TW201522041A - Transparent gas barrier film - Google Patents

Abstract

The present invention addresses the problem of obtaining a film having high gas barrier properties against water vapor, etc., while still having high transmittance. A film having, on a substrate, a cured-substance layer composed of a polymerizable resin composition containing at least one (meth)acrylate compound having a trimethylol propane skeleton or an isocyanuric skeleton, and having on the cured-substance layer a layer with a thickness of 50-500 nm including silicon and nitrogen, wherein the problem is addressed by using a transparent barrier film characterized in that the (meth)acrylate compound content is 40-99 weight parts per 100 weight parts of the polymerizable resin composition, the thickness of the cured layer being 0.1-20 [mu]m, and transmittance being 75% or more.

Description

Transparent gas barrier film

The present invention relates to a transparent gas barrier film.

The gas barrier film is used in a large amount to prevent deterioration of articles, foods, foods, and the like of various gases such as water vapor or oxygen. Further, it is used in liquid crystal display elements, solar cells, and organic electroluminescence (hereinafter, simply referred to as OLED (Organic Light Emitting Diode)). The gas barrier film generally used in the field of packaging may also have a low transparency or a high degree of gas barrier properties. Therefore, the gas barrier film cannot be used in the field of display materials. In recent years, the use of ruthenium oxide, ruthenium oxynitride, etc., which are not transparent materials such as alumina or magnesia, has been used to continuously develop a film having high transparency and high water vapor barrier properties, but transparency and resistance. A film having good gas, adhesion, and durability has not been developed, and various studies have been conducted.

In particular, in the field of OLEDs, in recent years, in addition to the requirements for enlargement and weight reduction, transparent films are required to have high long-term reliability, high degree of freedom of shape, surface display, and easy handling without cracking. . However, in the field of OLEDs, if a slight amount of water is contained, the display function is lowered, so that a high gas barrier property equivalent to that of glass is required. On the other hand, if the glass itself is used, there is a problem of cracking when it is bent or dropped. Therefore, it is impossible to use glass or its equivalent film.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-251429

[Patent Document 2] Japanese Patent Laid-Open No. 6-124785

[Patent Document 3] Japanese Patent No. 3484891

[Patent Document 4] Japanese Patent Laid-Open No. 2006-299145

[Patent Document 5] Japanese Patent Laid-Open No. 2011-201135

[Patent Document 6] Japanese Patent Laid-Open No. 2011-238355

[Non-patent literature]

[Non-Patent Document 1] Continued Learning Society Vol. 71 (2002) No. 4, P12-P16

[Non-Patent Document 2] Department of Mechanical Engineering, Tokai University Vol.31, No.1, 1991, P23-30

[Non-Patent Document 3] Nagoya University Graduate School of Engineering 2008 Annual Monk Paper Report No.: No. 8422, Fukaya

[Non-Patent Document 4] Ultraviolet curing system, integrated technology center (share) publication, Kato clears P259-P302

[Non-Patent Document 5] Japanese Ceramic Society Academic Papers 101 (1180), 1419-1422, 1993-12-01

[Non-Patent Document 6] Kiln Industry Association 88 (1021), 511-515, 1980-09-01

As a technique for the above problems, Patent Literature 1 to Patent Document 3 disclose techniques for a gas barrier film having a high barrier property. However, a film such as a transparent plastic has a problem of poor gas barrier properties against glass, and cannot be used in an OLED or the like. Patent Document 4 discloses a ceramic film formed by a sol-gel method using a metal alkoxide, and Patent Document 5 and Patent Document 6 disclose that the resistance is improved by using an inorganic compound and an organic compound. Gas technology. However, even with the above technique, it is not possible to obtain high transparency, high gas barrier properties, high adhesion, sufficient durability, and excellent productivity. membrane.

Among the above-mentioned proposals, techniques for improving physical properties of metal films by improving physical vapor phase growth (PVD) or chemical vapor deposition (CVD) are disclosed in Non-Patent Documents 1 to 3. It is known that the metal film obtained by the above method has high gas barrier properties. However, in spite of this, the gas barrier property is insufficient, and in particular, the adhesion of the metal film to the substrate is poor, and the flexibility of the metal film is largely lowered. Therefore, cracking occurs in the metal film when the film is bent, and gas barrier is caused. The sex is greatly reduced. In order to improve the adhesion or flexibility, it has been studied to apply a metal film to a cured resin layer formed of a (meth) acrylate compound. However, when applied to the cured layer of the resin, the surface is usually cloudy and haze is generated. The transparency is lowered, the adhesion is lowered, and the adhesion is lowered after the high temperature and high humidity test.

In order to solve the above-mentioned problems, the inventors of the present invention have conducted intensive studies, and as a result, have found that they are attached to a substrate and have at least one (meth) group having a trimethylolpropane skeleton or a hetero-cyanuric acid skeleton. a cured resin layer formed of a polymerizable resin composition of an acrylate compound, and a film containing a layer of cerium and nitrogen having a thickness of 50 nm to 500 nm on the resin cured layer, and the (meth) acrylate The content of the compound is from 40 parts by weight to 99 parts by weight based on 100 parts by weight of the polymerizable resin composition, the thickness of the cured resin layer is from 0.1 μm to 20 μm, and the transmittance of the film is more than 75%. High, high gas barrier properties, high adhesion, good durability, and excellent productivity.

