JP7165848B2 - Photocurable composition and laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photocurable composition that can be used to protect electronic parts and the like.

In recent years, electronic devices typified by mobile terminals such as smartphones and tablet terminals have been equipped with a printed wiring board and a touch panel equipped with a display member, and a liquid crystal display (hereinafter referred to as "LCD") that constitutes the touch panel. Electronic element laminates such as displays represented by organic electroluminescence displays (hereinafter also referred to as “OLED”) are being made thinner and higher in density by various methods.
For example, a smartphone uses many members (parts) in order to realize multiple functions in a limited space. Among components, a touch panel has a functional layer such as an inorganic layer (e.g., transparent electrode) having various functions on a base material, and an organic layer that protects the functional layer. Adequateness such as adhesion is required for lamination.
For example, light-emitting elements used in OLEDs are self-luminous elements that can be made lighter and thinner, so they are used not only in displays but also in lighting devices and the like. This OLED can be made into a flexible display by using a flexible substrate such as a plastic film. Unlike glass substrates, which are produced one by one, flexible displays use plastic film substrates to manufacture OLEDs by a roll-to-roll method, which is expected to increase production efficiency and reduce costs.

Since the light-emitting element of the OLED is easily deteriorated by water vapor, the light-emitting element is protected by forming an inorganic barrier layer (for example, a silicon nitride film) formed by vapor-depositing an inorganic compound on the base material. However, since the barrier layer has low flexibility and is easily cracked, an organic layer for protecting the barrier layer is required.

Patent Document 1 discloses a photocurable composition containing a trifunctional acrylate having a triazine skeleton and 3-vinylbenzoic acid, which is used for forming an organic layer that protects an inorganic layer.

JP-A-2007-30387

However, conventional compositions have low flexibility in the cured film, and cracks occur in the functional layer when stress such as bending is applied after the organic layer is formed. Therefore, for example, when protecting a transparent electrode as a functional layer, there is a problem that the resistance value increases after bending. Also, when protecting the barrier layer, there is a problem that cracks are generated and water vapor is easily permeable. Furthermore, there is also a problem of low adhesion to the substrate.

An object of the present invention is to provide a photocurable composition capable of forming an organic layer that has excellent adhesion to a functional layer containing an inorganic compound and that is less prone to cracking in the functional layer after bending, and a laminate.

The composition of the present invention contains an imide group-containing monomer, a polyfunctional radically polymerizable compound, and a photopolymerization initiator, and does not contain a benzophenone-based sensitizer and a thioxanthone-based sensitizer.

According to the present invention, there is provided a photocurable composition capable of forming an organic layer that has excellent adhesion to a functional layer containing an inorganic compound and that is less likely to crack in the functional layer after bending (hereinafter referred to as bending resistance), and the composition. can provide.

It is a typical sectional view showing an example of composition of a layered product for touch panels. 1 is a schematic cross-sectional view showing an example of the configuration of an OLED laminate. FIG. It is the top view (a) and side view (b) which show the outline of the flexibility test sheet|seat used for the resistance value change rate test of an Example.

Terms used in this specification will be explained. The monomer is an ethylenically unsaturated group-containing monomer and has radical polymerizability. Ethylenically unsaturated groups include, for example, vinyl groups and (meth)acryloyl groups. (Meth)acryloyl groups include acryloyl groups and methacryloyl groups.
A functional layer is a layer that contains an inorganic compound and has some functions necessary for an electronic device, such as barrier properties and conductivity. An electronic element is, for example, a main member for exhibiting a function as an electronic element laminate, and includes, for example, 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, ground wiring, and the like. The photocurable compound is, for example, a compound that is cured by a photopolymerization initiator such as an imide group-containing monomer and a polyfunctional radically polymerizable compound.

The photocurable composition of this specification contains an imide group-containing monomer, a polyfunctional radically polymerizable compound, and a photopolymerization initiator, and does not contain a benzophenone-based sensitizer and a thioxanthone-based sensitizer.
The photocurable composition is preferably used for forming an organic layer of an electronic element laminate having a functional layer containing an inorganic compound and an organic layer protecting the functional layer.

The photocurable composition of the present specification contains an imide group-containing monomer, so that an organic layer having high adhesion to an inorganic layer and high flexibility can be formed. Therefore, when the photocurable composition is used, for example, to protect a functional layer (transparent electrode layer) of a touch panel, for example, an effect that the resistance value is less likely to increase after bending can be obtained. In addition, when used to protect the functional layer (inorganic barrier layer) of OLED, for example, the effect of suppressing deterioration of water vapor barrier properties after bending can be obtained.

The photocurable composition of the present invention is preferably used, for example, as an organic layer for protecting an inorganic layer used in various members constituting a display. Such an organic layer has excellent adhesion to the functional layer, and when protecting the transparent electrode, the transparent electrode is less likely to crack and the resistance value is less likely to increase even after bending. is less likely to occur, and deterioration of water vapor barrier properties can be suppressed even after bending.

<Photocurable composition>
The photocurable composition contains an imide group-containing monomer, a polyfunctional radically polymerizable compound, and a photopolymerization initiator, and does not contain a benzophenone-based sensitizer and a thioxanthone-based sensitizer.

<Imido group-containing monomer>
The imide group-containing monomer is a (meth)acrylimide monomer containing an imide unit, and the imide unit contributes to improving adhesion to the inorganic layer. Also, the imide group-containing monomer preferably has a ring structure.

The reason why the photocurable composition of the present specification does not contain a benzophenone sensitizer and a thioxanthone sensitizer is that when the imide unit of the imide group-containing monomer is maleimide, the benzophenone sensitizer and the thioxanthone This is because if a system sensitizer is included, maleimide undergoes a dimerization reaction, which increases the cohesive force of the organic layer more than necessary, and the organic layer may not be able to follow bending.

Imido group-containing monomers include, for example, N-(meth)acryloyloxyethylhexahydrophthalimide, N-[2-(acryloyloxy)ethyl]phthalimide, and N-[2-(acryloyloxy)ethyl]succinimide.

The imide group-containing monomer can be used alone or in combination of two or more.

The imide group-containing monomer is preferably 1 to 80% by mass, more preferably 5 to 75% by mass, based on 100% by mass of the photocurable compound.

<Polyfunctional Radical Polymerizable Compound>
A polyfunctional radically polymerizable compound is a compound having two or more ethylenically unsaturated groups. The polyfunctional radically polymerizable compound preferably has 2 to 6 ethylenically unsaturated groups, more preferably 2 to 3.

Bifunctional radically polymerizable compounds (compounds having two ethylenically unsaturated groups) include, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate polyethylene glycol di(meth)acrylate, 1,6-hexanediol di (Meth)acrylates, ethoxylated 1,6-hexanediol di(meth)acrylate, neopentyl glycol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol di(meth)acrylate, 1,9-nonanediol diacrylate , tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, neopentyl glycol hydroxypivalate diacrylate, 1,3-butylene glycol diacrylate, ethoxylated tripropylene glycol diacrylate. Acrylate, neopentyl glycol-modified trimethylolpropane diacrylate, stearic acid-modified pentaerythritol diacrylate, tripropylene glycol di(meth)acrylate, bisphenol A diacrylate, bisphenol F diacrylate, cyclohexanedimethanol (meth)acrylate, dimethylol dicyclopentane diacrylate, dimethyloltricyclodecane diacrylate, isocyanuric acid diacrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate.

