WO2018147316A1 - Composition photodurcissable et écran - Google Patents

Composition photodurcissable et écran Download PDF

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WO2018147316A1
WO2018147316A1 PCT/JP2018/004184 JP2018004184W WO2018147316A1 WO 2018147316 A1 WO2018147316 A1 WO 2018147316A1 JP 2018004184 W JP2018004184 W JP 2018004184W WO 2018147316 A1 WO2018147316 A1 WO 2018147316A1
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layer
meth
acrylate
photocurable composition
compound
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PCT/JP2018/004184
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English (en)
Japanese (ja)
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中山　雄二
福地　良寿
鶴田　洋明
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東洋インキＳｃホールディングス株式会社
トーヨーケム株式会社
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Publication of WO2018147316A1 publication Critical patent/WO2018147316A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • H10K59/8731—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers

Definitions

  • the present invention relates to a photocurable composition that can be used for protecting electronic parts and the like.
  • Electronic devices typified by mobile terminals such as smartphones and tablet terminals have been required to be thinner.
  • Electronic devices such as portable terminals include a touch panel provided with a printed wiring board and a display member, a liquid crystal display (hereinafter referred to as “LCD”) and an organic electroluminescence display (hereinafter also referred to as “OLED”). Etc. are installed.
  • Electronic element laminates such as the display have been reduced in thickness and density by various methods.
  • a smartphone is used in a space where many members (parts) are limited in order to realize multiple functions.
  • the touch panel has a functional layer such as an inorganic layer having various functions and an organic layer for protecting the functional layer on a base material.
  • a light-emitting element used in an OLED is a self-luminous element and can be reduced in weight and thickness, and thus is used not only for a display but also for an illumination device or the like.
  • This OLED can produce a flexible display by using a flexible substrate such as a plastic film. Unlike glass substrates that are produced one by one, using a plastic film substrate can produce OLEDs in a roll-to-roll manner, thereby reducing costs.
  • the light emitting element of OLED is easily deteriorated by water vapor, the light emitting element is protected by forming a barrier layer (inorganic layer) in which an inorganic compound is deposited on a base material.
  • a barrier layer inorganic layer
  • an organic layer for protecting the barrier layer is required (for example, Patent Documents 1 to 6).
  • Patent Document 1 discloses a resin composition containing a resin selected from the group consisting of polyurea, polyurethane, polyamide, polyimide, polyacrylate and polymethacrylate having a carboxyl group or a phosphonic acid group, which is used for forming an organic layer. Is disclosed.
  • Patent Document 2 discloses a sealing compound for a display element containing a polymerizable compound containing a specific polythiol monomer and a specific polyene monomer, a photopolymerization initiator, and a specific monofunctional (meth) acrylic monomer. ing.
  • Patent Document 3 discloses a barrier laminate having an inorganic barrier layer and an organic layer formed from a polymerizable composition containing a specific polymerizable compound.
  • Patent Document 4 a step of forming a first organic layer made of a first organic composition containing a specific acidic compound, a polymerizable compound, and a silane coupling agent on an inorganic layer, and the first A specific manufacturing method for forming a second organic layer containing a polymerizable compound and a silane coupling agent on the organic layer is disclosed.
  • Patent Document 5 discloses a barrier laminate having an inorganic layer, a polyfunctional (meth) acrylate, and an organic layer containing a polymer obtained by polymerizing a polymerizable composition containing a specific compound.
  • Patent Document 6 discloses a photocurable resin composition for electronic devices containing a urethane oligomer having an alkoxyalkyl (meth) acrylamide group.
  • the formation of the organic layer is required to be cured at as low a temperature as possible and in a short time.
  • the conventional resin composition has a problem that curing is not completed in a low temperature and a short time of radiation. Further, the resin composition has a problem that the curing shrinkage at the time of curing is large and the adhesion to the functional layer is low.
  • An object of the present invention is to provide a photocurable composition that has excellent adhesion to a functional layer containing an inorganic compound and can form an organic layer that is rapidly cured by radiation.
  • the photocurable composition of the present invention is a photocurable composition for an organic layer that protects a functional layer containing an inorganic compound, A cyclic amide monomer, a polyfunctional (meth) acrylate compound, and a photopolymerization initiator; In 100% by mass of the photocurable composition, the cyclic amide monomer contains 20% by mass to 95% by mass,
  • the polyfunctional (meth) acrylate compound (excluding a urethane oligomer having an alkoxyalkyl (meth) acrylamide group) is selected from the group consisting of a bifunctional (meth) acrylate compound and a trifunctional (meth) acrylate compound 1
  • a photocurable composition comprising more than one species.
  • the present invention can provide a photocurable composition that is excellent in adhesion to a functional layer containing an inorganic compound and can form an organic layer that is rapidly cured by radiation.
  • the monomer is an ethylenically unsaturated group-containing monomer.
  • the functional layer includes an inorganic compound, and refers to a layer having some function necessary for an electronic device such as a barrier property and conductivity.
  • An electronic element is, for example, a main member for exerting a function as an electronic element laminate, such as a light emitting element in an OLED, a polarizing plate in an LCD, a transparent electrode in a touch panel, and a circuit in a printed wiring board. It means wiring and ground wiring.
  • the photocurable compound is a compound that is cured by a photopolymerization initiator such as an amide monomer or a polyfunctional (meth) acrylate compound, for example, a compound having an ethylenically unsaturated group such as a (meth) acryloyl group or a vinyl group. It is.
  • (meth) acrylate represents each of acrylate and methacrylate
  • (meth) acryloyl group represents each of acryloyl group and methacryloyl group.
  • the radiation includes ionizing radiation and non-ionizing radiation including ultraviolet rays and visible rays.
