WO2015056718A1 - Transparent gas barrier film - Google Patents

Transparent gas barrier film Download PDF

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Publication number
WO2015056718A1
WO2015056718A1 PCT/JP2014/077451 JP2014077451W WO2015056718A1 WO 2015056718 A1 WO2015056718 A1 WO 2015056718A1 JP 2014077451 W JP2014077451 W JP 2014077451W WO 2015056718 A1 WO2015056718 A1 WO 2015056718A1
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weight
parts
film
resin composition
layer
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PCT/JP2014/077451
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French (fr)
Japanese (ja)
Inventor
典明 望月
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日本化薬株式会社
株式会社ポラテクノ
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Priority to JP2015542638A priority Critical patent/JP6548578B2/en
Publication of WO2015056718A1 publication Critical patent/WO2015056718A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical

Definitions

  • the present invention relates to a transparent gas barrier film.
  • Gas barrier films are often used to prevent alteration in products, food packaging, industrial products, pharmaceuticals, etc. that require blocking of various gases such as water vapor and oxygen.
  • OLED organic electroluminescence
  • the gas barrier film normally used in the packaging field may have low transparency and may not have a high gas barrier property. Therefore, such a gas barrier film cannot be used in the display material field.
  • films with high transparency and high water vapor barrier properties have been developed using silicon oxide, silicon oxynitride, etc., instead of materials with low transparency such as aluminum oxide and magnesium oxide. A film having good properties, adhesion and durability has not been developed yet, and various studies have been made.
  • Patent Literatures 1 to 3 disclose technologies relating to gas barrier films having high barrier properties.
  • a film such as a transparent plastic has a problem that the gas barrier property is inferior to 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
  • Patent Documents 5 and 6 disclose a technique in which gas barrier properties are improved by using an inorganic compound and an organic compound. Has been.
  • a film having high transparency, high gas barrier properties, high adhesion, sufficiently high durability, and excellent productivity has not been obtained.
  • Non-Patent Documents 1 to 3 disclose techniques for improving physical vapor deposition (PVD) and chemical vapor deposition (CVD) to enhance the properties of metal films. It is known that the metal film obtained by such a method has a high gas barrier property. However, the gas barrier property is still not sufficient, in particular, the adhesion of the metal film to the base material is poor, and the flexibility of the metal film is greatly reduced, so when the film is folded, the metal film is cracked, The gas barrier property is greatly reduced.
  • the present inventors have conducted intensive studies, and as a result, formed on a substrate from a polymerizable resin composition containing at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton.
  • a film having a cured resin layer and a layer containing silicon and nitrogen having a thickness of 50 nm to 500 nm on the cured resin layer, and containing the (meth) acrylate compound The amount is 40 to 99 parts by weight with respect to 100 parts by weight of the polymerizable resin composition, the thickness of the cured resin layer is 0.1 to 20 ⁇ m, and the transmittance is 75% or more. It was newly found that a film characterized by the above has high transparency, high gas barrier properties, high adhesion, sufficiently good durability, and excellent productivity.
  • the present invention “(1) having a cured product layer formed on a base material from a polymerizable resin composition containing at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton, and A film having a layer containing silicon and nitrogen having a thickness of 50 nm to 500 nm on the cured product layer,
  • the content of the (meth) acrylate compound is 40 parts by weight to 99 parts by weight with respect to 100 parts by weight of the polymerizable resin composition
  • the thickness of the cured product layer is 0.1 ⁇ m to 20 ⁇ m
  • the polymerizable resin composition contains a (meth) acrylate compound having a dicyclopentadiene skeleton in an amount of 10 to 55 parts by weight with respect to 100 parts by weight of the polymerizable resin composition.
  • the polymerizable resin composition contains 0.01 to 1 part by weight of a fluorine-based compound having a branched perfluoroalkenyl group or a derivative thereof with respect to 100 parts by weight of the polymerizable resin composition.
  • the film according to (1) or (2), (4) The film according to any one of (1) to (3), wherein the layer containing silicon and nitrogen further contains aluminum as an element, (5) A liquid crystal display device using the film according to any one of (1) to (4), (6) An organic electroluminescence device using the film according to any one of (1) to (4), (7) The film according to any one of (1) to (4), wherein the layer containing silicon and nitrogen is formed by an ion beam assisted deposition method, (8) The film according to any one of (1) to (4), wherein the layer containing silicon and nitrogen is formed by a magnetron sputtering method. About.
  • the film of the present invention has high transparency, high gas barrier properties, high adhesiveness, sufficiently good durability, and excellent productivity.
  • the present invention has a cured product layer formed from a polymerizable resin composition containing at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton on a substrate, and the cured product layer A film having a thickness of 50 nm to 500 nm and having a layer containing silicon and nitrogen, wherein the content of the (meth) acrylate compound is 40 with respect to 100 parts by weight of the polymerizable resin composition.
  • the present invention relates to a film characterized in that the cured product layer has a thickness of 0.1 to 20 ⁇ m and a transmittance of 75% or more.
  • the base material in the present invention is not particularly limited as long as it is formed of an organic material that can maintain transparency and gas barrier properties.
  • the organic material include acrylic acid ester, methacrylic acid ester, polyethylene terephthalate (hereinafter abbreviated as “PET”), polyethylene naphthalate (hereinafter abbreviated as “PEN”), polycarbonate, polyarylate, and polychlorinated acid.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polycarbonate polyarylate
  • polychlorinated acid examples include organic materials composed of organic / inorganic hybrids based on vinyl, polyethylene, polypropylene, nylon, polyimide, polyamide, cycloolefin, triacetylcellulose, silsesquioxane, and the like. These organic materials have a thickness of 5 ⁇ m to 500 ⁇ m.
  • a film made of PET, PEN, or polycarbonate is preferable.
  • a film formed of an organic material composed of an organic / inorganic hybrid having cycloolefin, triacetylcellulose, and silsesquioxane as a basic skeleton is preferable.
  • films made of cycloolefin include Zeon manufactured by Zeon, JSR manufactured by ARTON, and Gunze manufactured by F film, and formed by an organic material composed of an organic / inorganic hybrid based on silsesquioxane.
  • the film include Nippon Steel Chemical's Sylplus and Chisso's Sila-DEC.
  • the film of the present invention is provided with a cured product layer formed to a thickness of 0.1 ⁇ m to 20 ⁇ m on a substrate.
  • the layer of the cured product is formed from a polymerizable resin composition, and the polymerizable resin composition includes at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton.
  • the polymerizable resin composition includes, for example, 90 to 99.9 parts by weight of a (meth) acrylate compound having at least one acryloyl group and 0.1 to 10 parts by weight of a polymerization initiator.
  • the polymerizable resin composition forming the cured product layer needs to contain at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton, and the content thereof is 100 weights of the polymerizable resin composition. 40 parts by weight to 99 parts by weight with respect to parts.
  • the (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton is 50% by weight or more, more preferably 60% by weight or more, and further preferably 70% by weight or more based on the amount of resin blended in the composition. Good because stability is improved.
  • the performance of the present invention is not exhibited, which is not preferable.
  • a (meth) acrylate compound having a trimethylolpropane skeleton is preferable because of high transparency.
  • Non-Patent Document 4 the acrylate monomer described in Non-Patent Document 4 can be used. It is not limited to them, and it is not particularly limited as long as it is a (meth) acrylate compound having at least one (meth) acryloyl group.
  • Components other than the (meth) acrylate compound described above, for example, various polymers and oligomers can be added to the polymerizable resin composition, and any component and its concentration that do not inhibit curing can be used without particular limitation.
  • the amount to be added may be blended in any proportion as long as the polymerizable resin composition can be cured, but it is more preferably 40 to 99 parts by weight with respect to 100 parts by weight of the polymerizable resin composition. .
  • Examples of the (meth) acrylate compound having a trimethylolpropane skeleton include trimethylolpropane triacrylate [Kayarad TMPTA manufactured by Nippon Kayaku Co., Ltd.], EO-modified trimethylolpropane triacrylate [SR-454 manufactured by Sartomer], and PO-modified trimethylolpropane.
  • Triacrylate manufactured by Nippon Kayaku Co., Ltd., TPA-310, TPA-320, TPA-330, etc.
  • trimethylolpropane trimethacrylate Sartomer SR-350
  • reaction product of trimethylolpropane triglycidyl ether and acrylic acid [ Denacol DA-321 (manufactured by Nagase Sangyo Co., Ltd.) is exemplified.
  • Examples of the (meth) acrylate compound having an isocyanuric skeleton include diacryloxyethyl isocyanurate [Aronix M-215 manufactured by Toagosei Co., Ltd.], trisacryloxyethyl isocyanurate [FA-731A manufactured by Hitachi Chemical Co., Ltd.], caprolactone-modified trisacryloxy Examples include ethyl isocyanurate [Aronix M-325 manufactured by Toagosei Co., Ltd.], trismethacryloxyethyl isocyanurate [FA-731M manufactured by Hitachi Chemical Co., Ltd.], and the like.
  • the polymerizable resin composition contains a (meth) acrylate compound having a dicyclopentadiene skeleton in an amount of 10 to 55 parts by weight with respect to 100 parts by weight of the polymerizable resin composition.
  • a film with high gas barrier properties, high adhesion, sufficiently good durability, and excellent productivity can be obtained.
  • the preferred content of the (meth) acrylate having a dicyclopentadiene skeleton is 15 to 50% by weight, and the more preferred content is 20 to 40% by weight.
  • a polymerizable resin composition for forming a layer of a preferable polymerizable resin cured product includes a (meth) acrylate compound containing a trimethylolpropane skeleton or an isocyanuric skeleton, and a (meth) acrylate having a dicyclopentadiene skeleton.
  • a polymerization resin composition for forming a layer of a more preferable polymerizable resin cured product a (meth) acrylate compound containing a trimethylolpropane skeleton, It is a composition comprised by the (meth) acrylate which has a dicyclopentadiene frame
  • the (meth) acrylate compound having a dicyclopentadiene skeleton refers to, for example, a resin having a dicyclopentanyl skeleton, a dicyclopentenyl skeleton, or an adamantane skeleton.
  • a resin having a dicyclopentanyl skeleton or a dicyclopentenyl skeleton is preferable, and a resin having a dicyclopentanyl skeleton is most preferable.
  • Examples of the compound having a dicyclopentanyl skeleton include dicyclopentanyl acrylate (FA-513A manufactured by Hitachi Chemical Co., Ltd.), dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) or dicyclopentanyl diacrylate ( Nippon Kayaku Co., Ltd. Kayalad R-684) is preferred.
  • Examples of the compound having a dicyclopentenyl skeleton include dicyclopentenyl acrylate (FA-511A manufactured by Hitachi Chemical Co., Ltd.), dicyclopentenyloxyethyl acrylate (FA-512A manufactured by Hitachi Chemical Co., Ltd.) or dicyclopentenyloxyethyl methacrylate (Hitachi). Chemical conversion FA-512M) is preferred.
  • Examples of the compound having an adamantane skeleton include 2-methyl-2-adamantyl methacrylate (Adamantate MM, manufactured by Idemitsu Kosan Co., Ltd.), 2-ethyl-2-adamantyl methacrylate (Adamantate EM, manufactured by Idemitsu Kosan Co., Ltd.), 3-hydroxy-1-adamantyl methacrylate (Idemitsu Kosan Co., Ltd.).
  • Adamantate HM 3-hydroxy-1-adamantyl acrylate
  • 2-methyl-2-adamantyl acrylate Idemitsu Kosan Co., Ltd. Adamantate MA
  • 2-ethyl-2-adamantyl acrylate manufactured by Idemitsu Kosan Co., Ltd., AdamantEA, etc. Illustrated.
  • the polymerization reaction is caused by the photopolymerization initiator by irradiating the ultraviolet rays.
  • the photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 (Irgacure 907 manufactured by Ciba Specialty Chemicals), 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty).
  • Irgacure 184 from Tea Chemicals 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone (Irgacure 2959 from Ciba Specialty Chemicals), 1- (4-dodecylphenyl)- 2-hydroxy-2-methylpropan-1-one (Merck Darocur 953), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Merck Darocur 1116), 2 -Hydroxy-2-methyl-1-phenyl Lopan-1-one (Irgacure 1173 manufactured by Ciba Specialty Chemicals), acetophenone compounds such as diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy- Benzoin compounds such as 2-phenylacetophenone (Irgacure 651
  • Kayacure CTX 2-methylthioxanthone, 2,4-dimethylthioxanthone (Nippon Kayaku Co., Ltd. Kayacure RTX), isopropylthioxanthone, 2,4-dichroothiox Thioxanes such as Sanson (Kayacure CTX manufactured by Nippon Kayaku Co., Ltd.), 2,4-diethylthioxanthone (Kayacure DETX manufactured by Nippon Kayaku Co., Ltd.), 2,4-diisopropylthioxanthone (Kayacure DITX manufactured by Nippon Kayaku Co., Ltd.) Compounds and the like.
  • 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 (Irgacure 907 manufactured by Ciba Specialty Chemicals), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals) Irgacure 184) or 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651 manufactured by Ciba Specialty Chemicals).
  • One or more of these photopolymerization initiators can be mixed and used at any blending ratio.
  • an auxiliary agent can be used in combination to promote the photopolymerization reaction.
  • auxiliaries include triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate, Michler's ketone, 4,4′-diethylaminophenone, 4-dimethylaminobenzoic acid.
  • amine compounds such as ethyl, ethyl 4-dimethylaminobenzoate (n-butoxy) or isoamyl 4-dimethylaminobenzoate.
  • the photopolymerization initiator and the auxiliary agent are preferably used in an addition amount within a range in which the polarization performance does not deteriorate.
  • the addition amount of the photopolymerization initiator is the (meth) acrylate compound 100 in the polymerizable resin composition. Preferably they are 0.1 weight part or more and 12 weight part or less with respect to a weight part, More preferably, they are about 2 weight part or more and 10 weight part or less. Further, the amount of the auxiliary added is preferably about 0.5 to 2 times the amount of the photopolymerization initiator.
  • the (meth) acrylate compound or (meth) acrylate resin composition used in the present invention is a thermosetting type
  • a polymerization initiator, a crosslinking agent and / or an initiation catalyst are used.
  • a crosslinking agent various well-known compounds, such as an isocyanate type, a boron type, a titanate type
  • the addition amount of the crosslinking agent is 0.1 to 20 parts by weight in 100 parts by weight of the polymerizable resin composition, and preferably about 1 to 10 parts by weight in 100 parts by weight of the composition.
  • the (meth) acrylate compound or polymerizable resin composition to be used is an ultraviolet curable type rather than a thermosetting type, the stability to light, the curing time, and the production cost in the curing process. It is useful from the point of view.
  • the layer of the polymerizable resin composition may be provided by a method of coating the base material layer. Not only a method of directly applying to a base material, but also a method of applying to a different film in advance and transferring the cured layer to the base material or laminating may be used.
  • the application method is not particularly limited, and examples thereof include a spin coating method, a wire bar coating method, a gravure coating method, a micro gravure coating method, a calendar coating method, a spray coating method, a meniscus coating method, and the like.
  • the polymerizable resin composition further contains 0.01 to 1 part by weight of a fluorine compound having a branched perfluoroalkenyl group or a derivative thereof with respect to 100 parts by weight of the polymerizable resin composition.
  • a fluorine compound having a branched perfluoroalkenyl group is a fluorine compound represented by the formula (1), and derivatives of the compound are also included.
  • the added amount is 0.05 to 0.9 parts by weight in 100 parts by weight of the cured product, more preferably about 0.1 to 0.8 parts by weight in 100 parts by weight of the composition. is there.