That is, the present invention relates to "(1) a film characterized in that it has a (meth) acrylate containing at least one skeleton having a trimethylolpropane skeleton or a hetero-cyanuric acid skeleton on a substrate. a cured layer formed of a polymerizable resin composition of a compound, and a film containing a layer of tantalum and nitrogen having a thickness of 50 nm to 500 nm is contained on the cured layer, and The content of the (meth) acrylate compound is 40 parts by weight to 99 parts by weight based on 100 parts by weight of the polymerizable resin composition, and the thickness of the cured layer is 0.1 μm to 20 μm, and the transmittance is 75% or more; (2) The film according to the above (1), wherein the polymerizable resin composition contains 10 parts by weight of the (meth) acrylate compound having a dicyclopentadiene skeleton to 100 parts by weight of the polymerizable resin composition. (3) The film according to the above-mentioned (1) or (2), wherein the polymerizable resin composition contains a fluorine-based compound having a branched perfluoroalkenyl group in an amount of 100 parts by weight based on 100 parts by weight of the polymerizable resin composition. The film according to any one of (1) to (3), wherein the layer containing ruthenium and nitrogen further contains aluminum as an element; (5) a film A liquid crystal display device using the film according to any one of (1) to (4), wherein the organic electroluminescence device is used according to any one of (1) to (4). (7) The film according to any one of (1) to (4) wherein the layer containing cerium and nitrogen is formed by ion beam assisted vapor deposition. (8) The film according to any one of (1) to (4) wherein the layer containing niobium and nitrogen is formed by magnetron sputtering.

The film of the present invention has high transparency, high gas barrier properties, high adhesion, and good durability, and excellent productivity.

The present invention relates to a film characterized in that it is attached to a substrate a cured layer formed of a polymerizable resin composition of at least one (meth) acrylate compound having a trimethylolpropane skeleton or a hetero-cyanuric acid skeleton, and having a thickness of 50 nm to 500 nm on the cured layer a film comprising a layer of cerium and nitrogen, and the content of the (meth) acrylate compound is 40 parts by weight to 99 parts by weight based on 100 parts by weight of the polymerizable resin composition, and the thickness of the cured layer is 0.1 From μm to 20 μm, the transmittance is 75% or more.

The substrate of the present invention is not particularly limited as long as it is formed of an organic material capable of maintaining transparency and gas barrier properties. The organic material may, for example, be acrylate, methacrylate or polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter, simply referred to as " PEN"), polycarbonate, polyarylate, polyvinyl chloride, polyethylene, polypropylene, nylon, polyimine, polyamine, cyclic olefin, triacetyl cellulose, sesquiterpene oxide as the basic skeleton As the organic or inorganic mixed organic material, a film having a thickness of 5 μm to 500 μm may be used as the substrate. A film comprising PET, PEN, or polycarbonate is preferred if cost or ease of acquisition is considered. In terms of birefringence, especially in that the phase difference is small, it is preferably formed by an organic or inorganic mixed organic material containing a cyclic olefin, triacetyl cellulose, and sesquiterpene alkane as a basic skeleton. membrane. Examples of the product of the film containing a cycloolefin include Zeonor manufactured by ZEON Co., Ltd., ARTON manufactured by JSR Corporation, and F film manufactured by Gunze Co., Ltd. as an organic or inorganic mixture containing sesquiterpene oxide as a basic skeleton. The film formed of the organic material can be exemplified by SILPLUS manufactured by Nippon Steel Chemical Co., Ltd. and Sila-DEC manufactured by Chisso Corporation.

The film of the present invention is provided with a layer formed of a cured product of 0.1 μm to 20 μm on a substrate. The layer of the cured product is formed of a polymerizable resin composition, and the polymerizable resin composition contains at least one (meth) acrylate compound having a trimethylolpropane skeleton or a hetero-cyanuric acid skeleton. The polymerizable resin composition contains, for example, 90 to 99.9 parts by weight of a (meth) acrylate compound having at least one propylene group, and 0.1 to 10 parts by weight of a polymerization initiator. Share. The polymerizable resin composition forming the cured layer must contain at least one (meth) acrylate compound having a trimethylolpropane skeleton or a hetero-cyanuric acid skeleton in an amount of 100 parts by weight relative to the polymerizable resin composition. The serving is from 40 parts by weight to 99 parts by weight. In order to improve the stability of hardening, the (meth) acrylate compound having a trimethylolpropane skeleton or an iso-cyanuric acid skeleton may be 50% by weight or more, more preferably 60% by weight based on the amount of the resin to which the composition is formulated. More than %, more preferably 70% by weight or more. When the (meth) acrylate compound having a trimethylolpropane skeleton or a hetero-cyanuric acid skeleton is 40% by weight or less, the performance of the present invention is not exhibited, which is not preferable. In the present invention, the (meth) acrylate compound having a trimethylolpropane skeleton is preferred because it has high transparency.

The polymerizable resin composition containing at least one of the (meth) acrylate compounds and the polymerization initiator can be cured to form a layer containing the polymerizable resin cured product. Specifically, as the (meth) acrylate compound, the acrylate monomer described in Non-Patent Document 4 can be used. The present invention is not limited to these, and is not particularly limited as long as it is a (meth) acrylate compound having at least one (meth) acrylonitrile group. In the polymerizable resin composition, a component other than the above (meth) acrylate compound, for example, various polymers or oligomers may be added, and it may be used without particular limitation as long as it is a component which does not inhibit hardening and its concentration. . The amount of the polymerizable resin composition may be adjusted in an arbitrary ratio, and is preferably 40 parts by weight to 99 parts by weight based on 100 parts by weight of the polymerizable resin composition.

As the (meth) acrylate compound having a trimethylolpropane skeleton, trimethylolpropane triacrylate [Kayarad TMPTA manufactured by Nippon Kayaku Co., Ltd.], EO-modified trimethylolpropane triacrylate can be exemplified. [SR-454 manufactured by Sartomer], PO modified trimethylolpropane triacrylate [TPA-310, TPA-320, TPA-330, etc. manufactured by Nippon Kayaku Co., Ltd.], trimethylolpropane trimethyl Acrylate [SR-350 manufactured by Sartomer], reaction product of trimethylolpropane triglycidyl ether and acrylic acid [DENACOL DA-321, manufactured by Nagase Industries Co., Ltd.], and the like.