  • the photocurable composition of the present invention is composed of 20% by mass to 95% by mass of a cyclic amide monomer, a bifunctional (meth) acrylate compound, and a trifunctional (meth) acrylate compound in 100% by mass of the photocurable composition. It is preferably used for forming an organic layer of an electronic device laminate comprising a specific polyfunctional (meth) acrylate compound containing at least one selected from the group consisting of and an organic layer for protecting the layer. Since the photocurable composition of the present invention contains a specific amount of a cyclic amide monomer, the curing can be completed by irradiation with radiation at a low temperature in a short time as compared with the conventional case.
  • a photocurable composition contains an amide unit, it has high adhesiveness with respect to an inorganic layer, and can form a highly flexible organic layer. Therefore, when the photocurable composition is used for protecting the functional layer (inorganic barrier layer) of the OLED, for example, an effect of suppressing a decrease in water vapor barrier property after bending can be obtained. Further, when the photocurable composition is used for protecting the functional layer (transparent electrode layer) of the touch panel, for example, an effect that the resistance value hardly increases after bending can be obtained.
  • the photocurable composition of the present invention is a photocurable composition for forming an organic layer of an electronic element laminate comprising a functional layer containing an inorganic compound and an organic layer for protecting the functional layer, A specific amount of a cyclic amide monomer, a polyfunctional (meth) acrylate compound, and a photopolymerization initiator are included.
  • the photocurable composition of the present invention is preferably used, for example, as a protective film for protecting an inorganic layer used in various members constituting a display. Such a protective film is highly productive because it cures at a low temperature for a very short time, and has excellent adhesion to a substrate having an inorganic layer.
  • Cyclic amide monomers contain amide units (also referred to as amide groups or amide bonds).
  • the photocurable composition cures rapidly due to the presence of the amino group of the amide monomer.
  • an amide unit contributes to the adhesive improvement with an inorganic layer.
  • cyclic amide monomer for example, a monomer in which a carboxyl group-containing compound and an amino group are dehydrated and condensed to form a ring is preferable.
  • examples of the cyclic amide monomer include acryloylmorpholine, N-vinylpyrrolidone, N-vinyl- ⁇ -caprolactam and the like.
  • a cyclic amide monomer is preferable from the viewpoint of curing speed and adhesion, and N-vinyl- ⁇ -caprolactam and acryloylmorpholine are more preferable.
  • the electron withdrawing group is a group other than the amide unit, and is, for example, a carbonyl group, a cyano group, a nitro group, or an ester group.
  • the electron withdrawing atom is, for example, halogen or oxygen.
  • the cyclic amide monomer can be used alone or in two kinds.
  • the cyclic amide monomer is preferably 20% by mass to 95% by mass, more preferably 30% by mass to 90% by mass, and still more preferably 50% by mass to 90% by mass in 100% by mass of the photocurable composition. 60 mass% or more and 90 mass% or less are the most preferable.
  • a polyfunctional (meth) acrylate compound is a compound having two or more (meth) acryloyl groups.
  • the polyfunctional (meth) acrylate compound includes at least one selected from the group consisting of a bifunctional (meth) acrylate compound and a trifunctional (meth) acrylate compound, and further includes a (meth) acryloyl group.
  • a polyfunctional (meth) acrylate having 4 or more, preferably 4 or more and 6 or less may be used in combination.
  • the urethane oligomer having an alkoxyalkyl (meth) acrylamide group is excluded from the polyfunctional (meth) acrylate compound.
  • Bifunctional (meth) acrylate compounds are, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexane.
  • Trifunctional (meth) acrylate compounds are, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylolpropane tri (meth) acrylate, caprolactone modified Examples include trimethylolpropane tri (meth) acrylate and tri (2-hydroxyethyl isocyanurate) tri (meth) acrylate.
  • Examples of the tetra- or higher functional (meth) acrylate compound include ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate.
  • These polyfunctional (meth) acrylate compounds may be used alone or in combination of two or more as required.
  • the multiple (meth) acryloyl groups present in one molecule of the polyfunctional (meth) acrylate compound may be the same acryloyl group or methacryloyl group, or a combination of an acryloyl group and a methacryloyl group.
  • the polyfunctional (meth) acrylate compound is preferably a bifunctional (meth) acrylate compound because it is easy to achieve both curability and adhesion, and an alkyleneoxy group-containing bifunctional (meta) compound in terms of improving flexibility.
  • Acrylate compounds are more preferred.
  • alkyleneoxy group examples include an ethyleneoxy group and a propyleneoxy group. Among these, a propyleneoxy group is more preferable. Further, the alkyleneoxy group may be single or plural. The number of repeating alkyleneoxy groups is preferably 2 or more, 50 or less, more preferably 2 or more and 30 or less, and still more preferably 2 or more and 15 or less.
  • the polyfunctional (meth) acrylate compound is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 40% by mass or less, in 100% by mass of the photocurable composition.
  • a photopolymerization initiator is used for curing by radiation.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • the radical photopolymerization initiator is preferably an intramolecular cleavage type or a hydrogen abstraction type.
  • the intramolecular cleavage type photoradical polymerization initiator is a type of radical initiator that generates radicals by cleavage of the initiator molecule when irradiated with radiation.
  • Examples of the intramolecular cleavage type radical photopolymerization initiator include benzyl ketal radical photopolymerization initiator, ⁇ -hydroxyacetophenone radical photopolymerization initiator, benzoin radical radical polymerization initiator, aminoacetophenone radical photoinitiator, oxime A ketone photoradical polymerization initiator, an acylphosphine oxide photoradical polymerization initiator, a titanocene photoradical polymerization initiator, and the like are preferable.
  • benzyl ketal photoradical polymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one (benzyldimethylketal / 2,2-dimethoxy-2-phenylacetophenone).
  • ⁇ -Hydroxyacetophenone photoradical polymerization initiators include, for example, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one 1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, 1-benzoyl-1-hydroxy-1-methylethane, 1- [ 4- (2-hydroxyethoxy
  • benzoin-based radical photopolymerization initiator examples include benzoin, benzoin isobutyl ether, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
  • Aminoacetophenone photo radical polymerization initiators include, for example, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho And linophenyl) -butanone-1.