Trifunctional radically polymerizable compounds (compounds having three ethylenically unsaturated groups) include, for example, trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, tri(2- hydroxyethyl isocyanurate) triacrylate.
Tetra- or more functional radically polymerizable compounds (compounds having 4 or more ethylenically unsaturated groups) include, for example, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate.

Among these, the polyfunctional radically polymerizable compound is preferably a bifunctional radically polymerizable compound because it is easy to achieve both curability and adhesion at high levels. Moreover, a bifunctional radical polymerizable compound is more preferable in terms of further improving flexibility.

A polyfunctional radically polymerizable compound can be used individually or in combination of 2 or more types.

The polyfunctional radically polymerizable compound is preferably 2 to 50% by mass, more preferably 3 to 30% by mass, based on 100% by mass of the photocurable compound.

<Amido group-containing monomer>
The photocurable composition can further contain an amide group-containing monomer. When an imide group-containing monomer and an amide group-containing monomer are used in combination, both adhesion to the functional layer and bending resistance can be improved.
Amide group-containing monomers can be classified into cyclic amide group-containing monomers and chain amide group-containing monomers.
The cyclic amide group-containing monomer is preferably, for example, a monomer in which a carboxyl group-containing compound and an amino group are dehydrated to form a ring. Cyclic amide group-containing monomers include, for example, acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam and the like.

A chain amide group-containing monomer is a monomer having a chain hydrocarbon group and an amide unit.
Examples of linear amide group-containing monomers include acrylamide, methacrylamide, dimethylacrylamide, isopropylacrylamide, diethylacrylamide, dimethylaminopropylacrylamide, dimethylaminopropylacrylamide methyl chloride quaternary salt, and hydroxyethylacrylamide.

Amido group-containing monomers can be used alone or in combination of two or more.

The amide group-containing monomer is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, based on 100% by mass of the photocurable compound.

<Other radically polymerizable compounds>
The photocurable composition can contain radically polymerizable compounds other than imide group-containing monomers, polyfunctional radically polymerizable compounds, and amide group-containing monomers. Other photocurable compounds include alkyl (meth)acrylates, carboxyl group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates, fluorine-containing (meth)acrylates, and the like.

Alkyl (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate and the like.
Carboxyl group-containing (meth)acrylates are, for example, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-methylol (meth)acrylamide , 2-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, dimethylacrylamide, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate ) acrylate, 2-methyl-3,4-epoxy-cyclohexyl (meth)acrylate and the like.
Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate and the like.
Fluorine-containing (meth)acrylates include, for example, 2,2,2-trifluoroethyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, 2-(perfluorobutyl)ethyl methacrylate, and the like. is mentioned.

A urethane acrylate oligomer is a compound having two or more (meth)acryloyl groups and having a weight average molecular weight of 800 to 20,000.

Commercially available urethane acrylate oligomers include, for example, the “Ebecryl” series manufactured by Daicel UCB, the “CN series” manufactured by Sartomer, the “Laromer series” manufactured by BASF, the “Photomer series” manufactured by Cognis, and the “Art Resin Series", Nippon Gosei Co., Ltd. "Shiko Series", and Nippon Kayaku Co., Ltd. "Kayarad Series".

Other photocurable compounds can be used alone or in combination of two or more.

Other photocurable compounds preferably contain 10 to 95% by mass, more preferably 20 to 90% by mass, based on 100% by mass of the photocurable compound.

<Photoinitiator>
A photoinitiator is used. The photopolymerization initiator is preferably a photoradical polymerization initiator.
The radical photopolymerization initiator is preferably of intramolecular cleavage type.
The intramolecularly cleavable radical photopolymerization initiator is a radical initiator of the type in which the compound is cleaved to generate radicals upon irradiation with an active energy ray. Intramolecularly cleaved photoradical polymerization initiators include, for example, benzyl ketal initiators, α-hydroxyacetophenone initiators, benzoin initiators, aminoacetophenone initiators, oxime ketone initiators, and acylphosphine oxide initiators. agents, titanocene-based initiators, and the like are preferred.

Benzyl ketal photoradical polymerization initiators include, for example, 2,2-dimethoxy-1,2-diphenylethan-1-one (benzyldimethylketal/2,2-dimethoxy-2-phenylacetophenone).
α-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)-benzoyl]-1-hydroxy-1-methylethane, 1-[4-(acryloyloxyethoxy)-benzoyl]-1-hydroxy-1-methylethane, phenyl-1-hydroxy-cyclohexyl ketone , 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomers, and the like.
Benzoin-based photoradical polymerization initiators include, for example, benzoin, benzoin isobutyl ether, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Aminoacetophenone photoradical polymerization initiators include, for example, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morphol linophenyl)-butanone-1 and the like.
Oxime ketone photoradical polymerization initiators include, for example, 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 acylphosphine oxide photoradical polymerization initiators include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.
Titanocene photoradical polymerization initiators include, for example, 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.

Among these, the photopolymerization initiator is preferably an acylphosphine oxide initiator, and more preferably 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. .

A photoinitiator can be used individually or in combination of 2 or more types.

The photopolymerization initiator is preferably contained in an amount of 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, with respect to 100 parts by mass of the photocurable compound.

<Resin>
The photocurable composition can contain a resin. The photocurable composition can appropriately adjust the hardness, flexibility, etc. of the organic layer by containing a resin.
Resins include, for example, acrylic resins, epoxy resins, polyurethane resins, polyurethane urea resins, (modified) styrene maleic anhydride copolymers, (modified) vinyl chloride vinyl acetate copolymers, (modified) vinyl chloride vinyl acetate maleic anhydride Examples thereof include copolymers, ketone aldehyde resins, polyester resins, polypropylene resins, polylactic acid resins, cellulose acetate resins, cellulose acetate butyrate resins, esterified cellulose resins, butyral resins. In addition, the resin can have photocurability by adding a radically polymerizable functional group.

The resin can be used alone or in combination of two or more.

The number average molecular weight of the resin is preferably 300-30,000, more preferably 500-20,000.

The resin preferably contains 1 to 20% by mass, more preferably 1.5 to 15% by mass, based on 100% by mass of the non-volatile content of the photocurable composition.

<Solvent>
The photocurable composition can contain a solvent. When a solvent is included, the viscosity of the photocurable composition can be easily adjusted to suit printing (coating). The solvent can be appropriately selected according to the solubility of the resin to be used, the printing or coating method, and the like.

Examples of the solvent include ester-based solvents, ketone-based solvents, glycol ether-based solvents, aliphatic hydrocarbon-based solvents, aromatic hydrocarbon-based solvents, alcohol-based solvents, ether-based solvents, and water.