  • Examples of the ionicity of the fluorine compound having a branched perfluoroalkenyl group or a derivative thereof include anionic, cationic, nonionic, and amphoteric types.
  • Examples of the fluorine compound or its derivative further include an oligomer type and a reactive oligomer type.
  • Nonionic type is preferable, since non-depletion type is preferable because it shows the effect when added in a small amount, does not precipitate from the cured resin layer, and does not hinder the recoatability to deposit or sputter a layer containing silicon and nitrogen later. Are more preferable, and nonionic type reactive oligomers are more preferable.
  • Examples of the fluorine compound having a branched perfluoroalkenyl group having a skeleton of the formula (1) or a derivative thereof include a tangent series owned by Neos.
  • the target series 710FL, 710FM, 710FS, 730LM, 601AD, 602A, and 650A are preferable, and 601A, 602A, and 650A are particularly preferable.
  • the transparency is high, the gas barrier property is high, the adhesion is high, and the durability is high. It is possible to obtain a film having sufficiently good properties and excellent productivity.
  • a deterioration preventing aid may be added.
  • Deterioration prevention aids indicate antioxidants and light stabilizers.
  • the antioxidant include phenolic antioxidants such as hindered phenols and semihindered phenols, amine antioxidants such as phenylenediamines, and phosphorus antioxidants such as phosphites and phosphonites. And sulfur-based antioxidants such as thioethers.
  • light stabilizers include ultraviolet absorbers such as benzophenone, benzotriazole, and triazine, excitation energy absorbers (Quencher) such as organic nickel complexes, ultraviolet shielding agents such as carbon black and titanium oxide, and basic skeletons.
  • HALS hindered amine light stabilizers having a 2,2,6,6-tetramethylbiperidine skeleton.
  • the addition concentration is not particularly limited, and can be arbitrarily added depending on the ability of the deterioration preventing aid. Generally, 0.01 wt% to 5 wt%, preferably 0.05 wt% to 3 wt% is added to the polymerizable resin composition excluding the solvent.
  • the polymerizable resin cured layer is formed, the polymerizable resin composition is diluted directly or using an appropriate solvent and applied to the substrate. Thereafter, the solvent is removed by heating or the like, and the polymerizable resin cured product can be obtained by heating or irradiating with ultraviolet rays.
  • the solvent of the solution of the composition used for 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 and does not cause deterioration in surface properties.
  • solvents examples include water, aromatic hydrocarbons such as toluene and xylene, ethers such as anisole, dioxane, and tetrahydrofuran, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, and 3-pentanone.
  • Ketones such as 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone or 2,6-dimethyl-4-heptanone, n-butanol, 2-butanol, cyclohexanol or isopropyl alcohol Alcohols, cellosolves such as methyl cellosolve and methyl cellosolve, ethyl acetate, butyl acetate, methyl lactate, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, methoxy acetate Esters such as chill or fence San ethoxyethyl, dimethyl sulfoxide, acetonitrile, N, including but N- dimethylacetamide dimethylformamide without limitation.
  • cellosolves such as methyl cellosolve and methyl cellosolve, ethyl acetate, butyl acetate, methyl lactate, propylene
  • the solvent may be a single solvent or a mixture.
  • concentration of the composition at the time of dissolving the composition varies depending on solvent solubility, wettability on the substrate, thickness after coating, etc., but is preferably 5 to 95% by weight, more preferably 10 to 80% by weight. %.
  • leveling agent various compounds such as silicon-based, fluorine-based, polyether-based, acrylic acid copolymer-based or titanate-based compounds can be used.
  • the addition amount is 0.0001 to 10 parts by weight in 100 parts by weight of the polymerizable resin composition, preferably about 0.1 to 5 parts by weight in 100 parts by weight of the composition.
  • crosslinking agents may be added to the composition to improve them.
  • various cross-linking agent various compounds such as isocyanate, boron, titanate, or silicon can be used.
  • the addition amount is 0.0001 part by weight or more and 20 parts by weight or less in 100 parts by weight of the polymerizable resin composition, more preferably about 0.1 part by weight or more and 10 parts by weight or less in 100 parts by weight of the composition. .
  • the polymerizable resin cured layer of the film of the present invention is sufficiently polymerized by heating or ultraviolet irradiation and has as little unreacted content as possible.
  • the unreacted (meth) acrylate compound in 100 parts by weight of the cured resin after curing is 0 to 5 parts by weight, more preferably 0 to 3 parts by weight, and even more preferably 0 to 1 part by weight. Less than parts by weight.
  • a method for obtaining such a layer for example, a method for optimizing the thickness of the layer of the resin composition after coating, a method for optimizing the kind and amount of the photopolymerization initiator to be added, sufficient heating or ultraviolet rays are used.
  • a method of irradiating, a method of changing the atmosphere at the time of ultraviolet irradiation, such as performing in an inert gas such as nitrogen, and the like, can be mentioned.
  • the method of optimizing the thickness of the resin composition layer is the simplest because it can be optimized only by changing the resin concentration or changing the resin coating amount.
  • the thickness of the cured resin layer obtained by curing the polymerizable resin composition is 0.1 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 18 ⁇ m, and still more preferably 2 ⁇ m to 16 ⁇ m.
  • the thickness of the layer is greater than 20 ⁇ m, the residual unreacted monomer increases, the durability is insufficient, and the polarizing plate may turn red in a dry heat durability test, which is not suitable.
  • the polarizing plate may turn red in a dry heat durability test, which is not suitable.
  • a layer having a thickness of less than 0.1 ⁇ m light resistance cannot be improved much.
  • the dose of ultraviolet rays, kind of (meth) acrylate compounds, the addition amount and kind of the photopolymerization initiator varies depending thickness, for example, it is preferably about 100 ⁇ 2000mJ / cm 2.
  • the film of the present invention it is necessary to further provide a layer containing silicon and nitrogen having a thickness of 50 nm to 500 nm in the cured resin layer. If the thickness of the layer containing silicon and nitrogen is 50 nm to 500 nm, the film of the present invention can be achieved, but it is preferably 70 nm to 300 nm, more preferably 90 nm to 210 nm.
  • the layer containing silicon and nitrogen can be formed by a known method.
  • Examples of a method for forming a layer containing silicon and nitrogen include physical vapor deposition methods (hereinafter referred to as “PVD”) such as vapor deposition, sputtering, and ion plating, and chemical vapor deposition ( Hereinafter, it is referred to as “CVD”).
  • PVD physical vapor deposition methods
  • CVD chemical vapor deposition
  • the most preferable method for forming a layer containing silicon and nitrogen is an ion beam assisted deposition method or a magnetron sputtering method.
  • Examples of the ion beam assisted deposition method include a method of forming iron nitride in Japanese Patent Laid-Open No. 10-140326, and techniques disclosed in Non-Patent Document 1, Non-Patent Document 2, and the like. The method currently disclosed by literature 3 is mentioned.
  • the surface is usually clouded, haze is generated, transparency is lowered, adhesion is lowered, Adhesiveness decreases after a high humidity test, but if it is a cured resin layer formed from the polymerizable resin composition of the present invention, it has high transparency, high gas barrier properties, high adhesion, and durability. Is sufficiently good, and a film excellent in productivity can be obtained.
  • the film of the present invention obtained by the ion beam assisted vapor deposition method has very high transparency and extremely low gas permeability such as water vapor. Furthermore, if the ion beam assisted deposition method is used, only about 50 ° C.
  • the film of the present invention obtained by magnetron sputtering is a very good film that has very high transparency, very high adhesion, and does not cause surface cracks even when subjected to a bending test. is there.
  • the transparent layer containing nitrogen and silicon examples include silicon nitrite (Si 3 N 4 ) and silicon nitride containing oxygen (SiO x N y , where x and y are arbitrary integers).
  • the film of the present invention provided with a layer of silicon nitrite has good high gas barrier properties.
  • the layer containing silicon and nitrogen further contains aluminum as an element, the film of the present invention containing nitrogen and silicon with higher flexibility is obtained.
  • the content of oxygen in silicon nitride (SiO x N y ) can be measured by the methods described in Non-Patent Document 5 and Non-Patent Document 6.
  • a cured resin layer having a thickness of 50 nm to 500 nm, and a layer containing silicon and nitrogen, and the content of the (meth) acrylate compound is 40 with respect to 100 parts by weight of the polymerizable resin composition.
  • a film characterized by having a transmittance of 75% or more can be obtained.
  • the film of the present invention may be provided with a transparent protective layer on one side or both sides via an adhesive or the like.
  • a transparent protective layer By providing the transparent protective layer, the shape can be stabilized, and appearance damage such as scratches can be reduced.
  • the transparent polymer or film forming the transparent protective layer is preferably a transparent polymer or film having high mechanical strength and good thermal stability.
  • the film of the present invention thus obtained can be used as a sealing film that requires a gas barrier such as water vapor.
  • This transparent sealing film can be usefully used for a photoelectric conversion element and an OLED element.
  • light emission from the element is not hindered, so that the light emission efficiency is not lowered and a highly reliable OLED can be obtained.
  • a photoelectric conversion element when used in a photoelectric conversion barrier film, it is highly transparent and has a high barrier property, so that it functions stably as a barrier film for photoelectric conversion over a long period of time. It is possible to obtain a solar cell that functions without causing it.
  • Total light transmittance Measurement was performed using U-4100 manufactured by Hitachi High-Technologies Corporation.
  • Adhesion 100 squares were produced with a cutter at a 1 mm interval in a layer of a cured polymer resin of the film of the present invention and a layer containing silicon and nitrogen, and after attaching cello tape (registered trademark) firmly, 90 It peeled at a stretch in the direction of a degree, and evaluated in accordance with the following reference
  • Good 100/100 Good adhesion Bad: Peeling occurred
  • the film of the present invention is exposed to an environment of a temperature of 60 ° C. and a relative humidity of 90% for 48 hours, and 100 square grids are cut at intervals of 1 mm into a layer of a cured polymer resin and a layer containing silicon and nitrogen. After the cellotape (registered trademark) was firmly adhered, it was peeled off at 90 degrees and evaluated according to the following criteria. Good: 100/100 Good adhesion Bad: Peeling occurred
  • the gas barrier property was measured by measuring water vapor transmission rate using AQUATRAN (registered trademark) manufactured by MOCON at a temperature of 40 ° C. and a relative humidity of 90% RH.
  • Example 1 To 500 cc Kolben, 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA), 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone (trade name: 2 parts of Irgacure 907, manufactured by BASF), 5 parts of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by BASF) and 100 parts of toluene are mixed and dissolved at room temperature to obtain a trimethylolpropane skeleton having a solid content of 50%. A composition containing at least one (meth) acrylate compound containing was prepared.
  • the obtained resin composition was applied on a 200 ⁇ m polyethylene naphthalate film (trade name: Teonex Q65FA 200 ⁇ m, manufactured by Teijin DuPont Films) with a bar coater, dried in an 80 ° C. dryer for 2 minutes, and then a 120 W high pressure mercury lamp.
  • the film was cured with an integrated light quantity of 400 mJ / cm 2 while purging with nitrogen using an ultraviolet irradiation device provided with a film having a cured resin layer with a thickness of 8 ⁇ m.
  • silicon was used as a target atom with an ion beam assisted vapor deposition apparatus (SGC-26SA-IAD manufactured by Showa Vacuum Co., Ltd.), a beam voltage of 500 V, a beam current of 800 mA, an AVcc value of 800 V, and a source gas.
  • SGC-26SA-IAD ion beam assisted vapor deposition apparatus
  • a silicon nitride layer having a thickness of 150 nm was provided as nitrogen under the condition of a flow rate of 70 sccm to obtain a transparent barrier film.
  • Example 2 Except that 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1 was used instead of 93 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330). A transparent barrier film was obtained in the same manner as in Example 1.
  • KAYARAD TMPTA trimethylolpropane triacrylate
  • PO-modified trimethylolpropane triacrylate trade name: KAYARAD TPA-330
  • Example 3 Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 93 parts by weight of tris (acryloxyethyl) isocyanurate (trade name: FA-731A manufactured by Hitachi Chemical Co., Ltd.) was used. A transparent barrier film was obtained in the same manner as in Example 1 except that.
  • trimethylolpropane triacrylate trade name: KAYARAD TMPTA
  • 93 parts by weight of tris (acryloxyethyl) isocyanurate trade name: FA-731A manufactured by Hitachi Chemical Co., Ltd.
  • Example 4 Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 62 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) and dicyclopentanyl diacrylate (trade name) : KAYARAD R-684) A transparent barrier film was obtained in the same manner as in Example 1 except that 31 parts by weight was used.
  • KAYARAD TMPTA trimethylolpropane triacrylate
  • KAYARAD R-684 dicyclopentanyl diacrylate
  • Example 5 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 62 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330) and dicyclopentanyl diacrylate ( Product name: KAYARAD R-684) A transparent barrier film was obtained in the same manner as in Example 1 except that 31 parts by weight was used.
  • Example 6 A transparent barrier film was obtained in the same manner as in Example 5 except that the silicon nitride layer was 70 nm.
  • Example 7 A transparent barrier film was obtained in the same manner as in Example 5 except that the silicon nitride layer was 350 nm.
  • Example 8 Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 62 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA), dicyclopentanyl diacrylate (trade name) : KAYARAD R-684) 30.5 parts by weight and 0.5 part by weight of a fluorine compound having a branched perfluoroalkenyl group having a skeleton of the formula (1) (trade name: FERENTENT 602A manufactured by Neos) A transparent barrier film was obtained in the same manner as in Example 1 except that.
  • a fluorine compound having a branched perfluoroalkenyl group having a skeleton of the formula (1) (trade name: FERENTENT 602A manufactured by Neos)
  • Example 9 Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 62 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330), dicyclopentanyldi Acrylate (trade name: KAYARAD R-684) 30.5 parts by weight, and a fluorine compound having a branched perfluoroalkenyl group having a skeleton of formula (1) (trade name: Neos Inc., Footent 602A) 0.5 weight A transparent barrier film was obtained in the same manner as in Example 1 except that the part was used.
  • KAYARAD TMPTA trimethylolpropane triacrylate
  • KAYARAD TPA-330 PO-modified trimethylolpropane triacrylate
  • dicyclopentanyldi Acrylate trade name: KAYARAD R-684
  • Example 10 On the surface of the cured resin layer obtained in Example 9, a high-frequency magnetron sputtering apparatus (MPS-2000-HC3 manufactured by Showa Vacuum Co., Ltd.) was used. The degree of vacuum was 1 ⁇ 10 ⁇ 6 Pa, the target atoms were silicon and aluminum 2 Dimensional co-sputtering, a frequency of 13.56 MHz, a base temperature of room temperature, a reactive gas having a gas pressure of 0.1 to 0.2 Pa as nitrogen, and a silicon nitride layer containing aluminum having a thickness of 150 nm is provided to obtain a transparent barrier film It was.
  • MPS-2000-HC3 manufactured by Showa Vacuum Co., Ltd.
  • Example 11 On the surface of the cured resin layer obtained in Example 9, silicon was used as a target atom with an ion beam assisted deposition apparatus (SGC-26SA-IAD manufactured by Showa Vacuum Co., Ltd.), a beam voltage of 300 V, a beam current of 800 mA, and an AVcc value of 1000 V.
  • a transparent barrier film was obtained by providing a silicon nitride layer with a thickness of 150 nm under the condition of a source gas of nitrogen and a flow rate of 70 sccm.