  • Examples of the oxime ketone photo radical polymerization initiator include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) and the like.
  • Examples of the acylphosphine oxide photo radical polymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like.
  • titanocene photo radical polymerization initiators include bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -di-chloro-titanium, bis (cyclopentadienyl) -bis (2, 3,4,5,6 pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrol-1-yl) phenyl) titanium, and the like.
  • a benzophenone photo radical initiator As the hydrogen abstraction type photo radical polymerization initiator, a benzophenone photo radical initiator, a thioxanthone photo radical polymerization initiator, an anthraquinone photo initiator, and the like are preferable.
  • the benzophenone photo radical initiator include benzophenone, 4-methylbenzophenone, 3-benzoylbiphenyl, 4- (4-methylphenylthio) benzophenone, methyl 2-benzoylbenzoate, 4-phenylbenzophenone, 4,4′-bis ( Dimethoxy) benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 2-benzoylbenzoic acid methyl ester, 2-methylbenzophenone, 3-methylbenzophenone, 3,3′- Benzophenone derivatives such as dimethyl-4-methoxybenzophenone and 2,4,6-trimethylbenzophen
  • Examples of the thioxanthone photo radical polymerization initiator include thioxanthone, xanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 1- And thioxanthone derivatives such as chloro-4-propoxythioxanthone and 2,4-diethylthioxanthen-9-one.
  • Examples of the anthraquinone photoinitiator include anthraquinone, 2-ethylanthraquinone, 2-hydroxyanthraquinone, 2-aminoanthraquinone and the like.
  • an acylphosphine compound as the photopolymerization initiator.
  • the acylphosphine compounds include acylphosphine oxide photoradical polymerization initiators. Among them, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)- Phenylphosphine oxide is preferred.
  • a commercially available product may be used as the acylphosphine compound, and for example, lucillin TPO (manufactured by BASF Japan) or the like can be suitably used.
  • the photopolymerization initiator can be used alone or in combination of two or more.
  • the photopolymerization initiator is preferably contained in an amount of 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the photocurable compound.
  • a sensitizer can be used in combination with the photopolymerization initiator.
  • the sensitizer is preferably an amine compound.
  • the amine compound include trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine, 4′-bis ( Diethylamino) benzophenone and the like.
  • Sensitizers can be used alone or in combination of two or more.
  • the sensitizer is preferably contained in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the photocurable compound.
  • the photocurable composition of this invention can contain other photocurable compounds other than an amide monomer and a polyfunctional (meth) acrylate compound.
  • Other photocurable compounds include alkyl (meth) acrylates, carboxyl group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylates, fluorine-containing (meth) acrylates, and the like.
  • Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate.
  • Examples of the carboxyl group-containing (meth) acrylate include (meth) acrylic acid.
  • Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxybutyl (meth) acrylate and the like.
  • Examples of fluorine-containing (meth) acrylates include 2,2,2-trifluoroethyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, and 2- (perfluorobutyl) ethyl methacrylate. Is mentioned.
  • Suitable (meth) acrylates include dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 2-methyl-3,4. -Epoxy-cyclohexyl (meth) acrylate and the like.
  • the urethane acrylate oligomer is a compound having a weight average molecular weight of 800 to 20,000 having two or more (meth) acryloyl groups.
  • the urethane acrylate oligomer preferably does not have an alkoxyalkyl (meth) acrylamide group (unit).
  • urethane acrylate oligomers include, for example, “Ebecryl” series manufactured by Daicel UCB, “CN Series” manufactured by Sartomer, “Laromer Series” manufactured by BASF, “Photomer Series” manufactured by Cognis, and “Art” manufactured by Negami Kogyo. “Resin series”, “Nippon Gosei Co., Ltd.” “Shikko series”, Nippon Kayaku Co., Ltd. “Kayarad series”, etc.
  • a chain amide monomer can also be used.
  • the chain amide monomer is a monomer having a chain hydrocarbon group in which carbon atoms are arranged in a line and an amide unit.
  • Examples of the chain amide monomer include acrylamide, methacrylamide, dimethylacrylamide, isopropylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylacrylamide methyl chloride quaternary salt, and hydroxyethylacrylamide.
  • photo-curable compounds can be used alone or in combination of two or more.
  • photocurable compounds are preferably contained in an amount of 10% by mass to 95% by mass and more preferably 20% by mass to 90% by mass in 100% by mass of the photocurable composition.
  • the photocurable composition of the present invention can contain a resin.
  • a photocurable composition can adjust the hardness of an organic layer, a softness
  • the resin include acrylic resin, epoxy resin, polyurethane resin, polyurethane urea resin, (modified) styrene maleic anhydride copolymer, (modified) vinyl chloride vinyl acetate copolymer, (modified) vinyl chloride vinyl acetate maleic anhydride
  • Examples include copolymers, ketone aldehyde resins, polyester resins, polypropylene resins, polylactic acid resins, cellulose acetate resins, cellulose acetate butyrate resins, esterified cellulose resins, and butyral resins.
  • Resin can be used alone or in combination of two or more.
  • the resin is preferably contained in an amount of 1% by mass to 20% by mass, more preferably 5% by mass to 15% by mass, in 100% by mass of the nonvolatile content of the photocurable composition.
  • the photocurable composition of the present invention can contain a solvent. By mix
  • the solvent can be appropriately selected according to the solubility of each component used, the printing or coating method, and the like.
  • solvent examples include ester solvents, ketone solvents, glycol ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, alcohol solvents, ether solvents, water, and the like.
  • Solvents can be used alone or in combination of two or more.
  • the solvent is preferably contained in an amount of 0% by mass to 50% by mass in 100% by mass of the photocurable composition.
  • the photocurable composition of the present invention can contain other additives as required.
  • Other additives include, for example, plasticizers, surface conditioners, ultraviolet light inhibitors, light stabilizers, antioxidants, and polymerization inhibitors.
  • the photocurable composition of the present invention may use a polymerization inhibitor from the viewpoint of improving the storage stability.