Solvents can be used alone or in combination of two or more.

The solvent is preferably contained in an amount of 1 to 50% by mass based on 100% by mass of the photocurable composition.

The photocurable composition can contain a surface modifier. When the photocurable composition contains a surface modifier, the surface smoothness of the organic layer is further improved, and optical properties are further improved when another layer is laminated. The surface modifier shown in the present invention has the ability to reduce the static surface tension of ink by 1 mN/m or more when 4.0% by weight or less of the surface modifier is added to an ink containing no surface modifier. material with
Examples of surface conditioners include silicone-based compounds, fluorine-based compounds, and (meth)acrylate-based compounds.
Silicone compounds include BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325 manufactured by BYK Chemie, BYK-330, BYK-331, BYK-333, BYK-337, BYK-344, BYK-345, BYK-347, BYK-348, BYK-349, BYK-370, BYK-375, BYK-377, BYK- 3500, BYK-3510, BYK-3510, BYK-3530, BYK-3455, BYK-UV3570, Evonik Degussa TEGO® GLIDE 450, 440, 435, 432, 410, 406, 130, 110, 100, TEGO -Rad2100, TEGO-Rad2200N, TEGO-Rad2250, TEGO-Rad2300, TEGO-Rad2500, TEGO-Rad2600, TEGO-Rad2700, Silface SAG001 of Nissin Chemical Co., Ltd., Silface SAG003, Silface SAG005, Dow Corning Toray Co., Ltd. L-7001, L-7002, 57 ADDITIVE, FZ-2105, AFCONA-3231, 3236, 3238, 3250, 3280 of AFCONA, Granol 100, Granol 115, Granol 400, Granol 410, Granol 435 of Kyoeisha Chemical Co., Ltd., Granol 440, Granol 450, B-1484, Polyflow ATF-2, KL-600, UCR-L72, UCR-L93, Shin-Etsu Chemical KF-353 and the like. Among these, BYK-3500, BYK-3510, BYK-3530, BYK-3530, BYK-307 and BYK-377 manufactured by BYK-Chemie are preferred.

Examples of fluorine-based compounds include ZX-022H, ZX-007C, ZX-049 and ZX-047-D manufactured by Fuji Kasei Kogyo Co., Ltd.

The (meth)acrylate compound is, for example, Polyflow No. of Kyoeisha Chemical Co., Ltd. 36, Polyflow No. 56, Polyflow No. 75, Polyflow No. 85HF, Polyflow No. 99C, Evonik Industries AG TEGO Rad 2010, 2011, 2100, 2200N, 2250, 2300, 2500, 2600, 2700, BYK-Chemie BYK-350, BYK-352, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-392, BYK-394, BYK-3550, BYK-UV3570, 3575, 3576 and the like. Among these, Polyflow No. 75 manufactured by Kyoeisha Chemical Co., Ltd. is preferable.

It is preferable that the surface conditioner is contained in an amount of 0.001 to 10% by mass in 100 parts by mass of the photocurable composition.

Surface conditioners can be used alone or in combination of two or more.

<Other additives>
The photocurable composition can contain other additives as needed. Other additives include, for example, plasticizers, ultraviolet inhibitors, light stabilizers, antioxidants, and polymerization inhibitors.

The photocurable composition can contain an inorganic compound as long as the problem can be solved.

The photocurable composition can be produced by blending an imide group-containing monomer, a polyfunctional radically polymerizable compound, and a photopolymerization initiator and mixing them with a stirrer. A known stirring device such as a disper can be used as the stirrer.

As examples of organic layer formation, the photocurable composition of the present invention is preferably used as a protective layer for a transparent electrode layer in a touch panel display and a protective layer for an inorganic barrier layer in an organic EL device.

An electronic element laminate will be described below as one of the uses of the laminate using the photocurable composition. Needless to say, the photocurable composition can be applied to other than electronic element laminates.
<Electronic element laminate>
An electronic device laminate includes a functional layer containing an inorganic compound and an organic layer that protects the functional layer. The functional layer is a layer that constitutes the electronic element or a layer that has some function with respect to the electronic element. Examples of electronic elements include signal wiring, transparent conductive layers, liquid crystal elements, and OLED light emitting elements. The signal wiring includes a wiring circuit, an antenna circuit, and a ground wiring made of copper or the like. It goes without saying that electronic devices are not limited to display-related devices in this way.

Examples of electronic element laminates include rigid printed wiring boards, flexible printed wiring boards, semiconductor elements, touch panels, smartphones, tablet terminals, notebook personal computers, LCD laminates, OLED laminates, smart watches, game terminals, and the like. be done.

<Light transmissive substrate>
The light-transmitting substrate is a plastic film capable of transmitting light. Examples of plastic films include cellulose esters, polyesters, polyolefins, vinyl compounds, acrylic resins, and other plastics.
Examples of cellulose esters include diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose, nitrocellulose and the like.
Polyesters include, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxy rate, polybutylene terephthalate, and the like.
Polyolefins include, for example, polyethylene, polypropylene (PP), polymethylpentene, polytetrafluoroethylene, cycloolefin polymer (COP), and the like.
Examples of vinyl compounds include polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride.
Examples of acrylic resins include polymethyl methacrylate (PMMA) and polyacrylic acid esters.
Other plastics 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.
Among these, polyethylene terephthalate (PET), polycarbonate (PC), cycloolefin polymer (COP), polyimide (PI), and polyethylene naphthalate (PEN) are preferred.

The thickness of the light-transmitting substrate is usually about 10-200 μm.

<Function layer>
A functional layer is a layer containing an inorganic compound and having some function. The functional layer may contain an organic compound in addition to the inorganic compound.
Examples of the functional layer include a transparent electrode layer, an inorganic barrier layer, a carbon-dispersed conductive layer, a silver nanowire layer, and the like.
As an inorganic compound contained in the functional layer, the transparent electrode layer contains, for example, ITO (indium tin oxide). Also, 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 nanotubes. A silver nanowire layer contains a silver compound, for example. Among these, the functional layer is preferably a transparent electrode layer or an inorganic barrier layer.

The functional layer need not be formed over the entire surface of the substrate, and may be formed partially. "Partially" includes, for example, stripes, meshes, islands, and the like. In addition, the functional layer can contain an organic compound in addition to the inorganic compound.

<Transparent electrode layer>
As an example of embodiments of the present invention, a laminate including a transparent electrode layer to be mounted in a touch panel display will be described with reference to FIG. In addition, it cannot be overemphasized that the aspect including a transparent electrode layer is not limited to FIG.
According to FIG. 1, a light-transmissive substrate 11, an IM (index matching) layer 12, a transparent electrode layer) 13, an organic layer 14, a transparent electrode layer 13, a protective layer 14, an adhesive layer 15, and a light-transmissive substrate 11 are A mode in which layers are sequentially laminated is mentioned.
The light-transmissive substrate 11 may be light-transmissive, and examples thereof include polyethylene terephthalate, polycarbonate, cycloolefin polymer, polyethylene naphthalate, and glass. The thickness of the base material 11 is approximately 5 to 200 μm.