As the (meth) acrylate compound having a hetero-cyanuric acid skeleton, dimethicone ethyl isocyanurate (Aronix M-215 manufactured by Toagosei Co., Ltd.), tripropylene sulfonate isocyanurate can be exemplified. Ethyl ester [FA-731A manufactured by Hitachi Chemical Co., Ltd.], caprolactone-modified tripropylene methoxyethyl isocyanurate [Aronix M-325 manufactured by Toagosei Co., Ltd.], trimethyl propylene sulfoxyl isocyanurate Ethyl ester [FA-731M manufactured by Hitachi Chemical Co., Ltd.].

Furthermore, by containing 10 parts by weight to 55 parts by weight of the (meth) acrylate compound having a dicyclopentadiene skeleton with respect to 100 parts by weight of the polymerizable resin composition, transparency can be obtained. Further, the film has a high gas barrier property, high adhesion, high durability, and excellent productivity. The preferred content of the (meth) acrylate having a dicyclopentadiene skeleton is 15% by weight to 50% by weight, and more preferably 20% by weight to 40% by weight. In the present invention, the polymerizable resin composition for forming a layer of a preferred polymerizable resin cured product contains a (meth) acrylate compound containing a trimethylolpropane skeleton or a hetero-cyanuric acid skeleton, and has two A composition of a (meth) acrylate of a cyclopentadiene skeleton and a polymerization initiator thereof, and a polymerizable resin composition for forming a layer of a further polymerizable resin cured product, which comprises a trimethylolpropane. A composition of a (meth) acrylate compound of a skeleton, a (meth) acrylate having a dicyclopentadiene skeleton, and a polymerization initiator thereof.

The (meth) acrylate compound having a dicyclopentadiene skeleton means, for example, a resin having a biscyclopentyl skeleton, a dicyclopentenyl skeleton or an adamantane skeleton. Among them, in order to further improve the wet heat durability, a resin having a bicyclopentyl skeleton or a dicyclopentenyl skeleton is preferred, and a resin having a bicyclopentyl skeleton is preferred. As the compound having a bicyclopentyl skeleton, for example, dicyclopentyl acrylate (FA-513A manufactured by Hitachi Chemical Co., Ltd.), dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), or dicyclopentyldiamide is preferable. Acrylate (Kayarad R-684, manufactured by Nippon Kayaku Co., Ltd.), etc. The compound having a dicyclopentenyl skeleton is preferably, for example, dicyclopentenyl acrylate (FA-511A manufactured by Hitachi Chemical Co., Ltd.) or dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd.). FA-512A) or dicyclopentenyloxyethyl methacrylate (FA-512M manufactured by Hitachi Chemical Co., Ltd.). Examples of the compound having an adamantane skeleton include 2-methyl-2-adamantyl methacrylate (Adamantate MM manufactured by Idemitsu Kosan Co., Ltd.) and 2-ethyl-2 adamantyl methacrylate (light-emitting) Adamantate EM manufactured by Hsinchu Co., Ltd., 3-hydroxy-1-adamantyl methacrylate (Adamantate HM manufactured by Idemitsu Kosan Co., Ltd.), 3-hydroxy-1-adamantyl acrylate (Adamantate manufactured by Idemitsu Kosan Co., Ltd.) HA), 2-methyl-2-adamantyl acrylate (Adamantate MA manufactured by Idemitsu Kosan Co., Ltd.) or 2-ethyl-2-adamantyl acrylate (Adamantate EA manufactured by Idemitsu Kosan Co., Ltd.).

When the (meth) acrylate compound or the polymerizable resin composition used in the present invention is polymerized by ultraviolet rays, ultraviolet rays are irradiated and a polymerization reaction is carried out by a photopolymerization initiator. The photopolymerization initiator may, for example, be 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1 (Irgacure-907, manufactured by Ciba Specialty Chemicals Co., Ltd.). 1-hydroxycyclohexyl phenyl ketone (Irgacure-184, manufactured by Ciba Specialty Chemicals, Inc.), 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl) ketone (manufactured by Ciba Specialty Chemicals Co., Ltd.) Irgacure-2959), 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one (Darocure-953, manufactured by Merck), 1-(4-isopropyl Phenyl)-2-hydroxy-2-methylpropan-1-one (Darocure-1116, manufactured by Merck), 2-hydroxy-2-methyl-1-phenylpropan-1-one (Ciba Specialty Chemicals, Inc.) Manufacture of Irgacure-1173), diethoxyacetophenone and other acetophenone-based compounds, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-2 A benzoin-based compound such as phenylacetophenone (Irgacure-651, manufactured by Ciba Specialty Chemicals Co., Ltd.), benzamidine benzoic acid, methyl benzhydrazide, 4-phenylbenzophenone, hydroxybenzophenone 4-Benzylmercapto-4'-methyldiphenyl sulfide , benzophenone-based compound such as 3,3'-dimethyl-4-methoxybenzophenone (kayacure MBP manufactured by Nippon Kayaku Co., Ltd.), thioxanthone, 2-chlorothioxanthone (Japanese Kayacure CTX), 2-methylthioxanthone, 2,4-dimethylthioxanthone (kayacure RTX manufactured by Nippon Kayaku Co., Ltd.) Isopropyl thioxanthone, 2,4-dichlorothioxanthone (kayacure CTX manufactured by Nippon Kayaku Co., Ltd.), 2,4-diethylthioxanthone (kayacure DETX manufactured by Nippon Kayaku Co., Ltd.), 2, A thioxanthone compound such as 4-diisopropylthioxanthone (kayacure DITX manufactured by Nippon Kayaku Co., Ltd.). More preferably, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1 (Irgacure-907, manufactured by Ciba Specialty Chemicals, Inc.), 1-hydroxycyclohexyl phenyl ketone (Irgacure-184, manufactured by Ciba Specialty Chemicals, Inc.) or 2,2-dimethoxy-2-phenylacetophenone (Irgacure-651, manufactured by Ciba Specialty Chemicals, Inc.). These photopolymerization initiators may be used in combination of one kind or a plurality of types in any ratio.

