JP6384073B2 - Active energy ray polymerizable composition, coating agent, and adhesive, and laminate comprising them - Google Patents

Description

  The present invention relates to a novel active energy ray polymerizable composition, a coating agent, an adhesive, and a laminate using them.

In addition to various characteristics such as fast polymerization rate, good workability due to the absence of solvent, energy saving of extremely low energy requirements, active energy ray polymerization technology has recently reduced environmental pollution due to environmental pollution problems. Therefore, the field of use is expanding in the fields of building materials, packaging materials, printing materials, display materials, electrical and electronic component materials, optical devices, displays, and the like.

These contain a resin that can be polymerized with active energy rays and a monomer having an α, β-ethylenically unsaturated double bond group, and the coating film is formed because the monomer also functions as a solvent. There is an advantage that the solvent does not volatilize sometimes. And as this resin having active energy ray polymerizability, α, β-ethylenically unsaturated double bond group at the molecular terminal of low molecular weight polyester resin, polyurethane resin, polyepoxy resin, polyacrylic resin, etc. And oligomers having an α, β-ethylenically unsaturated double bond group are used.

In recent years, the development and generalization of information communication equipment including displays has been remarkable, and these display devices have further improved performance and productivity of coating agents, adhesives, or sealing agents. Various proposals using active energy ray polymerizable materials have been made. For such display devices, various films such as an antireflection film for preventing reflection from an external light source and a protective film (protection film) for preventing scratches on the surface of the display device are usually used. For example, in a liquid crystal cell member constituting an LCD, a polarizing plate and a retardation film are laminated.

Further, the flat panel display (FPD) is not only used as a display device, but also provided with a touch panel function on the surface thereof, and may be used as an input device. A protective film, an antireflection film, an ITO vapor deposition resin film, or the like is also used for the touch panel.

Such a film is attached to an adherend via an adhesive and is used in a display device as a laminate for an optical element, and an active energy ray polymerizable composition is used as an adhesive as one form. .

The specific example which uses an active energy ray polymeric composition as an adhesive agent is given. Polarizers used in the fields related to liquid crystal displays are usually produced by uniaxially stretching polyvinyl alcohol (PVA) with iodine or dye adsorbed, but this polyvinyl alcohol polarizer is contracted by heat or moisture. However, the polarization performance is deteriorated. Then, what stuck the protective film on the surface of the PVA type | system | group polarizer is used as a polarizing plate. As an adhesive for sticking a protective film to a polarizer, an aqueous solution of a polyvinyl alcohol resin (PVA adhesive) has been widely used (see Patent Document 2). However, the water-based adhesive requires a drying process after coating, and the PVA polarizer has low heat resistance, so that drying at a low temperature for a long time is required, resulting in poor production efficiency. For the reasons described above, it has been proposed to use an ultraviolet curable adhesive instead of a water-based adhesive (see Patent Document 3).

Patent Document 4 discloses a urethane (meth) acrylate in which a layer composed of a polarizer made of polyvinyl alcohol and a protective film is obtained from a polyisocyanate compound, a polyol compound, and a hydroxyl group-containing (meth) acrylate compound, and A polarizing plate which is a cured product of a base material permeable monomer having permeability to a protective film is disclosed. However, the durability performance required for polarizing plates has become strict, and the durability under harsh environments is required under high humidity, so the polarizing plates satisfy the durability under the harsh environments. I couldn't do it.

Furthermore, the specific example which uses an active energy ray polymeric composition as a coating agent is given. Proposals have been made to replace the configuration itself of the “adhesive and protective film” on the surface of the PVA polarizer described above with an active energy ray-polymerizable coating agent and to reduce the thickness and weight of mobile devices in recent years. For example, in JP 2000-199819 A (Patent Document 5), at least one surface of a polarizing film made of a hydrophilic polymer is coated with a resin solution using a solvent that does not dissolve the polarizing film, and is dried. An invention for forming a transparent thin film layer (protective film) having good durability is disclosed. Japanese Patent Application Laid-Open No. 2003-185842 (Patent Document 6) discloses an active energy ray polymerizable compound having a high moisture permeability and having a dicyclopentanyl residue or a dicyclopentenyl residue (for example, dicyclopentenyloxyethyl methacrylate). In the invention of forming a protective film with a composition containing), Japanese Patent Application Laid-Open No. 2004-245924 (Patent Document 7) has a protective film mainly composed of an epoxy resin on at least one surface of a polarizing film. In JP-A-2005-92112 (Patent Document 8), the invention of a polarizing plate is a polarizing plate having a structure in which at least one surface of a polyvinyl alcohol polarizing film is protected with a resin. An invention of a polarizing plate comprising a compound and a cationic active energy ray-curable compound is disclosed. .

However, since the coating agent is required to have durability under a harsh environment like the polarizing plate, the above invention cannot achieve both adhesion and durability.

JP 2010-248387 A JP-A-2005-208456 JP 2008-233874 A JP 2008-066511 JP 2000-199819 A JP 2003-185842 A JP 2004-245924 A Japanese Patent Laying-Open No. 2005-092112

    The present invention is a novel active energy ray polymerizable composition having excellent adhesiveness, a coating agent, and an adhesive, and further a laminate excellent in punching workability and durability against heat and humidity as compared with the conventional one, It aims at providing the laminated body for optical elements especially.

 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned target can be achieved by the active energy ray-polymerizable composition shown below, and have completed the present invention.

That is, the present invention relates to an α, β-ethylenically unsaturated double bond group-containing compound (C) having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures in the molecule,
The present invention relates to an active energy ray polymerizable composition, a coating agent and an adhesive containing an epoxy acrylate oligomer (M1) and / or a polyester acrylate oligomer (M2).
However, the active energy ray polymerizable composition is (1) or (2).
(1) The epoxy acrylate oligomer (M1) is
An epoxy compound containing two or more epoxy groups in the molecule;
It is formed by reacting a carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound.
(2) The polyester acrylate oligomer (M2)
A polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol;
Carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, epoxy group-containing α, β-ethylenically unsaturated double bond group It is formed by reacting a compound containing or an isocyanato group-containing α, β-ethylenically unsaturated double bond group-containing compound.

Furthermore, the present invention includes the above active energy ray-polymerizable, wherein the polyhydric alcohol which is a raw material component of the polyester acrylate oligomer (M2) includes a polyhydric alcohol in which two or more hydroxyl groups are introduced into a branched alkane. The present invention relates to a composition, a coating agent, and an adhesive.

Further, in the present invention, the epoxy acrylate oligomer (M1)
An epoxy compound containing two or more epoxy groups in the molecule;
A carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound;
The present invention relates to the active energy ray-polymerizable composition, the coating agent and the adhesive, characterized by reacting with a polybasic acid.

As a result of the completion of the present invention, it is possible to provide a laminate, particularly a laminate for an optical element, which is superior in punching workability and durability against heat and humidity as compared with the conventional art.

The active energy ray-polymerizable composition of the present invention comprises an α, β-ethylenically unsaturated double bond group-containing compound having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures in the molecule (C ) And an epoxy acrylate oligomer (M1) and / or a polyester acrylate oligomer (M2) as essential components.

 The compound (C) of the present invention is particularly suitable in terms of adhesiveness, heat resistance and moisture resistance when the active energy ray polymerizable composition of the present invention is used as a coating agent or an adhesive. The compound (C) is a compound having two or more cycloalkane skeletons and / or cycloalkene skeletons and one or more α, β-ethylenically unsaturated double bonds. As the compound (C), a cycloalkene skeleton having two or more ring structures and / or a compound (c1) in which the ring structure is separated from the ring structure by an alkyl group, an ether group, an ester group, and the like, and Examples thereof include a compound having a bridge structure of a cyclo ring such as a compound (c2) having a norbornane or norbornene skeleton, and a compound (c3) having an adamantane structure.

As an α, β-ethylenically unsaturated double bond group-containing compound (c1) having a cycloalkane skeleton and / or a cycloalkene skeleton having two or more ring structures, the ring structure and the ring structure being separated from each other Examples include hydrogenated biphenol A diacrylate and 3,3-dicyclopropyl acrylate.
The α, β-ethylenically unsaturated double bond group-containing compound (c2) having norbornene and / or norbornane skeleton may have at least one norbornene and / or norbornane skeleton and ethylenically unsaturated double bond. For example, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol (meth) Acrylate, isobornyl (meth) acrylate, etc. are mentioned.

 Among the above compounds (c2), the compound (c2 ′) having 3 or more cyclic skeletons is particularly preferable because it suppresses curing shrinkage by increasing the bulk and improves the adhesive force. ') Includes dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, and the like.

The α, β-ethylenically unsaturated double bond group-containing compound (c3) having an adamantane skeleton is a radically polymerizable compound having three or more cyclic skeletons similar to the above compound (c2 ′). Adhesion is improved. Specific examples of the compound (c3) include 3-hydroxy-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, and 2-propyl. -2-adamantyl (meth) acrylate, 3,5-dihydroxy-1-adamantyl (meth) acrylate, 1,3-adamantyldiol di (meth) acrylate, 1,3,5-adamantyltri (meth) acrylate, 3- Examples include hydroxy-1,5-adamantyl di (meth) acrylate and 3,5-dihydroxy-1-adamantyl (meth) acrylate.
3-hydroxy-1-adamantyl acrylate with one α, β-ethylenically unsaturated double bond, 2-methyl-2-adamantyl acrylate, and 2-ethyl-2-adamantyl acrylate are particularly preferred because of their excellent adhesion. .