  • Example 12 Trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1 instead of 93 parts by weight, 58 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAAD TPA-330) and tricyclodecane dimethylol Using 35 parts by weight of diacrylate (trade name: Aronix M-203s, manufactured by Toa Gosei Co., Ltd.), the resin composition was applied onto a 100 ⁇ m cycloolefin film (trade name: ARTON manufactured by JSR) with a bar coater and 80 ° C.
  • the film was cured with an integrated light quantity of 400 mJ / cm 2 while purging with an ultraviolet irradiation device equipped with a 120 W high-pressure mercury lamp to obtain a film having a cured resin layer with a thickness of 8 ⁇ m. Except for this, a barrier film was obtained in the same manner as in Example 1.
  • Example 13 The same as in Example 4 except that the film thickness of the cured resin layer was 16 ⁇ m and a 150 nm silicon nitride layer was provided on the other surface of the polyethylene naphthalate film having no cured resin layer. A barrier film was obtained.
  • Example 14 The same as Example 9 except that the film thickness of the cured resin layer was 16 ⁇ m and a 150 nm silicon nitride layer was provided on the other side of the polyethylene naphthalate film having no cured resin layer. Thus, a barrier film was obtained.
  • Example 15 A barrier film was obtained in the same manner as in Example 12 except that a 150 nm silicon nitride layer was provided on the other surface of the cycloolefin film having no resin cured product layer.
  • Example 1 A transparent film was obtained in the same manner as in Example 1 except that a silicon nitride layer was provided on a 150 nm polyethylene naphthalate film without providing a cured resin layer.
  • Example 2 Example 1 except that 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. Similarly, a transparent barrier film was obtained.
  • KAYARAD DPHA dipentaerythritol hexaacrylate
  • KAYARAD TMPTA trimethylolpropane triacrylate
  • Example 3 Example except that 93 parts by weight of 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. In the same manner as in Example 1, a transparent barrier film was obtained.
  • tetrafunctional tetraacrylate trade name: KAYARAD R-9591
  • trimethylolpropane triacrylate trade name: KAYARAD TMPTA
  • Trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1 instead of 93 parts by weight, 62 parts by weight of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA) and dicyclopentanyl diacrylate (trade name) : KAYARAD R-684)
  • a transparent barrier film was obtained in the same manner as in Example 1 except that 31 parts by weight was used.
  • Example 6 instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 62 parts by weight of a reaction product of bisphenol A diglycidyl ether and acrylic acid (trade name: KAYARAD R-115) A transparent barrier film was obtained in the same manner as in Example 1 except that 31 parts by weight of biphenyl group-containing acrylate (trade name: KAYARAD OPP-1) was used.
  • KAYARAD TMPTA trimethylolpropane triacrylate
  • KAYARAD R-115 a reaction product of bisphenol A diglycidyl ether and acrylic acid
  • Example 8 Trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1 instead of 93 parts by weight 52 parts by weight of bisphenol A-modified acrylate (trade name: FA-320A manufactured by Hitachi Chemical Co., Ltd.) and biphenyl phosphate group-containing A transparent barrier film was obtained in the same manner as in Example 1 except that 41 parts by weight of acrylate (trade name: KAYARAD R-9663H) was used.
  • KAYARAD TMPTA Trimethylolpropane triacrylate
  • FA-320A manufactured by Hitachi Chemical Co., Ltd.
  • biphenyl phosphate group-containing A transparent barrier film was obtained in the same manner as in Example 1 except that 41 parts by weight of acrylate (trade name: KAYARAD R-9663H) was used.
  • Example 12 58 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330) and 35 parts by weight of tricyclodecane dimethylol diacrylate (trade name: Aronix M-203s manufactured by Toa Gosei Co., Ltd.) used in Example 12 Instead of the composition, 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 Toa Gosei Co., Ltd.) are used. A transparent barrier film was obtained in the same manner as in Example 12 except for the above.
  • Example 13 58 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330) and 35 parts by weight of tricyclodecane dimethylol diacrylate (trade name: Aronix M-203s manufactured by Toa Gosei Co., Ltd.) used in Example 12 In place of the composition, 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-manufactured by Toa Gosei Co., Ltd.) 203 s) A transparent barrier film was obtained in the same manner as in Example 12 except that 35 parts by weight of the composition was used.
  • Comparative Example 14 A transparent barrier film was obtained in the same manner as in Comparative Example 5, except that a silicon nitride layer having a thickness of 150 nm was provided on the other surface of the polyethylene naphthalate film having no cured resin layer.
  • Comparative Example 15 A transparent barrier film was obtained in the same manner as in Comparative Example 6 except that a silicon nitride layer having a thickness of 150 nm was provided on the other surface of the polyethylene naphthalate film not having a cured resin layer.
  • the film of the present invention has transmittance, cloudiness, It can be seen that both the adhesion and gas barrier properties are good films. That is, by providing not only a base material and a layer of nitrogen and silicon but also a cured resin layer, each performance is improved. Furthermore, when Example 4 and Example 8 or Example 5 and Example 9 are compared, the gas barrier property is further improved by containing a fluorine compound having a branched perfluoroalkenyl group or a derivative thereof. I understand that.
  • the film of the present invention thus obtained can be used as a sealing film that requires gas barrier properties such as water vapor.
  • This transparent sealing film can be usefully used for a photoelectric conversion element and an OLED element.
  • OLED since light emission from the element is not hindered, a light emitting efficiency is not lowered and a highly reliable OLED can be obtained.
  • a photoelectric conversion element when used in a photoelectric conversion barrier film, it is highly transparent and has a high barrier property, so that it functions stably as a barrier film for photoelectric conversion over a long period of time. It is possible to obtain a solar cell that functions without causing it.

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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 µm, and transmittance being 75% or more.

Description

透明ガスバリアフィルムTransparent gas barrier film
　本発明は、透明ガスバリアフィルムに関するものである。 The present invention relates to a transparent gas barrier film.
　ガスバリア性フィルムは、水蒸気や酸素等の各種ガスの遮断を必要とする物品や食品の包装、工業用品、医薬品等で変質を防止するために多く用いられている。また、包装用途以外にも液晶表示素子、太陽電池、有機エレクトロルミネッセンス（以下、ＯＬＥＤと省略する）用途で使用されている。包装用分野で通常使用されるガスバリア性フィルムは、透明度が低くても良く、また、高度なガスバリア性を有さなくても良い。そのため、かかるガスバリア性フィルムは、ディスプレイ材料分野では使用できない。近年、酸化アルミニウムや酸化マグネシウムなどの透明性が低い材料ではなく、酸化ケイ素、酸化窒化珪素などを用いて透明度が高く、かつ、水蒸気バリア性が高いフィルムが開発されつつあるが、透明性、ガスバリア性、密着性および耐久性のすべてが良好なフィルムは、まだ開発されておらず、種々の検討がなされている。 Gas barrier films are often used to prevent alteration in products, food packaging, industrial products, pharmaceuticals, etc. that require blocking of various gases such as water vapor and oxygen. In addition to packaging applications, they are used in liquid crystal display elements, solar cells, and organic electroluminescence (hereinafter abbreviated as OLED) applications. The gas barrier film normally used in the packaging field may have low transparency and may not have a high gas barrier property. Therefore, such a gas barrier film cannot be used in the display material field. In recent years, films with high transparency and high water vapor barrier properties have been developed using silicon oxide, silicon oxynitride, etc., instead of materials with low transparency such as aluminum oxide and magnesium oxide. A film having good properties, adhesion and durability has not been developed yet, and various studies have been made.
　特に、ＯＬＥＤの分野では、透明フィルムにおいて、近年、大型化および軽量化という要求に加え、長期信頼性が高く、形状の自由度が高く、曲面表示可能で、割れず、運搬しやすいことが要求されている。しかしながら、ＯＬＥＤの分野では、わずかな水分でも含有すると、その表示機能が低下してしまうことからガラスと同等な高いガスバリア性が要求される。一方で、ガラス自体を用いると、曲げた時や落とした場合に割れてしまうという問題を有している。そのため、ガラスまたはそれ同等のフィルムを用いることは出来ていない。 In particular, in the field of OLEDs, in recent years, in transparent films, in addition to the demands for larger size and lighter weight, long-term reliability, high degree of freedom in shape, curved surface display, breakage, and ease of transportation are required. Has been. However, in the field of OLED, when even a small amount of moisture is contained, the display function is deteriorated, so that a high gas barrier property equivalent to that of glass is required. On the other hand, when glass itself is used, it has a problem of being broken when bent or dropped. Therefore, glass or an equivalent film cannot be used.
特開平２－２５１４２９号JP-A-2-251429 特開平６－１２４７８５号JP-A-6-124785 特許第３４８４８９１号Japanese Patent No. 3484891 特開２００６－２９９１４５号JP 2006-299145 A 特開２０１１－２０１１３５号JP2011-201135A 特開２０１１－２３８３５５号JP2011-238355A
　そういった問題に対する技術として、特許文献１乃至特許文献３には、バリア性の高いガスバリアフィルムに関する技術が開示されている。しかしながら、透明プラスチック等のフィルムは、ガラスに対してガスバリア性が劣る問題があり、ＯＬＥＤ等では使用できない。特許文献４には、金属アルコキシドを用いたゾル－ゲル法によって形成されるセラミック膜、特許文献５および特許文献６には、無機化合物と有機化合物を用いることによってガスバリア性を向上させた技術が開示されている。しかしながら、そういった技術によってもなお、透明性が高く、ガスバリア性が高く、密着性が高く、耐久性も十分に良好であり、かつ、生産性に優れたフィルムは得られてない。
　そういった要望の中、物理的気相成長法（ＰＶＤ）や化学的気相成長法（ＣＶＤ）を改良し、より金属膜性質を高める技術が非特許文献１乃至３に開示されている。このような手法によって得られた金属膜は、ガスバリア性が高いことが知られている。しかしながら、それでもなおガスバリア性は十分でなく、特に、金属膜の基材への密着性が悪く、金属膜の柔軟性が大きく低下してしまうため、フィルムを折り曲げる際に金属膜に亀裂が入り、ガスバリア性が大きく低下してしまう。その密着性や柔軟性を改善するために、（メタ）アクリレート化合物から形成された樹脂硬化物層に金属膜を適用することが検討されてきたが、かかる樹脂硬化物層に適用すると、通常、表面が白濁する、ヘイズが発生して透明度が低下する、密着性が低下する、高温高湿試験後に密着性が低下する等の問題があった。 As technologies for such problems, Patent Literatures 1 to 3 disclose technologies relating to gas barrier films having high barrier properties. However, a film such as a transparent plastic has a problem that the gas barrier property is inferior to 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 Documents 5 and 6 disclose a technique in which gas barrier properties are improved by using an inorganic compound and an organic compound. Has been. However, even with such a technique, a film having high transparency, high gas barrier properties, high adhesion, sufficiently high durability, and excellent productivity has not been obtained.
In such a demand, Non-Patent Documents 1 to 3 disclose techniques for improving physical vapor deposition (PVD) and chemical vapor deposition (CVD) to enhance the properties of metal films. It is known that the metal film obtained by such a method has a high gas barrier property. However, the gas barrier property is still not sufficient, in particular, the adhesion of the metal film to the base material is poor, and the flexibility of the metal film is greatly reduced, so when the film is folded, the metal film is cracked, The gas barrier property is greatly reduced. In order to improve the adhesion and flexibility, it has been studied to apply a metal film to a cured resin layer formed from a (meth) acrylate compound, but when applied to such a cured resin layer, There have been problems such as the surface becoming cloudy, haze being generated and the transparency being lowered, the adhesion being lowered, and the adhesion being lowered after the high temperature and high humidity test.
　前記課題を解決すべく、本発明者らは鋭意検討を行った結果、基材上に、トリメチロールプロパン骨格またはイソシアヌル骨格を有する（メタ）アクリレート化合物を少なくとも１種含む重合性樹脂組成物から形成された樹脂硬化物層を有し、且つ、該樹脂硬化物層上に、５０ｎｍ乃至５００ｎｍの厚さを有する、珪素と窒素を含む層を有するフィルムであって、該（メタ）アクリレート化合物の含有量が該重合性樹脂組成物１００重量部に対して４０重量部乃至９９重量部であり、該樹脂硬化物層の厚さが０．１μｍ乃至２０μｍであり、透過率が７５％以上であることを特徴とするフィルムが、透明性が高く、ガスバリア性が高く、密着性が高く、耐久性も十分に良好であり、かつ、生産性にも優れることを新規に見出した。 In order to solve the above-mentioned problems, the present inventors have conducted intensive studies, and as a result, formed on a substrate from a polymerizable resin composition containing at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton. A film having a cured resin layer and a layer containing silicon and nitrogen having a thickness of 50 nm to 500 nm on the cured resin layer, and containing the (meth) acrylate compound The amount is 40 to 99 parts by weight with respect to 100 parts by weight of the polymerizable resin composition, the thickness of the cured resin layer is 0.1 to 20 μm, and the transmittance is 75% or more. It was newly found that a film characterized by the above has high transparency, high gas barrier properties, high adhesion, sufficiently good durability, and excellent productivity.
　すなわち、本発明は、
　「（１）基材上に、トリメチロールプロパン骨格またはイソシアヌル骨格を有する（メタ）アクリレート化合物を少なくとも１種含む重合性樹脂組成物から形成される硬化物層を有し、且つ、
　該硬化物層上に、５０ｎｍ乃至５００ｎｍの厚さを有する、珪素と窒素とを含む層を有するフィルムであって、
　該（メタ）アクリレート化合物の含有量が、該重合性樹脂組成物１００重量部に対して４０重量部乃至９９重量部であり、
　該硬化物層の厚さが０．１μｍ乃至２０μｍであり、
　透過率が７５％以上であることを特徴とする、フィルム、
　（２）前記重合性樹脂組成物が、ジシクロペンタジエン骨格を有する（メタ）アクリレート化合物を、該重合性樹脂組成物１００重量部に対して１０重量部乃至５５重量部含有することを特徴とする、（１）に記載のフィルム、
　（３）前記重合性樹脂組成物が、分岐型パーフルオロアルケニル基を有するフッ素系化合物またはその誘導体を、該重合性樹脂組成物１００重量部に対して０．０１重量部乃至１重量部含有することを特徴とする、（１）または（２）に記載のフィルム、
　（４）前記珪素と窒素とを含む層に、元素としてアルミニウムを更に含有することを特徴とする、（１）乃至（３）のいずれか一項に記載のフィルム、
　（５）（１）乃至（４）のいずれか一項に記載のフィルムを用いた液晶表示装置、
　（６）（１）乃至（４）のいずれか一項に記載のフィルムを用いた有機エレクトロルミネッセンス素子、
　（７）前記珪素と窒素とを含む層が、イオンビームアシスト蒸着法によって形成されることを特徴とする、（１）乃至（４）のいずれか一項に記載のフィルム、
　（８）前記珪素と窒素とを含む層が、マグネトロンスパッタ法によって形成されることを特徴とする、（１）乃至（４）のいずれか一項に記載のフィルム」
に関する。 That is, the present invention
“(1) having a cured product layer formed on a base material from a polymerizable resin composition containing at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton, and
A film having a layer containing silicon and nitrogen having a thickness of 50 nm to 500 nm on the cured product layer,
The content of the (meth) acrylate compound is 40 parts by weight to 99 parts by weight with respect to 100 parts by weight of the polymerizable resin composition,
The thickness of the cured product layer is 0.1 μm to 20 μm,
A film characterized by having a transmittance of 75% or more,
(2) The polymerizable resin composition contains a (meth) acrylate compound having a dicyclopentadiene skeleton in an amount of 10 to 55 parts by weight with respect to 100 parts by weight of the polymerizable resin composition. The film according to (1),
(3) The polymerizable resin composition contains 0.01 to 1 part by weight of a fluorine-based compound having a branched perfluoroalkenyl group or a derivative thereof with respect to 100 parts by weight of the polymerizable resin composition. The film according to (1) or (2),
(4) The film according to any one of (1) to (3), wherein the layer containing silicon and nitrogen further contains aluminum as an element,
(5) A liquid crystal display device using the film according to any one of (1) to (4),
(6) An organic electroluminescence device using the film according to any one of (1) to (4),
(7) The film according to any one of (1) to (4), wherein the layer containing silicon and nitrogen is formed by an ion beam assisted deposition method,
(8) The film according to any one of (1) to (4), wherein the layer containing silicon and nitrogen is formed by a magnetron sputtering method.