When a benzophenone-based compound or a thioxanthone-based compound is used as a photopolymerization initiator, an auxiliary agent may be used in combination in order to promote photopolymerization. Examples of such an auxiliary agent include triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate, and Michelin. Ketone, 4,4'-diethylaminobenzophenone, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy)ethyl ester or 4-dimethyl An amine compound such as isoamyl benzoate.

The photopolymerization initiator and the auxiliary agent are preferably used in an amount which does not cause a decrease in the polarizing performance, and the photopolymerization initiator is added in an amount relative to the (meth) acrylate in the polymerizable resin composition. 100 parts by weight of the compound is preferably 0.1 part by weight or more and 12 parts by weight or less, more preferably 2 parts by weight or more and 10 parts by weight or less. Further, the amount of the auxiliary agent added is preferably about 0.5 to 2 times the amount relative to the photopolymerization initiator.

When the (meth) acrylate compound or the (meth) acrylate resin composition used in the present invention is a thermosetting type, a polymerization initiator, a crosslinking agent and/or a starting catalyst are used. As the crosslinking agent, various known compounds such as an isocyanate type, a boron type, and a titanate type can be used, and it is not limited as long as it promotes polymerization. The amount of the crosslinking agent to be added is 0.1 part by weight or more and 20 parts by weight or less based on 100 parts by weight of the polymerizable resin composition, and preferably 1 part by weight or more and 10 parts by weight or less or less based on 100 parts by weight of the composition. .

In the present invention, a (meth) acrylate compound or a polymerizable resin composition is used. In the case of the ultraviolet curing type, it is more useful in the hardening treatment from the viewpoint of light stability, hardening time, and manufacturing cost as compared with the case of the heat curing type.

The layer of the polymerizable resin composition may also be provided by a method of applying to the substrate layer. It is possible to use not only a method of directly applying to a substrate but also a method of transferring a substrate or laminating a layer which is previously applied to another film and cured.

The method of coating is not particularly limited, and examples thereof include a spin coating method, a bar coating method, a gravure coating method, a micro gravure coating method, a calender coating method, a spray coating method, or a liquid surface bending method. Method of coating method, etc.

In the present invention, the polymerizable resin composition may further contain 0.01 parts by weight to 1 part by weight of a fluorine compound having a branched perfluoroalkenyl group or a derivative thereof, based on 100 parts by weight of the polymerizable resin composition. A film having high transparency, high gas barrier properties, high adhesion, sufficient durability, and excellent productivity. The fluorine compound having a branched perfluoroalkenyl group is a fluorine compound represented by the formula (1), and also includes a derivative of the compound. The amount thereof is 0.05 parts by weight or more and 0.9 parts by weight or less based on 100 parts by weight of the cured product, and more preferably 0.1 parts by weight or more and 0.8 parts by weight or less or less based on 100 parts by weight of the composition. Examples of the ionicity of the fluorine compound having a branched perfluoroalkenyl group or a derivative thereof include anionic, cationic, nonionic, and amphoteric types. Further, examples of the fluorine compound or a derivative thereof include an oligomer type and a reactive oligomer type. It shows that the effect is shown in a small amount, does not precipitate from the cured layer of the resin, and does not hinder the recoatability for depositing or sputtering a layer containing niobium and nitrogen afterwards, preferably non- The ionic type is more preferably a nonionic oligomer, and further preferably a nonionic reactive oligomer.

[Chemical 1]

The fluorine compound or a derivative thereof containing a branched perfluoroalkenyl group having a skeleton of the formula (1) may, for example, be a FTERGENT series owned by NEOS. Among the FTERGENT series, it is preferably 710FL, 710FM, 710FS, 730LM, 601AD, 602A, 650A, especially 601A, 602A, 650A, which can obtain higher transparency, higher gas barrier property and higher adhesion. A film which is sufficiently durable and excellent in productivity.

In order to make the hardened layer of the polymerizable resin more stable, an anti-deterioration aid may be added. The anti-deterioration aid refers to an antioxidant and a light stabilizer. Examples of the antioxidant include a phenolic antioxidant such as a hindered phenol or a semi-hindered phenol, an amine antioxidant such as a phenylenediamine, a phosphorus antioxidant such as a phosphite or a phosphonite, and a thioether. It is a sulfur-based antioxidant or the like. Examples of the light stabilizer include a benzophenone type or a benzotriazole type, and three An ultraviolet absorber such as an ultraviolet absorber or an organic nickel complex such as an excitation energy absorber (Quencher), carbon black or titanium oxide, or a 2,2,6,6-tetramethylpiperidine skeleton as a basic skeleton. A hindered amine light stabilizer (HALS) or the like. The concentration to be added is not particularly limited, and may be arbitrarily added depending on the ability of the anti-deterioration aid. Usually, it is added in an amount of 0.01% by weight to 5% by weight, preferably 0.05% by weight to 3% by weight, based on the polymerizable resin composition from which the solvent is removed.

In the case of forming a polymerizable resin cured layer, the polymerizable resin composition is diluted directly or by using a suitable solvent to be applied to a substrate. Thereafter, the solvent is removed by heating or the like, heated or irradiated with ultraviolet rays, whereby a polymerizable resin cured product can be obtained. The solvent of the solution of the composition used at the time of coating is not particularly limited as long as it is excellent in solubility of the composition and wettability on the substrate at the time of coating without causing a decrease in surface properties. limit. Examples of such a solvent include aromatic hydrocarbons such as water, toluene, and xylene, and anisole and Ethers such as alkane and tetrahydrofuran, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2- Ketones such as heptanone, 3-heptanone, 4-heptanone or 2,6-dimethyl-4-heptanone, alcohols such as n-butanol, 2-butanol, cyclohexanol or isopropanol, Cellulose, cellosolve such as methyl cellosolve, ethyl acetate, butyl acetate, methyl lactate, propylene glycol monomethyl ether acetate, propylene glycol diethyl ether acetate, methoxyethyl acetate or An ester such as ethoxyethyl acetate, dimethyl hydrazine, acetonitrile or N,N-dimethylacetamidine, but is not limited thereto. Among them, toluene, cyclopentanone or ethyl acetate is preferred. Further, the solvent may be either a single or a mixture. The concentration of the composition when the composition is dissolved is different depending on solvent solubility, wettability on a substrate, thickness after coating, etc., preferably 5 to 95% by weight, more preferably 10 ~80% by weight or so.