 Of the above compounds (C), norbornane, norbornene, or the compound (c2) or compound (c3) having an adamantane skeleton is more preferable than the compound (c1) because of excellent heat resistance. More preferred is compound (c2), and most preferred is compound (c2 ′).

 The epoxy acrylate oligomer (M1) will be described. The epoxy acrylate oligomer (M1) is obtained by at least reacting an epoxy compound containing two or more epoxy groups in the molecule with a carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound.

 The epoxy compound containing two or more epoxy groups in the molecule is not particularly limited as long as it is a compound containing two epoxy groups in the molecule. Specifically, for example, a cresol novolac type epoxy compound, a phenol novolac type epoxy compound, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy Resin, bisphenol F / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, glycerin / epichlorohydrin adduct polyglycidyl ether, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether , Dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, dihydrohexahydrophthalate Zyl ester, hydrogenated bisphenol A type diglycidyl ether, dihydroxyanthracene type epoxy resin, polypropylene glycol diglycidyl ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluorenediglycidyl Ether, biscresol fluorenediglycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, special JP 2004-156024 A, JP 2004-315595 A, JP 2004-323 A. Examples thereof include an epoxy compound excellent in flexibility disclosed in No. 777, an epoxy compound having a structure represented by the following formulas (1) to (3), and the like.

Formula (1)

Formula (2)

Formula (3)

 Among them, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferable for imparting flexibility to the finally obtained epoxy acrylate oligomer (M1). Chlorohydrin type epoxy resins and bisphenol F / epichlorohydrin type epoxy resins are preferred in the case of imparting wet heat resistance to the finally obtained epoxy acrylate oligomer (M1). Thus, in the present invention, an epoxy compound containing two or more epoxy groups in the molecule can be selected according to the purpose, and these may be used alone or in combination. It doesn't matter.

 The carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound used for the production of the epoxy acrylate oligomer (M1) includes (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, phthalic anhydride Acid half-esterified with alkyl alcohol, itaconic anhydride half-esterified with alkyl alcohol, acrylic acid dimer, and these carboxyl group-containing α, β-ethylenically unsaturated double bond groups Examples include compounds obtained by adding several moles of ε-caprolactone to the compound. Of these, (meth) acrylic acid is preferred from the viewpoint of reaction control.

 Furthermore, the epoxy acrylate oligomer (M1) reacts an epoxy compound containing two or more epoxy groups in the molecule, a carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, and a polybasic acid. It is preferable that

 Examples of the polybasic acid include aliphatic, alicyclic, and aromatic groups, which can be used without any particular limitation. More specifically, examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, and dodecanedioic acid. Examples thereof include acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, and the like, and these aliphatic dicarboxylic acids and anhydrides thereof can be used. Derivatives of succinic anhydride (methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl anhydride Succinic acid, etc.), glutaric anhydride derivatives (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, etc. ), Maleic anhydride derivatives (2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecyl Maleic anhydride, 2,3-dichloromaleic anhydride, phenyl maleic anhydride Phosphate, also anhydride derivative of 2,3-diphenyl maleic anhydride, etc.) and the like can be used.

 More specifically, as the alicyclic polybasic acid, for example, as the alicyclic dicarboxylic acid, for example, dimer acid, cyclopropane-1α, 2α-dicarboxylic acid, cyclopropane-1α, 2β-dicarboxylic acid , Cyclopropane-1β, 2α-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, cyclobutane-1α, 2β-dicarboxylic acid, cyclobutane-1α, 3β-dicarboxylic acid, cyclobutane-1α, 3α-dicarboxylic acid, (1R) -Cyclopentane-1β, 2α-dicarboxylic acid, trans-cyclopentane-1,3-dicarboxylic acid, (1β, 2β) -cyclopentane-1,3-dicarboxylic acid, (1β, 3β) -cyclopentane-1, 3-dicarboxylic acid, (1S, 2S) -1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, , 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid Saturated cycloaliphatic dicarboxylic acids such as hexahydrophthalic acid and tetrahydrophthalic acid, 1-cyclobutene-1,2-dicarboxylic acid, 3-cyclobutene-1,2-dicarboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid Acid, 4-cyclopentene-1,3-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene- 1,3-dicarboxylic acid, 2,5-hexadiene-1α, 4α-dicar Unsaturated double bond in such phosphate rings include one or two unsaturated alicyclic dicarboxylic acid having, like these alicyclic dicarboxylic acids and anhydrides thereof can be used.

 Also, derivatives of hexahydrophthalic anhydride ((3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride), tetrahydrophthalic anhydride derivatives (1,2,3,6-tetrahydrophthalic anhydride, 3 -Methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.) The hydrogenated phthalic anhydride derivative can also be used as an alicyclic dicarboxylic acid anhydride.

 More specifically, examples of the aromatic polybasic acid include, for example, o-phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, 2,5-dimethylterephthalic acid, 2 , 2'-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindanedicarboxylic acid 1,2-azulene dicarboxylic acid, 1,3-azulene dicarboxylic acid, 4,5-azulene dicarboxylic acid, (−)-1,3-acenaphthene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,5- Anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid, 2,3-anthracenedical Acid, 1,2-phenanthrene dicarboxylic acid, 4,5-phenanthrene dicarboxylic acid, aromatic dicarboxylic acid such as 3,9-perylene dicarboxylic acid, and aromatic dicarboxylic acid such as phthalic anhydride and 4-methylphthalic anhydride An anhydride is mentioned, These aromatic dicarboxylic acid and its anhydride etc. can be utilized.

 Furthermore, chlorendic anhydride, het anhydride, biphenyldicarboxylic anhydride, hymic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3 , 6-tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, octahydro- Acid anhydrides such as 1,3-dioxo-4,5-isobenzofurandicarboxylic acid anhydride can also be used as the polybasic acid.

 Reaction of an epoxy compound containing two or more epoxy groups in the molecule with a polybasic acid, a carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound is carried out by a known method, and epoxy acrylate An oligomer (M1) can be obtained. When a polybasic acid is not used, “the amount of carboxyl group of the carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound” and “epoxy compound epoxy compound containing two or more epoxy groups in the molecule” It is preferable to carry out the reaction so that the “base amount” is within the equimolar amount ± 10%. In addition, when using a polybasic acid, first, “the carboxyl group content of the carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound <the epoxy compound containing two or more epoxy groups in the molecule” The amount of carboxyl groups of the compound containing a carboxyl group-containing α, β-ethylenically unsaturated double bond group is equal to the amount of the remaining epoxy groups. It is preferable to carry out the reaction so that the molar amount is within ± 10%. In addition, an epoxy compound containing two or more epoxy groups in the molecule, a polybasic acid, a carboxyl group-containing α, β-ethylenically unsaturated diester All of the heavy bond group-containing compounds may be reacted together, but in this case, “the amount of carboxyl groups of the carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound + Carboxyl group amount of Motosan "and" epoxy group of the epoxy compound containing two or more epoxy groups in a molecule "it is preferably reacted such that the 10% equivalents mol amount ±. When the balance between the “carboxyl group amount” and the “epoxy group amount” in the entire reaction system exceeds the equimolar amount ± 10%, the carboxyl group or epoxy group remains in the active energy ray-polymerizable composition of the present invention and is being stored. This is not preferable because the storage stability deteriorates due to the progress of the reaction.

The polyester acrylate oligomer (M2) will be described. The polyester acrylate oligomer (M2) includes a polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol, a carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, a hydroxyl group-containing α, β-ethylene. An unsaturated double bond group-containing compound or an isocyanato group-containing α, β-ethylenically unsaturated double bond group-containing compound is reacted.
As said polybasic acid, what was mentioned above as a raw material of an epoxy acrylate oligomer (M1) can be used arbitrarily.

 Polyhydric alcohols include relatively low molecular weight polyols having a number average molecular weight (Mn) of about 50 to 500, but can be used without any particular limitation.

 More specific examples of relatively low molecular weight polyols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2, 4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (Addition mole number 10 or less), polyoxypropylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol 1,9-nonanediol, neopentyl glycol, Aliphatic or cycloaliphatic diols such as octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, dimer diol;

 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4, 4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4′-isopropylidenephenol, addition-type bisphenol obtained by adding alkylene oxide to bisphenol Aromatic diols and the like.

Examples of the raw material bisphenol of addition-type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide.

  In addition, a polyol containing three or more hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol may be used.

  Among the above polyhydric alcohols, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3 To branched alkanes such as' -dimethylol heptane, 2-butyl-2-ethyl-1,3-propanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, trimethylolpropane, pentaerythritol Those having two or more hydroxyl groups introduced are preferred in terms of the adhesion and heat resistance of the oligomer.

 First, the polyester acrylate oligomer (M2) is obtained by polycondensing a polybasic acid and a polyhydric alcohol by a known method. At this time, the molecular weight and the terminal functional group are adjusted by the balance between the amount of carboxyl groups contained in the polybasic acid and the amount of hydroxyl groups of the polyhydric alcohol.

 When “the amount of carboxyl groups contained in the polybasic acid> the amount of hydroxyl groups contained in the polyhydric alcohol”, the terminal functional group is a carboxyl group, and the hydroxyl-containing α, β-ethylenically unsaturated double bond group-containing compound The target polyester acrylate oligomer (M2) can be obtained by subjecting the hydroxyl group of the compound to a condensation reaction or an addition reaction of the epoxy group of the epoxy group-containing α, β-ethylenically unsaturated double bond group-containing compound. .