About.
　本発明のフィルムは、透明性が高く、ガスバリア性が高く、密着性が高く、また、耐久性も十分に良好であり、かつ、生産性に優れる。 The film of the present invention has high transparency, high gas barrier properties, high adhesiveness, sufficiently good durability, and excellent productivity.
　本発明は、基材上に、トリメチロールプロパン骨格またはイソシアヌル骨格を有する（メタ）アクリレート化合物を少なくとも１種含む重合性樹脂組成物から形成される硬化物層を有し、且つ、該硬化物層上に、５０ｎｍ乃至５００ｎｍの厚さを有する、珪素と窒素とを含む層を有するフィルムであって、該（メタ）アクリレート化合物の含有量が、該重合性樹脂組成物１００重量部に対して４０重量部乃至９９重量部であり、該硬化物層の厚さが０．１μｍ乃至２０μｍであり、透過率が７５％以上であることを特徴とするフィルムに関する。 The present invention has a cured product layer formed from a polymerizable resin composition containing at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton on a substrate, and the cured product layer A film having a thickness of 50 nm to 500 nm and having a layer containing silicon and nitrogen, wherein the content of the (meth) acrylate compound is 40 with respect to 100 parts by weight of the polymerizable resin composition. The present invention relates to a film characterized in that the cured product layer has a thickness of 0.1 to 20 μm and a transmittance of 75% or more.
　本発明における基材とは、透明性とガスバリア性を保持することができる有機材料で形成されたものであれば特に限定されるものではない。かかる有機材料としては、例えば、アクリル酸エステル、メタクリル酸エステル、ポリエチレンテレフタレート（以下、「ＰＥＴ」と省略する）、ポリエチレンナフタレート（以下、「ＰＥＮ」と省略する）、ポリカーボネート、ポリアリレート、ポリ塩化ビニル、ポリエチレン、ポリプロピレン、ナイロン、ポリイミド、ポリアミド、シクロオレフィン、トリアセチルセルロース、シルセスキオキサンを基本骨格とした有機・無機ハイブリットよりなる有機材料などが例示され、それら有機材料を５μｍ乃至５００μｍの厚さのフィルムに形成したものを基材として用いることが出来る。コストや入手が容易な点を考慮すると、ＰＥＴ、ＰＥＮ、またはポリカーボネートよりなるフィルムが好ましい。複屈折、特に位相差が少ないという点では、シクロオレフィン、トリアセチルセルロース、シルセスキオキサンを基本骨格とした有機・無機ハイブリットよりなる有機材料によって形成されたフィルムが好ましい。シクロオレフィンよりなるフィルムの製品としては、ゼオン社製　Ｚｅｏｎｏｒ、ＪＳＲ社製　ＡＲＴＯＮ、グンゼ社製　Ｆフィルムが例示され、シルセスキオキサンを基本骨格とした有機・無機ハイブリットよりなる有機材料によって形成されたフィルムとしては、新日鉄化学社製　シルプラス、チッソ社製　Ｓｉｌａ－ＤＥＣが例示される。 The base material in the present invention is not particularly limited as long as it is formed of an organic material that can maintain transparency and gas barrier properties. Examples of the organic material include acrylic acid ester, methacrylic acid ester, polyethylene terephthalate (hereinafter abbreviated as “PET”), polyethylene naphthalate (hereinafter abbreviated as “PEN”), polycarbonate, polyarylate, and polychlorinated acid. Examples include organic materials composed of organic / inorganic hybrids based on vinyl, polyethylene, polypropylene, nylon, polyimide, polyamide, cycloolefin, triacetylcellulose, silsesquioxane, and the like. These organic materials have a thickness of 5 μm to 500 μm. What was formed in the film of this length can be used as a base material. In view of cost and availability, a film made of PET, PEN, or polycarbonate is preferable. From the viewpoint of low birefringence, particularly a retardation, a film formed of an organic material composed of an organic / inorganic hybrid having cycloolefin, triacetylcellulose, and silsesquioxane as a basic skeleton is preferable. Examples of films made of cycloolefin include Zeon manufactured by Zeon, JSR manufactured by ARTON, and Gunze manufactured by F film, and formed by an organic material composed of an organic / inorganic hybrid based on silsesquioxane. Examples of the film include Nippon Steel Chemical's Sylplus and Chisso's Sila-DEC.
　本発明のフィルムは、基材上に０．１μｍ乃至２０μｍに形成された硬化物の層が設けられている。硬化物の層は、重合性樹脂組成物から形成され、重合性樹脂組成物は、トリメチロールプロパン骨格またはイソシアヌル骨格を有する（メタ）アクリレート化合物を少なくとも１種含む。該重合性樹脂組成物は、例えば、アクリロイル基を少なくとも１つ有する（メタ）アクリレート化合物９０乃至９９．９重量部と、重合開始剤０．１乃至１０重量部とを含む。該硬化物層を形成する重合性樹脂組成物は、トリメチロールプロパン骨格またはイソシアヌル骨格を有する（メタ）アクリレート化合物を少なくとも１種含むことが必要であり、その含有量は重合性樹脂組成物１００重量部に対して４０重量部乃至９９重量部である。トリメチロールプロパン骨格またはイソシアヌル骨格を有する（メタ）アクリレート化合物が、組成物が配合した樹脂量に対して５０重量％以上、より好ましくは６０重量％以上、さらに好ましくは７０重量％以上が、硬化の安定性が向上するため良い。トリメチロールプロパン骨格またはイソシアヌル骨格を有する（メタ）アクリレート化合物が、４０重量％以下であると、本発明の性能を発揮しないため好ましくない。本発明では、トリメチロールプロパン骨格を有する（メタ）アクリレート化合物の方が、透明性が高くなるため好ましい。 The film of the present invention is provided with a cured product layer formed to a thickness of 0.1 μm to 20 μm on a substrate. The layer of the cured product is formed from a polymerizable resin composition, and the polymerizable resin composition includes at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton. The polymerizable resin composition includes, for example, 90 to 99.9 parts by weight of a (meth) acrylate compound having at least one acryloyl group and 0.1 to 10 parts by weight of a polymerization initiator. The polymerizable resin composition forming the cured product layer needs to contain at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton, and the content thereof is 100 weights of the polymerizable resin composition. 40 parts by weight to 99 parts by weight with respect to parts. The (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton is 50% by weight or more, more preferably 60% by weight or more, and further preferably 70% by weight or more based on the amount of resin blended in the composition. Good because stability is improved. When the (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton is 40% by weight or less, the performance of the present invention is not exhibited, which is not preferable. In the present invention, a (meth) acrylate compound having a trimethylolpropane skeleton is preferable because of high transparency.
　（メタ）アクリレート化合物少なくとも１種と重合開始剤とを配合した重合性樹脂組成物を硬化させて、重合性樹脂硬化物よりなる層を形成することができる。（メタ）アクリレート化合物としては、具体的には、非特許文献４に記載のアクリレートモノマーを用いることができる。それらに限定されるものではなく、（メタ）アクリロイル基を少なくとも１つ有する（メタ）アクリレート化合物であれば、特に限定されない。重合性樹脂組成には、前記した（メタ）アクリレート化合物以外の成分、例えば、各種ポリマーや、オリゴマー等を添加でき、硬化を阻害しない成分およびその濃度であれば特に限定されず用いることが出来る。添加する量としては、重合性樹脂組成物が硬化できれば、任意の割合で配合しても良いが、重合性樹脂組成物１００重量部に対して４０重量部乃至９９重量部であることがより好ましい。 It is possible to cure a polymerizable resin composition containing at least one (meth) acrylate compound and a polymerization initiator to form a layer made of a cured polymer resin. As the (meth) acrylate compound, specifically, the acrylate monomer described in Non-Patent Document 4 can be used. It is not limited to them, and it is not particularly limited as long as it is a (meth) acrylate compound having at least one (meth) acryloyl group. Components other than the (meth) acrylate compound described above, for example, various polymers and oligomers can be added to the polymerizable resin composition, and any component and its concentration that do not inhibit curing can be used without particular limitation. The amount to be added may be blended in any proportion as long as the polymerizable resin composition can be cured, but it is more preferably 40 to 99 parts by weight with respect to 100 parts by weight of the polymerizable resin composition. .
　トリメチロールプロパン骨格を有する（メタ）アクリレート化合物としては、トリメチロールプロパントリアクリレート[日本化薬社製　カヤラッドＴＭＰＴＡ]、ＥＯ変性トリメチロールプロパントリアクリレート[サートマー社製　ＳＲ－４５４]、ＰＯ変性トリメチロールプロパントリアクリレート[日本化薬社製　ＴＰＡ－３１０，ＴＰＡ－３２０，ＴＰＡ－３３０など]、トリメチロールプロパントリメタクリレート[サートマー製　ＳＲ－３５０]、トリメチロールプロパントリグリシジルエーテルとアクリル酸との反応生成物[デナコールＤＡ－３２１　長瀬産業（株）製]などが例示される。 Examples of the (meth) acrylate compound having a trimethylolpropane skeleton include trimethylolpropane triacrylate [Kayarad TMPTA manufactured by Nippon Kayaku Co., Ltd.], EO-modified trimethylolpropane triacrylate [SR-454 manufactured by Sartomer], and PO-modified trimethylolpropane. Triacrylate [manufactured by Nippon Kayaku Co., Ltd., TPA-310, TPA-320, TPA-330, etc.], trimethylolpropane trimethacrylate [Sartomer SR-350], reaction product of trimethylolpropane triglycidyl ether and acrylic acid [ Denacol DA-321 (manufactured by Nagase Sangyo Co., Ltd.) is exemplified.
　イソシアヌル骨格を有する（メタ）アクリレート化合物としては、ジアクリロキシエチルイソシアヌレート[東亞合成社製　アロニックスＭ－２１５]、トリスアクリロキシエチルイソシアヌレート [日立化成社製　ＦＡ－７３１Ａ]、カプロラクトン変性トリスアクリロキシエチルイソシアヌレート[東亞合成社製　アロニックスＭ－３２５]、トリスメタクリロキシエチルイソシアヌレート[日立化成社製　ＦＡ－７３１Ｍ]などが例示される。 Examples of the (meth) acrylate compound having an isocyanuric skeleton include diacryloxyethyl isocyanurate [Aronix M-215 manufactured by Toagosei Co., Ltd.], trisacryloxyethyl isocyanurate [FA-731A manufactured by Hitachi Chemical Co., Ltd.], caprolactone-modified trisacryloxy Examples include ethyl isocyanurate [Aronix M-325 manufactured by Toagosei Co., Ltd.], trismethacryloxyethyl isocyanurate [FA-731M manufactured by Hitachi Chemical Co., Ltd.], and the like.
　さらに、前記重合性樹脂組成物が、ジシクロペンタジエン骨格を有する（メタ）アクリレート化合物を、重合性樹脂組成物１００重量部に対して１０重量部乃至５５重量部含有することで、さらに透明性が高く、ガスバリア性が高く、密着性が高く、耐久性も十分に良好であり、かつ、生産性に優れるフィルムが得られる。ジシクロペンタジエン骨格を有する（メタ）アクリレートの好ましい含有量としては、１５重量％乃至５０重量％、さらに好ましい含有量としては２０重量％乃至４０重量％である。本発明において、好ましい重合性樹脂硬化物の層を形成するための重合性樹脂組成物は、トリメチロールプロパン骨格またはイソシアヌル骨格を含む（メタ）アクリレート化合物と、ジシクロペンタジエン骨格を有する（メタ）アクリレートと、その重合開始剤とによって構成される組成物であり、さらに好ましい重合性樹脂硬化物の層を形成させるための重合性樹脂組成物は、トリメチロールプロパン骨格を含む（メタ）アクリレート化合物と、ジシクロペンタジエン骨格を有する（メタ）アクリレートと、その重合開始剤とによって構成される組成物である。 Further, the polymerizable resin composition contains a (meth) acrylate compound having a dicyclopentadiene skeleton in an amount of 10 to 55 parts by weight with respect to 100 parts by weight of the polymerizable resin composition. A film with high gas barrier properties, high adhesion, sufficiently good durability, and excellent productivity can be obtained. The preferred content of the (meth) acrylate having a dicyclopentadiene skeleton is 15 to 50% by weight, and the more preferred content is 20 to 40% by weight. In the present invention, a polymerizable resin composition for forming a layer of a preferable polymerizable resin cured product includes a (meth) acrylate compound containing a trimethylolpropane skeleton or an isocyanuric skeleton, and a (meth) acrylate having a dicyclopentadiene skeleton. And a polymerization resin composition for forming a layer of a more preferable polymerizable resin cured product, a (meth) acrylate compound containing a trimethylolpropane skeleton, It is a composition comprised by the (meth) acrylate which has a dicyclopentadiene frame | skeleton, and its polymerization initiator.
　ジシクロペンタジエン骨格を有する（メタ）アクリレート化合物とは、例えば、ジシクロペンタニル骨格、ジシクロペンテニル骨格又はアダマンタン骨格を有する樹脂を指す。中でも、より湿熱耐久性を向上させるためには、ジシクロペンタニル骨格又はジシクロペンテニル骨格を有する樹脂が好ましく、ジシクロペンタニル骨格を有する樹脂が最も好ましい。ジシクロペンタニル骨格を有する化合物としては、例えば、ジシクロペンタニルアクリレート（日立化成社製ＦＡ－５１３Ａ）、ジシクロペンタニルメタクリレート（日立化成社製ＦＡ－５１３Ｍ）又はジシクロペンタニルジアクリレート（日本化薬社製カヤラッドＲ－６８４）などが好ましい。ジシクロペンテニル骨格を有する化合物としては、例えば、ジシクロペンテニルアクリレート（日立化成社製ＦＡ－５１１Ａ）、ジシクロペンテニルオキシエチルアクリレート（日立化成社製ＦＡ－５１２Ａ）又はジシクロペンテニルオキシエチルメタクリレート（日立化成ＦＡ－５１２Ｍ）などが好ましい。アダマンタン骨格を有する化合物としては、例えば、２－メチルー２－アダマンチルメタクリレート（出光興産社製　ＡｄａｍａｎｔａｔｅＭＭ）,２－エチルー２アダマンチルメタクリレート（出光興産社製　ＡｄａｍａｎｔａｔｅＥＭ）,３－ヒドロキシー１－アダマンチルメタクリレート（出光興産社製　ＡｄａｍａｎｔａｔｅＨＭ）,３－ヒドロキシー１－アダマンチルアクリレート（出光興産社製　ＡｄａｍａｎｔａｔｅＨＡ）,２－メチルー２－アダマンチルアクリレート（出光興産社製　ＡｄａｍａｎｔａｔｅＭＡ）又は２－エチルー２－アダマンチルアクリレート（出光興産社製　ＡｄａｍａｎｔａｔｅＥＡ）などが例示される。 The (meth) acrylate compound having a dicyclopentadiene skeleton refers to, for example, a resin having a dicyclopentanyl skeleton, a dicyclopentenyl skeleton, or an adamantane skeleton. Among these, in order to further improve the wet heat durability, a resin having a dicyclopentanyl skeleton or a dicyclopentenyl skeleton is preferable, and a resin having a dicyclopentanyl skeleton is most preferable. Examples of the compound having a dicyclopentanyl skeleton include dicyclopentanyl acrylate (FA-513A manufactured by Hitachi Chemical Co., Ltd.), dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) or dicyclopentanyl diacrylate ( Nippon Kayaku Co., Ltd. Kayalad R-684) is preferred. Examples of the compound having a dicyclopentenyl skeleton include dicyclopentenyl acrylate (FA-511A manufactured by Hitachi Chemical Co., Ltd.), dicyclopentenyloxyethyl acrylate (FA-512A manufactured by Hitachi Chemical Co., Ltd.) or dicyclopentenyloxyethyl methacrylate (Hitachi). Chemical conversion FA-512M) is preferred. Examples of the compound having an adamantane skeleton include 2-methyl-2-adamantyl methacrylate (Adamantate MM, manufactured by Idemitsu Kosan Co., Ltd.), 2-ethyl-2-adamantyl methacrylate (Adamantate EM, manufactured by Idemitsu Kosan Co., Ltd.), 3-hydroxy-1-adamantyl methacrylate (Idemitsu Kosan Co., Ltd.). Adamantate HM), 3-hydroxy-1-adamantyl acrylate (Idemitsu Kosan Co., Ltd. Adamantate HA), 2-methyl-2-adamantyl acrylate (Idemitsu Kosan Co., Ltd. Adamantate MA), or 2-ethyl-2-adamantyl acrylate (manufactured by Idemitsu Kosan Co., Ltd., AdamantEA, etc.) Illustrated.
