one of claims 1 to 8, which protects the electronic device from water vapor;
Electronic parts. The gas barrier film laminate is transparent,
The electronic device is an OLED device or an OPV device.
The electronic component according to claim 9.

Images