The IM layer 12 is an optical adjustment layer for preventing the bones of the transparent electrode pattern from being visible (invisibility). Any known IM layer can be used.
The thickness of the IM layer 12 is approximately 0.1 to 10 μm.

The transparent electrode layer 13 is a thin film layer having both visible light transmittance 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 shape of the transparent electrode layer 13 may be a mesh shape, a stripe shape, or the like, although not shown. Materials for the transparent electrode layer 13 include conductive metals such as gold, silver and copper, alloys thereof, indium tin oxide (ITO), zinc oxide (ZnO), carbon nanotubes (CNT), fullerene, graphene and the like. Conductive materials are also preferred. In addition, when using carbon materials, such as CNT, a transparent conductive layer can also contain binder resin.

The thickness of the transparent electrode layer 13 is usually about 5 nm to 100000 nm. For example, in the case of ITO, it is about 5 to 500 nm. A transparent electrode layer is generally formed by vapor deposition or sputtering.

The protective layer 14 is a cured film (organic layer) formed from the photocurable composition of the present specification. The thickness of the protective layer 14 is preferably 3 to 30 μm, more preferably 4 to 10 μm. When the thickness of the protective layer is 3 μm or more, the protective function of the transparent electrode layer is improved and the flexibility is further improved. Further, when the thickness of the protective layer 14 is 30 μm or less, the productivity is improved, the cost is reduced, and the transparency is further improved. It is also preferable to further provide a second protective layer formed from a photocurable composition on the protective layer. This further improves flexibility.

As a method for forming the protective layer 14 on the substrate having the transparent electrode layer 13, a known printing or coating method can be used. Examples of printing methods include screen printing, flexographic printing, offset printing, gravure printing, and gravure offset printing. Coating methods include, for example, dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and slide coating. Moreover, it is preferable to carry out a drying/curing step after printing or coating. For the drying and curing step, known drying devices such as UV lamps (eg, high-pressure mercury lamps), hot air ovens, infrared ovens, microwave ovens, and composite ovens combining these may be used. The conditions for thermal drying and curing using a hot air oven are preferably 50° C. to 130° C. and about 1 minute. The amount of light irradiation is about 10 to 3000 mJ/m ² .

Light for curing the photocurable composition is preferably a light source that generates ultraviolet rays. Examples of the light source include high-pressure mercury lamps, constant-pressure mercury lamps, metal halide lamps, ultraviolet lasers, and LED lamps. Among these, an LED lamp having a center wavelength of 365 nm or more is preferable, and an LED lamp having a center wavelength of 385 nm or more is preferable because it has little effect on the organic EL element.

Examples of the adhesive layer 15 include an acrylic adhesive, a urethane adhesive, a polyester adhesive, a silicone adhesive, and a rubber-based adhesive. The thickness of the adhesive layer 15 is approximately 10 to 300 μm.

<Inorganic barrier layer>
As an example of the embodiment of the present invention, an embodiment of a laminate for protecting an inorganic barrier layer used for OLED applications will be described with reference to FIG. In addition, it cannot be overemphasized that the aspect including an inorganic barrier layer is not limited to FIG.

According to FIG. 2, an organic EL element 24 in which a substrate 21, an electrode 22, an organic compound layer 23 and an electrode 22' are sequentially laminated, a light transmissive substrate 26, an inorganic barrier layer 27, an organic layer 28 and an inorganic barrier layer 27 are arranged. FIG. 3 is a configuration diagram in which barrier laminates 29 that are sequentially laminated are laminated together with an adhesive layer 25. FIG.

Details of each element constituting the organic EL element 24 will be described below.

<Organic EL element>
As the substrate 21, widely known substrates used for organic EL elements can be adopted. The substrate 21 may be a light transmissive base material or a gas barrier laminate. Gas barrier laminates described in JP-A-2004-136466, JP-A-2004-148566, JP-A-2005-246716, JP-A-2005-262529, etc. can also be preferably used.

The thickness of the substrate 21 is usually about 30 μm to 700 μm, preferably 40 μm to 200 μm, more preferably 50 μm to 150 μm. The haze of the substrate 21 is preferably 3% or less, preferably 2% or less, and more preferably 1% or less. The substrate 21 preferably has a total light transmittance of 70% or more, more preferably 80% or more, and even more preferably 90% or more. Satisfying the haze and total light transmittance improves the visibility of the OLED.

The organic EL element 24 has a substrate and both electrodes consisting of a cathode 22' and an anode 22 provided on the substrate, and an organic compound layer 23 including a light-emitting layer between the electrodes. At least one electrode of the anode 22 and the cathode 22' is transparent due to the nature of the light emitting device.
The anode 22 usually has a function as an electrode that supplies holes to the organic compound layer, and its shape, structure, size, etc. are not particularly limited, and it can be used depending on the application and purpose of the light-emitting element. Therefore, it can be appropriately selected from known electrode materials. The anode is usually provided as a transparent anode. The transparent anode is described in detail in "New Development of Transparent Electrode Films" supervised by Yutaka Sawada, published by CMC (1999). When a plastic base material with low heat resistance is used as the substrate, a transparent anode formed by using ITO or IZO and forming a film at a low temperature of 150° C. or less is preferable.

The cathode 22' usually has a function as an electrode for injecting electrons into the organic compound layer, and its shape, structure, size, etc. are not particularly limited, and can be selected depending on the application and purpose of the light emitting device. Therefore, it can be appropriately selected from known electrode materials. Materials constituting the cathode include, for example, metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Examples of the material include group 2 metals (eg, Mg, Ca, etc.), rare earth metals such as gold, silver, lead, aluminum, lithium-aluminum alloys, magnesium-silver alloys, indium, and ytterbium. These can be used singly or in combination of two or more. A material mainly composed of aluminum is preferable as the material constituting the cathode.
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 group II metal (eg, lithium-aluminum alloy, magnesium-aluminum alloy, etc.). The materials for the cathode are described in detail in JP-A-2-15595 and JP-A-5-121172. Further, a dielectric layer made of a fluoride, oxide, or the like of an alkali metal or group II metal 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 viewed as a kind of electron injection layer.

The thickness of the cathode is usually about 10 nm to 5 μm, preferably 50 nm to 1 μm.
Also, the cathode may be transparent or opaque. The transparent cathode can be formed by forming a thin film of a cathode material with a thickness of 1 to 10 nm and laminating a transparent conductive material such as ITO or IZO.

As a mode of stacking the organic compound layers, a mode in which a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are stacked in this order from the anode side is preferable. Furthermore, a charge blocking layer or the like may be provided between the hole-transporting layer and the light-emitting layer or between the light-emitting layer and the electron-transporting 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. Further, 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. Further, each layer may be divided into multiple sublayers.