  • the polymerization inhibitor can be appropriately selected from known ones.
  • examples of the polymerization inhibitor include hindered phenols, hindered amines, quinones, nitrosamines, phenothiazines, piperidine-1-oxyls, among which piperidipiperidine-1-oxyls are preferable, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl is more preferred.
  • 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl for example, Polystop P7300 manufactured by Hakuto Co., Ltd. can be used.
  • the content ratio is 0.001 mass% or more and 0.2 mass% or less in 100 mass% of photocurable compositions from the point which makes storage stability and photocurability compatible. It is preferably 0.01% by mass or more and 0.1% by mass or less.
  • the photocurable composition can contain an inorganic compound as long as it can be used to form the organic layer as long as the problem can be solved.
  • the photocurable composition of the present invention can be produced by blending a cyclic amide monomer, a polyfunctional (meth) acrylate compound, and a photopolymerization initiator and mixing them with a stirrer.
  • a known stirrer such as a disper can be used as the stirrer.
  • the photocurable composition of the present invention is excellent in adhesion to a functional layer containing an inorganic compound, and can form an organic layer that is rapidly cured by radiation, so that the functional layer containing an inorganic compound is protected. It can be suitably used as a composition for an organic layer.
  • the said organic layer can be used suitably as an organic layer of an electronic element laminated body, such as a protective layer of the transparent electrode layer in a touch panel display, and a protective layer of the inorganic barrier layer of an organic EL device, for example.
  • the electronic element laminate includes a functional layer containing an inorganic compound and an organic layer that protects the functional layer.
  • the functional layer is a layer constituting an electronic element or a layer having some function with respect to the electronic element.
  • Examples of the electronic element include a transparent conductive layer, a liquid crystal element, and an OLED light emitting element.
  • the electronic element is not limited to display-related.
  • Examples of the electronic element laminate include a rigid printed wiring board, a flexible printed wiring board, a semiconductor element, a touch panel, a smartphone, a tablet terminal, a notebook personal computer, an LCD, an OLED, a smart watch, and a game terminal.
  • the functional layer contains an inorganic compound and has a certain function.
  • the functional layer include a transparent electrode layer, an inorganic barrier layer, a carbon-dispersed conductive layer, and a silver nanowire layer.
  • the transparent electrode layer contains, for example, ITO (indium tin oxide).
  • the inorganic barrier layer contains, for example, silicon nitride, silicon oxide, and aluminum oxide.
  • the carbon dispersed conductive layer contains, for example, carbon black, graphite, and carbon nanotube.
  • a silver nanowire layer contains a silver compound, for example.
  • the functional layer does not need to be formed on the entire surface of the substrate, and may be formed partially.
  • the said inorganic layer does not necessarily need to be an inorganic compound, and can contain an inorganic compound and an organic compound.
  • the functional layer is preferably a transparent electrode layer or an inorganic barrier layer.
  • FIG. 1 is a schematic cross-sectional view illustrating an example of the configuration of the touch panel 10.
  • the base material 11, the index matching layer (IM layer) 12, the transparent electrode layer 13, the protective layer 14, the transparent electrode layer 13, the protective layer 14, the adhesive layer 15, and the base material 11 are sequentially laminated.
  • the transparent electrode layer 13 is a functional layer containing an inorganic compound
  • the protective layer 14 is a cured product of the photocurable composition according to the present invention.
  • the substrate 11 include polyethylene terephthalate (PET), polycarbonate (PC), cycloolefin polymer (COP), and glass.
  • the IM layer 12 is an optical adjustment layer for preventing (invisibility) the transparent electrode pattern from showing bone.
  • a known IM layer can be used.
  • the thickness of the IM layer 12 is about 0.1 to 10 ⁇ m.
  • the transparent electrode layer 13 is a thin film layer having both visible light transparency and electrical conductivity, and is widely used as a transparent electrode for liquid crystal elements, organic EL elements, touch panels, solar cells, and the like.
  • the material of the transparent electrode layer 13 is made of conductive metals such as gold, silver and copper, and alloys thereof, and indium tin oxide (ITO), zinc oxide (ZnO), carbon nanotube (CNT), fullerene, graphene and the like. Conductive materials are also preferred.
  • a transparent conductive layer contains binder resin.
  • the thickness of the transparent electrode layer 13 is usually about 5 nm to 100,000 nm. For example, in the case of ITO, it is about 5 to 500 nm.
  • the transparent electrode layer is generally formed by vapor deposition or sputtering.
  • the protective layer 14 is a cured film (organic layer) formed from a photocurable composition.
  • the thickness of the protective layer 14 is usually preferably 3 ⁇ m or more and 30 ⁇ m or less, and more preferably 4 ⁇ m or more and 10 ⁇ m or less.
  • the thickness of the protective layer is 3 ⁇ m or more, the protective function of the transparent electrode layer is improved and the flexibility is further improved.
  • the thickness of the protective layer 14 is 30 ⁇ m or less, the transparency is further improved in addition to the improvement in productivity and cost reduction.
  • a known printing or coating method can be used as a method for forming the protective layer 14 on the substrate having the transparent electrode layer 13.
  • the printing method include screen printing, flexographic printing, offset printing, gravure printing, and gravure offset printing.
  • the coating method include a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, and a slide coating method.
  • drying / curing step examples include known drying apparatuses such as a UV lamp (for example, a high-pressure mercury lamp), a hot air oven, an infrared oven, a microwave oven, and a composite oven in which these are combined.
  • the conditions for heat drying and curing using a hot air oven are preferably 50 ° C. to 130 ° C. for about 1 minute.
  • the amount of light irradiation is about 10 to 3000 mJ / m 2 .
  • the radiation for curing the photocurable composition is preferably a light source that generates ultraviolet rays.
  • the light source include a high pressure mercury lamp, a constant pressure mercury lamp, a metal halide lamp, an ultraviolet laser, and an LED lamp.