 Examples of the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ( 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (Meth) ethyl acrylate-α- (hydroxymethyl) Monofunctional (meth) acrylic acid glycerol, or (meth) acrylic acid glycidyl laurate, (meth) acrylic acid glycidyl oleate, (meth) acrylic acid glycidyl stearate, etc. Or a (meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, or the hydroxyl group-containing α, Hydroxyl group-containing aliphatic (meth) such as alkylene oxide-added (meth) acrylic acid ester obtained by repeatedly adding alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to β-ethylenically unsaturated double bond group-containing compound Acrylic acid Ethers, and the like.

 Further, when “the amount of carboxyl groups contained in the polybasic acid <the amount of hydroxyl groups contained in the polyhydric alcohol”, the terminal functional group is a hydroxyl group, and the carboxyl group-containing α, β-ethylenically unsaturated double bond group The target polyester acrylate oligomer (M2) is obtained by condensation reaction of the carboxyl group of the containing compound or addition reaction of the isocyanato group of the isocyanato group-containing α, β-ethylenically unsaturated double bond group-containing compound. be able to.

 Examples of the epoxy group-containing α, β-ethylenically unsaturated double bond group-containing compound include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,2-glycidoxyethyl (meth) acrylate, and 3,4- Examples thereof include epoxycyclohexyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 4,5-epoxypentyl (meth) acrylate.

 Examples of the isocyanato group-containing α, β-ethylenically unsaturated double bond group-containing compound include vinyl isocyanate, allyl isocyanate, isocyanate (meth) acryloyl, isocyanatoalkyl (meth) acrylate and the like.

  In addition, as a polyhydric alcohol, it is more preferable from points, such as adhesiveness and heat resistance, to use the polyhydric alcohol by which two or more hydroxyl groups were introduce | transduced into the branched alkane. Among the above exemplary compounds, for example, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3, 3'-dimethylol heptane, 2-butyl-2-ethyl-1,3-propanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, trimethylolpropane, pentaerythritol and the like can be mentioned.

 The weight average molecular weight (hereinafter referred to as Mw) of the epoxy acrylate oligomer (M1) and the polyester acrylate oligomer (M2) is compatible with the polymer coating film, good durability (heat resistance, heat and humidity resistance), and aggregation inside the cured film From the viewpoint of force, it is preferably in the range of 3000 to 100,000. Furthermore, the range where Mw is 3000-50000 is more preferable. When the Mw of the oligomer (D) exceeds 100,000, the fluidity decreases and the compatibility with the compounds other than the oligomer (M1) and (M2) also decreases. Therefore, when the active energy ray polymerizable composition is used. When workability is reduced, or when an active energy ray polymerizable adhesive is used, durability such as adhesion of the polymerized coating film may be decreased, or the coating film may be whitened. When Mw is less than 3000, the agglomeration force inside the cured film of the active energy ray-polymerizable adhesive layer may be lowered after the active energy ray-polymerizable adhesive is coated and laminated on various substrates.

 The active energy ray polymerizable composition of the present invention may further contain a urethane acrylate oligomer (M3). The urethane acrylate oligomer (M3) includes a urethane prepolymer obtained by at least polyaddition reaction of a polyhydric alcohol and a polyvalent isocyanate, a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound or an isocyanate group-containing α, A β-ethylenically unsaturated double bond group-containing compound is reacted.

 More specifically, after reacting with “the amount of hydroxyl group of polyhydric alcohol” <“isocyanato group contained in polyisocyanate” to obtain a urethane prepolymer of a terminal isocyanato group, a hydroxyl group-containing α, β-ethylenically unsaturated group is obtained. When it is obtained by reacting a compound containing a double bond group, and after reacting with “the amount of hydroxyl group of the polyhydric alcohol”> “isocyanato group contained in the polyvalent isocyanate” to form a urethane prepolymer of the terminal hydroxyl group, the isocyanate group containing In some cases, it is obtained by reacting an α, β-ethylenically unsaturated double bond group-containing compound.

 When passing through a urethane prepolymer having a terminal isocyanato group, a compound having two or more amino groups is reacted with an amount of amino group smaller than the amount of isocyanate group present in the urethane prepolymer having the terminal isocyanato group. The urethane acrylate oligomer (M3) includes a urea bond group obtained by reacting a hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound via a urethane urea prepolymer having a terminal isocyanato group. .

 Among the polyvalent isocyanates, the aromatic polyisocyanate is more specifically, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4, Examples thereof include 4′-diphenyl ether diisocyanate and 4,4 ′, 4 ″ -triphenylmethane triisocyanate.

Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

As alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Examples thereof include methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

In addition, 2-methylpentane-2,4-diol adduct of the above polyisocyanate, trimer having an isocyanurate ring, etc. can be used in combination. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, modified polyisocyanate thereof, and the like can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups.

More specifically, examples of the compound having two or more amino groups include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2 , 2,4-trimethylhexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2- Hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) diamine (Di-2-hydroxypropyl ethylene) diamine, aliphatic such as piperazine polyamine;
Cycloaliphatic polyamines such as isophoronediamine and dicyclohexylmethane-4,4′-diamine;
Phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-bis- ( Aromatic diamines such as sec-butyl) diphenylmethane can be used.

The Mw of the urethane acrylate oligomer (M3) needs to be in the range of 300 to 30,000 in terms of compatibility of the polymer coating film, good durability (heat resistance, heat and humidity resistance), and aggregation density. Furthermore, Mw is more preferably in the range of 400 to 20,000. If the Mw of the urethane acrylate oligomer (M3) exceeds 30,000, the fluidity decreases, and the compatibility with the components of the active energy ray-polymerizable composition other than the urethane acrylate oligomer (M3) also decreases. When the coating property of the energy ray polymerizable composition is reduced, or when the active energy ray polymerizable adhesive is used, the durability of the polymerized coating film is deteriorated, or the coating film is whitened. If the Mw of the urethane acrylate oligomer (M3) is less than 300, the active energy ray polymerizable adhesive layer may be coherently broken after being coated and laminated on various substrates. May be more likely to occur.

 In addition to the compound (C), the epoxy acrylate oligomer (M1), the polyester acrylate oligomer (M2), and the urethane acrylate oligomer (M3) described above, the active energy ray polymerizable composition of the present invention includes other α, β -There is no restriction | limiting in using an ethylenically unsaturated double bond group containing compound (m) (henceforth a compound (m)) as needed.

Examples of other α, β-ethylenically unsaturated double bond group-containing compound (m) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, (meth) 2-propyl acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate , (Meth) acrylic acid iso-amyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-octyl, (meth) acrylic acid iso-octyl, (meth) acrylic Acid n-nonyl, (meth) acrylic iso-nonyl, decyl (meth) acrylate, dodecyl (meth) acrylate, octa (meth) acrylate (Meth) acrylic acid alkyl esters such as decyl, lauryl (meth) acrylate, stearyl (meth) acrylate;

For example, cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, (meth ) 1-methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate , Benzyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-oxo-1,2-phenylethyl (meth) acrylate, 2-oxo- (meth) acrylate 1,2-diphenylethyl, (meth) acrylic acid (ethoxylated o-phenylphenol), ( T) 1-naphthyl acrylate, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, (meth) acrylic acid 9-anthryl, (meth) acrylic acid 9-anthrylmethyl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) One cycloalkane skeleton or cycloalkene skeleton such as acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, etc. Have an aromatic ring (Meth) acrylic acid esters having;

For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, (meth) acrylic acid 2-chloro-2-propenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid 2- (2-propenyloxy) ethyl, (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, It further contains unsaturated groups such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl acrylate, vinyl (meth) acrylate, and the like. Meth) acrylic acid esters;
For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic propenoic acid 2-perf Orodeshiruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

 For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxy (meth) acrylate Butyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy (meth) acrylate Octyl, cyclohexanedimethanol mono (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional ( (Meth) glycerol acrylate or (meta) Fatty acid ester-based (meth) acrylic acid esters such as glycidyl lauric acid acrylate, (meth) acrylic acid glycidyl oleate, (meth) acrylic acid glycidyl stearate, or the above-mentioned hydroxyl-containing α, β-ethylenic acid (Meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the saturated double bond group-containing compound or the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound Hydroxyl group-containing aliphatic (meth) acrylic acid esters such as alkylene oxide addition (meth) acrylic acid esters obtained by repeatedly adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc .;

 For example, repeated addition of hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, or alkylene oxide such as ethylene oxide or propylene oxide Hydroxyl group-containing aliphatic vinyl ethers such as alkylene oxide addition vinyl ethers having a hydroxyl group at the terminal end;

 For example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether , Hydroxyoctyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, or alkylene oxides such as ethylene oxide and propylene oxide Hydroxyl group-containing aliphatic (meth) allyl alcohols such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal of repeating addition of Or (meth) allyl ethers;

For example, α, β-ethylenically unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glycerol di (meth) acrylate;
For example, N-hydroxyethyl (meth) acrylamide [N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide are collectively referred to as “N-hydroxyethyl (meth) acrylamide”. The same applies below. ], Hydroxyl-containing (meth) acrylamides such as N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide;

  For example, monomers having a hydroxyl group and an ethenyl group such as vinyl alcohol

  For example, glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic Acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran-4- Yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2,2-dimethyl-5 -Oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydro Lan-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5, 5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3 , 3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, etc. Heterocycle-containing (meth) acrylic acid esters having an oxygen atom;