An organic EL device has at least one organic compound layer including a light-emitting layer, and the organic compound layers other than the organic light-emitting layer include, as described above, a hole transport layer, an electron transport layer, and a charge blocking layer. , a hole injection layer, an electron injection layer, and the like.

When an electric field is applied, the organic light emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer, 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 a field for light emission. The light-emitting layer may be composed only of a light-emitting material, or may be a mixed layer of a host material and a 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 or two or more. Preferably, the host material is a charge transport material. The number of host materials may be one or two or more, and examples thereof include a configuration in which an electron-transporting host material and a hole-transporting host material are mixed. Furthermore, the light-emitting layer may contain a material that does not have a charge-transporting property and does not emit light. Further, the light-emitting layer may be one layer or two or more layers, and each layer may emit light of a different color.

Examples of the fluorescent light-emitting material include benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatic compounds, and perinone. derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyraridine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, diketopyrrolopyrroles derivatives, aromatic dimethylidine compounds, various metal complexes represented by metal complexes of 8-quinolinol derivatives and metal complexes of pyrromethene derivatives, polymer compounds such as polythiophene, polyphenylene, and polyphenylene vinylene, compounds such as organic silane derivatives, and the like. .

Phosphorescent materials include, for example, complexes containing transition metal atoms and lanthanide atoms.
Transition metal atoms include, for example, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum. Among these, rhenium, iridium and platinum are preferred.
Lanthanide atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutecium. Among these, neodymium, europium, and gadolinium are preferred.

As the ligand of the complex, for example, G. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press, 1987, H. Yersin, "Photochemistry and Photophysics of Coordination Compounds", Springer-Verlag, 1987, Akio Yamamoto Examples include ligands described in "Organometallic Chemistry - Fundamentals and Applications -" published by Shokabosha in 1982.

Host materials contained in the light-emitting layer include, for example, compounds having any one of a carbazole skeleton, a diarylamine skeleton, a pyridine skeleton, a pyrazine skeleton, a triazine skeleton, and an arylsilane skeleton. Compounds exemplified in the later-described hole injection layer, hole transport layer, electron injection layer, and electron transport layer are also included.

A hole injection layer and a hole transport layer are layers having a function of receiving holes from the anode or from the anode side and transporting them to the cathode side. Compounds contained in the hole injection layer and the hole transport layer include, for example, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, aryl Amine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidine compounds, porphyrin compounds, organosilane derivatives, Carbon etc. are mentioned.

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. Compounds contained in the electron injection layer and the electron transport layer are, for example, 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, naphthalene, perylene and other aromatic ring tetracarboxylic acid anhydrides; metal complexes of phthalocyanine derivatives and 8-quinolinol derivatives; metal phthalocyanine, benzoxazole and benzothiazole A metal complex as a child; an organic silane derivative, and the like.

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. In the present invention, a hole blocking layer can be provided as an organic compound layer adjacent to the light emitting layer on the cathode side. Further, the electron transport layer/electron injection layer may also function as a hole blocking layer.
Examples of the organic compound forming the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like.
Also, a layer having a function of preventing electrons transported from the cathode to the light-emitting layer from passing through to the anode 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.

<Barrier laminate>
The barrier laminate 29 has a structure in which an inorganic barrier layer 27, an organic layer 28, and an inorganic barrier layer 27 are sequentially laminated on a light transmissive substrate .

The light transmissive base material 26 can use the already described base material. The thickness of the light transmissive substrate 26 is usually about 10-200 μm.

The inorganic barrier layer 27 is a thin film made of a metal compound. The method for forming the inorganic barrier layer includes, for example, a vapor deposition method, a sputtering method, a physical vapor deposition method (PVD) such as an ion plating method, a chemical vapor deposition method (CVD), a liquid phase growth method such as plating and a sol-gel method. law. Among these, the CVD method and the sputtering method are preferable because they facilitate the formation of a dense film.
Materials for the inorganic barrier layer 27 include, for example, oxides such as silicon and aluminum, nitrides thereof, and carbides thereof. Among these, silicon-containing oxides, nitrides, and carbides are preferred, and silicon nitride and silicon oxide are more preferred.

The material of the inorganic barrier layer 27 can be used alone or in combination of two or more. Note that the inorganic barrier layer 27 may have a multi-layer structure without being limited to a single-layer structure.

The thickness of the inorganic barrier layer is preferably 15-1200 nm, more preferably 20-1000 nm. When the thickness satisfies the predetermined range, pinholes and cracks are less likely to occur, and barrier properties are further improved. The barrier properties are water vapor barrier properties.

Organic layer 28 is a cured film formed from the photocurable composition herein. The thickness of the organic layer is preferably 1 to 30 μm, more preferably 4 to 10 μm. When the thickness of the organic layer is 3 μm or more, the protective function for the inorganic barrier layer is improved and the flexibility is improved. Further, when the thickness of the organic layer is 30 μm or less, productivity is improved, cost is reduced, and transparency is improved. It is also preferable to provide a second organic layer on the organic layer. Flexibility and barrier properties are thereby further improved.

As a method for forming the organic layer on the inorganic barrier layer, a known printing or coating method can be used as in the case of forming the transparent electrode layer.

An adhesive layer 25 is used to laminate the organic EL element 24 and the barrier laminate 29 . For the adhesive layer 25, the adhesive described in the adhesive layer 15 can be used, and a known adhesive can be used. The thickness of the adhesive layer 25 is approximately 10 to 300 μm.

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". The compounding amounts in the table are parts by mass.

<Example 1>
N-acryloyloxyethylhexahydrophthalimide (M-140, imide group-containing monomer, manufactured by Toagosei Co., Ltd.) 54 parts, dimethylacrylamide (DMAA, monofunctional monomer, manufactured by KJ Chemicals) 36 parts, dipropylene glycol diacrylate (Miramer M222, bifunctional monomer, manufactured by Miwon) 10 parts, Luricin TPO (acylphosphine-based photopolymerization initiator, manufactured by BASF Japan) 5 parts, Polyflow No. 75 (surface conditioner, manufactured by Kyoeisha Chemical Co., Ltd.) 4 parts, police A photocurable composition was obtained by mixing 0.05 part of Top 7300P (polymerization inhibitor, manufactured by Hakuto Co., Ltd.).

<Example 2>
Imidoacrylate having a phthalic acid skeleton is synthesized by the same method described in Japanese Patent Application Laid-Open No. 50-59481, using the intermediate N-hydroxyethylphthalimide as a starting material, and obtaining N-[2-(acryloyloxy ) to give ethyl]phthalimide.
Obtained N- [2- (acryloyloxy) ethyl] phthalimide (imido group-containing monomer) 54 parts, dimethylacrylamide 36 parts, dipropylene glycol diacrylate 10 parts, luricin TPO 5 parts, Polyflow No. 75 4 parts, poly 0.05 part of Top 7300P was mixed to obtain a photocurable composition.