  • an LED lamp having a central wavelength of 365 nm or more that has little influence on the organic EL layer is preferable, and an LED lamp having a central wavelength of 385 nm or more is preferable.
  • Examples of the adhesive layer 15 include an acrylic adhesive, a urethane adhesive, a polyester adhesive, a silicone adhesive, and a rubber adhesive.
  • the thickness of the adhesive layer 15 is about 10 to 300 ⁇ m.
  • OLED Organic electroluminescence display
  • an embodiment of the display according to the present invention includes an organic EL element 24 having a pair of electrodes 22 a and 22 b and an organic light emitting layer 23 positioned between the electrodes, and a film substrate 26.
  • the OLED 20 has a structure in which a barrier film 29 in which a first inorganic barrier layer 27, an organic layer 28, and a second inorganic barrier layer 27 are laminated in this order is bonded via an adhesive layer 25.
  • the organic layer 28 in FIG. 2 is a cured product of the photocurable composition according to the present invention.
  • the OLED 20 shown in the example of FIG. 3 includes an organic EL element 24 having a pair of electrodes 22a and 22b and an organic light emitting layer 23 positioned between the electrodes, a barrier layer 27 covering the electrode 22b, and the barrier layer 27.
  • the barrier layer 27 contains an inorganic compound, and the organic layer 28 is a cured product of the photocurable composition according to the present invention.
  • a second organic layer may be further provided on the second barrier layer 27.
  • a third barrier layer 27 may be provided on the second organic layer 28.
  • a plurality of barrier layers 27 and organic layers 28 may be stacked as necessary.
  • the substrate 21 may be a resin film or a gas barrier film.
  • the gas barrier films described in JP 2004-136466 A, JP 2004-148666 A, JP 2005-246716 A, JP 2005-262529 A, and the like can also be preferably used.
  • the thickness of the substrate 21 is usually about 5 ⁇ m to 700 ⁇ m, preferably 10 ⁇ m to 200 ⁇ m, more preferably 15 ⁇ m to 150 ⁇ m.
  • the substrate 21 preferably has a haze of 3% or less, preferably 2% or less, and more preferably 1% or less. Further, the substrate 21 preferably has a total light transmittance of 70% or more, more preferably 80% or more, and further preferably 90% or more. When the haze and the total light transmittance are satisfied, the visibility of the OLED is improved.
  • the organic EL element 24 includes a base material 21, a pair of electrodes 22a and 22b that constitute a cathode and an anode provided on the substrate, and an organic light emitting layer 23 including a light emitting layer between both electrodes.
  • the electrode 22a can be an anode and the electrode 22b can be a cathode. Due to the nature of the light emitting element, at least one of the anode and the cathode is transparent.
  • the anode usually has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from known electrode materials. When using a plastic substrate with low heat resistance as the substrate, ITO or IZO is used, and a transparent anode formed at a low temperature of 150 ° C. or lower is preferable.
  • the cathode usually has a function as an electrode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials.
  • the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof.
  • the material include rare earth metals such as Group 2 metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, lithium-aluminum alloy, magnesium-silver alloy, indium, ytterbium. These can be used alone or in combination of two or more.
  • a material mainly composed of aluminum As a material constituting the cathode, a material mainly composed of aluminum is preferable.
  • the material mainly composed of aluminum refers to aluminum alone or an alloy of aluminum and 0.01 to 10% by mass of an alkali metal or a Group 2 metal (for example, lithium-aluminum alloy, magnesium-aluminum alloy).
  • the material for the cathode is described in detail in JP-A-2-15595 and JP-A-5-121172.
  • a dielectric layer made of an alkali metal or a Group 2 metal fluoride, oxide or the like may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer.
  • the thickness of the cathode is usually about 10 nm to 5 ⁇ m, preferably 50 nm to 1 ⁇ m. Further, the cathode may be transparent or opaque.
  • the transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.
  • the organic compound layer is preferably laminated from the anode side in the order of a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.
  • a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer.
  • a hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer.
  • the light emitting layer may be a single layer, or the light emitting layer may be divided into a first light emitting layer, a second light emitting layer, a third light emitting layer, and the like. Furthermore, each layer may be divided into a plurality of secondary layers.
  • the organic EL element has at least one organic compound layer including a light emitting layer, and as the organic compound layer other than the organic light emitting layer, as described above, a hole transport layer, an electron transport layer, a charge blocking layer , Hole injection layer, electron injection layer and the like.
  • the organic light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, and receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines the holes and electrons. It is a layer having a function of providing light and emitting light.
  • the light emitting layer may be composed of only the light emitting material, or may be a mixed layer of the host material and the light emitting material.
  • the light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the dopant may be one type or two or more types.
  • the host material is preferably a charge transport material.
  • the host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed.
  • the light emitting layer may include a material that does not have charge transporting properties and does not emit light. Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.
  • fluorescent light-emitting material examples include benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatic compounds, and perinones.
  • oxadiazole derivatives oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, diketopyrrolopyrrole Derivatives, aromatic dimethylidin compounds, metal complexes of 8-quinolinol derivatives and metal complexes of pyromethene derivatives Metal complexes, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.
  • Examples of the phosphorescent material include a complex containing a transition metal atom or a lanthanoid atom.
  • Examples of the transition metal atom include ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum. Among these, rhenium, iridium, and platinum are preferable.
  • Examples of the lanthanoid atom include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.
  • ligands of the complex are described in, for example, G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press 1987, H.Yersin, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag 1987. And a ligand.
  • Examples of the host material contained in the light emitting layer include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and those having an arylsilane skeleton. And materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later.
  • the hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side.
  • the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines.
  • Derivatives amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon , Etc. are preferable.
  • the electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side.
  • the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various metal complexes typified by metal complexe
  • the hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side.
  • a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side.
  • the electron transport layer / electron injection layer may also function as a hole blocking layer. Examples of the organic compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like.
  • a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side can be provided at a position adjacent to the light emitting layer on the anode side.
  • the hole transport layer / hole injection layer may also serve this function.
