JP7082582B2 - Active energy ray-curable composition and cured product for adhesives - Google Patents

Description

The present invention relates to an active energy ray-curable composition for a pressure-sensitive adhesive and a cured product.

Conventionally, in the fields of smartphones and tablet terminals, a touch panel that combines an image display device such as a liquid crystal display and a position input device such as a touch pad has been widely used.
Further, in the above-mentioned touch panel, an adhesive which is an active energy ray-curable composition is used for the purpose of bonding optical members (see Patent Document 1).
In addition, a colorant and / or a metal oxide powder may be added to the pressure-sensitive adhesive for the purpose of imparting a function to the pressure-sensitive adhesive and / or improving the physical properties of the pressure-sensitive adhesive.
Here, the active energy ray-curable composition used as a pressure-sensitive adhesive is a polymer having a molecular weight of about tens of thousands to hundreds of thousands of the monomer contained in the active energy ray-curable composition from the viewpoint of developing adhesive force after curing. It is necessary to polymerize so as to be, and generally, a method of irradiating with low light and UV for a long time using a chemical lamp is adopted. Therefore, as described above, when the colorant and / or the metal oxide powder is added to the pressure-sensitive adhesive, the colorant and the metal oxide powder inhibit the curing by attenuating or shielding the active energy rays. However, there is a problem that the curability is insufficient, and curling wrinkles and shrinkage occur.

Japanese Unexamined Patent Publication No. 2016-199663

The present invention has been made in view of the above problems, and an object of the present invention is to cure with a low energy amount even if it contains a colorant and / or a metal oxide powder that attenuates or shields irradiation light. It is an object of the present invention to provide an active energy ray-curable composition for a pressure-sensitive adhesive.

［一般式（１）及び（２）において、Ｒ^１～Ｒ^２６は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１～１８の炭化水素基又は炭素数１～１８のアルコキシ基であり；前記炭素数１～１８の炭化水素基中のメチレン基は酸素原子で置換されていてもよく、水素原子はハロゲン原子で置換されていてもよく；前記炭素数１～１８のアルコキシ基中のメチレン基は酸素原子で置換されていてもよく、水素原子はハロゲン原子で置換されていてもよく；ａ～ｄ、ｆ及びｇはそれぞれ独立に、０～４の整数であり；ｅ及びｈは１～４の整数であり、かつｅ＝ｈである。］ The present inventors have reached the present invention as a result of diligent studies to achieve the above object.
That is, the present invention comprises a photoradical initiator (A), an acid generator (B), a radically polymerizable monomer (C1), a cationically polymerizable monomer (C2), a colorant (D) and / or a metal. An active energy ray-curable composition for a pressure-sensitive adhesive containing an oxide powder (E), wherein the radically polymerizable monomer (C1) has a monofunctional (meth) acrylic monomer (C11) and a polyfunctional (meth). ) The monomer (C21) containing the acrylic monomer (C12) and the cationically polymerizable monomer (C2) being represented by the general formula (1) and / or the monomer (C22) represented by the general formula (2). The active energy ray-curable composition for a pressure-sensitive adhesive (Z) containing the above; a cured product obtained by curing the active energy ray-curable composition for a pressure-sensitive adhesive.

[In the general formulas (1) and (2), R ¹ to R ²⁶ are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms; The methylene group in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom; methylene in the alkoxy group having 1 to 18 carbon atoms. The group may be substituted with an oxygen atom and the hydrogen atom may be substituted with a halogen atom; a to d, f and g are independently integers of 0 to 4; e and h are 1 It is an integer of ~ 4 and e = h. ]

The active energy ray-curable composition (Z) for a pressure-sensitive adhesive of the present invention contains a colorant and / or a metal oxide powder, but has excellent curability.

The active energy ray-curable composition (Z) for a pressure-sensitive adhesive in the present invention comprises a photoradical initiator (A), an acid generator (B), a radically polymerizable monomer (C1), and a cationically polymerizable monomer (C2). ), And an active energy radical curable composition for a pressure-sensitive adhesive containing a colorant (D) and / or a metal oxide powder (E).
The radically polymerizable monomer (C1) contains a monofunctional (meth) acrylic monomer (C11) and a polyfunctional (meth) acrylic monomer (C12).
Further, the cationically polymerizable monomer (C2) contains a monomer (C21) represented by the above general formula (1) and / or a monomer (C22) represented by the above general formula (2).
In the present invention, the notation of "(meth) acrylic" means acrylic and / or methacryl, and the notation of "(meth) acrylate" means acrylate and / or methacrylate, and "(meth) acryloyl". Notation means acryloyl and / or methacryloyl, and the notation of "(meth) acryloyloxy" means acryloyloxy and / or methacryloyloxy.