For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Meth) acrylic acid 2- (ethoxyca (Rubonyloxy) butyl, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, (meth) 2- (Butoxycarbonyloxy) ethyl acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, 2- (octyloxy) (meth) acrylate Aliphatic (meth) acrylic acid esters having one carbonyl group such as carbonyloxy) butyl;

For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylic acid 2-oxobutanoyloctyl, (meth) acrylic acid 2-oxobutanoyldecyl, (meth) acrylic acid 2-oxobutanoyldodecyl, (meth) acrylic acid 3-oxobutanoylethyl, ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylate (Meth) acrylic acid 4-cyanooxobutanoylethyl, (meth) acrylic acid 4-cyanooxobutanoylpropyl, (meth) acrylic acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoyl Ruhexyl, 4-cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, ( Aliphatic (meth) acrylic acid esters having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl (meth) acrylate and 2,3-di (oxobutanoyl) octyl (meth) acrylate Kind;

  For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrime Kishishiran, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

For example, sulfomethyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 2-sulfobutyl (meth) acrylate, (meth) 4-sulfobutyl acrylate, 2-sulfobutyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, sulfooctyl (meth) acrylate, sulfodecyl (meth) acrylate, sulfolauryl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters containing a sulfonyl group such as sulfostearyl acrylate;

For example, metal salts and ammonium of (meth) acrylic acid esters containing sulfonyl groups such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate salt;

For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, ( (Meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, phenyl-2- (meth) acryloyloxyethyl phosphate, (meth) acrylic acid Phosphonic acid group-containing (meth) acrylic acid esters such as acid phosphooxyethylene oxide (ethylene oxide addition moles: 4 to 10) and (meth) acrylic acid acid phosphooxypropylene oxide (propylene oxide addition moles: 4 to 10) Kind;

For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate Alkoxy group-containing (meth) acrylic acid esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

  For example, alkylene oxide-containing (meth) acrylic acid derivatives such as an alkylene oxide adduct of (meth) acrylic acid;

For example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di (Meth) acrylic acid dipropylene glycol, di (meth) acrylic acid tripropylene glycol, di (meth) acrylic acid polypropylene glycol, di (meth) acrylic acid 1,2-butanediol, di (meth) acrylic acid 1,2 -Pentanediol, di (meth) acrylic acid 2,2-dimethylpropyldiol, di (meth) acrylic acid hydroxypivalyl hydroxypivalate, di (meth) acrylic acid hydroxypivalyl hydroxypivalate dicaprolactonate, di ( Meta) acrylic acid 1 4-butanediol, 1,5-heptanediol di (meth) acrylic acid, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,2 di (meth) acrylic acid -Hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7-heptanediol, di (meth) acrylic acid 1 , 8-octanediol, di (meth) acrylic acid 1,2-octanediol, di (meth) acrylic acid 1,9-nonanediol di, di (meth) acrylic acid 1,2-decanediol, di (meth) 1,10-decanediol acrylate, 1,2-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, di ( T) 1,2-dodecanediol acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,2-tetradecanediol di (meth) acrylate, 1,16-hexadecanediol di (meth) acrylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, di (meth) acrylate ) 2-methyl-2-propyl-1,3-propanediol acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1 di (meth) acrylate , 3-propanediol, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate 2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl-1,8 di (meth) acrylate -Octanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di (meth) acrylic acid 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3-di (meth) acrylate Propanediol, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexane di (meth) acrylate Sundiol, di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, di (meth) acrylic acid 2-butyl-2-ethyl-1,3-propanediol, di (meth) acrylic acid 2 , 4-diethyl-1,5-pentanediol, di (meth) acrylic acid 1,1,1-trishydroxymethylethane, di (meth) acrylic acid ethylene oxide modified isocyanuric acid and other bifunctional (meth) acrylic acid esters Kind;

For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, Tri (meth) acrylate pentaerythritol, tri (meth) acrylate ethylene oxide modified isocyanate Trifunctional (meth) acrylic acid esters such as null acid;

For example, tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, tetra ( (Meth) acrylic acid di-2,2-dimethylpropane-1,3- All, tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethyloloctane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol , Hepta (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meta ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate Polyfunctional (meth) acrylic acid esters such as real sharp emission oxide;
For example, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acid, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, palmitoyl vinyl valerate, stearoyl valerate, pyrvoyl Vinyl Rerin acid, 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, aliphatic vinyl compounds of having an acyl group such as 2-acetoacetoxyethyl octyl vinyl ether;
For example, ethyl vinyl ether, 1-propyl vinyl ether, 2-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, n-amyl vinyl ether, n-hexyl, 2-ethylhexyl vinyl ether, n -Aliphatic vinyl ethers such as octyl vinyl ether, iso-octyl vinyl ether, n-nonyl vinyl ether, iso-nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether;

For example, fluorine-containing ethenyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;
For example, (meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxy Alkoxysilyl group-containing α, β-unsaturated double bond group-containing compounds such as vinylsilane and vinyltris (2-methoxyethoxy) silane;

For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;
For example, metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
Metal salts and ammonium salts of 2-methyl-2-propenylsulfonic acid such as ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, and potassium 2-methyl-2-propenylsulfonate;

  For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleami , Fumaramide, mesaconamide, citraconic amide, itaconic amide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N Aliphatic (meth) acrylamides such as' -dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethanamide, N-vinylacetamide;

For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- 2-methoxyethyl (meth) acrylamide, N- (oxetane-2-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N, N-di (methoxymethyl) (Meth) acrylamides containing N-alkoxy groups such as (meth) acrylamide and N, N-di (ethoxymethyl) (meth) acrylamide;

  Heterocycle-containing (meth) acrylamides such as (meth) acryloylmorpholine;

  For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( (Meth) acrylamides having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;
For example, nitrile group-containing α, such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itacononitrile, 2-propenenitrile, 2-methacrylic acid (meth) acrylate, etc. β-unsaturated double bond group-containing compounds;

For example, saturated carboxylic acids such as (meth) allyl acetate, (meth) allyl propionate, (meth) allyl butyrate, (meth) allyl caprate, (meth) allyl laurate, allyl octylate, coconut oil fatty acid, vinyl pivalate, etc. (Meth) allyl esters of acids;
For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxirane;

For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovaleric acid (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2- Ethylhexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Stearoyl acetate (meth) allyl, (meth) allyl Aliphatic (meth) allyl compounds having an acyl group such as hydrin;

For example, vinyl esters such as vinyl chloride, vinylidene chloride and allyl chloride;
For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;
For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Α, β-unsaturated double bond group-containing compounds containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

  For example, ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as polybutene-1, polypentene-1, poly-4-methylpentene-1, and the like. In particular, it is not limited to these. These may use only 1 type or may use multiple types together.

The above-mentioned other α, β-ethylenically unsaturated double bond group-containing compound (m) is preferably a compound having a (meth) acryloyl group from the viewpoint of reactivity, and further active as an active energy ray polymerizable composition. From the viewpoint of the energy ray polymerization rate, it is preferable to contain bifunctional or higher (meth) acrylic acid esters.
In addition, as other α, β-ethylenically unsaturated double bond group-containing compound (m), from the viewpoint of adhesion to a hydrophilic substrate, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2 to 18 carbon atoms such as 2-hydroxypropyl, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 1 to 2 mol of ε-caprolactone and 2-hydroxyethyl (meth) acrylate It is preferable to use a certain α, β-ethylenically unsaturated double bond group-containing compound.

Furthermore, as other α, β-ethylenically unsaturated double bond group-containing compound (m), glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, (meth) acrylic acid (3- A heterocycle-containing (meth) acrylic acid ester having a 3-membered or 4-membered ring oxygen atom, such as methyl-3-oxetanyl) methyl, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, and the like. If necessary, known photoacid generators such as sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), WPI-113 (Japanese) Iodonium salt such as Rp-2074 (manufactured by Rhodia Japan), etc. It is preferable to use those exemplified in the above in order to form a coat layer and an adhesive layer that are excellent in durability against heat and humidity due to progress of crosslinking.

  In the present invention, the notation with (meth) acryl indicates methacryl or acryl, the notation with (meth) acrylate indicates methacrylate or acrylate, and the notation with (meth) allyl indicates methallyl or allyl. The notation with (meth) acryloyl indicates methacryloyl or acryloyl, and the notation with (meth) acryloxy indicates methacryloxy or acryloxy.

 As a preferred ratio of the components constituting the active energy ray polymerizable composition of the present invention, when the total amount of the active energy ray polymerizable composition is 100% by weight, the compound (C) is 5 to 60% by weight, epoxy acrylate The total amount of the oligomer (M1) and the polyester acrylate oligomer (M2) is 5 to 90% by weight, the urethane acrylate oligomer (M3) is 0 to 30% by weight, and contains other α, β-ethylenically unsaturated double bond groups. The compound (m) is preferably 0 to 70% by weight.

 The active energy ray polymerizable composition of the present invention may further contain an active energy ray polymerization initiator (E). The active energy ray polymerization initiator (E) can be arbitrarily selected from known ones, and specific examples thereof include, for example, 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthofluorenone, Benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4-oxanthone, camphorquinone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one etc. It is. Commercially available products include, for example, Irgacure 184,907,651,1700,1800,819,369,261, DAROCUR-TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF), Darocur- 1173 (manufactured by Merck), Ezacure KIP150, TZT (manufactured by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.) and the like.