  • the barrier film 29 has a configuration in which an inorganic barrier layer 27, an organic layer 28, and an inorganic barrier layer 27 are sequentially laminated on a film substrate 26.
  • the film substrate 26 used for the barrier film is, for example, diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose, etc. in the case of cellulose ester;
  • polyesters include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxyl.
  • polystyrene resin for example, polyethylene, polypropylene (PP), polymethylpentene, polytetrafluoroethylene, cycloolefin polymer (COP), etc .
  • vinyl compound examples include polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride.
  • acrylic resin for example, polymethyl methacrylate (PMMA), polyacrylic acid ester, etc .
  • Others include, for example, polystyrene (PS), polycarbonate (PC), polyamide, polyimide (PI), polyurethane, polysulfone, polyethersulfone, polyetherketone, polyetherimide, polyoxyethylene, norbornene resin, AS resin (SAN). , Vinylidene chloride resin (PVDC), epoxy resin and the like.
  • PVDC Vinylidene chloride resin
  • PET polyethylene terephthalate
  • PC polycarbonate
  • COP cycloolefin polymer
  • PI polyimide
  • the thickness of the film substrate is usually about 10 to 200 ⁇ m.
  • the inorganic barrier layer 27 is a thin film layer made of a metal compound.
  • the inorganic barrier layer forming method include physical vapor deposition methods (PVD) such as vapor deposition, sputtering, and ion plating, various chemical vapor deposition methods (CVD), plating, and sol-gel methods. There is a phase growth method.
  • the CVD method and the sputtering method are preferable in that a dense inorganic barrier layer having excellent barrier performance can be formed.
  • the composition of the inorganic barrier layer is preferably an oxide, nitride, carbide, or a mixture containing silicon and / or aluminum, and more preferably an oxide, nitride, carbide, or a mixture containing silicon.
  • the inorganic barrier layer may have a single layer structure made of the above-described materials, or a multilayer structure made of a plurality of layers having the same composition or different compositions.
  • the thickness of the inorganic barrier layer is not particularly limited, but is preferably 15 to 1200 nm, more preferably 20 to 1000 nm per layer. When the thickness is in the range of 15 to 1200 nm, pinholes are less likely to occur during layer formation, and cracks are less likely to occur.
  • the organic layer 28 is a cured film formed from a photocurable composition.
  • the thickness of the organic layer is usually preferably 1 to 30 ⁇ m and more preferably 4 to 10 ⁇ m.
  • the protective function for the inorganic barrier layer is improved and the flexibility is improved.
  • the thickness of the organic layer is 30 ⁇ m or less, transparency is improved in addition to productivity improvement and cost reduction.
  • a known printing or coating method can be used similarly to the formation of the transparent electrode layer.
  • the barrier layer 27 and the organic layer 28 may be formed not only on the barrier film but also on the electrode 22b.
  • the method of forming the barrier layer 27 and the organic layer 28 on the electrode 22b can be the same as the method of forming on the film substrate 26.
  • part means “part by mass”
  • % means “% by mass”.
  • surface is a mass part.
  • Example 1 90 parts of N-vinyl- ⁇ -caprolactam (V-cap / RC, amide monomer, manufactured by Ashland), 10 parts of trimethylolpropane triacrylate (TMPTA, polyfunctional (meth) acrylate compound, manufactured by Nippon Kayaku Co., Ltd.), lucillin 5 parts of TPO (photopolymerization initiator, manufactured by BASF Japan) was mixed to obtain a photocurable composition.
  • V-cap / RC amide monomer, manufactured by Ashland
  • TMPTA trimethylolpropane triacrylate
  • lucillin 5 parts of TPO photopolymerization initiator, manufactured by BASF Japan
  • a photocurable composition was obtained by mixing 50 parts of N-vinyl- ⁇ -caprolactam, 40 parts of phenoxyethyl acrylate (M140, manufactured by MIWON), 10 parts of trimethylolpropane triacrylate, and 5 parts of lucillin TPO.
  • Example 3 30 parts of N-vinyl- ⁇ -caprolactam, 50 parts of phenoxyethyl acrylate, 20 parts of dipropylene glycol diacrylate M222, manufactured by MIWON) and 5 parts of lucillin TPO were mixed to obtain a photocurable composition.
  • Example 4 22 parts of N-vinyl- ⁇ -caprolactam, 73 parts of phenoxyethyl acrylate, 5 parts of trimethylolpropane triacrylate, and 5 parts of lucillin TPO were mixed to obtain a photocurable composition.
  • Example 5 80 parts of N-vinylpyrrolidone (V-Pyrol / RC, amide monomer, manufactured by ASLAND), 20 parts of dipropylene glycol diacrylate, and 5 parts of lucillin TPO were mixed to obtain a photocurable composition.
  • V-Pyrol / RC N-vinylpyrrolidone
  • dipropylene glycol diacrylate 20 parts of dipropylene glycol diacrylate
  • lucillin TPO 5 parts
  • a photocurable composition was obtained by mixing 80 parts of acryloylmorpholine (ACMO, amide monomer, manufactured by KJ Chemicals), 20 parts of dipropylene glycol diacrylate, and 5 parts of lucillin TPO.
  • ACMO acryloylmorpholine
  • dipropylene glycol diacrylate 20 parts of dipropylene glycol diacrylate
  • lucillin TPO 5 parts
  • a photocurable composition was obtained by mixing 40 parts of phenoxyethyl acrylate, 50 parts of lauryl acrylate (LA, manufactured by Kyoeisha Chemical Co., Ltd.), 10 parts of dipropylene glycol diacrylate, and 5 parts of lucillin TPO.
  • a photocurable composition was obtained by mixing 85 parts of phenoxyethyl acrylate, 10 parts of lauryl acrylate, 5 parts of trimethylolpropane triacrylate, and 5 parts of lucillin TPO.
  • a photocurable composition was obtained by mixing 100 parts of trimethylolpropane triacrylate and 5 parts of lucillin TPO.