Examples of the photoradical initiator (A) in the present invention include a benzoin compound (A-1), an alkylphenone compound (A-2), an anthraquinone compound (A-3), a thioxanthone compound (A-4), and a ketal compound (A). -5), benzophenone compound (A-6), phosphine oxide compound (A-7), oxime ester compound (A-8) and the like can be mentioned.

Examples of the benzoin compound (A-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether.

Examples of the alkylphenone compound (A-2) include acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 2-hydroxy-2-methyl-. Phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2- (dimethylamino)- Examples thereof include 2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone.

Examples of the anthraquinone compound (A-3) include 2-ethylanthraquinone, 2-t-butyl anthraquinone, 2-chloroanthraquinone and 2-amyl anthraquinone.

Examples of the thioxanthone compound (A-4) include 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and the like.

Examples of the ketal compound (A-5) include acetophenone dimethyl ketal and benzyl dimethyl ketal.

Examples of the benzophenone compound (A-6) include benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and 4,4'-bismethylaminobenzophenone.

Examples of the phosphine oxide compound (A-7) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and bis (2,4-trimethylpentylphosphine oxide). 2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.

Examples of the oxime ester compound (A-8) include 1- [4- (phenylthio) phenyl] -1,2-octanedione2- (O-benzoyloxime) and etanone-1- [9-ethyl-6- (2). -Methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) and the like can be mentioned.

Among the photoradical initiators (A), the phosphine oxide compound (A-7) is preferable from the viewpoint of curability, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2, 6-trimethylbenzoyldiphenylphosphine oxide) are more preferable. 4,6-trimethylbenzoyl) -phenylphosphine oxide.
As the photoradical initiator (A), one type may be used alone, or two or more types may be used in combination.

The photoradical initiator (A) preferably has a base dissociation constant (pK _b ) of 6 to 25 from the viewpoint of curability.
Initiators in which pK _b is in the above preferred range include 2,4,6-trimethylbenzoyldiphenylphosphine oxide [pK _b : 13] and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [pK. _b : 24] and the like.

From the viewpoint of curability, the photoradical initiator (A) preferably has a molar extinction coefficient (ε) of 5 to 1200 ml / g · cm at a wavelength of 405 nm measured in acetonitrile or methanol.
Initiators in which ε is in the above preferred range include 2,4,6-trimethylbenzoyldiphenylphosphine oxide [ε: 165] and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [ε: 899]. ] Etc. can be mentioned.

The acid generator (B) in the present invention means a compound that generates an acid by active light, radicals or heat.
As the acid generator (B), an acid generator composed of a cation component and an anion component is preferable from the viewpoint of curability, and a more preferable acid generator (B1) in which the cation component is sulfonium. ) And the acid generator (B2) in which the cation component is iodonium, and particularly preferable is an acid generator (B2) in which the cation component is iodonium.

Examples of the acid generator (B1) in which the cation component is sulfonium include compounds represented by the following general formula (3) or the following general formula (4).

In the general formula (3) or (4), Ar ¹ to Ar ⁷ each independently has at least one benzene ring skeleton, and is a halogen atom, an acyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. , Alkoxy group with 1 to 20 carbon atoms, alkylthio group with 1 to 20 carbon atoms, alkylsilyl group with 1 to 20 carbon atoms, nitro group, carboxy group, hydroxyl group, mercapto group, amino group, cyano group, phenyl group, naphthyl An aromatic hydrocarbon group which may be substituted with at least one group (α) selected from the group consisting of a group, a phenoxy group and a phenylthio group, or a complex which may be substituted with the above group (α). It is a ring group.
Ar ¹ to Ar ⁴ , Ar ⁶ and Ar ⁷ are monovalent groups, and Ar ⁵ is a divalent group.