Moreover, when it is applied to a substrate, when the wettability on the substrate is insufficient or the surface property of the layer of the polymerizable resin composition to be applied is poor, in order to improve the Various leveling agents are added to the composition. As the leveling agent, various compounds such as an anthraquinone type, a fluorine type, a polyether type, an acrylic copolymer type, or a titanate type can be used. The amount thereof is 0.0001 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the polymerizable resin composition, and preferably 0.1 part by weight or more and 5 parts by weight or less or less based on 100 parts by weight of the composition.

When the composition layer applied to the substrate is cured and the adhesion between the cured layer and the protective film is inferior, various crosslinking agents may be added to the composition in order to improve the properties. As the crosslinking agent, various compounds such as an isocyanate system, a boron system, a titanate system or a ruthenium system can be used. The amount of the polymerizable resin composition is 0.0001 part by weight or more and 20 parts by weight or less, more preferably 0.1 part by weight or more and 10 parts by weight or less per 100 parts by weight of the composition.

The polymerizable resin hardened layer of the film of the present invention is preferably sufficiently polymerized by heating or ultraviolet irradiation to minimize the amount of unreacted components. The unreacted (meth) acrylate compound in 100 parts by weight of the hardened resin after curing is 0 parts by weight or more and 5 parts by weight or less, more preferably 0 parts by weight or more and 3 parts by weight or less, and further preferably 0% by weight. It is more than 1 part by weight and 1 part by weight or less. Examples of the method for obtaining such a layer include a method of optimizing the thickness of the layer of the resin composition after coating, and a method of optimizing the type or amount of the added photopolymerization initiator; A method of heating or irradiating ultraviolet rays; a method of curing the environment by ultraviolet irradiation or the like in an inert gas such as nitrogen gas. Among them, the method of optimizing the thickness of the layer of the resin composition can be optimized by merely changing the resin concentration or changing the amount of resin coating, which is the easiest. The thickness of the cured resin layer obtained by curing the polymerizable resin composition is from 0.1 μm to 20 μm, more preferably from 0.5 μm to 18 μm, still more preferably from 2 μm to 16 μm. When the thickness of the layer is thicker than 20 μm, the amount of residual unreacted monomers increases, the durability is insufficient, and there is a possibility that the polarizing plate becomes red in the drying durability test, which is not preferable. In the layer having a thickness of less than 0.1 μm, the improvement in light resistance is hardly obtained. The amount of the ultraviolet ray to be irradiated varies depending on the type of the (meth) acrylate compound, the type and amount of the photopolymerization initiator, and the film thickness, and is preferably, for example, about 100 to 2,000 mJ/cm ² .

In the present invention, it is further necessary to provide a layer containing ruthenium and nitrogen having a thickness of 50 nm to 500 nm in the resin cured layer. The thickness of the layer containing cerium and nitrogen may be from 50 nm to 500 nm, and may be from the film of the invention, preferably from 70 nm to 300 nm, and more preferably from 90 nm to 210 nm. A layer containing cerium and nitrogen can be formed by a known method. As a method of forming a layer containing cerium and nitrogen, for example, a physical vapor phase growth method (hereinafter referred to as "PVD") such as a vapor deposition method, a sputtering method, or an ion plating method, or a chemical vapor phase growth method (hereinafter, , called "CVD"). The best method for forming a layer comprising germanium and nitrogen is ion beam assisted vapor deposition and magnetron sputtering. The ion beam-assisted vapor deposition method is a method of forming iron nitride in Japanese Patent Laid-Open No. Hei 10-140326, Non-Patent Document 1, Non-Patent Document 2, and the like. The disclosed technology is a method disclosed in Non-Patent Document 3 as a magnetron sputtering method. When the PVD or CVD is applied to a cured layer of a resin formed of a (meth) acrylate compound, the surface is usually cloudy, or haze is generated to lower the transparency, or the adhesion is lowered, or after the high temperature and high humidity test. The resin cured layer formed of the polymerizable resin composition of the present invention has high transparency, high gas barrier properties, high adhesion, sufficient durability, and excellent productivity. The film. The film of the present invention obtained by the ion beam assisted vapor deposition method has a very high transparency and a very low gas permeability such as water vapor. Further, when the ion beam assisted vapor deposition method is used, even if it is high, only about 50 ° C of heat is applied, and the treatment can be performed at a low temperature. Therefore, the film of the substrate does not deteriorate, and the dimensional change after the application is not caused. No cracks are formed in the layer containing niobium and nitrogen. On the other hand, the film of the present invention obtained by the magnetron sputtering method has a very high transparency, a very high adhesion, and does not cause a very good film such as cracking of the surface even if a bending test is performed.

Examples of the transparent layer containing nitrogen and cerium include a layer of cerium nitride (Si ₃ N ₄ ) and cerium nitride containing oxygen (SiO _x N _y , x and y are arbitrary integers). In particular, the film of the invention provided with a layer of tantalum nitride has a good high gas barrier property. When the layer containing bismuth and nitrogen further contains aluminum as an element, a film of the present invention containing nitrogen and hydrazine having higher flexibility can be obtained. The content of oxygen in the cerium nitride (SiO _x N _y ) can be measured by the methods described in Non-Patent Document 5 and Non-Patent Document 6.

