WO2015056718A1 - Film barrière au gaz transparent - Google Patents

Film barrière au gaz transparent 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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Prior art keywords
weight
parts
film
resin composition
layer
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PCT/JP2014/077451
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English (en)
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/ja
Publication of WO2015056718A1 publication Critical patent/WO2015056718A1/fr

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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

　La présente invention aborde le problème portant sur l'obtention d'un film présentant de hautes propriétés barrière au gaz contre la vapeur d'eau, etc., tout en offrant cependant une haute transmittance. L'invention concerne un film présentant, sur un substrat, une couche de substance durcie constituée d'une composition de résine polymérisable contenant au moins un composé méthacrylate présentant un squelette triméthylol-propane ou un squelette isocyanurique, et étant pourvu, sur la couche de substance durcie, d'une couche d'une épaisseur de 50 à 500 nm comprenant du silicium et de l'azote, le problème étant résolu par l'utilisation d'un film barrière transparent caractérisé en ce que la teneur en composé de méthacrylate est de 40 à 99 % en parties en poids de la composition de résine polymérisable, l'épaisseur de la couche durcie étant comprise entre 0,1 et 20 µm et la transmittance étant égale ou supérieure à 75 %.
PCT/JP2014/077451 2013-10-16 2014-10-15 Film barrière au gaz transparent WO2015056718A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018525257A (ja) * 2015-08-19 2018-09-06 スリーエム イノベイティブ プロパティズ カンパニー 多層バリアアセンブリを含む複合材物品及びその製造方法
WO2024135403A1 (fr) * 2022-12-21 2024-06-27 富士フイルム株式会社 Film barrière aux gaz

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JP2004009395A (ja) * 2002-06-05 2004-01-15 Sumitomo Bakelite Co Ltd 透明水蒸気バリアフィルム及びその製造方法
JP2004175094A (ja) * 2002-10-02 2004-06-24 Teijin Chem Ltd 高分子樹脂積層体、およびその製造方法、ならびに車両用窓材
JP2006335677A (ja) * 2005-06-01 2006-12-14 Nippon Shokubai Co Ltd パーフルオロアルケニル誘導体
JP2010194814A (ja) * 2009-02-24 2010-09-09 Fujifilm Corp 機能性フィルムの製造方法、及び製造装置
JP2012020516A (ja) * 2010-07-15 2012-02-02 Fujifilm Corp バリア性積層体、ガスバリアフィルムおよびこれらを用いたデバイス、ならびに、バリア性積層体の製造方法

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JP5334900B2 (ja) * 2010-03-25 2013-11-06 富士フイルム株式会社 ガスバリアフィルムおよびデバイス
JP5402818B2 (ja) * 2010-05-06 2014-01-29 コニカミノルタ株式会社 ガスバリア性フィルム、及びガスバリア性フィルムの製造方法

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
JP2004009395A (ja) * 2002-06-05 2004-01-15 Sumitomo Bakelite Co Ltd 透明水蒸気バリアフィルム及びその製造方法
JP2004175094A (ja) * 2002-10-02 2004-06-24 Teijin Chem Ltd 高分子樹脂積層体、およびその製造方法、ならびに車両用窓材
JP2006335677A (ja) * 2005-06-01 2006-12-14 Nippon Shokubai Co Ltd パーフルオロアルケニル誘導体
JP2010194814A (ja) * 2009-02-24 2010-09-09 Fujifilm Corp 機能性フィルムの製造方法、及び製造装置
JP2012020516A (ja) * 2010-07-15 2012-02-02 Fujifilm Corp バリア性積層体、ガスバリアフィルムおよびこれらを用いたデバイス、ならびに、バリア性積層体の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018525257A (ja) * 2015-08-19 2018-09-06 スリーエム イノベイティブ プロパティズ カンパニー 多層バリアアセンブリを含む複合材物品及びその製造方法
WO2024135403A1 (fr) * 2022-12-21 2024-06-27 富士フイルム株式会社 Film barrière aux gaz

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