 An active energy ray polymerization initiator having at least one (meth) acryloyl group in the molecule can also be used. These active energy ray polymerization initiators (E) can be used alone or as a mixture of two or more.

 The blending ratio of the active energy ray polymerization initiator (E) is reactive (compound (C), epoxy acrylate oligomer (M1), polyester acrylate oligomer (M2), urethane acrylate oligomer (M3), etc.) It is preferable to contain 0.01 to 20 parts by weight of the active energy ray polymerization initiator (E) with respect to a total of 100 parts by weight of the α, β-ethylenically unsaturated double bond group-containing compound (m). Preferably it is 0.1-10 weight part.

 The active energy ray-polymerizable composition of the present invention preferably contains substantially no water or organic solvent in terms of drying equipment and drying energy. However, when the active energy ray polymerization initiator (E) becomes hardly soluble or the active energy ray polymerization composition becomes highly viscous, a small amount of the active energy ray polymerization initiator (E) is dissolved. Water or organic solvents may be included. The content of water or organic solvent in the active energy ray polymerizable composition is within 5% by weight. The organic solvent that can be used is not particularly limited, but specifically, methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene and other hydrocarbons An organic solvent such as a system solvent or water can be further added to adjust the viscosity of the active energy ray polymerizable composition, or the active energy ray polymerizable composition can be heated to lower the viscosity. .

  Furthermore, in order to improve the performance of the active energy ray polymerization initiator (E), an active energy ray sensitizer may be used in combination. Examples of active energy ray sensitizers include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds. Anthracene, benzophenone, thioxanthone, perylene, phenothiazine, rose bengal and the like are preferably used.

 In the active energy ray polymerizable composition of the present invention, additives other than the above-described components can be appropriately blended as long as the effects of the present invention are not impaired. For example, blending organic or inorganic fillers from the viewpoints of polymerization cure shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, coloring improvement, etc. it can. As such a filler, polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, and the like can be used, and the shape is not particularly limited, such as particles and fibers. In addition, when blending the above polymers, flexibility imparting agents, plasticizers, flame retardants, storage stabilizers, antioxidants, ultraviolet absorbers, thixotropy imparting agents, dispersion stabilizers, fluidity imparting agents, dissipators. It is also possible to dissolve, semi-dissolve or micro-disperse in the active energy ray-polymerizable composition as a polymer blend or a polymer alloy, not as a filler, such as a foaming agent.

The active energy ray-polymerizable composition of the present invention can be used in any form of liquid, paste, and film, but is preferably liquid from the viewpoint of ease of use.
In the active energy ray polymerizable composition in the present invention, it is important that the viscosity of the active energy ray polymerizable composition layer is 1 to 1500 mPa · s when the film thickness of the active energy ray polymerizable composition layer is 0.1 to 6 μm depending on the intended use. Preferably 10 to 1300 mPa · s, more preferably 20 to 1000 mPa · s. When the viscosity is higher than 1500 mPa · s, when the base material (F) is coated, a thin film coating of 0.1 to 6 μm cannot be performed, and optical characteristics such as transmittance are deteriorated. On the other hand, when the viscosity is lower than 1 mPa · s, it becomes difficult to control the film thickness of the active energy ray polymerizable composition layer.

 In addition, when the film thickness of the active energy ray polymerizable composition layer is 6 to 300 μm depending on the intended use, it is important that the viscosity is 1500 to 100,000 mPa · s, preferably 3,000 to 50. More preferably, it is 1,000 mPa · s.

Next, the coating process of the active energy ray polymerizable composition will be described.
A compound having an α, β-unsaturated bond group by applying an active energy ray-polymerizable composition to one or both sides of a substrate according to a conventional method and irradiating the coating layer with active energy rays. Can be cured by active energy ray polymerization to obtain a cured layer of the active energy ray polymerizable composition. In this case, the active energy ray polymerizable composition of the present invention serves as a coating layer for the substrate.
In addition, an active energy ray polymerizable composition is applied to one side or both sides of a base material by an appropriate method according to a conventional method, and another base material is laminated on the surface of the active energy ray polymerizable composition. A laminated body can also be formed by irradiating the coating layer with active energy rays. Irradiation with active energy rays may be before or after lamination. In this case, the active energy ray polymerizable composition of the present invention serves as an adhesive layer of the substrate.
When the required film thickness of the active energy ray polymerizable composition layer is 0.1 to 6 μm depending on the intended use, the thickness of the active energy ray polymerizable composition layer is 0.1 to 6 μm thin film coating. It is preferable that it is 0.1 μm to 3 μm. When the thickness is less than 0.1 μm, sufficient adhesion and adhesive strength may not be obtained. When the thickness exceeds 3 μm, characteristics such as adhesion and adhesion are often not improved further.

On the other hand, when the required film thickness of the active energy ray polymerizable composition layer is 6 to 300 μm depending on the intended use, the thickness of the active energy ray polymerizable composition layer is 6 to 300 μm thick coating. It is preferably 20 μm to 250 μm. When the thickness is less than 6 μm, sufficient stress relaxation properties may not be obtained. When the thickness exceeds 300 μm, coating properties such as streaking often decrease.
The method for applying the active energy ray polymerizable composition of the present invention to a substrate or the like is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, micro gravure coater, lip coater. Various coating methods such as a comma coater, a curtain coater, a knife coater, a reverse coater, and a spin coater can be used, but they can be used depending on applications such as thin film coating and thick film coating, and are not particularly limited.

 The active energy ray irradiation light source that can be used for curing the active energy ray polymerizable composition of the present invention is mainly composed of light in the wavelength range of 150 to 550 nm, and includes a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, High pressure mercury lamps, chemical lamps, black light lamps, microwave excitation mercury lamps, LED lamps, xenon lamps, metal halide lamps, and the like are suitable. In addition, laser beams, electron beams, and the like can also be used as active energy rays for exposure.

The irradiation intensity of the active energy ray is preferably 10 to 500 mW / cm ² . If the light irradiation intensity is less than 10 mW / cm ² , a long time is required for curing, and if it exceeds 500 mW / cm ² , the substrate may be deteriorated in various substrates (F) due to the heat radiated from the lamp. This is not preferable because of its properties. The integrated dose expressed as the product of irradiation intensity and irradiation time is preferably 50 to 5,000 mJ / cm ² . When the integrated irradiation amount is less than 50 mJ / cm ² , it takes a long time for polymerization and curing, and when it is larger than 5,000 mJ / cm ² , the irradiation time becomes very long and the productivity is inferior.

Next, the base material (F) will be described.
When the active energy ray polymerizable composition of the present invention is used, the substrate (F) can be used without particular limitation, such as a film-like substrate, a glass plate, and a processed paper product. On the other hand, when using as an adhesive to bond two or more base materials (F), it is necessary to use a base material that easily transmits active energy rays in order to polymerize by irradiation with active energy rays. In particular, it is preferable to use a transparent film or a transparent glass plate. Even when using a base material that does not easily transmit active energy rays on one side, such as wood, metal plates, plastic plates, and paper products, the other side uses a transparent film or transparent glass plate. It can be used if it is irradiated from the plate side and polymerized and cured.

 The active energy ray polymerizable composition of the present invention preferably uses a film-like substrate among the substrates (F), and the film-like substrate may be a film-like substrate such as cellophane, various plastic films or paper. Although materials are mentioned, it is preferable to use various transparent plastic films. Moreover, as a film-form base material, as long as it is transparent, a single-layer thing may be used, and the thing in the multilayer state formed by laminating | stacking a several base material can also be used.

 Here, the laminated body characterized by laminating | stacking on the single side | surface or both surfaces of a base material (F) using an active energy ray polymeric composition is demonstrated generally.

When using the polymerization reaction by the active energy ray of the active energy ray polymerizable composition of the present invention, that is, among the above-mentioned base material (F), at least one of the transparent film which is a film-like base material and the transparent film It is preferably used for the formation of a laminate comprising an active energy ray-polymerizable composition layer positioned on the surface.
The laminate of the transparent film of the present invention can be obtained as follows using the active energy ray polymerizable composition of the present invention as an active energy ray polymerizable adhesive.

 The adhesive of the present invention is applied to one side of a transparent film that is a film-like substrate, and another transparent film is laminated on the surface of the adhesive layer, or an adhesive is applied to one or both sides of this laminate. Furthermore, a laminated body can be obtained by laminating on another transparent film, glass, or transparent molded body.

 The active energy ray polymerization reaction of the adhesive proceeds at the time of coating or laminating the adhesive, and further by irradiating the active energy ray after laminating. It is preferable to proceed.

The transparent film of the present invention will be described.
The transparent film of this invention can be used for optical films, such as information communication apparatuses, such as a display and a touch panel.

Here, a general description of the optical element laminate will be given.
The basic laminate structure of the optical laminate is a sheet-like laminate such as transparent film / adhesive layer / transparent film or transparent film / adhesive layer / transparent film / adhesive layer / transparent film. Furthermore, a multilayer for optical elements in which a multilayer optical film such as transparent film / adhesive layer / transparent film / adhesive layer / transparent film / adhesive layer / (transparent film or glass, or optical molded body) is fixed to an optical member. Used as a body.