　本発明で使用される（メタ）アクリレート化合物または重合性樹脂組成物が、紫外線によって重合する場合には、紫外線を照射して光重合開始剤により重合反応を生じさせる。光重合開始剤としては例えば、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１（チバスペシャリティーケミカルズ社製イルガキュアー９０７）、１－ヒドロキシシクロヘキシルフェニルケトン（チバスペシャリティーケミカルズ社製イルガキュアー１８４）、４－（２－ヒドロキシエトキシ）－フェニル（２－ヒドロキシ－２－プロピル）ケトン（チバスペシャリティーケミカルズ社製イルガキュアー２９５９）、１－（４－ドデシルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン（メルク社製ダロキュアー９５３）、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン（メルク社製ダロキュアー１１１６）、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン（チバスペシャリティーケミカルズ社製イルガキュアー１１７３）、ジエトキシアセトフェノン等のアセトフェノン系化合物、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、２，２－ジメトキシ－２－フェニルアセトフェノン（チバスペシャリティーケミカルズ社製イルガキュアー６５１）等のベンゾイン系化合物、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、ヒドロキシベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、３，３’－ジメチル－４－メトキシベンゾフェノン（日本化薬社製カヤキュアーＭＢＰ）等のベンゾフェノン系化合物、チオキサンソン、２－クロルチオキサンソン（日本化薬社製カヤキュアーＣＴＸ）、２－メチルチオキサンソン、２，４－ジメチルチオキサンソン（日本化薬社製カヤキュアーＲＴＸ）、イソプロピルチオキサンソン、２，４－ジクロオチオキサンソン（日本化薬社製カヤキュアーＣＴＸ）、２，４－ジエチルチオキサンソン（日本化薬社製カヤキュアーＤＥＴＸ）、２，４－ジイソプロピルチオキサンソン（日本化薬社製カヤキュアーＤＩＴＸ）等のチオキサンソン系化合物等が挙げられる。より好ましくは、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１（チバスペシャリティーケミカルズ社製イルガキュアー９０７）、１－ヒドロキシシクロヘキシルフェニルケトン（チバスペシャリティーケミカルズ社製イルガキュアー１８４）又は２，２－ジメトキシ－２－フェニルアセトフェノン（チバスペシャリティーケミカルズ社製イルガキュアー６５１）である。これらの光重合開始剤は１種類でも複数でも任意の配合割合で混合して使用することができる。 When the (meth) acrylate compound or the polymerizable resin composition used in the present invention is polymerized by ultraviolet rays, the polymerization reaction is caused by the photopolymerization initiator by irradiating the ultraviolet rays. Examples of the photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 (Irgacure 907 manufactured by Ciba Specialty Chemicals), 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty). Irgacure 184 from Tea Chemicals), 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone (Irgacure 2959 from Ciba Specialty Chemicals), 1- (4-dodecylphenyl)- 2-hydroxy-2-methylpropan-1-one (Merck Darocur 953), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Merck Darocur 1116), 2 -Hydroxy-2-methyl-1-phenyl Lopan-1-one (Irgacure 1173 manufactured by Ciba Specialty Chemicals), acetophenone compounds such as diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy- Benzoin compounds such as 2-phenylacetophenone (Irgacure 651 manufactured by Ciba Specialty Chemicals), benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3 Benzophenone compounds such as 3,3′-dimethyl-4-methoxybenzophenone (Kayacure MBP manufactured by Nippon Kayaku Co., Ltd.), thioxanthone, 2- Lorthioxanthone (Nippon Kayaku Co., Ltd. Kayacure CTX), 2-methylthioxanthone, 2,4-dimethylthioxanthone (Nippon Kayaku Co., Ltd. Kayacure RTX), isopropylthioxanthone, 2,4-dichroothiox Thioxanes such as Sanson (Kayacure CTX manufactured by Nippon Kayaku Co., Ltd.), 2,4-diethylthioxanthone (Kayacure DETX manufactured by Nippon Kayaku Co., Ltd.), 2,4-diisopropylthioxanthone (Kayacure DITX manufactured by Nippon Kayaku Co., Ltd.) Compounds and the like. More preferably, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 (Irgacure 907 manufactured by Ciba Specialty Chemicals), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals) Irgacure 184) or 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651 manufactured by Ciba Specialty Chemicals). One or more of these photopolymerization initiators can be mixed and used at any blending ratio.
　光重合開始剤としてベンゾフェノン系化合物やチオキサンソン系化合物を用いる場合には、光重合反応を促進させるために、助剤を併用することも可能である。そのような助剤としては例えば、トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、ｎ－ブチルアミン、Ｎ－メチルジエタノールアミン、ジエチルアミノエチルメタアクリレート、ミヒラーケトン、４，４’―ジエチルアミノフェノン、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸（ｎ－ブトキシ）エチル又は４－ジメチルアミノ安息香酸イソアミル等のアミン系化合物が挙げられる。 When a benzophenone compound or a thioxanthone compound is used as a photopolymerization initiator, an auxiliary agent can be used in combination to promote the photopolymerization reaction. Examples of such auxiliaries include triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate, Michler's ketone, 4,4′-diethylaminophenone, 4-dimethylaminobenzoic acid. Examples include amine compounds such as ethyl, ethyl 4-dimethylaminobenzoate (n-butoxy) or isoamyl 4-dimethylaminobenzoate.
　前記光重合開始剤および助剤は、偏光性能の低下が起こらない範囲の添加量で使用することが好ましく、光重合開始剤の添加量は、重合性樹脂組成物中の（メタ）アクリレート化合物１００重量部に対して、好ましくは０．１重量部以上１２重量部以下、より好ましくは２重量部以上１０重量部以下程度である。また、助剤の添加量は、光重合開始剤に対して、０．５倍から２倍量程度が好ましい。 The photopolymerization initiator and the auxiliary agent are preferably used in an addition amount within a range in which the polarization performance does not deteriorate. The addition amount of the photopolymerization initiator is the (meth) acrylate compound 100 in the polymerizable resin composition. Preferably they are 0.1 weight part or more and 12 weight part or less with respect to a weight part, More preferably, they are about 2 weight part or more and 10 weight part or less. Further, the amount of the auxiliary added is preferably about 0.5 to 2 times the amount of the photopolymerization initiator.
　本発明で使用される（メタ）アクリレート化合物または（メタ）アクリレート樹脂組成物が熱硬化型の場合には、重合開始剤、架橋剤および／または開始触媒を用いる。架橋剤としては、イソシアネート系、ホウ素系、チタネート系等の種々の公知の化合物を用いることができ、重合を促進させるものであれば限定されない。架橋剤の添加量は、重合性樹脂組成物１００重量部中に０．１重量部以上２０重量部以下、好ましくは該組成物１００重量部中に１重量部以上１０重量部以下程度である。 When the (meth) acrylate compound or (meth) acrylate resin composition used in the present invention is a thermosetting type, a polymerization initiator, a crosslinking agent and / or an initiation catalyst are used. As a crosslinking agent, various well-known compounds, such as an isocyanate type, a boron type, a titanate type | system | group, can be used, If it accelerates | stimulates polymerization, it will not be limited. The addition amount of the crosslinking agent is 0.1 to 20 parts by weight in 100 parts by weight of the polymerizable resin composition, and preferably about 1 to 10 parts by weight in 100 parts by weight of the composition.
　本発明では、使用される（メタ）アクリレート化合物または重合性樹脂組成物が、熱硬化型の場合よりも紫外線硬化型の場合の方が、硬化処理において、光に対する安定性や硬化時間、製造コストの観点から有用である。 In the present invention, when the (meth) acrylate compound or polymerizable resin composition to be used is an ultraviolet curable type rather than a thermosetting type, the stability to light, the curing time, and the production cost in the curing process. It is useful from the point of view.
　重合性樹脂組成物の層は、基材層へコーティングする方法で設けられても良い。直接基材に塗布する方法だけではなく、あらかじめ別のフィルムに塗布し、硬化した層を基材転写、または積層させる方法を使用しても良い。 The layer of the polymerizable resin composition may be provided by a method of coating the base material layer. Not only a method of directly applying to a base material, but also a method of applying to a different film in advance and transferring the cured layer to the base material or laminating may be used.
　塗布する方法は特に限定されず、例えば、スピンコート方式、ワイヤーバーコート方式、グラビアコート方式、マイクログラビアコート方式、カレンダーコート方式、スプレーコート方式又はメニスカスコート方式等などによる方法が挙げられる。 The application method is not particularly limited, and examples thereof include a spin coating method, a wire bar coating method, a gravure coating method, a micro gravure coating method, a calendar coating method, a spray coating method, a meniscus coating method, and the like.
　本発明では、さらに、重合性樹脂組成物が、分岐型パーフルオロアルケニル基を有するフッ素化合物またはその誘導体を、重合性樹脂組成物１００重量部に対して０．０１重量部乃至１重量部含有することで、より透明性が高く、ガスバリア性が高く、密着性が高く、耐久性が十分に良好であり、かつ、生産性に優れるフィルムを得ることができる。分岐型パーフルオロアルケニル基を有するフッ素化合物は、式（１）に示されるフッ素化合物であり、その化合物の誘導体も含まれる。その添加量は、硬化物１００重量部中に０．０５重量部以上０．９重量部以下、より好ましくは該組成物１００重量部中に０．１重量部以上０．８重量部以下程度である。分岐型パーフルオロアルケニル基を有するフッ素化合物またはその誘導体のイオン性としては、アニオン性、カチオン性、ノニオン性、両性のタイプが挙げられる。当該フッ素化合物またはその誘導体としてはさらに、オリゴマータイプ、反応性を有するオリゴマータイプが挙げられる。少量添加で効果を示し、樹脂硬化物層からの析出がなく、かつ、後に珪素および窒素を含有した層を蒸着またはスパッタするためのリコート性を阻害しないという点から、ノニオンタイプが好ましく、ノニオンタイプのオリゴマーがより好ましく、ノニオンタイプの反応性オリゴマーがさらに好ましい。 In the present invention, the polymerizable resin composition further contains 0.01 to 1 part by weight of a fluorine compound having a branched perfluoroalkenyl group or a derivative thereof with respect to 100 parts by weight of the polymerizable resin composition. Thus, it is possible to obtain a film having higher transparency, higher gas barrier properties, higher adhesiveness, sufficiently good durability, and excellent productivity. The fluorine compound having a branched perfluoroalkenyl group is a fluorine compound represented by the formula (1), and derivatives of the compound are also included. The added amount is 0.05 to 0.9 parts by weight in 100 parts by weight of the cured product, more preferably about 0.1 to 0.8 parts by weight in 100 parts by weight of the composition. is there. Examples of the ionicity of the fluorine compound having a branched perfluoroalkenyl group or a derivative thereof include anionic, cationic, nonionic, and amphoteric types. Examples of the fluorine compound or its derivative further include an oligomer type and a reactive oligomer type. Nonionic type is preferable, since non-depletion type is preferable because it shows the effect when added in a small amount, does not precipitate from the cured resin layer, and does not hinder the recoatability to deposit or sputter a layer containing silicon and nitrogen later. Are more preferable, and nonionic type reactive oligomers are more preferable.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（１）の骨格を有する分岐型パーフルオロアルケニル基を有するフッ素化合物またはその誘導体としては、ネオス社が所有するフタージェントシリーズが例示される。タージェントシリーズの中でも、７１０ＦＬ、７１０ＦＭ、７１０ＦＳ、７３０ＬＭ、６０１ＡＤ、６０２Ａ、６５０Ａが好ましく、特に、６０１Ａ、６０２Ａ、６５０Ａは特に好ましく、さらに透明性が高く、ガスバリア性が高く、密着性が高く、耐久性も十分に良好であり、かつ、生産性に優れるフィルムを得ることができる。 Examples of the fluorine compound having a branched perfluoroalkenyl group having a skeleton of the formula (1) or a derivative thereof include a tangent series owned by Neos. Among the target series, 710FL, 710FM, 710FS, 730LM, 601AD, 602A, and 650A are preferable, and 601A, 602A, and 650A are particularly preferable. Further, the transparency is high, the gas barrier property is high, the adhesion is high, and the durability is high. It is possible to obtain a film having sufficiently good properties and excellent productivity.
　重合性樹脂硬化層をより安定にするために、劣化防止助剤を添加しても良い。劣化防止助剤とは、酸化防止剤、光安定剤を示す。酸化防止剤としては、例えば、ヒンダートフェノール系やセミヒンダートフェノール系などのフェノール系酸化防止剤、フェニレンジアミン系などのアミン系酸化防止剤、フォスファイト系やホスホナイト系などのリン系酸化防止剤、チオエーテル系などのイオウ系酸化防止剤などが挙げられる。光安定剤としては、例えば、ベンゾフェノン系やベンゾトリアゾール系、トリアジン系などの紫外線吸収剤、有機ニッケル錯体などの励起エネルギー吸収剤（Ｑｕｅｎｃｈｅｒ）、カーボンブラックや酸化チタンなどの紫外線遮蔽剤、基本骨格として２,２,６,６－テトラメチルビペリジン骨格を有するヒンダートアミン系光安定剤（ＨＡＬＳ）などが挙げられる。添加濃度は、特に限定されず、劣化防止助剤の能力により任意に添加できる。一般的には、溶剤を除いた重合性樹脂組成物に対して、０．０１重量％乃至５重量％、好ましくは０．０５重量％乃至３重量％を添加する。 In order to make the polymerizable resin cured layer more stable, a deterioration preventing aid may be added. Deterioration prevention aids indicate antioxidants and light stabilizers. Examples of the antioxidant include phenolic antioxidants such as hindered phenols and semihindered phenols, amine antioxidants such as phenylenediamines, and phosphorus antioxidants such as phosphites and phosphonites. And sulfur-based antioxidants such as thioethers. Examples of light stabilizers include ultraviolet absorbers such as benzophenone, benzotriazole, and triazine, excitation energy absorbers (Quencher) such as organic nickel complexes, ultraviolet shielding agents such as carbon black and titanium oxide, and basic skeletons. And hindered amine light stabilizers (HALS) having a 2,2,6,6-tetramethylbiperidine skeleton. The addition concentration is not particularly limited, and can be arbitrarily added depending on the ability of the deterioration preventing aid. Generally, 0.01 wt% to 5 wt%, preferably 0.05 wt% to 3 wt% is added to the polymerizable resin composition excluding the solvent.