Ar ¹ to Ar ⁷ in the general formula (3) and the general formula (4) are groups having absorption in the ultraviolet to visible light region.
The number of benzene ring skeletons in Ar ¹ to Ar ⁷ is preferably 1 to 5, and more preferably 1 to 4.
Examples of the case of having one benzene ring skeleton include residues obtained by removing one or two hydrogen atoms from a heterocyclic compound such as benzene, benzofuran, benzothiophene, indole, quinoline and coumarin.
As an example of having two benzene ring skeletons, one or two hydrogen atoms are removed from heterocyclic compounds such as naphthalene, biphenyl, fluorene, dibenzofuran, dibenzothiophene, xanthone, xanthene, thioxanthone, aclysine, phenothiazine and thianthrene. Residues and the like can be mentioned.
An example of having three benzene ring skeletons is a residue obtained by removing one or two hydrogen atoms from a heterocyclic compound such as anthracene, phenanthrene, terphenyl, p- (thioxanthyl mercapto) benzene and naphthobenzothiophene. And so on.
Examples of the case of having four benzene ring skeletons include residues obtained by removing one or two hydrogen atoms from naphthacene, pyrene, benzoanthracene, triphenylene and the like.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and fluorine and chlorine are preferable.

Examples of the acyl group having 1 to 20 carbon atoms include a formyl group, an acetyl group, a propionyl group, an isobutyryl group, a valeryl group and a cyclohexylcarbonyl group.

Examples of the above-mentioned alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n- or iso-propyl group, an n-, sec- or tert-butyl group, an n-, iso- or neo-pentyl group, and a hexyl. Groups, heptyl groups, octyl groups and the like can be mentioned.

The alkoxy group having 1 to 20 carbon atoms includes a methoxy group, an ethoxy group, an n- or iso-propoxy group, an n-, sec- or tert-butoxy group, an n-, iso-, or a neo-pentyloxy group. , Hexyloxy group, heptyloxy group, octyloxy group and the like.

Examples of the alkylthio group having 1 to 20 carbon atoms include a methylthio group, an ethylthio group, an n- or iso-propylthio group, an n-, sec- or tert-butylthio group, an n-, iso- or neo-pentylthio group, and a hexylthio. Groups, heptylthio groups, octylthio groups and the like can be mentioned.

Examples of the alkylsilyl group having 1 to 20 carbon atoms include a trialkylsilyl group (trimethylsilyl group, triisopropylsilyl group, etc.) and the like.

The group (α) substituting with Ar ¹ to Ar ⁷ is preferably a halogen atom, a cyano group, a phenyl group, a naphthyl group, a phenoxy group, a phenylthio group and 1 to 20 carbon atoms from the viewpoint of acid generation efficiency. An alkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms and an acyl group having 1 to 20 carbon atoms are more preferable, and a halogen atom, a cyano group, a phenyl group and 1 to 20 carbon atoms are more preferable. Fifteen alkyl groups, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms and an acyl group having 1 to 15 carbon atoms are particularly preferable, and a halogen atom and an alkyl group having 1 to 10 carbon atoms are particularly preferable. , An alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms and an acyl group having 1 to 10 carbon atoms. The above alkyl moiety may be linear, branched or cyclic.

As Ar ¹ to Ar ⁴ , Ar ⁶ and Ar ⁷ , phenyl group, p-methylphenyl group, p-methoxyphenyl group, p-tert-butylphenyl group, 2,4 are preferable from the viewpoint of acid generation efficiency. 6-trimethylphenyl group, p- (thioxanthyl mercapto) phenyl group and m-chlorophenyl group.

Phenylene group, 2- or 3-methylphenylene group, 2- or 3-methoxyphenylene group, 2- or 3-butylphenylene group and 2- or 3-chloro are preferable as Ar ⁵ from the viewpoint of acid generation efficiency. It is a phenylene group.