 As the transparent film used as the optical film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is used. Various transparent films are also referred to as various plastic films and plastic sheets. For example, polyvinyl alcohol films, polytriacetyl cellulose films, polypropylene, polyethylene, polycycloolefin, polyolefin-based films such as ethylene-vinyl acetate copolymer, polyethylene Polyester film such as terephthalate and polybutylene terephthalate, polycarbonate film, polynorbornene film, polyarylate film, polyacrylic film, polyphenylene sulfide film, polystyrene film, polyvinyl film, polyamide film, polyimide film And polyoxirane films.

The transparent film of the present invention may have the same composition or different when used in multiple layers. For example, a polycycloolefin film may be used on one side, and a polyacrylic film may be used on the other side.
Although the thickness of a transparent film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin layer property. 1-300 micrometers is especially preferable, and 5-150 micrometers is more preferable.

 In addition, when providing a transparent film on the both sides of the polarizer of the polarizing film which is an optical film, you may use the transparent film which consists of the same polymer material by the front and back, and uses the transparent film (H) which consists of a different polymer material etc. May be.

Next, the optical film will be described.
As the laminate for an optical element in the present invention, among the above-mentioned various transparent films, an optical film mainly used for optical applications is preferably used. As the optical film, the transparent film is subjected to a special treatment, and an optical film having optical functions (various functions such as light transmission, light diffusion, light collection, refraction, scattering, and HAZE) is an optical film. It is called. These optical films are used alone or as a laminate for optical elements by laminating several kinds of optical films in multiple layers with a coating agent or an adhesive. For example, hard coat film, antistatic coat film, antiglare coat film, polarizing film, retardation film, elliptically polarizing film, antireflection film, light diffusion film, brightness enhancement film, prism film (also called prism sheet), light guide Examples thereof include a film (also referred to as a light guide plate).

 A polarizing film is also called a polarizing plate, and a polytriacetylcellulose-based protective film (hereinafter referred to as “TAC film”), which is a polyacetylcellulose-based film on both sides of a polyvinyl alcohol-based polarizer, or a polyvinyl alcohol-based polarized light. It is a multilayered sheet-like laminate for optical elements in which one or both sides of the element are laminated with an adhesive such as polycycloolefin film, polyacrylic film, polycarbonate film, polyester film, which is a polynorbornene film. Yes, the active energy ray polymerizable adhesive of the present invention can be suitably used as the adhesive.

 The optical film laminate using the active energy ray-polymerizable adhesive of the present invention is attached to a glass plate such as a liquid crystal display device, a PDP module, a touch panel module, or an organic EL module, or a transparent film such as the above-described various plastic films. Thus, it is preferably used as a laminate for optical elements.

 More specifically, the polarizing plate (polarizing film) using the active energy ray-polymerizable adhesive can be obtained as follows.

(I) An active energy ray-polymerizable adhesive is applied to one surface of the protective film, which is the first transparent film, to form a first polymerizable adhesive layer (2 ′),
Applying an active energy ray-polymerizable adhesive on one surface of the second protective film, which is a transparent film, to form a second active energy ray-polymerizable adhesive layer,

   Next, the first active energy ray-polymerizable adhesive layer and the second active energy ray-polymerizable adhesive layer surface are simultaneously and / or sequentially superimposed on each surface of the polyvinyl alcohol-based polarizer, and then irradiated with active energy rays. And a method of producing the first active energy ray-polymerizable adhesive layer and the second active energy ray-polymerizable adhesive layer by polymerizing and curing.

 (II) An active energy ray-polymerizable adhesive is applied to one surface of a polyvinyl alcohol polarizer to form a first active energy ray-polymerizable adhesive layer. The surface of the adhesive layer is covered with a first protective film, which is a transparent film, and then an active energy ray-polymerizable adhesive is applied to the other surface of the polyvinyl alcohol polarizer, so that the second active energy ray-polymerizable property is obtained. An adhesive layer is formed, the surface of the formed second active energy ray polymerizable adhesive layer is covered with a second protective film, irradiated with active energy rays, and the first active energy ray polymerizable adhesive layer and the second A method for producing an active energy ray-polymerizable adhesive layer by polymerizing and curing.

 (III) The edge part of the 2nd protective film piled up on the surface which did not have the 1st protective film of the polyvinyl alcohol type polarizer, and the edge part which piled up the protective film and polyvinyl alcohol type polarizer which are the 1st transparent films After the active energy ray-polymerizable adhesive is put on, it is passed between rolls to spread the adhesive between the layers. Next, there is a method of producing by irradiating active energy rays and polymerizing and curing the active energy ray polymerizable adhesive, but it is not particularly limited.

Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. In the present specification, Examples 1 to 6 and 11 to 16 are reference examples.
The “weight average molecular weight” is a value measured using gel permeation chromatography “HLC-8220GPC” manufactured by Tosoh Corporation. Separation columns: “TSK-GEL SUPER H5000” and “TSK” manufactured by Tosoh Corporation. -GEL SUPER H4000 "," TSK-GEL SUPER H3000 ", and" TSK-GEL SUPER H2000 "are connected in series and measured at a flow rate of 0.6 ml / min using tetrahydrofuran at a temperature of 40 ° C as the mobile phase. The weight average molecular weight in terms of polystyrene.
Moreover, the acid value said by this invention was measured as follows. About 1 g of sample in a stoppered Erlenmeyer flask
Weighed precisely and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

Moreover, the hydroxyl value said by this invention was measured as follows. About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red. As the value of the resin in the dry state, the hydroxyl value (mgKOH / g) was determined by the following formula.
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Non-volatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

<Synthesis example of epoxy acrylate oligomer (M1-1)>
In a 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 96.9 parts of bisphenol F type epoxy resin (Mitsubishi Chemical Corporation: JER1007P, epoxy equivalent 2250) and acrylic acid 3.2 parts, 0.1 part of hydroquinone monomethyl ether and 20 parts of MEK were charged and heated to 60 ° C. and dissolved while introducing dry air. To this, 0.5 part of tetrabutylammonium borate was added, the temperature was raised to 100 ° C., and the mixture was reacted for 8 hours to obtain an oligomer (M1-1). The weight average molecular weight of the oligomer (M1-1) was 5100.

<Synthesis example of epoxy acrylate oligomer (M1-2)>
In a 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 56.2 parts 1,6-hexanediol diglycidyl ether and 36.8 parts azelaic acid (polybasic acid) Then, 20 parts of MEK was charged and dissolved by heating to 60 ° C. while introducing dry air. To this, 0.5 part of tetrabutylammonium borate was added, and the temperature was raised to 100 ° C. and reacted for 5 hours. The acid value at this time was 0.2 mgKOH / g. 7.0 parts of acrylic acid was further added thereto, and the mixture was further reacted at 100 ° C. for 10 hours to obtain an oligomer (M1-2). The weight average molecular weight of the oligomer (M1-2) was 3200.

<Synthesis example of polyester acrylate oligomer (M2-1)>
In a 5-neck separable flask equipped with a stirrer, a distillation tube, a gas introduction tube, and a thermometer, 503 parts of adipic acid, 497 parts of 2-butyl-2-ethyl-1,3-propanediol, and 0.04 of zinc oxide Esterification was carried out while distilling condensed water at a temperature of about 210 ° C. while passing dry air through the part under normal pressure to obtain polyester dicarboxylic acid having an acid value of 43 mgKOH / g. Next, 15.5 parts of 4-hydroxybutyl acrylate glycidyl ether, 0.5 part of tetrabutylammonium borate and 0.1 part of hydroquinone monomethyl ether are added to 100 parts of this polyester dicarboxylic acid, and the acid value becomes 1 mgKOH / g or less. The polyester acrylate oligomer (M2-1) was obtained by carrying out addition reaction at 100 ° C. The weight average molecular weight of the oligomer (M2-1) was 5800.

<Synthesis example of polyester acrylate oligomer (M2-2)>
In a 5-neck separable flask equipped with a stirrer, a distillation tube, a gas introduction tube, and a thermometer, 497 parts of adipic acid, 503 parts of 3-methyl-1,5-pentanediol, and 0.04 part of zinc oxide are subjected to normal pressure. Esterification was performed while distilling condensed water at a temperature of about 210 ° C. while passing nitrogen gas. When the acid value of the polyester was 0.3 or less, a vacuum pump was connected to gradually raise the degree of vacuum and the reaction was completed to obtain a polyester polyol having a hydroxyl value of 28 mgKOH / g. Next, 3.6 parts of acrylic acid and 0.1 part of hydroquinone monomethyl ether were added to 100 parts of this polyester polyol and esterified at 180 ° C. to obtain a polyester acrylate oligomer (M2-2). The weight average molecular weight of the oligomer (M2-2) was 7100.

<Synthesis example of polyester acrylate oligomer (M2-3)>
In a 5-neck separable flask equipped with a stirrer, a distillation tube, a gas introduction tube, and a thermometer, 78 parts of terephthalic acid, 252 parts of isophthalic acid, 338 parts of azelaic acid, 146 parts of neopentyl glycol, 186 parts of ethylene glycol, zinc oxide 0.04 part was charged, and esterification was performed while distilling condensed water at a temperature of about 210 ° C. while passing nitrogen gas under normal pressure. When the acid value became 15 or less, a vacuum pump was connected to gradually raise the degree of vacuum and the reaction was completed to obtain a polyester polyol having a hydroxyl value of 13 mgKOH / g. 100 parts of this polyester polyol is dissolved in 70 parts of ethyl acetate, then 3.6 parts of 2-isocyanatoethyl methacrylate, 0.05 part of dibutyltin dilaurate and 0.1 part of hydroquinone monomethyl ether are added, A time reaction was performed to obtain a polyester acrylate oligomer (M2-3). The weight average molecular weight of the oligomer (M2-3) was 15900.