  • the coated glass plate is transferred to a glove box filled with argon whose oxygen concentration is kept at 1 ppm or less, and using a UV irradiator using an LED having a wavelength of 385 nm as a light source, an integrated light quantity of 400 mJ / cm 2 (UV ⁇ (Measured in the range of A) By irradiation, a glass plate having a cured organic layer formed on the silicon nitride film was obtained.
  • a tape adhesion test was carried out using the obtained coated glass plate for test.
  • the tape adhesion test was performed in accordance with JISK5600. Insert a cutter knife to form a total of 100 squares of 10 squares x 10 squares at a depth of 1 mm wide at a depth reaching the base material on the protective film, and paste cellophane tape (25 mm wide, manufactured by Nichiban Co., Ltd.) on the printing surface After that, the cellophane tape was quickly peeled off by hand, and the adhesion was evaluated by the number of remaining cells.
  • the examples have excellent adhesion, the coating film hardness is as high as HB or higher, and both hardness and adhesion are compatible.
  • the comparative examples generally had poor adhesion, and even a flexible coating film with low coating film hardness had low adhesion to the substrate.
  • ⁇ Preparation of water vapor barrier test sample> A silicon nitride layer having a thickness of 100 nm was formed on a polyethylene terephthalate film using a sputtering apparatus. On top of that, the polymerizable compound composition prepared in the example was applied using a wire bar so that the cured film thickness was 6 ⁇ m. After coating, the film was transferred to a glove box in which the oxygen concentration was kept at 2.5 ppm or less, and a cured film was obtained by irradiating ultraviolet rays with an integrated light quantity of 1000 mJ / cm 2 with an LED light source having a central wavelength of 365 nm.
  • a silicon nitride layer having a film thickness of 100 nm was laminated on the inorganic layer-organic layer laminate using a sputtering apparatus to prepare a three-layer laminate of inorganic layer-organic layer-inorganic layer.
  • the bendability test was performed using a bend resistance tester (planar body unloaded U-shaped stretch tester manufactured by Yuasa System Equipment Co., Ltd.), set in the apparatus so that the protective film was on the bottom, a diameter of 3 mm, Bending was performed 50,000 times at a rate of 30 times / minute.
  • a bend resistance tester planar body unloaded U-shaped stretch tester manufactured by Yuasa System Equipment Co., Ltd.
  • Example 7 N-vinyl- ⁇ -caprolactam 85 parts, trimethylolpropane triacrylate 15 parts, Lucyrin TPO 5 parts, Polyflow No. 75 (surface conditioner, manufactured by Kyoeisha Chemical Co., Ltd.) 0.5 parts, Polystop 7300P (polymerization inhibitor, A photocurable composition was obtained by mixing 0.05 parts of Hakutosha Co., Ltd.
  • Example 8 Light by mixing 45 parts of N-vinyl- ⁇ -caprolactam, 45 parts of phenoxyethyl acrylate, 10 parts of trimethylolpropane triacrylate, 5 parts of Lucyrin TPO, 0.5 part of Polyflow No. 75, 0.05 part of Polystop 7300P A curable composition was obtained.
  • Example 9 Light by mixing 25 parts of N-vinyl- ⁇ -caprolactam, 55 parts of phenoxyethyl acrylate, 20 parts of dipropylene glycol diacrylate, 5 parts of Lucyrin TPO, 0.5 part of Polyflow No. 75, 0.05 part of Polystop 7300P A curable composition was obtained.
  • Example 10 Light by mixing 22 parts of N-vinyl- ⁇ -caprolactam, 73 parts of phenoxyethyl acrylate, 5 parts of trimethylolpropane triacrylate, 5 parts of Lucyrin TPO, 0.5 part of Polyflow No. 75, 0.05 part of Polystop 7300P A curable composition was obtained.
  • a photo-curable composition was obtained by mixing 83 parts of N-vinylpyrrolidone, 17 parts of dipropylene glycol diacrylate, 5 parts of Lucyrin TPO, 0.5 part of Polyflow No. 75, and 0.05 part of Polystop 7300P.
  • a photocurable composition was obtained by mixing 83 parts of acryloylmorpholine, 17 parts of dipropylene glycol diacrylate, 5 parts of Lucyrin TPO, 0.5 part of Polyflow No. 75, and 0.05 part of Polystop 7300P.
  • Example 13 83 parts of N-vinyl- ⁇ -caprolactam, 17 parts of dipropylene glycol diacrylate, 5 parts of Lucyrin TPO, 0.5 part of Polyflow No. 75, 0.05 part of Polystop 7300P, VARIPLUS SK (ketone aldehyde resin, EVONIK) 10 parts were mixed to obtain a photocurable composition.
  • Example 14 N-vinyl- ⁇ -caprolactam 17 parts, acryloylmorpholine 66 parts, dipropylene glycol diacrylate 17 parts, Lucyrin TPO 5 parts, Polyflow No. 75 0.5 part, Polystop 7300P 0.05 part, VARIPLUS SK 10 parts Were mixed to obtain a photocurable composition.
  • Example 15 83 parts of acryloylmorpholine ACMO, 17 parts of dipropylene glycol diacrylate M222, 5 parts of Lucyrin TPO, 0.5 part of Polyflow No. 75, 0.05 part of Polystop 7300P, 10 parts of VARIPLUS SK I got a thing.
  • Example 16 Mix 83 parts of acryloylmorpholine ACMO, 17 parts of dipropylene glycol diacrylate M222, 5 parts of Lucyrin TPO, 0.5 part of Polyflow No. 75, 0.05 part of Polystop 7300P, 10 parts of Joncry 611 (acrylic resin, BASF) Thus, a photocurable composition was obtained.
  • Example 17 83 parts of acryloylmorpholine ACMO, 17 parts of dipropylene glycol diacrylate M222, 5 parts of Lucyrin TPO, 0.5 part of Polyflow No. 75, 0.05 part of Polystop 7300P, CAB-551-0.01 (cellulose acetate butyrate Resin, Eastman Chemical Co.) 10 parts were mixed to obtain a photocurable composition.