　重合性樹脂硬化層を形成させる場合、重合性樹脂組成物を直接または適当な溶剤を用いて希釈し、基材に塗布する。その後加熱等により溶剤を除去し、加熱、または紫外線を照射することにより重合性樹脂硬化物を得ることができる。塗布する際に用いられる該組成物の溶液の溶剤としては、該組成物の溶解性、塗布時の基板上へのぬれ性に優れ表面性の低下を起こさないものであれば特に制限されない。そのような溶剤としては、例えば水、トルエン、キシレン等の芳香族炭化水素類、アニソール、ジオキサン、テトラヒドロフラン等のエーテル類、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ペンタノン、３－ペンタノン、２－ヘキサノン、３－ヘキサノン、２－ヘプタノン、３－ヘプタノン、４－ヘプタノン又は２，６－ジメチル－４－ヘプタノン等のケトン類、ｎ－ブタノール、２－ブタノール、シクロヘキサノール又はイソプロピルアルコール等のアルコール類、メチルセロソルブ、酢酸メチルセロソルブ等のセロソルブ類、酢酸エチル、酢酸ブチル、乳酸メチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、酢酸メトキシエチル又はサクサンエトキシエチル等のエステル類、ジメチルスルホキシド、アセトニトリル、Ｎ，Ｎ－ジメチルアセトホルムアミドが挙げられるがこれらに限定されない。中でも、トルエン、シクロペンタノン又は酢酸エチルが好ましい。また、溶剤は単一でも混合物でもよい。該組成物を溶解する際の該組成物の濃度は、溶剤溶解性、基板上へのぬれ性、塗布後の厚みなどによって異なるが、好ましくは５～９５重量％、より好ましくは１０～８０重量％程度である。 When the polymerizable resin cured layer is formed, the polymerizable resin composition is diluted directly or using an appropriate solvent and applied to the substrate. Thereafter, the solvent is removed by heating or the like, and the polymerizable resin cured product can be obtained by heating or irradiating with ultraviolet rays. The solvent of the solution of the composition used for 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 and does not cause deterioration in surface properties. Examples of such solvents include water, aromatic hydrocarbons such as toluene and xylene, ethers such as anisole, dioxane, and tetrahydrofuran, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, and 3-pentanone. , Ketones such as 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone or 2,6-dimethyl-4-heptanone, n-butanol, 2-butanol, cyclohexanol or isopropyl alcohol Alcohols, cellosolves such as methyl cellosolve and methyl cellosolve, ethyl acetate, butyl acetate, methyl lactate, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, methoxy acetate Esters such as chill or fence San ethoxyethyl, dimethyl sulfoxide, acetonitrile, N, including but N- dimethylacetamide dimethylformamide without limitation. Of these, toluene, cyclopentanone or ethyl acetate is preferable. The solvent may be a single solvent or a mixture. The concentration of the composition at the time of dissolving the composition varies depending on solvent solubility, wettability on the substrate, thickness after coating, etc., but is preferably 5 to 95% by weight, more preferably 10 to 80% by weight. %.
　また、基板上へ塗布する際、該基板上へのぬれ性が乏しい場合や、塗布された重合性樹脂組成物の層の表面性が悪い場合には、それらを改善するために該組成物中に種々のレベリング剤を添加することも可能である。レベリング剤としては、シリコン系、フッ素系、ポリエーテル系、アクリル酸共重合物系又はチタネート系等の種々の化合物を用いることができる。その添加量は、重合性樹脂組成物１００重量部中に０．０００１重量部以上１０重量部以下、好ましくは該組成物１００重量部中に０．１重量部以上５重量部以下程度である。 In addition, when applying on the substrate, if the wettability on the substrate is poor, or if the surface property of the layer of the applied polymerizable resin composition is poor, in the composition to improve them It is also possible to add various leveling agents. As the leveling agent, various compounds such as silicon-based, fluorine-based, polyether-based, acrylic acid copolymer-based or titanate-based compounds can be used. The addition amount is 0.0001 to 10 parts by weight in 100 parts by weight of the polymerizable resin composition, preferably about 0.1 to 5 parts by weight in 100 parts by weight of the composition.
　基板上へ塗布された該組成物層を硬化した後、硬化した層と保護フィルムとの密着性が悪い場合には、それらを改善するために該組成物中に種々の架橋剤を添加することも可能である。架橋剤としては、イソシアネート系、ホウ素系、チタネート系又はシリコン系等の種々の化合物を用いることができる。その添加量は、重合性樹脂組成物１００重量部中に０．０００１重量部以上２０重量部以下、より好ましくは該組成物１００重量部中に０．１重量部以上１０重量部以下程度である。 After the composition layer applied on the substrate is cured, if the adhesion between the cured layer and the protective film is poor, various crosslinking agents may be added to the composition to improve them. Is also possible. As the cross-linking agent, various compounds such as isocyanate, boron, titanate, or silicon can be used. The addition amount is 0.0001 part by weight or more and 20 parts by weight or less in 100 parts by weight of the polymerizable resin composition, more preferably about 0.1 part by weight or more and 10 parts by weight or less in 100 parts by weight of the composition. .
　本発明のフィルムの重合性樹脂硬化層は、加熱または紫外線照射により十分に重合し、未反応分が極力少ないことが好ましい。硬化後の樹脂硬化物１００重量部中の未反応の（メタ）アクリレート化合物は、０重量部以上５重量部以下、より好ましくは０重量部以上３重量部以下、さらに好ましくは０重量部以上１重量部以下である。そのような層を得る方法としては、例えば塗布後の樹脂組成物の層の厚さを最適化する方法、添加する光重合開始剤の種類や量を最適化する方法、十分な加熱または紫外線を照射する方法、窒素等の不活性ガス中で行うなどの紫外線照射時の雰囲気を変えて硬化させる方法などが挙げられる。この中でも、樹脂組成物の層の厚さを最適化する方法が、樹脂濃度を変えたり、樹脂塗布量を変えるだけで最適化できるので、最も簡易的である。重合性樹脂組成物を硬化させて得られた樹脂硬化物層の厚さは、０．１μｍ乃至２０μｍ、より好ましくは０．５μｍ乃至１８μｍ、さらに好ましくは２μｍ乃至１６μｍである。当該層の厚さが２０μｍより厚いと、残留未反応モノマーが増えて、耐久性が不十分であり、かつ、乾熱耐久性試験において偏光板が赤変する可能性があるため不適である。厚さが０．１μｍより薄い層では逆に耐光性向上はあまり得られない。紫外線の照射量は、（メタ）アクリレート化合物の種類、光重合開始剤の種類と添加量、膜厚によって異なるが、例えば１００～２０００ｍＪ／ｃｍ２程度が好ましい。 It is preferable that the polymerizable resin cured layer of the film of the present invention is sufficiently polymerized by heating or ultraviolet irradiation and has as little unreacted content as possible. The unreacted (meth) acrylate compound in 100 parts by weight of the cured resin after curing is 0 to 5 parts by weight, more preferably 0 to 3 parts by weight, and even more preferably 0 to 1 part by weight. Less than parts by weight. As a method for obtaining such a layer, for example, a method for optimizing the thickness of the layer of the resin composition after coating, a method for optimizing the kind and amount of the photopolymerization initiator to be added, sufficient heating or ultraviolet rays are used. A method of irradiating, a method of changing the atmosphere at the time of ultraviolet irradiation, such as performing in an inert gas such as nitrogen, and the like, can be mentioned. Among these, the method of optimizing the thickness of the resin composition layer is the simplest because it can be optimized only by changing the resin concentration or changing the resin coating amount. The thickness of the cured resin layer obtained by curing the polymerizable resin composition is 0.1 μm to 20 μm, more preferably 0.5 μm to 18 μm, and still more preferably 2 μm to 16 μm. If the thickness of the layer is greater than 20 μm, the residual unreacted monomer increases, the durability is insufficient, and the polarizing plate may turn red in a dry heat durability test, which is not suitable. On the other hand, in a layer having a thickness of less than 0.1 μm, light resistance cannot be improved much. The dose of ultraviolet rays, kind of (meth) acrylate compounds, the addition amount and kind of the photopolymerization initiator varies depending thickness, for example, it is preferably about 100 ~ 2000mJ / cm 2.
　本発明では、さらに５０ｎｍ乃至５００ｎｍの厚さを有する珪素と窒素とを含む層を、樹脂硬化物層に設けることが必要となる。珪素と窒素とを含む層の厚さは５０ｎｍ乃至５００ｎｍであれば本発明のフィルムを達成しえるが、好ましくは７０ｎｍ乃至３００ｎｍ、さらに好ましくは９０ｎｍ乃至２１０ｎｍである。珪素と窒素とを含む層は、公知の方法で形成させることができる。珪素と窒素とを含む層を形成させる方法としては、例えば、蒸着法、スパッタ法、イオンプレーティング法などの物理的気相成長法（以下、「ＰＶＤ」という）、化学的気相成長法（以下、「ＣＶＤ」という）などが例示される。珪素と窒素とを含む層を形成する最も好ましい方法は、イオンビームアシスト蒸着法、マグネトロンスパッタ法である。イオンビームアシスト蒸着法としては、特開平１０－１４０３２６号で窒化鉄を形成する方法や非特許文献１、非特許文献２などが開示している技術が挙げられ、マグネトロンスパッタ法としては、非特許文献３で開示している方法が挙げられる。かかるＰＶＤやＣＶＤを、（メタ）アクリレート化合物から形成される樹脂硬化物層に適用すると通常は、表面が白濁したり、ヘイズが発生して透明度が低下したり、密着性が低下したり、高温高湿試験後に密着性が低下してしまうが、本発明の重合性樹脂組成物から形成される樹脂硬化物層であれば、透明性が高く、ガスバリア性が高く、密着性が高く、耐久性も十分に良好であり、かつ、生産性に優れたフィルムを得ることが出来る。イオンビームアシスト蒸着法によって得られる本発明のフィルムは、透明度が非常に高く、かつ、水蒸気などのガス透過率が非常に低い。さらには、イオンビームアシスト蒸着法を使用すれば、高くても５０℃程度の熱しかかからず、低温で処理できるため基材となるフィルムが劣化せず、処理適用後の寸法変化などが起こらないため、珪素および窒素を含む層にクラックなどが生じない。一方、マグネトロンスパッタ法によって得られる本発明のフィルムは、透明度が非常に高く、密着性が非常に高く、かつ、折れ曲げ試験を行っても、表面のひび割れ等が起こらない非常に良好なフィルムである。 In the present invention, it is necessary to further provide a layer containing silicon and nitrogen having a thickness of 50 nm to 500 nm in the cured resin layer. If the thickness of the layer containing silicon and nitrogen is 50 nm to 500 nm, the film of the present invention can be achieved, but it is preferably 70 nm to 300 nm, more preferably 90 nm to 210 nm. The layer containing silicon and nitrogen can be formed by a known method. Examples of a method for forming a layer containing silicon and nitrogen include physical vapor deposition methods (hereinafter referred to as “PVD”) such as vapor deposition, sputtering, and ion plating, and chemical vapor deposition ( Hereinafter, it is referred to as “CVD”). The most preferable method for forming a layer containing silicon and nitrogen is an ion beam assisted deposition method or a magnetron sputtering method. Examples of the ion beam assisted deposition method include a method of forming iron nitride in Japanese Patent Laid-Open No. 10-140326, and techniques disclosed in Non-Patent Document 1, Non-Patent Document 2, and the like. The method currently disclosed by literature 3 is mentioned. When such PVD or CVD is applied to a cured resin layer formed from a (meth) acrylate compound, the surface is usually clouded, haze is generated, transparency is lowered, adhesion is lowered, Adhesiveness decreases after a high humidity test, but if it is a cured resin layer formed from the polymerizable resin composition of the present invention, it has high transparency, high gas barrier properties, high adhesion, and durability. Is sufficiently good, and a film excellent in productivity can be obtained. The film of the present invention obtained by the ion beam assisted vapor deposition method has very high transparency and extremely low gas permeability such as water vapor. Furthermore, if the ion beam assisted deposition method is used, only about 50 ° C. heat is applied at the highest, and since the film can be processed at a low temperature, the base film is not deteriorated, and a dimensional change after the processing is applied. Therefore, no crack or the like occurs in the layer containing silicon and nitrogen. On the other hand, the film of the present invention obtained by magnetron sputtering is a very good film that has very high transparency, very high adhesion, and does not cause surface cracks even when subjected to a bending test. is there.
　透明な、窒素と珪素とを含む層としては、シリコンナイトライト（Ｓｉ３Ｎ４）、酸素を含有した窒化珪素（ＳｉＯｘＮｙ，ｘとｙは任意の整数）の層が例示される。特にシリコンナイトライトの層を設けた本発明のフィルムは、良好な高いガスバリア性を有する。珪素と窒素とを含む層に、元素としてアルミニウムを更に含有すると、より柔軟性が高い窒素と珪素を含む本発明のフィルムを得るに至る。窒化珪素（ＳｉＯｘＮｙ）中の酸素の含有量は、非特許文献５、非特許文献６に記載された方法などによって測定することが出来る。 Examples of the transparent layer containing nitrogen and silicon include silicon nitrite (Si 3 N 4 ) and silicon nitride containing oxygen (SiO x N y , where x and y are arbitrary integers). In particular, the film of the present invention provided with a layer of silicon nitrite has good high gas barrier properties. When the layer containing silicon and nitrogen further contains aluminum as an element, the film of the present invention containing nitrogen and silicon with higher flexibility is obtained. The content of oxygen in silicon nitride (SiO x N y ) can be measured by the methods described in Non-Patent Document 5 and Non-Patent Document 6.
　以上の方法によって、基材と；構成する化合物としてトリメチロールプロパン骨格またはイソシアヌル骨格を有する（メタ）アクリレート化合物を少なくとも１種含む重合性樹脂組成物から形成される０．１μｍ乃至２０μｍの厚さを有する樹脂硬化物層と；５０ｎｍ乃至５００ｎｍの厚さを有する珪素と窒素とを含む層と；を備え、該（メタ）アクリレート化合物の含有量が該重合性樹脂組成物１００重量部に対して４０重量部乃至９９重量部であり、透過率が７５％以上であることを特徴とするフィルムを得ることができる。 By the above method, a thickness of 0.1 μm to 20 μm formed from a base material and a polymerizable resin composition comprising at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton as a constituent compound A cured resin layer having a thickness of 50 nm to 500 nm, and a layer containing silicon and nitrogen, and the content of the (meth) acrylate compound is 40 with respect to 100 parts by weight of the polymerizable resin composition. A film characterized by having a transmittance of 75% or more can be obtained.
　本発明のフィルムには、その片面又は両面に、接着剤等を介して、透明保護層を設けても良い。透明保護層を設けることによって、形状が安定したり、傷などの外観損傷を低下させたりすることも出来る。透明保護層を形成する透明ポリマー又はフィルムとしては、機械的強度が高く、熱安定性が良好な透明ポリマー又はフィルムが好ましい。 The film of the present invention may be provided with a transparent protective layer on one side or both sides via an adhesive or the like. By providing the transparent protective layer, the shape can be stabilized, and appearance damage such as scratches can be reduced. The transparent polymer or film forming the transparent protective layer is preferably a transparent polymer or film having high mechanical strength and good thermal stability.