<Synthesis example of polyester acrylate oligomer (M2-4)>
In a 5-neck separable flask equipped with a stirrer, a distillation tube, a gas introduction tube, and a thermometer, 497 parts of adipic acid, 503 parts of 1,6-hexanediol and 0.04 part of zinc oxide were passed through nitrogen gas under normal pressure. Esterification was performed while distilling condensed water at a temperature of about 210 ° C. When the acid value of the polyester was 0.3 or less, a vacuum pump was connected to gradually raise the degree of vacuum and the reaction was completed to obtain a polyester polyol having a hydroxyl value of 28 mgKOH / g. Next, 3.6 parts of acrylic acid and 0.1 part of hydroquinone monomethyl ether were added to 100 parts of this polyester polyol and esterified at 180 ° C. to obtain a polyester acrylate oligomer (M2-4). The weight average molecular weight of the oligomer (M2-2) was 7300.

<Synthesis example of polyurethane acrylate oligomer (M3-1)>
44. Polypropylene glycol (manufactured by Sanyo Chemical Co., Ltd .: PP-4000, hydroxyl value 28 mgKOH / g) is added to a 5-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel. 4 parts and 3.29 parts of isophorone diisocyanate were charged, and the temperature was raised to 60 ° C. while introducing dry air. To this, 0.04 part of dibutyltin dilaurate was added and allowed to react for 1 hour. Methanol 0.03 part was added, and also it stirred at 45-55 degreeC for 40 minutes. Subsequently, 0.76 part of 2-hydroxyethyl acrylate was added and stirred at 55 to 70 ° C. for 90 minutes. The infrared absorption spectrum confirmed that there was no absorption peak of the isocyanato group, and the reaction was terminated to obtain a polyurethane acrylate oligomer (M3-1). The weight average molecular weight of the product was 20000.

[Examples 1-9, Comparative Examples 1-5]
Charged into a light-shielded 300 ml mayonnaise bottle substituted with an oxygen concentration of 10% or less at the ratio (parts by weight) shown in Table 1, thoroughly stirred with a disper, fully defoamed, and then activated Each energy beam polymerizable composition was obtained. Using this active energy ray polymerizable composition as a coating agent, laminates were prepared and evaluated by the following methods.

<Example of production of laminate A>
Using the active energy ray-polymerizable composition blended in the ratio of Table 1 as a coating agent, the energy ray-curable composition was applied to both sides of a polyvinyl alcohol (PVA) polarizer so as to have a thickness of 20 μm, and the active energy was applied. A layered product A composed of a coat layer / PVA polarizer / coat layer is obtained by irradiating ultraviolet rays having a maximum illuminance of 300 mW / cm ² and an integrated light quantity of 300 mJ / cm ^{2 with} a line irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation). The method was evaluated.

<Adhesion>
After the obtained laminate A was bonded to glass through an adhesive, 25 square 2 mm squares were cut with a cutter knife on the surface of the coating layer, and an adhesive tape (manufactured by Nichiban: Cellophane tape) was applied thereto. Then, the test of peeling was performed, and the number of the grids remaining without being peeled out of the 25 grids was counted and evaluated in three stages.
Number of remaining grids 21 to 25: ○
The number of remaining grids is 11-20:
Number of remaining grids 0-10: × (no practicality)

<Moisture-resistant light transmittance>
The obtained laminate A was exposed for 200 hours under conditions of a temperature of 60 ° C. and a humidity of 90%. The light transmittance before and after the exposure test was evaluated in three stages by measuring the average transmittance in a wavelength range of 400 to 700 nm with a spectrophotometer.
Increase rate of light transmittance after exposure test to less than 5% before exposure test: ○
Increase rate of light transmittance after exposure test with respect to before exposure test is 5% or more and less than 10%: Δ
Increase ratio of light transmittance after exposure test to 10% or more after exposure test: x (no practicality)

なお、表１中の略称は以下の通りである。
水添ＢｉｓＡＥＯＤＡ：水添ビスフェノールＡのエチレンオキサイド変性ジアクリレート
ＤＣＰＡ：ジシクロペンタニルアクリレート
ＩＢＸＡ:ノルボルニルアクリレート
ＤＣＰＤＭＤＡ：トリシクロデカンジメタノールジアクリレート
３Ｈ１ＡＤＭＡ：３-ヒドロキシ-1-アダマンチルアクリレート
ＨＥＡ：アクリル酸２−ヒドロキシエチル
４ＨＢＡ：アクリル酸４−ヒドロキシブチル
ＢｚＡ：ベンジルアクリレート
ＶＥＥＡ：２−（２−ビニロキシエトキシ）エチルアクリレート
ＢＤＤＡ：１，４−ブタンジオールジアクリレート
ＩＮＡＴＡ：イソシアヌル酸ＥＯ変性トリアクリレート（東亞合成化学社製：アロニックスＭ−３１５）
ＧＭＡ：メタクリル酸グリシジル
ＴＰＯ：２，４，６−トリメチルベンゾイル-ジフェニル-フォスフィンオキサイト゛
ＣＰＩ−１１０Ｐ：サンアプロ社製 トリアリールスルホニウム塩タイプの光酸発生剤

Abbreviations in Table 1 are as follows.
Hydrogenated BisAEODA: Hydrogenated Bisphenol A ethylene oxide-modified diacrylate DCPA: Dicyclopentanyl acrylate IBXA: Norbornyl acrylate DCPDMDA: Tricyclodecane dimethanol diacrylate 3H1ADMA: 3-hydroxy-1-adamantyl acrylate HEA: Acrylic acid 2-hydroxyethyl 4HBA: 4-hydroxybutyl acrylate BzA: benzyl acrylate VEEA: 2- (2-vinyloxyethoxy) ethyl acrylate BDDA: 1,4-butanediol diacrylate IINA: isocyanuric acid EO-modified triacrylate (Toagosei Co., Ltd.) Chemical Company: Aronix M-315)
GMA: glycidyl methacrylate TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide CPI-110P: photoacid generator of triarylsulfonium salt type manufactured by San Apro

As shown in Table 1, when the active energy ray polymerizable composition of the present invention is used as a coating agent, as shown in Examples 1 to 10 of Table 1, it has good adhesion and moisture-light transmittance. Suitable for practical use. On the other hand, in Comparative Examples 1 to 7, since the compound (C), the oligomer (M1) or the oligomer (M2) essential for the present invention is not contained at the same time, either or both of the adhesion and the moisture-resistant light transmittance are bad.

[Examples 11 to 22, Comparative Examples 8 to 16]
A light-shielded 300 ml mayonnaise bottle substituted with an oxygen concentration of 10% or less was charged at the ratios (parts by weight) shown in Tables 2 and 3 and sufficiently stirred with a disper to sufficiently degas. Thereafter, an active energy ray polymerizable composition was obtained. Using this active energy ray polymerizable composition as an adhesive, a laminate was prepared and evaluated by the following method.

<Example of production of laminate B>
As the transparent film (1) and transparent film (2), ZF: ZF-14 manufactured by Nippon Zeon Co., Ltd. Polynorbornene-based film (100 μm) containing no UV absorber, HBD: HBD-002 UV absorber manufactured by Mitsubishi Rayon Co., Ltd. Polyacrylic film (50 μm) that does not contain TAC: TAC50μ manufactured by Fuji Film Business Supply Co., Ltd. Polytriacetylcellulose-based film (thickness 50 μm) that does not contain an ultraviolet absorber is used, and 300 W · min / m ^{2 on} the surface thereof. The corona treatment is performed with the discharge amount, and within 1 hour after the surface treatment, the active energy ray-polymerizable adhesive shown in Tables 1 and 2 is applied to a film thickness of 4 μm using a wire bar coater, and the active energy A linear polymerizable adhesive layer is formed, and between the active energy ray polymerizable adhesive layer Sandwiching the polyvinyl alcohol-based polarizer, to obtain a transparent film (1) / adhesive layer / PVA-based polarizer / adhesive layer / made of transparent film (2) laminate.

Four sides were fixed with a cellophane tape so that the transparent film (1) of this laminate was in contact with the tin plate, and was fixed to the tin plate. A laminated body B (polarizing plate) was prepared by irradiating ultraviolet rays having a maximum illuminance of 300 mW / cm ² and an integrated light amount of 300 mJ / cm ² from the transparent film (2) side with an active energy ray irradiation device (high pressure mercury lamp manufactured by Toshiba Corporation). .

 With respect to the obtained laminate B, peel strength, punching workability, heat resistance, and moist heat resistance were determined according to the following methods, and the results are similarly shown in Tables 2 and 3.