<Example 3>
54 parts of N-acryloyloxyethylhexahydrophthalimide, 36 parts of dimethylacrylamide, 10 parts of dimethyloltricyclodecane diacrylate (DCP-A, bifunctional monomer, manufactured by Kyoei Co., Ltd.), 5 parts of lucilin TPO, 4 parts of Polyflow No. 75, A photocurable composition was obtained by mixing 0.05 part of Polystop 7300P.

<Example 4>
54 parts of N-acryloyloxyethylhexahydrophthalimide, 36 parts of dimethylacrylamide, 10 parts of bisphenol FEO-modified diacrylate (M-208, bifunctional monomer, manufactured by Toagosei Co., Ltd.), 5 parts of Lucirin TPO, 4 parts of Polyflow No. 75 , and 0.05 part of Polystop 7300P were mixed to obtain a photocurable composition.

<Example 5>
N-acryloyloxyethylhexahydrophthalimide 54 parts, dimethylacrylamide 36 parts, 2-hydroxy-3-acryloyloxypropyl methacrylate (G-201, bifunctional monomer, manufactured by Kyoei Co., Ltd.), Lucirin TPO 5 parts, Polyflow No. 75 4 parts, A photocurable composition was obtained by mixing 0.05 part of Polystop 7300P.
<Example 6>
57 parts of N-acryloyloxyethylhexahydrophthalimide, 38 parts of dimethylacrylamide, 5 parts of dimethyloltricyclodecane diacrylate (DCP-A, bifunctional monomer, manufactured by Kyoei Co., Ltd.), 5 parts of lucilin TPO, 4 parts of Polyflow No. 75, A photocurable composition was obtained by mixing 0.05 part of Polystop 7300P.
<Example 7>
42 parts of N-acryloyloxyethylhexahydrophthalimide, 28 parts of dimethylacrylamide, 30 parts of dimethyloltricyclodecane diacrylate (DCP-A, bifunctional monomer, manufactured by Kyoei Co., Ltd.), 5 parts of lucilin TPO, 4 parts of polyflow No. 75, A photocurable composition was obtained by mixing 0.05 part of Polystop 7300P.

<Example 8>
54 parts of N-acryloyloxyethylhexahydrophthalimide, 36 parts of dimethylacrylamide, trimethylolpropane triacrylate (TMPTA, trifunctional monomer, manufactured by Nippon Kayaku Co., Ltd.), 5 parts of Lucirin TPO, 4 parts of Polyflow No. 75, Polystop 7300P 0.05 part was mixed to obtain a photocurable composition.

<Example 9>
54 parts of N-acryloyloxyethylhexahydrophthalimide, 36 parts of dimethylacrylamide, 10 parts of dimethyloltricyclodecane diacrylate, 5 parts of Lucirin TPO, 0.3 parts of Polyflow No. 75, and 0.05 parts of Polystop 7300P were mixed. to obtain a photocurable composition.

<Example 10>
N-acryloyloxyethylhexahydrophthalimide 54 parts, dimethylacrylamide 36 parts, dimethyloltricyclodecane diacrylate 10 parts, lucilin TPO 5 parts, BYK-307 (surface conditioner, manufactured by BYK) 0.3 parts, polystop 0.05 part of 7300P was mixed to obtain a photocurable composition.

<Example 11>
N-acryloyloxyethylhexahydrophthalimide 54 parts, dimethylacrylamide 36 parts, dimethyloltricyclodecane diacrylate 10 parts, lucilin TPO 5 parts, BYK-377 (surface conditioner, manufactured by BYK) 0.3 parts, polystop 0.05 part of 7300P was mixed to obtain a photocurable composition.

<Example 12>
N-acryloyloxyethylhexahydrophthalimide 54 parts, dimethylacrylamide 36 parts, dimethyloltricyclodecane diacrylate 10 parts, lucilin TPO 5 parts, BYK-UV3500 (surface conditioner, manufactured by BYK) 0.3 parts, polystop 0.05 part of 7300P was mixed to obtain a photocurable composition.

<Example 13>
N-acryloyloxyethylhexahydrophthalimide 54 parts, dimethylacrylamide 36 parts, dimethyloltricyclodecane diacrylate 10 parts, lucilin TPO 5 parts, BYK-UV3510 (surface conditioner, manufactured by BYK) 0.3 parts, polystop 0.05 part of 7300P was mixed to obtain a photocurable composition.

<Example 14>
N-acryloyloxyethylhexahydrophthalimide 54 parts, dimethylacrylamide 36 parts, dimethyloltricyclodecane diacrylate 10 parts, lucilin TPO 5 parts, BYK-UV3530 (surface conditioner, manufactured by BYK) 0.3 parts, polystop 0.05 part of 7300P was mixed to obtain a photocurable composition.

<Example 15>
N-acryloyloxyethylhexahydrophthalimide 54 parts, diethylacrylamide (DEAA, monofunctional monomer, manufactured by KJ Chemicals) 36 parts, dimethyloltricyclodecane diacrylate (DCP-A, bifunctional monomer, manufactured by Kyoei Co., Ltd.) 10 parts, A photocurable composition was obtained by mixing 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500 and 0.05 parts of Polystop 7300P.

<Example 16>
Mix 70 parts of N-acryloyloxyethylhexahydrophthalimide, 20 parts of dimethylacrylamide, 10 parts of dimethyloltricyclodecane diacrylate, 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500, and 0.05 parts of Polystop 7300P. A photocurable composition was obtained.

<Example 17>
Mix 10 parts of N-acryloyloxyethylhexahydrophthalimide, 80 parts of dimethylacrylamide, 10 parts of dimethyloltricyclodecane diacrylate, 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500, and 0.05 parts of Polystop 7300P. A photocurable composition was obtained.

<Example 18>
N-acryloyloxyethylhexahydrophthalimide 54 parts, dimethylacrylamide 36 parts, dimethyloltricyclodecane diacrylate 10 parts, lucilin TPO 5 parts, BYK-UV3500 0.3 parts, polystop 7300P 0.05 parts, VARIPLUS SK ( A photocurable composition was obtained by mixing 2.5 parts of a ketone aldehyde resin (manufactured by EVONIK).

<Example 19>
N-acryloyloxyethylhexahydrophthalimide 54 parts, dimethylacrylamide 36 parts, dimethyloltricyclodecane diacrylate 10 parts, lucilin TPO 5 parts, BYK-UV3500 0.3 parts, polystop 7300P 0.05 parts, Joncryl 611 (acrylic 2.5 parts of resin (manufactured by BASF) were mixed to obtain a photocurable composition.

<Example 20>
N-acryloyloxyethylhexahydrophthalimide 54 parts, dimethylacrylamide 36 parts, dimethyloltricyclodecane diacrylate 10 parts, lucilin TPO 5 parts, BYK-UV3500 0.3 parts, polystop 7300P 0.05 parts, CAB-551 -0.01 (cellulose acetate butyrate resin, manufactured by Eastman Chemical Company) was mixed with 2.5 parts to obtain a photocurable composition.