　こうして得られた本発明のフィルムは、水蒸気などのガスバリアが要求される封止フィルムとして用いることが出来る。かかる透明封止フィルムは、光電変換素子、ＯＬＥＤ素子に有用に用いることができる。特に、ＯＬＥＤに用いた場合、素子からの発光を妨げないため発光効率を低下させず、信頼性の高いＯＬＥＤを得ることができる。また、光電変換用バリアフィルムとして光電変換素子に用いた場合には、透明性が高く、バリア性も高いので、長期にわたり光電変換用バリアフィルムとして安定して機能するため、太陽光の受光を低下させることなく機能する太陽電池を得ることができる。 The film of the present invention thus obtained can be used as a sealing film that requires a gas barrier such as water vapor. This transparent sealing film can be usefully used for a photoelectric conversion element and an OLED element. In particular, when used in an OLED, light emission from the element is not hindered, so that the light emission efficiency is not lowered and a highly reliable OLED can be obtained. In addition, when used in a photoelectric conversion element as a photoelectric conversion barrier film, it is highly transparent and has a high barrier property, so that it functions stably as a barrier film for photoelectric conversion over a long period of time. It is possible to obtain a solar cell that functions without causing it.
　以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらによって限定されるものではない。なお、実施例に示すフィルムの評価は以下のようにして行った。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, evaluation of the film shown in an Example was performed as follows.
　（全光線透過率）
　(株)日立ハイテクノロジーズ社製　Ｕ－４１００を使用し測定した。 (Total light transmittance)
Measurement was performed using U-4100 manufactured by Hitachi High-Technologies Corporation.
　（フィルムの白濁の有無）
　目視にて白濁の有無を確認した。 (Whether the film is cloudy)
The presence or absence of cloudiness was confirmed visually.
　（密着性）
　本発明のフィルムの重合性樹脂硬化物の層と、珪素と窒素を含む層とに、１ｍｍ間隔で１００個のマス目をカッターで作製し、セロテープ(登録商標）をしっかり密着させた後、９０度方向に一気に剥がし、下記の基準に従い、評価を実施した。
　　良：１００／１００密着良好
　　悪：剥れ発生 (Adhesion)
100 squares were produced with a cutter at a 1 mm interval in a layer of a cured polymer resin of the film of the present invention and a layer containing silicon and nitrogen, and after attaching cello tape (registered trademark) firmly, 90 It peeled at a stretch in the direction of a degree, and evaluated in accordance with the following reference | standard.
Good: 100/100 Good adhesion Bad: Peeling occurred
　（恒温恒湿試験後の密着性）
　本発明のフィルムを温度６０℃、相対湿度９０％の環境下に４８時間暴露し、重合性樹脂硬化物の層と、珪素と窒素を含む層とに、１ｍｍ間隔で１００個のマス目をカッターで作製し、セロテープ（登録商標）をしっかり密着させた後、９０度方向に一気に剥がし、下記の基準に従い、評価を実施した。
　　良：１００／１００密着良好
　　悪：剥れ発生 (Adhesion after constant temperature and humidity test)
The film of the present invention is exposed to an environment of a temperature of 60 ° C. and a relative humidity of 90% for 48 hours, and 100 square grids are cut at intervals of 1 mm into a layer of a cured polymer resin and a layer containing silicon and nitrogen. After the cellotape (registered trademark) was firmly adhered, it was peeled off at 90 degrees and evaluated according to the following criteria.
Good: 100/100 Good adhesion Bad: Peeling occurred
　（ガスバリア性の測定）
　ガスバリア性の測定は、ＭＯＣＯＮ社製　ＡＱＵＡＴＲＡＮ（登録商標）を用い、温度４０℃、相対湿度９０％ＲＨにて水蒸気透過率測定により行った。 (Measurement of gas barrier properties)
The gas barrier property was measured by measuring water vapor transmission rate using AQUATRAN (registered trademark) manufactured by MOCON at a temperature of 40 ° C. and a relative humidity of 90% RH.
　［実施例１］
　５００ｃｃコルベンに、トリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）９３重量部、２-メチル-１-[４-(メチルチオ)フェニル]-２-(４-モルホリニル)-１-プロパノン（商品名：イルガキュアー９０７、ＢＡＳＦ製）２部、１－ヒドロキシシクロヘキシルフェニルケトン（商品名：イルガキュアー１８４、ＢＡＳＦ製）５部、トルエン１００部を室温で混合溶解し、固形分５０％のトリメチロールプロパン骨格を含む（メタ）アクリレート化合物を少なくとも１種を含む組成物を作製した。得られた樹脂組成物を、２００μｍのポリエチレンナフタレートフィルム（帝人デュポンフィルム社製　商品名：テオネックスＱ６５ＦＡ　２００μｍ）上にバーコーターにて塗布し、８０℃乾燥機中で２分乾燥後、１２０Ｗ高圧水銀灯を設置した紫外線照射装置により、窒素パージしながら積算光量４００ｍＪ／ｃｍ２にて硬化させ、膜厚８μｍの樹脂硬化物層を有するフィルムを得た。得られた樹脂硬化物層の面に、イオンビームアシスト蒸着装置（昭和真空社製　ＳＧＣ－２６ＳＡ－ＩＡＤ）にて珪素をターゲット原子とし、ビーム電圧 ５００Ｖ，ビーム電流 ８００ｍＡ，ＡＶｃｃ値 ８００Ｖ，ソースガスを窒素として流量７０ｓｃｃｍの条件にて、１５０ｎｍの厚さの窒化珪素の層を設けて、透明バリアフィルムを得た。 [Example 1]
To 500 cc Kolben, 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA), 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone (trade name: 2 parts of Irgacure 907, manufactured by BASF), 5 parts of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by BASF) and 100 parts of toluene are mixed and dissolved at room temperature to obtain a trimethylolpropane skeleton having a solid content of 50%. A composition containing at least one (meth) acrylate compound containing was prepared. The obtained resin composition was applied on a 200 μm polyethylene naphthalate film (trade name: Teonex Q65FA 200 μm, manufactured by Teijin DuPont Films) with a bar coater, dried in an 80 ° C. dryer for 2 minutes, and then a 120 W high pressure mercury lamp. The film was cured with an integrated light quantity of 400 mJ / cm 2 while purging with nitrogen using an ultraviolet irradiation device provided with a film having a cured resin layer with a thickness of 8 μm. On the surface of the obtained cured resin layer, silicon was used as a target atom with an ion beam assisted vapor deposition apparatus (SGC-26SA-IAD manufactured by Showa Vacuum Co., Ltd.), a beam voltage of 500 V, a beam current of 800 mA, an AVcc value of 800 V, and a source gas. A silicon nitride layer having a thickness of 150 nm was provided as nitrogen under the condition of a flow rate of 70 sccm to obtain a transparent barrier film.
　［実施例２］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ＰＯ変性トリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＰＡ－３３０）　９３重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Example 2]
Except that 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1 was used instead of 93 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330). A transparent barrier film was obtained in the same manner as in Example 1.
　［実施例３］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、トリス（アクリロキシエチル）イソシアヌレート（商品名：日立化成社製　ＦＡ－７３１Ａ）　９３重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Example 3]
Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 93 parts by weight of tris (acryloxyethyl) isocyanurate (trade name: FA-731A manufactured by Hitachi Chemical Co., Ltd.) was used. A transparent barrier film was obtained in the same manner as in Example 1 except that.
　［実施例４］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、トリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　６２重量部およびジシクロペンタニルジアクリレート（商品名：ＫＡＹＡＲＡＤ　Ｒ－６８４）　３１重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Example 4]
Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 62 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) and dicyclopentanyl diacrylate (trade name) : KAYARAD R-684) A transparent barrier film was obtained in the same manner as in Example 1 except that 31 parts by weight was used.
　［実施例５］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部を、ＰＯ変性トリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＰＡ－３３０）　６２重量部およびジシクロペンタニルジアクリレート（商品名：ＫＡＹＡＲＡＤ　Ｒ－６８４）　３１重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Example 5]
93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 62 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330) and dicyclopentanyl diacrylate ( Product name: KAYARAD R-684) A transparent barrier film was obtained in the same manner as in Example 1 except that 31 parts by weight was used.
　［実施例６］
　窒化珪素の層を７０ｎｍとしたこと以外は実施例５と同様にして、透明バリアフィルムを得た。 [Example 6]
A transparent barrier film was obtained in the same manner as in Example 5 except that the silicon nitride layer was 70 nm.
　［実施例７］
　窒化珪素の層を３５０ｎｍとしたこと以外は実施例５と同様にして、透明バリアフィルムを得た。 [Example 7]
A transparent barrier film was obtained in the same manner as in Example 5 except that the silicon nitride layer was 350 nm.
　［実施例８］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、トリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　６２重量部、ジシクロペンタニルジアクリレート（商品名：ＫＡＹＡＲＡＤ　Ｒ－６８４）　３０．５重量部、および式（１）の骨格を有する分岐型パーフルオロアルケニル基を有するフッ素化合物（商品名：ネオス社製　フタージェント６０２Ａ）　０．５重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Example 8]
Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 62 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA), dicyclopentanyl diacrylate (trade name) : KAYARAD R-684) 30.5 parts by weight and 0.5 part by weight of a fluorine compound having a branched perfluoroalkenyl group having a skeleton of the formula (1) (trade name: FERENTENT 602A manufactured by Neos) A transparent barrier film was obtained in the same manner as in Example 1 except that.
　［実施例９］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ＰＯ変性トリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＰＡ－３３０）　６２重量部、ジシクロペンタニルジアクリレート（商品名：ＫＡＹＡＲＡＤ　Ｒ－６８４）　３０．５重量部、および式（１）の骨格を有する分岐型パーフルオロアルケニル基を有するフッ素化合物（商品名：ネオス社製　フタージェント６０２Ａ）　０．５重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Example 9]
Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 62 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330), dicyclopentanyldi Acrylate (trade name: KAYARAD R-684) 30.5 parts by weight, and a fluorine compound having a branched perfluoroalkenyl group having a skeleton of formula (1) (trade name: Neos Inc., Footent 602A) 0.5 weight A transparent barrier film was obtained in the same manner as in Example 1 except that the part was used.
　［実施例１０］
　実施例９において得られた樹脂硬化物層の面に、高周波マグネトロンスパッタ装置（昭和真空社製　ＭＰＳ－２０００－ＨＣ３）にて、真空度１×１０－６Ｐａ、ターゲット原子を珪素、アルミニウムの２次元同時スパッタリングとし、周波数が１３．５６ＭＨｚ、基盤温度は常温、ガス圧０．１～０．２Ｐａの反応ガスを窒素として、アルミニウムを含有する窒化珪素の層を１５０ｎｍ設けて、透明バリアフィルムを得た。 [Example 10]
On the surface of the cured resin layer obtained in Example 9, a high-frequency magnetron sputtering apparatus (MPS-2000-HC3 manufactured by Showa Vacuum Co., Ltd.) was used. The degree of vacuum was 1 × 10 −6 Pa, the target atoms were silicon and aluminum 2 Dimensional co-sputtering, a frequency of 13.56 MHz, a base temperature of room temperature, a reactive gas having a gas pressure of 0.1 to 0.2 Pa as nitrogen, and a silicon nitride layer containing aluminum having a thickness of 150 nm is provided to obtain a transparent barrier film It was.
　［実施例１１］
　実施例９において得られた樹脂硬化物層の面に、イオンビームアシスト蒸着装置（昭和真空社製　ＳＧＣ－２６ＳＡ－ＩＡＤ）にて珪素をターゲット原子とし、ビーム電圧 ３００Ｖ，ビーム電流 ８００ｍＡ，ＡＶｃｃ値 １０００Ｖ，ソースガスを窒素として流量７０ｓｃｃｍの条件にて、窒化珪素の層を１５０ｎｍ設けて、透明バリアフィルムを得た。 [Example 11]
On the surface of the cured resin layer obtained in Example 9, silicon was used as a target atom with an ion beam assisted deposition apparatus (SGC-26SA-IAD manufactured by Showa Vacuum Co., Ltd.), a beam voltage of 300 V, a beam current of 800 mA, and an AVcc value of 1000 V. A transparent barrier film was obtained by providing a silicon nitride layer with a thickness of 150 nm under the condition of a source gas of nitrogen and a flow rate of 70 sccm.
　［実施例１２］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ＰＯ変性トリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＰＡ－３３０）　５８重量部およびトリシクロデカンジメチロールジアクリレート（商品名：東亜合成社製　アロニックスＭ－２０３ｓ）　３５重量部を用い、樹脂組成物を１００μｍのシクロオレフィンフィルム（ＪＳＲ社製　商品名：ＡＲＴＯＮ）上にバーコーターにて塗布し、８０℃乾燥機中で２分乾燥後、１２０Ｗ高圧水銀灯を設置した紫外線照射装置により、窒素パージしながら積算光量４００ｍＪ／ｃｍ２にて硬化させ、膜厚８μｍの樹脂硬化物層を有するフィルムを得たこと以外は実施例１と同様にして、バリアフィルムを得た。 [Example 12]
Trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1 instead of 93 parts by weight, 58 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAAD TPA-330) and tricyclodecane dimethylol Using 35 parts by weight of diacrylate (trade name: Aronix M-203s, manufactured by Toa Gosei Co., Ltd.), the resin composition was applied onto a 100 μm cycloolefin film (trade name: ARTON manufactured by JSR) with a bar coater and 80 ° C. After drying in a dryer for 2 minutes, the film was cured with an integrated light quantity of 400 mJ / cm 2 while purging with an ultraviolet irradiation device equipped with a 120 W high-pressure mercury lamp to obtain a film having a cured resin layer with a thickness of 8 μm. Except for this, a barrier film was obtained in the same manner as in Example 1.
　［実施例１３］
　樹脂硬化物層の膜厚を１６μｍとし、かつ、樹脂硬化物層を有さないポリエチレンナフタレートフィルムのもう一方の面にも窒化珪素の層を１５０ｎｍ設けたこと以外は実施例４と同様にして、バリアフィルムを得た。 [Example 13]
The same as in Example 4 except that the film thickness of the cured resin layer was 16 μm and a 150 nm silicon nitride layer was provided on the other surface of the polyethylene naphthalate film having no cured resin layer. A barrier film was obtained.
　［実施例１４］
　樹脂硬化物層の膜厚を１６μｍとし、かつ、樹脂硬化物層を有さないポリエチレンナフタレートフィルムのもう一方の面にも１５０ｎｍの窒化珪素の層を設けたこと以外は実施例９と同様にして、バリアフィルムを得た。 [Example 14]
The same as Example 9 except that the film thickness of the cured resin layer was 16 μm and a 150 nm silicon nitride layer was provided on the other side of the polyethylene naphthalate film having no cured resin layer. Thus, a barrier film was obtained.
　［実施例１５］
　樹脂硬化物層を有さないシクロオレフィンフィルムのもう一方の面にも１５０ｎｍの窒化珪素の層を設けたこと以外は実施例１２と同様にして、バリアフィルムを得た。 [Example 15]
A barrier film was obtained in the same manner as in Example 12 except that a 150 nm silicon nitride layer was provided on the other surface of the cycloolefin film having no resin cured product layer.
　［比較例１］
　樹脂硬化物層を設けずに、１５０ｎｍのポリエチレンナフタレートフィルムに窒化珪素の層を設けたこと以外は実施例１と同様にして、透明フィルムを得た。 [Comparative Example 1]
A transparent film was obtained in the same manner as in Example 1 except that a silicon nitride layer was provided on a 150 nm polyethylene naphthalate film without providing a cured resin layer.