According to the above method, a film comprising: a substrate; a resin cured layer comprising at least one skeleton having a trimethylolpropane skeleton or an iso-cyanuric acid skeleton (methyl group) is provided. An acrylate compound formed as a polymerizable resin composition of a constituent compound and having a thickness of 0.1 μm to 20 μm; and a layer containing cerium and nitrogen having a thickness of 50 nm to 500 nm; and the (meth) acrylate compound The content is 40% by weight to 99 parts by weight based on 100 parts by weight of the polymerizable resin composition, and the transmittance is 75% or more.

The film of the present invention may be provided with a transparent protective layer on one or both sides via an adhesive or the like. It is also possible to stabilize the shape or reduce the appearance damage such as scratches by providing a transparent protective layer. As the transparent polymer or film forming the transparent protective layer, a transparent polymer or film having high mechanical strength and good thermal stability is preferred.

The film of the present invention thus obtained can be used as a sealing film which is required to block a gas such as water vapor. The transparent sealing film can be usefully used for a photoelectric conversion element, an OLED element. Especially in the case of an OLED, an OLED having higher reliability can be obtained in order not to hinder the light emission from the element without lowering the luminous efficiency. In addition, when it is used as a photoelectric conversion element as a photoelectric conversion resistive film, since it has high transparency and high barrier property, it functions stably as a photoelectric conversion barrier film for a long period of time, so that it is possible to obtain no reduction in the sun. A solar cell that functions as a light.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto. Further, the evaluation of the film shown in the examples was carried out in the following manner.

(total light transmittance)

The measurement was carried out using U-4100 manufactured by Hitachi High-Technologies Co., Ltd.

(The presence or absence of white turbidity of the film)

The presence or absence of white turbidity was confirmed by visual observation.

(adhesiveness)

In the layer of the polymerizable resin cured product of the film of the present invention and the layer containing niobium and nitrogen, 100 squares are formed at intervals of 1 mm by a cutter, and Cellotape (registered trademark) is tightly bonded, and is oriented in the direction of 90 degrees. The diameter was self-peeled, and evaluation was performed based on the following criteria.

Good: 100/100 is well connected

Poor: Peeling

(Adhesion after constant temperature and humidity test)

The film of the present invention is exposed to an environment having a temperature of 60 ° C and a relative humidity of 90% for 48 hours. In the layer of the cured polymer resin and the layer containing ruthenium and nitrogen, 100 squares are formed at intervals of 1 mm by a cutter, and Cellotape (registered trademark) is tightly bonded, and then peeled off in a 90-degree direction. The benchmark is described and the evaluation is carried out.

Good: 100/100 is well connected

Poor: Peeling

(Measurement of gas barrier properties)

The gas barrier property was measured by a water vapor transmission rate at a temperature of 40 ° C and a relative humidity of 90% RH using AQUATRAN (registered trademark) manufactured by MOCON Corporation.

[Example 1]

93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) in a 500 cc flask, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-? 2 parts of morphyl)-1-propanone (trade name: Irgacure-907, manufactured by BASF), 1 part of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure-184, manufactured by BASF), and 100 parts of toluene at room temperature The mixture was dissolved by mixing to prepare a composition comprising a (meth) acrylate compound containing at least one solid content of 50% of a trimethylolpropane skeleton. The obtained resin composition was applied onto a 200 μm polyethylene naphthalate film (trade name: Teonex Q65FA 200 μm manufactured by Teijin DuPont Films Co., Ltd.) using a bar coater, and dried in a dryer at 80 ° C. 2 After that, the film was cured by a nitrogen irradiation apparatus equipped with a 120 W high-pressure mercury lamp while being purged with nitrogen at a cumulative light amount of 400 mJ/cm ² to obtain a film having a resin cured layer having a thickness of 8 μm. On the surface of the obtained resin cured layer, an ion beam assisted vapor deposition apparatus (SGC-26SA-IAD manufactured by Showa Vacuum Co., Ltd.) was used as a target atom at a column voltage of 500 V, a beam current of 800 mA, and an AVcc value of 800 V. Under the condition that nitrogen gas was used as the source gas and the flow rate was 70 sccm, a layer of tantalum nitride having a thickness of 150 nm was provided to obtain a transparent barrier film.

[Embodiment 2]

93 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330) was used instead of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) 93 weight used in Example 1. A transparent barrier film was obtained in the same manner as in Example 1 except for the portions.

[Example 3]

93 parts by weight of tris(propylene methoxyethyl) isocyanurate (trade name: FA-731A manufactured by Hitachi Chemical Co., Ltd.) was used instead of trimethylolpropane triacrylate (trade name) used in Example 1. A transparent barrier film was obtained in the same manner as in Example 1 except that 93 parts by weight of KAYARAD TMPTA) was used.

[Example 4]

Instead of the trishydroxyl group used in Example 1, 62 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) and 31 parts by weight of dicyclopentyl diacrylate (trade name: KAYARAD R-684) were used. A transparent barrier film was obtained in the same manner as in Example 1 except that 93 parts by weight of a propane triacrylate (trade name: KAYARAD TMPTA) was used.

[Example 5]

62 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330) and 31 parts by weight of dicyclopentyl diacrylate (trade name: KAYARAD R-684) were used instead of the example 1. A transparent barrier film was obtained in the same manner as in Example 1 except that 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) was used.

[Embodiment 6]

A transparent barrier film was obtained in the same manner as in Example 5 except that the layer of tantalum nitride was changed to 70 nm.

[Embodiment 7]

The same layer as in Example 5 was used except that the layer of tantalum nitride was set to 350 nm. A transparent barrier film is obtained.

[Embodiment 8]

62 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA), 30.5 parts by weight of dicyclopentyl diacrylate (trade name: KAYARAD R-684), and a branch having a skeleton of the formula (1) 0.5 parts by weight of a perfluoroalkenyl fluoride compound (trade name: FTERGENT 602A manufactured by NEOS Co., Ltd.), in place of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, Except for this, a transparent barrier film was obtained in the same manner as in Example 1.