  • the coated material is transferred into a glove box substituted with argon, and irradiated with an integrated light amount of 500 mJ / cm 2 (measured in the range of UV-A) with a UV irradiator using an LED having a wavelength of 385 nm as a light source, and has an organic layer.
  • Sample B was obtained.
  • a tape adhesion test was performed using the obtained samples A to D.
  • the tape adhesion test was performed in accordance with JISK5600.
  • a cutter knife was inserted from the top of the organic layer to a depth reaching the substrate, and cuts were made so as to form a total of 100 squares of 10 squares ⁇ 10 squares in a grid pattern at intervals of 1 mm in width.
  • a commercially available cellophane tape (25 mm width) was affixed on the cut, and immediately after that, the commercially available cellophane tape was rapidly peeled by hand, and the adhesion was evaluated by the number of the remaining cells.
  • 100/100 it means that all the formed cells did not peel, and 0/100 means that all the cells were peeled.
  • ⁇ Preparation of film hardness test sample> The obtained photocurable composition was placed on a glass with a bar coater no. 5 was applied so that the film thickness was 7 ⁇ m. Next, the coated material is transferred into a glove box substituted with argon, and irradiated with an integrated light amount of 500 mJ / cm 2 (measured in the range of UV-A) with a UV irradiator using an LED having a wavelength of 385 nm as a light source, and has an organic layer. Sample E was obtained.
  • the coating film hardness was evaluated by a pencil hardness test based on the test method shown in JISK5400. Using the Clemens-type scratch hardness tester (manufactured by Tester Sangyo Co., Ltd.) from the organic layer of the obtained sample E, the hardness of the hardest pencil that was not damaged by four or more scratches by applying a load of 750 g was described. did.
  • the photo-curable compositions prepared in Examples and Comparative Examples on the ITO laminated film 31 were bar coater Nos. 5 was applied so that the film thickness was 7 ⁇ m, and a protective film 33 having a length of 15 mm ⁇ width of 70 mm was formed.
  • the coated material is transferred into a glove box substituted with argon, irradiated with an integrated light amount of 500 mJ / cm 2 (measured in the range of UV-A) with a UV irradiator using an LED having a wavelength of 385 nm as a light source, and a protective film (organic) Sample G having a layer) was obtained.
  • the resistance value is measured by directly applying a terminal to the ITO layer with a tester, the ITO layer is damaged and an accurate resistance value cannot be measured. Therefore, a resistance measurement terminal portion is formed on the ITO with silver paste, The resistance value was measured using a tester.
  • Rate of change (Surface resistance value after 50,000 bending bending before surface resistance test) / (Surface resistance value before test ⁇ 100) Evaluation criteria A: Surface resistance value change rate is less than 10% (excellent) B: Change rate of surface resistance value is 10% or more and less than 20% (good) C: The change rate of the surface resistance value is 20% or more and less than 30% (no problem in practical use) D: The rate of change of the surface resistance value is 30% or more (not practical)
  • the photo-curable compositions prepared in Examples and Comparative Examples are bar coater Nos. 5 was applied so that the film thickness was 7 ⁇ m.
  • the coated material is transferred into a glove box substituted with argon, and irradiated with an integrated light amount of 500 mJ / cm 2 (measured in the range of UV-A) with a UV irradiator using an LED having a wavelength of 385 nm as a light source, and has an organic layer.
  • Sample H was obtained.
  • ⁇ Preparation of water vapor barrier test sample> The photo-curable composition prepared in the example on the silicon nitride laminated film was coated with a bar coater No. 5 was applied so that the film thickness was 6 ⁇ m.
  • the coated film was transferred to a glove box filled with argon whose oxygen concentration was kept at 1 ppm or less, and ultraviolet rays were irradiated with an integrated light amount of 500 mJ / cm 2 with an LED light source having a central wavelength of 385 nm to obtain a cured film.
  • the flexibility test of the obtained cured film was performed in the same manner as the resistance value test.
  • Examples 7 to 17 can maintain the water vapor barrier property even before and after bending, and thus are suitable, for example, for use in forming an organic layer of an electronic device.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une composition photodurcissable qui est capable de former une couche organique qui est rapidement durcie au moyen d'un rayonnement et présente une excellente adhérence à une couche fonctionnelle qui contient un composé inorganique. L'invention concerne une composition photodurcissable pour une couche organique qui protège une couche fonctionnelle qui contient un composé inorganique, qui contient un monomère amide cyclique, un composé (méth)acrylate polyfonctionnel et un initiateur de photopolymérisation. Cette composition photodurcissable est configurée de telle sorte que : de 20 % en masse à 95 % en masse (inclus) du monomère amide cyclique sont contenus dans 100 % en masse de la composition photodurcissable ; et le composé (méth)acrylate polyfonctionnel (à l'exclusion des oligomères d'uréthane ayant un groupe alcoxyalkyle (méth)acrylamide) contient un ou plusieurs composés choisis dans le groupe constitué par les composés (méth)acrylate bifonctionnels et les composés (méth)acrylate trifonctionnels.
PCT/JP2018/004184 2017-02-08 2018-02-07 Composition photodurcissable et écran WO2018147316A1 (fr)

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TW202000801A (zh) * 2018-06-14 2020-01-01 日商捷恩智股份有限公司 聚合性組成物、噴墨用墨水、轉印鑄模及電極構件的形成方法

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WO2012014629A1 (fr) * 2010-07-27 2012-02-02 株式会社日立製作所 Film d'étanchéité et diode électroluminescente organique l'utilisant
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JP2011124228A (ja) * 2009-12-14 2011-06-23 Samsung Mobile Display Co Ltd 有機発光装置の製造方法及び有機発光装置
WO2012014629A1 (fr) * 2010-07-27 2012-02-02 株式会社日立製作所 Film d'étanchéité et diode électroluminescente organique l'utilisant
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