In the general formula (3) or (4), (X ¹ ) ^-and (X ² ) ^-represent the above-mentioned anion component.
The (X ¹ ) ^-and (X ² )-referred ^to as a halide anion, a hydroxide anion, a thiocyanate anion, a dialkyldithiocarbamate anion having 1 to 4 carbon atoms, a carbonate anion, a hydrogen carbonate anion, and a halogen. Aggregate or aromatic carboxy anions that may be substituted (benzoate anion, trifluoroacetate anion, perfluoroalkyl acetate anion, phenylglioxylate anion, etc.), aliphatic or aromatic sulfos that may be substituted with halogen. Xyane anion (trifluoromethanesulfonic acid anion, etc.), hexafluorinated antimonate anion (SbF _6- ⁾ , phosphin anion [six fluoride phosphin anion (PF _6- ⁾ and trifluoride trifluoride (perfluoroethyl) phosphin anion (PF) ₃ (C ₂ F ₅ ) _3- ⁾ , etc.] and borate anions (tetraphenylborate, butyltriphenylborate anion, etc.) and the like.
Of these, phosphine anions, halogen-substituted aliphatic sulfoxy ions and borate anions are preferable from the viewpoint of curability, phosphine anions are more preferable, and PF _6- ^or PF is particularly preferable. ₃ (C ₂ F ₅ ⁾ _3- .

In the general formula (4), A ¹ is an oxygen atom or a sulfur atom. Sulfur atoms are preferable from the viewpoint of acid generation efficiency.

As the acid generator (B1) in which the cation component is sulfonium, triphenylsulfonium, tri-p-tolylsulfonium or [p- (phenylmercapto) phenyl] diphenylsulfonium is preferable from the viewpoint of acid generation efficiency. Compounds having as a component and compounds represented by the following general formula (5) or (6) are more preferable, and compounds having [p- (phenylmercapto) phenyl] diphenylsulfonium as a cation component, and the following general formula ( It is a compound represented by 5) or (6).
The acid generator (B1) may be used alone or in combination of two or more.

(X ³ ) ^-to (X ⁴ ) ^-in the general formula (5) and the general formula (6) represent the above-mentioned anion component, and (X ¹ ) ^-or (X ² ) in the general formula (3) or (4). ) ^-Similar to those exemplified as-, and preferred ones as well.

Examples of the acid generator (B2) in which the cation component is iodonium include a compound represented by the following general formula (7).

In the general formula (7), Ar ⁸ to Ar ⁹ each independently has at least one benzene ring skeleton and may be substituted with the above group (α), or the above-mentioned aromatic hydrocarbon group. It is a heterocyclic group which may be substituted with a group (α).
Ar ⁸ to Ar ⁹ are monovalent groups.
Ar ⁸ to Ar ⁹ in the general formula (7) are groups in which the compound represented by the general formula (7) has absorption in the ultraviolet to visible light region.
The number of benzene ring skeletons in Ar ⁸ to Ar ⁹ is preferably 1 to 5, more preferably 1 to 4, and specific examples of Ar ⁸ to Ar ⁹ are the general formula (3) or the general formula (4). The same as those exemplified as Ar ¹ to Ar ⁷ of the above are mentioned, and the preferred one is an aromatic hydrocarbon group substituted with an alkyl group having 1 to 20 carbon atoms.

In the general formula (7), (X ⁵ ) ^-represents the above-mentioned anion component, and is similar to that exemplified as (X ¹ ) ^-or (X ² ) ^-in the general formula (3) or (4). The same applies to the preferred ones.

As the acid generator (B2) in which the cation component is iodonium, (4-methylphenyl) {4- (1-methylethyl) phenyl} iodonium and (4-methylphenyl) are preferable from the viewpoint of acid generation efficiency. ) {4- (2-Methylpropyl) phenyl} iodonium, [bis (4-t-butylphenyl)] iodonium, [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] iodonium, A compound having [bis (4-methoxyphenyl)] iodonium or [bis (4-methoxyphenyl)] iodonium as a cation component is more preferable, and (4-methylphenyl) {4- (1-methylethyl) phenyl is more preferable. } Iodonium, (4-methylphenyl) {4- (2-methylpropyl) phenyl} Iodonium or [bis (4-t-butylphenyl)] iodonium is a compound having iodonium as a cation component.
The acid generator (B2) may be used alone or in combination of two or more.

As described above, the radically polymerizable monomer (C1) contains a monofunctional (meth) acrylic monomer (C11) and a polyfunctional (meth) acrylic monomer (C12).