[Embodiment 9]

62 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330), 30.5 parts by weight of dicyclopentyl diacrylate (trade name: KAYARAD R-684), and having the formula (1) 0.5 parts by weight of a branched perfluoroalkenyl fluoride compound (trade name: FTERGENT 602A manufactured by NEOS Co., Ltd.) in place of trimethylolpropane triacrylate used in Example 1 (trade name: KAYARAD TMPTA) A transparent barrier film was obtained in the same manner as in Example 1 except for 93 parts by weight.

[Embodiment 10]

The surface of the cured resin layer obtained in Example 9 was subjected to a high-frequency magnetron sputtering apparatus (MPS-2000-HC3 manufactured by Showa Vacuum Co., Ltd.) to have a degree of vacuum of 1 × 10 ^-6 Pa, and the target atom was used. It is set as a two-dimensional simultaneous sputtering ring of tantalum and aluminum, the frequency is set to 13.56 MHz, the base temperature is set to normal temperature, the reaction gas of pressure 0.1 to 0.2 Pa is set to nitrogen, and the layer containing aluminum tantalum nitride is set to 150 nm. Transparent barrier film.

[Example 11]

The surface of the cured resin layer obtained in Example 9 was subjected to an ion beam assisted vapor deposition apparatus (SGC-26SA-IAD manufactured by Showa Vacuum Co., Ltd.) using ruthenium as a target atom at a column voltage of 300 V and a beam current. 800 mA, AVcc value of 1000 V, with nitrogen as the source gas and a flow rate of 70 sccm, the layer of tantalum nitride was set to 150 nm to obtain a transparent barrier. membrane.

[Embodiment 12]

58 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330) and tricyclodecane dimethylol diacrylate (trade name: Aronix M-203s manufactured by Toagosei Co., Ltd.) 35 parts by weight, instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, the resin composition was applied to a 100 μm cycloolefin film by a bar coater ( The product name: ARTON manufactured by JSR Co., Ltd. was dried in a dryer at 80 ° C for 2 minutes, and then hardened by a nitrogen irradiation apparatus equipped with a 120 W high-pressure mercury lamp, and the amount of accumulated light was 400 mJ/cm ² . A barrier film was obtained in the same manner as in Example 1 except that a film having a resin cured layer having a film thickness of 8 μm was obtained.

[Example 13]

The film thickness of the cured resin layer was set to 16 μm, and the layer of tantalum nitride was also provided on the other side of the polyethylene naphthalate film having no resin cured layer, and 150 nm was formed. In the same way, a barrier film is obtained.

[Embodiment 14]

The film thickness of the cured resin layer was set to 16 μm, and a layer of tantalum nitride of 150 nm was also provided on the other side of the polyethylene naphthalate film having no resin cured layer, and the examples were In the same manner, a barrier film is obtained.

[Example 15]

A barrier film was obtained in the same manner as in Example 12 except that a layer of tantalum nitride of 150 nm was provided on the other surface of the cycloolefin film having no resin cured layer.

[Comparative Example 1]

A transparent film was obtained in the same manner as in Example 1 except that the resin cured layer was not provided, and a layer of tantalum nitride was provided on the polyethylene naphthalate film of 150 nm.

[Comparative Example 2]

93 parts by weight of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA) was used instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, except In the same manner as in Example 1, a transparent barrier film was obtained.

[Comparative Example 3]

93 parts by weight of a tetrafunctional tetraacrylate (trade name: KAYARAD R-9591) was used instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, except A transparent barrier film was obtained in the same manner as in Example 1.

[Comparative Example 4]

62 parts by weight of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA) and 31 parts by weight of dicyclopentyl diacrylate (trade name: KAYARAD R-684) were used instead of trimethylolpropane three used in Example 1. A transparent barrier film was obtained in the same manner as in Example 1 except that 93 parts by weight of acrylate (trade name: KAYARAD TMPTA) was used.

[Comparative Example 5]

52 parts by weight of a reaction product of bisphenol A diglycidyl ether and acrylic acid (trade name: KAYARAD R-115) and 41 parts by weight of hexanediol diacrylate (trade name: Miramer M200 manufactured by Toyo Chemicals Co., Ltd.) were used instead of A transparent barrier film was obtained in the same manner as in Example 1 except that 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1 was used.

[Comparative Example 6]

In place of Example 1, 62 parts by weight of a reaction product of bisphenol A diglycidyl ether and acrylic acid (trade name: KAYARAD R-115) and 31 parts by weight of a biphenyl group-containing acrylate (trade name: KAYARAD OPP-1) were used. 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in the above, in addition to In the same manner as in Example 1, a transparent barrier film was obtained.

[Comparative Example 7]

52 parts by weight of bisphenol A modified acrylate (trade name: FA-320A manufactured by Hitachi Chemical Co., Ltd.) and 41 parts by weight of biphenyl group-containing acrylate (trade name: KAYARAD FRM-1000) were used instead of Example 1. A transparent barrier film was obtained in the same manner as in Example 1 except that 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) was used.

[Comparative Example 8]

52 parts by weight of bisphenol A modified acrylate (trade name: FA-320A manufactured by Hitachi Chemical Co., Ltd.) and 41 parts by weight of phenyl phosphate-containing acrylate (trade name: KAYARAD R-9663H) were used instead of Example 1. A transparent barrier film was obtained in the same manner as in Example 1 except that 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in the above was used.

[Comparative Example 9]

52 parts by weight of bisphenol A-modified acrylate (trade name: FA-320A manufactured by Hitachi Chemical Co., Ltd.), biphenyl-containing acrylate (trade name: KAYARAD FRM-1000) 40.5 parts by weight, and acrylic leveling 0.5 parts by weight of the agent (trade name: BYK-361N manufactured by BYK-Chemie Co., Ltd.), in place of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, except In the same manner as in Example 1, a transparent barrier film was obtained.