<Peel strength>
The adhesive strength was measured in accordance with JIS K6 854-4 Adhesive-Peel Adhesion Strength Test Method-Part 4: Floating Roller Method.
That is, the obtained laminate B was cut into a size of 25 mm × 150 mm using a cutter to obtain a measurement sample. The sample was stuck on a metal plate using a double-sided adhesive tape (DF8712S manufactured by Toyochem Co., Ltd.) using a laminator to obtain a measurement laminate. The measurement laminate was previously provided with a peeling peel between the transparent film and the polarizer, and the measurement laminate was 90 ° C. at a speed of 300 mm / min at 23 ° C. and a relative humidity of 50%. The film was peeled off at an angle of ° to obtain a peeling force. Under the present circumstances, the peeling force of both a polyvinyl alcohol-type polarizer and a transparent film (1) and a polyvinyl alcohol-type polarizer and a transparent film (2) was measured. This peeling force was evaluated as an adhesive force in four stages.
○: Peeling is impossible, or the polarizing plate is broken, or the peeling force is 2.0 (N / 25 mm) or more. Δ: The peeling force is 1.0 (N / 25 mm) or more and less than 2.0 (N / 25 mm). Is less than 1.0 (N / 25mm) (no practicality)

<Punching workability>
About the obtained laminated body B, it punched from the transparent film (1) side of the laminated body B using the 100 mm x 100 mm blade made from a dumbbell company.
The peripheral peeling distance of the punched polarizing plate was measured with a ruler and evaluated according to the following four levels.
○: Less than 3 mm ×: 3 mm or more (no practicality)

<Heat resistance>
The laminate A bonded with each adhesive was cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the condition of 80 ° C.-dry. After exposure, the presence or absence of peeling at the end of the polarizing plate was visually evaluated in the following three stages.
○: No peeling at 80 ° C.-dry condition Δ: Peeling of less than 1 mm under 80 ° C.-dry condition X: Peeling of 1 mm or more under 80 ° C.-dry condition (no practicality)

<Heat and heat resistance>
The laminate A bonded with each adhesive was cut into a size of 50 mm × 40 mm and exposed for 1000 hours under the condition of a temperature of 60 ° C. and a humidity of 90%. After exposure, the presence or absence of peeling at the end of the laminate A was visually evaluated in the following three stages. ○: No peeling at 60 ° C.-90% RH Δ: 60 ° C.-90% RH Exfoliation of less than 1 mm under conditions x: Exfoliation of 1 mm or more under conditions of 60 ° C.-90% RH (no practicality)

Abbreviations in Tables 2 and 3 are as follows.
Hydrogenated BisAEODA: Hydrogenated Bisphenol A ethylene oxide-modified diacrylate DCPA: Dicyclopentanyl acrylate IBXA: Norbornyl acrylate DCPDMDA: Tricyclodecane dimethanol diacrylate 3H1ADMA: 3-hydroxy-1-adamantyl acrylate 4HBA: Acrylic acid 4-hydroxybutyl HEA: 2-hydroxyethyl acrylate 2HPA: 2-hydroxypropyl acrylate DCPA: dicyclopentanyl acrylate EPPA: ethoxylated o-phenylphenol acrylate (A-LEN-10: manufactured by Shin-Nakamura Chemical Co., Ltd.)
BDDA: 1,4-butanediol diacrylate NPDA: neopentyl glycol diacrylate IINA: isocyanuric acid EO-modified triacrylate (manufactured by Toagosei Co., Ltd .: Aronix M-315)
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

Abbreviations for the transparent films (1) and (2) in Tables 2 and 3 are as follows.
ZF: ZF-14 manufactured by Nippon Zeon Co., Ltd. Polynorbornene-based film containing no UV absorber (100 μm)
HBD: Mitsubishi Rayon Co., Ltd. HBD-002 Polyacrylic film containing no UV absorber (50 μm)
TAC: TAC50μ manufactured by Fuji Film Business Supply Co., Ltd. Polytriacetylcellulose-based film containing no UV absorber (thickness 50μm)

When the active energy ray polymerizable composition of the present invention is used as an adhesive, as shown in Examples 9 to 20 in Table 2, it has good peel strength and resistance and is suitable for practical use. On the other hand, in Comparative Examples 8 to 15 in Table 3, since the compound (C), the oligomer (M1) or the oligomer (M2) essential for the present invention is not contained, the peel strength is low, or the processability Poor tolerance. In Comparative Example 16 in Table 3, only the oligomer (M3) was used instead of the oligomer (M1) or the oligomer (M2), but this was poor in heat resistance.

Claims (16)

Having two or more ring structures in the molecule, a cycloalkane skeleton and / or α having a cycloalkene skeleton, beta-ethylenically unsaturated double bond group-containing organic compound (C), and
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and 1 to 2 mol of ε-caprolactone ( An α, β-ethylenically unsaturated double bond group-containing compound (m) having 2 to 18 carbon atoms selected from the group consisting of ( meth) acrylic acid 2-hydroxyethyl;
An active energy ray-polymerizable composition containing an epoxy acrylate oligomer (M1) and / or a polyester acrylate oligomer (M2).
However, the active energy ray polymerizable composition is (1) or (2).
(1) The epoxy acrylate oligomer (M1) is
An epoxy compound containing two or more epoxy groups in the molecule;
It is formed by reacting a carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound.
(2) The polyester acrylate oligomer (M2)
A polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol;
Carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, epoxy group-containing α, β-ethylenically unsaturated double bond group It is formed by reacting a compound containing or an isocyanato group-containing α, β-ethylenically unsaturated double bond group-containing compound.   2. The active energy ray-polymerizable composition according to claim 1, wherein the polyhydric alcohol which is a raw material component of the polyester acrylate oligomer (M2) includes a polyhydric alcohol in which two or more hydroxyl groups are introduced into a branched alkane. . The epoxy acrylate oligomer (M1)
An epoxy compound containing two or more epoxy groups in the molecule;
A carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound;
The active energy ray-polymerizable composition according to claim 1 or 2, which is obtained by reacting with a polybasic acid. Having two or more ring structures in the molecule, a cycloalkane skeleton and / or α having a cycloalkene skeleton, beta-ethylenically unsaturated double bond group-containing organic compound (C), and
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and 1 to 2 mol of ε-caprolactone ( An α, β-ethylenically unsaturated double bond group-containing compound (m) having 2 to 18 carbon atoms selected from the group consisting of ( meth) acrylic acid 2-hydroxyethyl;
An active energy ray polymerizable coating agent containing an epoxy acrylate oligomer (M1) and / or a polyester acrylate oligomer (M2).
However, the active energy ray polymerizable coating agent is (1) or (2).
(1) The epoxy acrylate oligomer (M1) is
An epoxy compound containing two or more epoxy groups in the molecule;
It is formed by reacting a carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound.
(2) The polyester acrylate oligomer (M2)
A polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol;
Carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, epoxy group-containing α, β-ethylenically unsaturated double bond group It is formed by reacting a compound containing or an isocyanato group-containing α, β-ethylenically unsaturated double bond group-containing compound.   The active energy ray-polymerizable coating agent according to claim 4, wherein the polyhydric alcohol which is a raw material component of the polyester acrylate oligomer (M2) includes a polyhydric alcohol in which two or more hydroxyl groups are introduced into a branched alkane. .   The active energy ray-polymerizable coating agent according to claim 4 or 5, wherein the epoxy acrylate oligomer (M1) and / or the polyester acrylate oligomer (M2) has a weight average molecular weight of 3,000 to 100,000. The epoxy acrylate oligomer (M1)
An epoxy compound containing two or more epoxy groups in the molecule;
A carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound;
The active energy ray polymerizable coating agent according to any one of claims 4 to 6, which is obtained by reacting a polybasic acid.   The active energy ray polymerizable coating agent according to any one of claims 4 to 7, further comprising an active energy ray polymerization initiator (E). Having two or more ring structures in the molecule, a cycloalkane skeleton and / or α having a cycloalkene skeleton, beta-ethylenically unsaturated double bond group-containing organic compound (C), and
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, and 1 to 2 mol of ε-caprolactone ( An α, β-ethylenically unsaturated double bond group-containing compound (m) having 2 to 18 carbon atoms selected from the group consisting of ( meth) acrylic acid 2-hydroxyethyl;
An active energy ray polymerizable adhesive containing an epoxy acrylate oligomer (M1) and / or a polyester acrylate oligomer (M2).
However, the active energy ray polymerizable adhesive is (1) or (2).
(1) The epoxy acrylate oligomer (M1) is
An epoxy compound containing two or more epoxy groups in the molecule;
It is formed by reacting a carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound.
(2) The polyester acrylate oligomer (M2)
A polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol;
Carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound, epoxy group-containing α, β-ethylenically unsaturated double bond group It is formed by reacting a compound containing or an isocyanato group-containing α, β-ethylenically unsaturated double bond group-containing compound.   The active energy ray-polymerizable adhesive according to claim 9, wherein the polyhydric alcohol as a raw material component of the polyester acrylate oligomer (M2) includes a polyhydric alcohol in which two or more hydroxyl groups are introduced into a branched alkane. .   The active energy ray-polymerizable adhesive according to claim 9 or 10, wherein the epoxy acrylate oligomer (M1) and / or the polyester acrylate oligomer (M2) has a weight average molecular weight of 3,000 to 100,000. The epoxy acrylate oligomer (M1)
An epoxy compound containing two or more epoxy groups in the molecule;
A carboxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound;
The active energy ray-polymerizable adhesive according to any one of claims 9 to 11, which is obtained by reacting a polybasic acid.   The active energy ray polymerizable adhesive according to any one of claims 9 to 12, further comprising an active energy ray polymerization initiator (E).   A layer comprising the active energy ray-polymerizable coating agent according to any one of claims 4 to 8 and / or the active energy ray-polymerizable adhesive according to any one of claims 9 to 13 is provided on one side or both sides of the substrate (F). A laminated body characterized by being laminated.   The substrate (F) is a polyacetylcellulose film, polynorbornene film, polypropylene film, polyacryl film, polycarbonate film, polyester film, polyvinyl alcohol film or polyimide film. The laminate according to claim 14.   The laminated body for optical elements which uses the laminated body of Claim 14 or 15.