<Example 21>
10 parts of N-acryloyloxyethylhexahydrophthalimide, 24 parts of diethylacrylamide, 56 parts of acryloylmorpholine (ACMO, amide monomer, manufactured by KJ Chemicals), 10 parts of dimethyloltricyclodecane diacrylate, 5 parts of lucirin TPO, BYK- A photocurable composition was obtained by mixing 0.3 part of UV3500 and 0.05 part of Polystop 7300P.

<Example 22>
N- acryloyloxyethyl hexahydrophthalimide 10 parts, acrylic acid - (2-vinyloxyethoxy) ethyl (VEAA, manufactured by Nippon Shokubai Co., Ltd.) 24 parts, acryloyl morpholine (ACMO, amide monomer, manufactured by KJ Chemicals) 56 parts, A photocurable composition was obtained by mixing 10 parts of dimethyloltricyclodecane diacrylate, 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500 and 0.05 parts of Polystop 7300P.

<Example 23>
N-acryloyloxyethylhexahydrophthalimide 10 parts, α-allyloxymethyl acrylate (FX-AO-MA, manufactured by Nippon Shokubai Co., Ltd.) 24 parts, acryloyl morpholine (ACMO, amide monomer, manufactured by KJ Chemicals) 56 parts, di 10 parts of methyloltricyclodecane diacrylate, 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500 and 0.05 parts of Polystop 7300P were mixed to obtain a photocurable composition.

<Example 24>
N-acryloyloxyethylhexahydrophthalimide 10 parts, isobornyl acrylate (IB-XA, manufactured by Kyoeisha Chemical Co., Ltd.) 24 parts, acryloyl morpholine (ACMO, amide monomer, manufactured by KJ Chemicals) 56 parts, dimethyloltricyclode 10 parts of Kandiacrylate, 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500 and 0.05 parts of Polystop 7300P were mixed to obtain a photocurable composition.

<Example 25>
10 parts of N-acryloyloxyethylhexahydrophthalimide, 24 parts of tetrahydrofurfuryl acrylate (THF-A, manufactured by Kyoeisha Chemical Co., Ltd.), 56 parts of acryloylmorpholine (ACMO, amide monomer, manufactured by KJ Chemicals), dimethyloltricyclode 10 parts of Kandiacrylate, 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500 and 0.05 parts of Polystop 7300P were mixed to obtain a photocurable composition.

<Example 26>
10 parts of N-acryloyloxyethylhexahydrophthalimide, 24 parts of isoamyl acrylate (IAA, manufactured by Kyoeisha Chemical Co., Ltd.), 56 parts of acryloyl morpholine (ACMO, amide monomer, manufactured by KJ Chemicals), 10 parts of dimethyloltricyclodecane diacrylate , 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500 and 0.05 parts of Polystop 7300P were mixed to obtain a photocurable composition.

<Example 27>
N-acryloyloxyethylhexahydrophthalimide 10 parts, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (MEDOL-10, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 24 parts, acryloylmorpholine (ACMO, Amide monomer, manufactured by KJ Chemicals) 56 parts, 10 parts of dimethyloltricyclodecane diacrylate, 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500, and 0.05 parts of Polystop 7300P are mixed to form a photocurable composition. got

<Example 28>
N-acryloyloxyethylhexahydrophthalimide 10 parts, cyclic trimethylolpropane formal acrylate (Viscoat #200, CTFA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 24 parts, acryloyl morpholine (ACMO, amide monomer, manufactured by KJ Chemicals) 56 parts , 10 parts of dimethyloltricyclodecane diacrylate, 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500 and 0.05 parts of Polystop 7300P were mixed to obtain a photocurable composition.

<Example 29>
10 parts of N-acryloyloxyethylhexahydrophthalimide, γ-butyrolactone acrylate (GBLA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 24 parts, acryloyl morpholine (ACMO, amide monomer, manufactured by KJ Chemicals) 56 parts, dimethyloltricyclode 10 parts of Kandiacrylate, 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500 and 0.05 parts of Polystop 7300P were mixed to obtain a photocurable composition.

<Example 30>
N-acryloyloxyethylhexahydrophthalimide 10 parts, 2-methyladamantyl acrylate (MADA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 24 parts, acryloyl morpholine (ACMO, amide monomer, manufactured by KJ Chemicals) 56 parts, dimethyloltricyclo 10 parts of Decane Diacrylate, 5 parts of Lucirin TPO, 0.3 parts of BYK-UV3500 and 0.05 parts of Polystop 7300P were mixed to obtain a photocurable composition.

<Comparative Example 1>
90 parts of lauryl acrylate (LA, manufactured by Kyoeisha Chemical Co., Ltd.), 10 parts of dipropylene glycol diacrylate, 5 parts of Lucirin TPO, 4 parts of Polyflow No. 75, and 0.05 parts of Polystop 7300P were mixed to form a photocurable composition. got stuff

<Comparative Example 2>
54 parts of N-acryloyloxyethylhexahydrophthalimide, 36 parts of dimethylacrylamide, 10 parts of dipropylene glycol diacrylate, 5 parts of Lucirin TPO, 4 parts of Polyflow No. 75, 0.05 parts of Polystop 7300P, 4-methylbenzophenone (SPEEDCURE 0.5 part of MBP (manufactured by DKSH Japan) was mixed to obtain a photocurable composition.

<Comparative Example 3>
54 parts of N-acryloyloxyethylhexahydrophthalimide, 36 parts of dimethylacrylamide, 10 parts of dipropylene glycol diacrylate, 5 parts of Lucirin TPO, 4 parts of Polyflow No. 75, 0.05 parts of Polystop 7300P, 2,4-dimethylthioxanthone (SPEEDCURE DETX, manufactured by DKSH Japan) was mixed to obtain a photocurable composition.

<Preparation of sample for adhesion test on ITO laminated film>
The resulting photocurable composition was coated on an ITO laminated film using a bar coater No. 1. 5 was applied so that the film thickness after curing would be 7 μm. The coated film is transferred to a conveyor under nitrogen flow with an oxygen concentration of 300 ppm or less, and irradiated with an LED light source having a central wavelength of 395 nm with an integrated light amount of 500 mJ/cm ² (measured in the UV-A range) to form an organic layer. Sample A was obtained.
・ ITO laminated film: commercial product (surface resistance value of ITO layer: 150 Ω / square, base material: PET, thickness: 100 μm)

<Preparation of sample for adhesion test on silicon nitride laminated film>
A silicon nitride layer with a thickness of 200 nm was formed on a polyethylene terephthalate (PET) film with a thickness of 75 μm using a sputtering apparatus. The photocurable composition obtained on the silicon nitride layer was coated with a bar coater No. 1. 5 was applied so that the film thickness after curing would be 7 μm. The coated film is transferred to a conveyor under nitrogen flow with an oxygen concentration of 300 ppm or less, and irradiated with an LED light source having a central wavelength of 395 nm with an integrated light amount of 500 mJ/cm ² (measured in the UV-A range) to form an organic layer. Sample B was obtained.