[Comparative Example 10]

52 parts by weight of bisphenol A-modified acrylate (trade name: FA-320A manufactured by Hitachi Chemical Co., Ltd.), biphenyl-containing acrylate (trade name: KAYARAD FRM-1000) 40.5 parts by weight, and 3-mercaptopropyl acrylate 0.5 parts by weight of benzyl trimethoxy decane (trade name: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.), in place of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, except Beyond this, In the same manner as in Example 1, a transparent barrier film was obtained.

[Comparative Example 11]

52 parts by weight of bisphenol A-modified acrylate (trade name: FA-320A manufactured by Hitachi Chemical Co., Ltd.), biphenyl-containing acrylate (trade name: KAYARAD FRM-1000) 40.5 parts by weight, and acrylic polymer system 0.5 parts by weight of a leveling agent (trade name: Polyflow No. 75 manufactured by Kyoeisha Chemical Co., Ltd.), instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, Except for this, a transparent barrier film was obtained in the same manner as in Example 1.

[Comparative Example 12]

58 parts by weight of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA) and 35 parts by weight of tricyclodecane dimethylol diacrylate (trade name: Aronix M-203s manufactured by Toagosei Co., Ltd.) were used instead. 58 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330) used in Example 12 and tricyclodecane dimethylol diacrylate (trade name: manufactured by Toagosei Co., Ltd.) A transparent barrier film was obtained in the same manner as in Example 12 except for the composition of 35 parts by weight of Aronix M-203s.

[Comparative Example 13]

58 parts by weight of a reaction product of bisphenol A diglycidyl ether and acrylic acid (trade name: KAYARAD R-115) and tricyclodecane dimethylol diacrylate (trade name: Aronix M-203s manufactured by Toagosei Co., Ltd.) 35 parts by weight of the composition, instead of the PO modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330) used in Example 12, 58 parts by weight and tricyclodecane dimethylol diacrylate A transparent barrier film was obtained in the same manner as in Example 12 except that the ester (trade name: Aronix M-203s manufactured by Toagosei Co., Ltd.) was used in an amount of 35 parts by weight.

[Comparative Example 14]

The other side of the polyethylene naphthalate film which does not have a resin cured layer is also provided A transparent barrier film was obtained in the same manner as in Comparative Example 5 except that the layer of tantalum nitride was 150 nm.

[Comparative Example 15]

A transparent barrier film was obtained in the same manner as in Comparative Example 6, except that a layer of tantalum nitride was provided on the other side of the polyethylene naphthalate film having no resin cured layer.

From the results of the measurement of the transmittance, the presence or absence of white turbidity, the adhesion, the adhesion after the durability test, and the gas barrier properties in Examples 1 to 15 and Comparative Examples 1 to 15 of Table 1, it was found that the film system of the present invention was permeated. A film that is good in any of rate, white turbidity, adhesion, and gas barrier properties. In other words, by providing not only the substrate, but also the layers of nitrogen and antimony, and further providing the resin cured layer, the performance of each is improved. Further, when Comparative Example 4, Example 8, or Example 5 and Example 9 were compared, it was found that the gas barrier property was further improved by containing a fluorine compound having a branched perfluoroalkenyl group or a derivative thereof. The film of the present invention obtained in such a manner can be used as a sealing film which requires gas barrier properties such as water vapor. The transparent sealing film can be usefully used for a photoelectric conversion element, an OLED element. Particularly in the case of an OLED, an OLED having higher reliability can be obtained in order not to hinder the light emission from the element without lowering the luminous efficiency. In addition, when it is used as a photoelectric conversion element as a photoelectric conversion resistive film, since it has high transparency and high barrier property, it functions stably for a long time as a photoelectric conversion barrier film, so that sunlight can be obtained. A solar cell that functions as a function of light.

Claims (11)

A film having a hardening formed of a polymerizable resin composition containing at least one (meth) acrylate compound having a trimethylolpropane skeleton or a hetero-cyanuric acid skeleton on a substrate. a layer containing a film of a layer containing cerium and nitrogen having a thickness of 50 nm to 500 nm on the cured layer, and the content of the (meth) acrylate compound is 100 parts by weight based on 100 parts by weight of the polymerizable resin composition From 40 parts by weight to 99 parts by weight, the cured layer has a thickness of from 0.1 μm to 20 μm and a transmittance of 75% or more. The film of claim 1, wherein the polymerizable resin composition contains 10 parts by weight to 55 parts by weight of the (meth) acrylate compound having a dicyclopentadiene skeleton, based on 100 parts by weight of the polymerizable resin composition. . The film of claim 1, wherein the polymerizable resin composition contains 0.01 parts by weight to 1 part by weight of a fluorine-based compound having a branched perfluoroalkenyl group or a derivative thereof, based on 100 parts by weight of the polymerizable resin composition. . The film of claim 2, wherein the polymerizable resin composition contains 0.01 parts by weight to 1 part by weight of a fluorine-based compound having a branched perfluoroalkenyl group or a derivative thereof, based on 100 parts by weight of the polymerizable resin composition. . The film according to any one of claims 1 to 4, wherein the layer containing ruthenium and nitrogen further contains aluminum as an element. A liquid crystal display device using the film according to any one of claims 1 to 5. An organic electroluminescence device using the film according to any one of claims 1 to 5. The film of any one of claims 1 to 4, wherein the layer comprising cerium and nitrogen is It is formed by ion beam assisted vapor deposition. The film of claim 5, wherein the layer comprising ruthenium and nitrogen is formed by ion beam assisted evaporation. The film of any one of claims 1 to 4, wherein the layer comprising ruthenium and nitrogen is formed by magnetron sputtering. The film of claim 5, wherein the layer comprising niobium and nitrogen is formed by magnetron sputtering.