　［比較例２］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ジペンタエリスリトールヘキサアクリレート（商品名：ＫＡＹＡＲＡＤ　ＤＰＨＡ）　９３重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Comparative Example 2]
Example 1 except that 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. Similarly, a transparent barrier film was obtained.
　［比較例３］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、４官能のテトラアクリレート（商品名：ＫＡＹＡＲＡＤ　Ｒ－９５９１）　９３重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Comparative Example 3]
Example except that 93 parts by weight of 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. In the same manner as in Example 1, a transparent barrier film was obtained.
　［比較例４］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ジペンタエリスリトールヘキサアクリレート（商品名：ＫＡＹＡＲＡＤ　ＤＰＨＡ）　６２重量部およびジシクロペンタニルジアクリレート（商品名：ＫＡＹＡＲＡＤ　Ｒ－６８４）　３１重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Comparative Example 4]
Trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1 instead of 93 parts by weight, 62 parts by weight of dipentaerythritol hexaacrylate (trade name: KAYARAD DPHA) and dicyclopentanyl diacrylate (trade name) : KAYARAD R-684) A transparent barrier film was obtained in the same manner as in Example 1 except that 31 parts by weight was used.
　［比較例５］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ビスフェノールＡジグリシジルエーテルとアクリル酸との反応生成物（商品名：ＫＡＹＡＲＡＤ　Ｒ－１１５）　５２重量部およびヘキサンジオールジアクリレート（商品名：東洋ケミカルズ社製　Ｍｉｒａｍｅｒ　Ｍ２００）　４１重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Comparative Example 5]
52 parts by weight of a reaction product of bisphenol A diglycidyl ether and acrylic acid (trade name: KAYARAD R-115) instead of 93 parts by weight 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 that 41 parts by weight of hexanediol diacrylate (trade name: Miramer M200 manufactured by Toyo Chemicals Co., Ltd.) was used.
　［比較例６］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ビスフェノールＡジグリシジルエーテルとアクリル酸との反応生成物（商品名：ＫＡＹＡＲＡＤ　Ｒ－１１５）　６２重量部およびビフェニル基含有アクリレート（商品名：ＫＡＹＡＲＡＤ　ＯＰＰ－１）　３１重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Comparative Example 6]
Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 62 parts by weight of a reaction product of bisphenol A diglycidyl ether and acrylic acid (trade name: KAYARAD R-115) A transparent barrier film was obtained in the same manner as in Example 1 except that 31 parts by weight of biphenyl group-containing acrylate (trade name: KAYARAD OPP-1) was used.
　［比較例７］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ビスフェノールＡ変性アクリレート（商品名：日立化成社製　ＦＡ－３２０Ａ）　５２重量部およびビフェニル基含有アクリレート（商品名：ＫＡＹＡＲＡＤ　ＦＲＭ－１０００）　４１重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Comparative Example 7]
Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 52 parts by weight of bisphenol A modified acrylate (trade name: FA-320A manufactured by Hitachi Chemical Co., Ltd.) and biphenyl group-containing acrylate ( (Trade name: KAYARAD FRM-1000) A transparent barrier film was obtained in the same manner as in Example 1 except that 41 parts by weight was used.
　［比較例８］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ビスフェノールＡ変性アクリレート（商品名：日立化成社製　ＦＡ－３２０Ａ）　５２重量部およびリン酸ビフェニル基含有アクリレート（商品名：ＫＡＹＡＲＡＤ　Ｒ－９６６３Ｈ）　４１重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Comparative Example 8]
Trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1 instead of 93 parts by weight 52 parts by weight of bisphenol A-modified acrylate (trade name: FA-320A manufactured by Hitachi Chemical Co., Ltd.) and biphenyl phosphate group-containing A transparent barrier film was obtained in the same manner as in Example 1 except that 41 parts by weight of acrylate (trade name: KAYARAD R-9663H) was used.
　［比較例９］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ビスフェノールＡ変性アクリレート（商品名：日立化成社製　ＦＡ－３２０Ａ）　５２重量部、ビフェニル基含有アクリレート（商品名：ＫＡＹＡＲＡＤ　ＦＲＭ－１０００）　４０．５重量部、およびアクリル系レベリング剤（商品名：ビックケミー社製　ＢＹＫ－３６１Ｎ）　０．５重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Comparative Example 9]
Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 52 parts by weight of bisphenol A-modified acrylate (trade name: FA-320A manufactured by Hitachi Chemical Co., Ltd.), biphenyl group-containing acrylate ( Product name: KAYARAD FRM-1000) 40.5 parts by weight and acrylic leveling agent (trade name: BYK-361N manufactured by BYK-Chemie) 0.5 parts by weight A barrier film was obtained.
　［比較例１０］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ビスフェノールＡ変性アクリレート（商品名：日立化成社製　ＦＡ－３２０Ａ）　５２重量部、ビフェニル基含有アクリレート（商品名：ＫＡＹＡＲＡＤ　ＦＲＭ－１０００）　４０．５重量部、および３－メルカプトプロピルトリメトキシシラン（商品名：信越化学社製　ＫＢＭ－８０３）　０．５重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Comparative Example 10]
Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 52 parts by weight of bisphenol A-modified acrylate (trade name: FA-320A manufactured by Hitachi Chemical Co., Ltd.), biphenyl group-containing acrylate ( Product name: KAYARAD FRM-1000) 40.5 parts by weight and 3-mercaptopropyltrimethoxysilane (trade name: KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.) Thus, a transparent barrier film was obtained.
　［比較例１１］
　実施例１で用いたトリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＭＰＴＡ）　９３重量部に代えて、ビスフェノールＡ変性アクリレート（商品名：日立化成社製　ＦＡ－３２０Ａ）　５２重量部、ビフェニル基含有アクリレート（商品名：ＫＡＹＡＲＡＤ　ＦＲＭ－１０００）　４０．５重量部、およびアクリルポリマー系レベリング剤（商品名：共栄社化学社製　ホリフローＮｏ．７５）　０．５重量部を用いたこと以外は実施例１と同様にして、透明バリアフィルムを得た。 [Comparative Example 11]
Instead of 93 parts by weight of trimethylolpropane triacrylate (trade name: KAYARAD TMPTA) used in Example 1, 52 parts by weight of bisphenol A-modified acrylate (trade name: FA-320A manufactured by Hitachi Chemical Co., Ltd.), biphenyl group-containing acrylate ( Product name: KAYARAD FRM-1000) 40.5 parts by weight and acrylic polymer leveling agent (trade name: Kyoeisha Chemical Co., Ltd. Horiflow No. 75) 0.5 parts by weight Thus, a transparent barrier film was obtained.
　［比較例１２］
　実施例１２で用いたＰＯ変性トリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＰＡ－３３０）　５８重量部およびトリシクロデカンジメチロールジアクリレート（商品名：東亜合成社製　アロニックスＭ－２０３ｓ）　３５重量部の組成物に代えて、ジペンタエリスリトールヘキサアクリレート（商品名：ＫＡＹＡＲＡＤ　ＤＰＨＡ）　５８重量部およびトリシクロデカンジメチロールジアクリレート（商品名：東亜合成社製　アロニックスＭ－２０３ｓ）　３５重量部の組成物を用いたこと以外は実施例１２と同様にして、透明バリアフィルムを得た。 [Comparative Example 12]
58 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330) and 35 parts by weight of tricyclodecane dimethylol diacrylate (trade name: Aronix M-203s manufactured by Toa Gosei Co., Ltd.) used in Example 12 Instead of the composition, 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 Toa Gosei Co., Ltd.) are used. A transparent barrier film was obtained in the same manner as in Example 12 except for the above.
　［比較例１３］
　実施例１２で用いたＰＯ変性トリメチロールプロパントリアクリレート（商品名：ＫＡＹＡＲＡＤ　ＴＰＡ－３３０）　５８重量部およびトリシクロデカンジメチロールジアクリレート（商品名：東亜合成社製　アロニックスＭ－２０３ｓ）　３５重量部の組成物に代えて、ビスフェノールＡジグリシジルエーテルとアクリル酸との反応生成物（商品名：ＫＡＹＡＲＡＤ　Ｒ－１１５）　５８重量部およびトリシクロデカンジメチロールジアクリレート（商品名：東亜合成社製　アロニックスＭ－２０３ｓ）　３５重量部の組成物を用いたこと以外は実施例１２と同様にして、透明バリアフィルムを得た。 [Comparative Example 13]
58 parts by weight of PO-modified trimethylolpropane triacrylate (trade name: KAYARAD TPA-330) and 35 parts by weight of tricyclodecane dimethylol diacrylate (trade name: Aronix M-203s manufactured by Toa Gosei Co., Ltd.) used in Example 12 In place of the composition, 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-manufactured by Toa Gosei Co., Ltd.) 203 s) A transparent barrier film was obtained in the same manner as in Example 12 except that 35 parts by weight of the composition was used.
　［比較例１４］
　樹脂硬化物層を有さないポリエチレンナフタレートフィルムのもう一方の面にも窒化珪素の層を１５０ｎｍ設けたこと以外は比較例５と同様にして、透明バリアフィルムを得た。 [Comparative Example 14]
A transparent barrier film was obtained in the same manner as in Comparative Example 5, except that a silicon nitride layer having a thickness of 150 nm was provided on the other surface of the polyethylene naphthalate film having no cured resin layer.
　［比較例１５］
　樹脂硬化物層を有さないポリエチレンナフタレートフィルムのもう一方の面にも窒化珪素の層を１５０ｎｍ設けたこと以外は比較例６と同様にして、透明バリアフィルムを得た。 [Comparative Example 15]
A transparent barrier film was obtained in the same manner as in Comparative Example 6 except that a silicon nitride layer having a thickness of 150 nm was provided on the other surface of the polyethylene naphthalate film not having a cured resin layer.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１の実施例１乃至１５、比較例１乃至１５における透過率、白濁の有無、密着性、耐久性試験後の密着性、ガスバリア性の測定結果から、本発明のフィルムは透過率、白濁、密着、ガスバリア性のいずれにおいても、良好なフィルムになっていることが分かる。即ち、基材、および窒素と珪素との層だけでなく、樹脂硬化物層を更に設けることよって、それぞれの性能が向上する。さらに、実施例４と実施例８、または実施例５と実施例９とを比較すれば、分岐型パーフルオロアルケニル基を有するフッ素化合物またはその誘導体を含有することによって、よりガスバリア性が向上していることが分かる。このようにして得られた本発明のフィルムは、水蒸気などのガスバリア性が要求される封止フィルムとして用いることが出来る。かかる透明封止フィルムは、光電変換素子、ＯＬＥＤ素子に有用に用いることができる。特に、ＯＬＥＤに用いた場合、素子からの発光を妨げないため発光効率を低下させず、信頼性の高いＯＬＥＤを得ることができる。また、光電変換用バリアフィルムとして光電変換素子に用いた場合には、透明性が高く、バリア性も高いので、長期にわたり光電変換用バリアフィルムとして安定して機能するため、太陽光の受光を低下させることなく機能する太陽電池を得ることができる。 From the measurement results of transmittance, presence / absence of cloudiness, adhesion, adhesion after durability test, and gas barrier property in Examples 1 to 15 and Comparative Examples 1 to 15 in Table 1, the film of the present invention has transmittance, cloudiness, It can be seen that both the adhesion and gas barrier properties are good films. That is, by providing not only a base material and a layer of nitrogen and silicon but also a cured resin layer, each performance is improved. Furthermore, when Example 4 and Example 8 or Example 5 and Example 9 are compared, the gas barrier property is further improved by containing a fluorine compound having a branched perfluoroalkenyl group or a derivative thereof. I understand that. The film of the present invention thus obtained can be used as a sealing film that requires gas barrier properties such as water vapor. This transparent sealing film can be usefully used for a photoelectric conversion element and an OLED element. In particular, when used in an OLED, since light emission from the element is not hindered, a light emitting efficiency is not lowered and a highly reliable OLED can be obtained. In addition, when used in a photoelectric conversion element as a photoelectric conversion barrier film, it is highly transparent and has a high barrier property, so that it functions stably as a barrier film for photoelectric conversion over a long period of time. It is possible to obtain a solar cell that functions without causing it.

Claims (8)

  1. 　基材上に、トリメチロールプロパン骨格またはイソシアヌル骨格を有する（メタ）アクリレート化合物を少なくとも１種含む重合性樹脂組成物から形成される硬化物層を有し、且つ、
    　該硬化物層上に、５０ｎｍ乃至５００ｎｍの厚さを有する、珪素と窒素とを含む層を有するフィルムであって、
    　該（メタ）アクリレート化合物の含有量が、該重合性樹脂組成物１００重量部に対して４０重量部乃至９９重量部であり、
    　該硬化物層の厚さが０．１μｍ乃至２０μｍであり、
    　透過率が７５％以上であることを特徴とする、フィルム。     A cured product layer formed from a polymerizable resin composition containing at least one (meth) acrylate compound having a trimethylolpropane skeleton or an isocyanuric skeleton on a substrate; and
    A film having a layer containing silicon and nitrogen having a thickness of 50 nm to 500 nm on the cured product layer,
    The content of the (meth) acrylate compound is 40 parts by weight to 99 parts by weight with respect to 100 parts by weight of the polymerizable resin composition,
    The thickness of the cured product layer is 0.1 μm to 20 μm,
    A film having a transmittance of 75% or more.
  2. 　前記重合性樹脂組成物が、ジシクロペンタジエン骨格を有する（メタ）アクリレート化合物を、該重合性樹脂組成物１００重量部に対して１０重量部乃至５５重量部含有することを特徴とする、請求項１に記載のフィルム。 The polymerizable resin composition contains 10 to 55 parts by weight of a (meth) acrylate compound having a dicyclopentadiene skeleton with respect to 100 parts by weight of the polymerizable resin composition. 1. The film according to 1.
  3. 　前記重合性樹脂組成物が、分岐型パーフルオロアルケニル基を有するフッ素系化合物またはその誘導体を、該重合性樹脂組成物１００重量部に対して０．０１重量部乃至１重量部含有することを特徴とする、請求項１または２に記載のフィルム。 The polymerizable resin composition contains 0.01 to 1 part by weight of a fluorine-based compound having a branched perfluoroalkenyl group or a derivative thereof with respect to 100 parts by weight of the polymerizable resin composition. The film according to claim 1 or 2.
  4. 　前記珪素と窒素とを含む層が、元素としてアルミニウムを更に含有することを特徴とする、請求項１乃至３のいずれか一項に記載のフィルム。 The film according to any one of claims 1 to 3, wherein the layer containing silicon and nitrogen further contains aluminum as an element.
  5. 　請求項１乃至４のいずれか一項に記載のフィルムを用いた液晶表示装置。 A liquid crystal display device using the film according to any one of claims 1 to 4.
  6. 　請求項１乃至４のいずれか一項に記載のフィルムを用いた有機エレクトロルミネッセンス素子。 An organic electroluminescence device using the film according to any one of claims 1 to 4.
  7. 　前記珪素と窒素とを含む層が、イオンビームアシスト蒸着法によって形成されることを特徴とする、請求項１乃至４のいずれか一項に記載のフィルム。 The film according to any one of claims 1 to 4, wherein the layer containing silicon and nitrogen is formed by an ion beam assisted deposition method.
  8. 　前記珪素と窒素とを含む層が、マグネトロンスパッタ法によって形成されることを特徴とする、請求項１乃至４のいずれか一項に記載のフィルム。 The film according to any one of claims 1 to 4, wherein the layer containing silicon and nitrogen is formed by a magnetron sputtering method.
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