<Preparation of sample for adhesion test on silicon oxide laminated film>
A silicon oxide layer with a thickness of 200 nm was formed on a PET film with a thickness of 75 μm using a sputtering apparatus. The photocurable composition obtained on the silicon oxide layer was coated with a bar coater No. 1. 5 was applied so that the film thickness after curing would be 7 μm. The coated film is transferred to a conveyor under nitrogen flow with an oxygen concentration of 300 ppm or less, and irradiated with an LED light source having a central wavelength of 395 nm with an integrated light amount of 500 mJ/cm ² (measured in the UV-A range) to form an organic layer. Sample C was obtained.

<Preparation of sample for adhesion test on aluminum oxide laminated film>
A sputtering apparatus was used to form an aluminum oxide layer with a thickness of 200 nm on a PET film with a thickness of 75 μm. The photocurable composition obtained on the aluminum oxide layer was coated with a bar coater No. 1. 5 was applied so that the film thickness after curing would be 7 μm. Next, the coated material is transferred into an argon-substituted glove box and irradiated with a UV irradiation machine using an LED with a wavelength of 395 nm as a light source with an integrated light amount of 500 mJ/cm ² (measured in the UV-A range) to form an organic layer. A sample D was obtained.

<Evaluation of Adhesion>
Using the samples A to D obtained, a tape adhesion test was carried out. The tape adhesion test was carried out according to JISK5600. A cutter knife was inserted from above the organic layer to a depth reaching the PET film, and cuts were made in a grid pattern at intervals of 1 mm in width to form 100 squares in total of 10 squares×10 squares. Then, a commercially available cellophane tape (25 mm width) was attached on the cut, and immediately after that, the commercially available cellophane tape was quickly peeled off by hand, and the adhesion was evaluated by the number of remaining squares.
Note that the results of samples A to D = 100/100 mean that all the masses were not peeled, and 0/100 means that all the masses were peeled off.

<Preparation of sample for resistance value change rate test on ITO laminated film>
A method for preparing a sample will be described based on (a) a plan view and (b) a side view of FIG. Commercially available conductive paste (REXALPHA RA FS074, manufactured by Toyochem Co., Ltd.) was screen-printed on the ITO laminated film 31 so that the film thickness after drying was 5 μm, dried in an oven at 135° C. for 30 minutes, and cured. A resistance value measuring terminal portion 32-1 and a resistance value measuring terminal portion 32-2 each having a length of 15 mm and a width of 3.5 mm were formed with an interval of 75 mm. Next, the photocurable composition obtained on the ITO laminated film 31 was coated with a bar coater No. 1. 5 to form an organic layer 33 having a length of 15 mm and a width of 70 mm. Next, the coated material is transferred into an argon-substituted glove box and irradiated with a UV irradiation machine using an LED with a wavelength of 395 nm as a light source with an integrated light amount of 500 mJ/cm ² (measured in the UV-A range) to form an organic layer. Sample E was obtained.
If a terminal is directly applied to the ITO layer with a tester to measure the resistance, the ITO layer will be damaged and an accurate resistance cannot be measured. A tester was applied to measure the resistance value.

<Evaluation of resistance value change rate>
Using the obtained sample E, a flexibility test was carried out. The bending resistance test was performed using a bending resistance tester (Yuasa System Equipment Co., Ltd. planar body no-load U-shaped expansion tester). 50,000-fold bending was performed at a speed of 30 times/minute. The rate of change in surface resistance value was calculated from the following formula. In addition, the evaluation criteria are as follows.
Change rate = (Surface resistance value after bending 50,000 times Surface resistance value before test) / (Surface resistance value before test x 100)
・ Evaluation criteria ◎: The rate of change in surface resistance value is less than 10% (fairly good)
○: Change rate of surface resistance value is 10% or more and less than 20% (good)
△: Change rate of surface resistance value is 20% or more and less than 30% (practically no problem)
×: Change rate of surface resistance value is 30% or more (not practical)

The compositions and evaluation results are shown in Tables 1-4.

From the results in Tables 1 to 3, Examples 1 to 30 are excellent in adhesion to various film substrates. Furthermore, it suppresses an increase in resistance value before and after bending, and is suitable as an organic layer for protecting the functional layer.

<Preparation of sample for water vapor barrier test>
The photocurable composition obtained on the silicon nitride laminated film was coated with a bar coater No. 1. 5 was applied so that the film thickness after curing would be 7 μm. The coated film was transferred to a conveyor under nitrogen flow with an oxygen concentration of 300 ppm or less, and was irradiated with ultraviolet light with an integrated light amount of 500 mJ/cm ² from an LED light source with a central wavelength of 395 nm to obtain an organic layer. The flexibility test of the obtained organic layer was performed by the same method as the resistance value test.

<Evaluation of water vapor barrier property>
The water vapor transmission rate was measured using a water vapor transmission rate measuring device (PERMATRAN manufactured by MOCON). The conditions are 40° C., 100% R.I. H. A 168 hour test was performed. The detection limit is 0.01 g/m ² /day. Table 5 shows the results. The photocurable composition obtained in the comparative example was not tested because the adhesion to the inorganic layer was poor and the barrier laminate could not be produced.

<Evaluation results>
From the results in Table 5, Examples 1 to 30 can maintain the water vapor barrier properties even before and after bending, and are therefore suitable for use in forming organic layers of electronic devices, for example.

REFERENCE SIGNS LIST 11 light transmissive substrate 12 IM layer 13 transparent electrode layer 14 protective layer 15 adhesive layer 21 substrate 22 electrode (anode)
22' electrode (cathode)
23 Organic compound layer 24 Organic EL element 25 Adhesive layer 26 Light-transmitting base material 27 Inorganic barrier layer 28 Organic layer 29 Barrier laminate 31 ITO laminated film 32-1 Terminal for resistance measurement 32-2 Terminal for resistance measurement 33 organic layer

Claims (6)

A photocurable composition used for forming an organic layer of a laminate comprising a light-transmitting substrate, a functional layer containing an inorganic material, and an organic layer protecting the functional layer,
A photocurable composition containing an imide group-containing monomer, an amide group-containing monomer, a polyfunctional radically polymerizable compound, and a photopolymerization initiator, and containing neither a benzophenone-based sensitizer nor a thioxanthone-based sensitizer. 2. The photocurable composition according to claim 1, wherein the content of the amide group-containing monomer is 5 to 80% by mass based on 100% by mass of the photocurable compound. 3. The photocurable composition according to claim 1, further comprising a resin. 4. The photocurable composition according to any one of claims 1 to 3, wherein the polyfunctional radically polymerizable compound is a difunctional radically polymerizable compound. 5. The photocurable composition according to any one of claims 1 to 4, comprising 1 to 80% by mass of the imide group-containing monomer in the composition. Equipped with a light-transmitting substrate, a functional layer containing an inorganic material, and an organic layer protecting the functional layer,
The organic layer does not contain a benzophenone-based sensitizer and a thioxanthone-based sensitizer, and is a cured product of a photocurable composition containing an imide group-containing monomer, a polyfunctional radically polymerizable compound, and a photopolymerization initiator. laminate.

Images