[Monofunctional (meth) acrylic monomer (C11)]
Examples of the monomer (C11) include (meth) acrylic acid.
A monoesterified product of an alcohol having 1 to 20 carbon atoms and (meth) acrylic acid, a monoesterified product of an alkylene oxide adduct to an alcohol having 1 to 20 carbon atoms and (meth) acrylic acid,
A reaction product of a (meth) acrylic acid ester having a hydroxyl group and an acid anhydride,
Alkoxysilanes having a (meth) acryloyl group, lactone adducts to (meth) acrylic acid, and the like can be mentioned.
Further, the above-mentioned monomer (C11) is a compound in which the hydrogen atom contained in the above-mentioned compound is replaced with a halogen atom, a carboxy group, a cyano group, an amino group and / or an alkylamino group (dimethylamino group, diethylamino group, etc.). There may be.

Examples of the alcohol having 1 to 20 carbon atoms include a chain fatty alcohol having 1 to 20 carbon atoms, an alicyclic alcohol having 3 to 20 carbon atoms, and an aromatic alcohol having 6 to 15 carbon atoms.

Examples of the chain aliphatic alcohol having 1 to 20 carbon atoms include chain aliphatic monohydric alcohols having 1 to 20 carbon atoms [methanol, ethanol, 1-propanol, 1-butanol, t-butyl alcohol, 1-pen. Tanol, isoamyl alcohol, 1-hexanol, 2-ethylhexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, stearyl alcohol, butoxymethanol, etc.]; Alcohols [ethylene glycol, 1,2- or 1,3-propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decane Diol, dodecanediol, tetradecanediol, neopentylglycol and 2,2-diethyl-1,3-propanediol], chain aliphatic trihydric alcohols having 3 to 20 carbon atoms [glycerin, trimethylolethane, trimethylolpropane, etc.] And 1,3,5-triazine-2,4,6-triol, etc.]; Glycerin, dipentaerythritol, etc.] and the like.

Examples of the alicyclic alcohol having 3 to 20 carbon atoms include hydroxycyclohexane, 4-n-butylcyclohexinol, borneyl alcohol, isobornyl alcohol, 1,3-cyclopentanediol, and 1,4-cyclohexanediol. Examples thereof include 1,4-cyclohexanedimethanol, 1,4-cycloheptanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,3,5-cyclohexanetriol and glycidol.

Examples of the aromatic alcohol having 6 to 15 carbon atoms include phenol, 4-butylphenol, cresol, pyrogallol, catechol, resorcinol, hydroquinone, dihydroxynaphthalene, bisphenol A, bisphenol F, bisphenol S, phenoxymethanol and benzyl alcohol. Be done.

Specific examples of the monoesterified product of the chain aliphatic alcohol having 1 to 20 carbon atoms and (meth) acrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate. tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, 2,3-dimethylhexyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) ) Acrylate, Isodecyl (meth) acrylate, Stearyl (meth) acrylate, Isostearyl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, 2-Hydroxyethyl (meth) acrylate, 3-Hydroxypropyl (meth) acrylate, 2- Examples thereof include hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and butoxymethyl (meth) acrylate.
Further, with respect to the monoesterified product of the above-mentioned chain aliphatic alcohol having 1 to 20 carbon atoms and (meth) acrylic acid, the hydrogen atom having a hydrogen atom is a halogen atom, a carboxy group, a cyano group, an amino group and / or an alkylamino group ( Compounds substituted with (dimethylamino group, diethylamino group, etc.) include 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H. , 2H-Perfluorodecyl (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, cyanoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethyl Aminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, β-carboxyethyl (meth) acrylate and the like can be mentioned.

Specific examples of the monoesterified product of the alicyclic alcohol having 3 to 20 carbon atoms and (meth) acrylic acid include glycidyl (meth) acrylate, cyclohexyl (meth) acrylate, and 4-n-butylcyclohexyl (meth). ) Acrylate, Bornyl (meth) acrylate, Isobornyl (meth) acrylate and the like.

Specific examples of the monoesterified product of the aromatic alcohol having 6 to 15 carbon atoms and (meth) acrylic acid include benzyl (meth) acrylate, 4-butylphenyl (meth) acrylate, and phenyl (meth) acrylate, 2. , 4,5-Tetramethylphenyl (meth) acrylate, phenoxymethyl (meth) acrylate and the like.
Further, regarding the monoesterified product of the above aromatic alcohol having 6 to 15 carbon atoms and (meth) acrylic acid, the hydrogen atom having a hydrogen atom is a halogen atom, a carboxy group, a cyano group, an amino group and / or an alkylamino group (dimethylamino). Examples of the compound substituted with (group, diethylamino group, etc.) include 4-chlorophenyl (meth) acrylate and the like.

Specific examples of the alkylene oxide as a raw material for the monoesterified product of the alkylene oxide adduct to the alcohol having 1 to 20 carbon atoms and (meth) acrylic acid include alkylene oxides having 2 to 4 carbon atoms. Examples thereof include ethylene oxide, 1,2- or 1,3-propylene oxide and 1,2-, 1,3-, 1,4- or 2,3-butylene oxide.
The number of moles of alkylene oxide added to the alcohol having 1 to 20 carbon atoms is preferably 1 to 40 mol.
Examples of the monoesterified product of the alkylene oxide adduct to the alcohol having 1 to 20 carbon atoms and the (meth) acrylic acid include 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, and methoxypropylene mono (meth). Meta) acrylate, 3-methoxybutyl (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) ) Acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monomethyl ether ( Meta) acrylate, oligopropylene oxide monomethyl ether (meth) acrylate, butoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene oxide [hereinafter abbreviated as EO. May] modified phenol (meth) acrylate, EO modified cresol (meth) acrylate, EO modified nonylphenol (meth) acrylate, propylene oxide [hereinafter sometimes abbreviated as PO] modified nonylphenol (meth) acrylate, EO modified- 2-Ethylhexyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, etc. Can be mentioned.

The (meth) acrylic acid ester having a hydroxyl group, which is a raw material for the reaction product of the (meth) acrylic acid ester having a hydroxyl group and the acid anhydride, includes the above-mentioned alcohol having 1 to 20 carbon atoms and (meth) acrylic. Of the monoesters with acids and alkylene oxide additions to alcohols with 1 to 20 carbon atoms and monoesterides with (meth) acrylic acid, divalent or higher alcohols are used as alcohols with 1 to 20 carbon atoms. Examples include the compounds that have been present.
Examples of the acid anhydride include acid anhydrides having 4 to 10 carbon atoms, and specific examples thereof include succinic anhydride, maleic anhydride, phthalic anhydride and hexahydrophthalic anhydride.
Examples of the reaction product of the (meth) acrylic acid ester having a hydroxyl group and the acid anhydride include 2- (meth) acryloyloxyethyl succinic acid and 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 4 -Hydroxybutyl (meth) acrylate succinic acid adduct, 1,4-cyclohexanedimethanol mono (meth) acrylate succinic acid adduct, 1,4-benzenedimethanol mono (meth) acrylate succinic acid adduct, 2- (meth) ) Acryloyloxyethyl-phthalic acid and alkylene oxide (2-4 carbon atoms) adduct (addition) of divalent to 6-valent, preferably divalent, 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms. Numbers 1 to 30) Mono (meth) acrylate Succinic acid ester and the like can be mentioned.

Examples of the alkoxysilane having a (meth) acryloyl group include trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, and trimethylsilylpropyl (meth) acrylate.

Examples of the lactone as a raw material for the lactone adduct to the (meth) acrylic acid include lactones having 2 to 12 carbon atoms, and specific examples thereof include acetolactone, propiolactone, butyrolactone, valerolactone, and caprolactone. And laurolactone and the like.
The number of moles of the lactone added to the alcohol having 1 to 20 carbon atoms is preferably 1 to 15 mol.
Examples of the lactone adduct to the (meth) acrylic acid include ω-carboxy-caprolactone mono (meth) acrylate and ω-carboxy-di- (caprolactone) mono (meth) acrylate.

Among the (meth) acrylic monomers (C11), a monoesterified product of an alcohol having 1 to 20 carbon atoms and (meth) acrylic acid is preferable from the viewpoint of adhesiveness, and butyl (meth) is more preferable. ) Acrylate and 2-ethylhexyl (meth) acrylate.
The monofunctional (meth) acrylic monomer (C11) may be used alone or in combination of two or more.

[Polyfunctional (meth) acrylic monomer (C12)]
Examples of the polyfunctional (meth) acrylic monomer (C12) include a bifunctional (meth) acrylic monomer (C121), a trifunctional (meth) acrylic monomer (C122), and a tetrafunctional or higher (meth) acrylic monomer (C123). Can be mentioned.

[Bifunctional (meth) acrylic monomer (C121)],
The monomer (C121) is an esterified product of 1 mol of a divalent or higher alcohol among the alcohols having 1 to 20 carbon atoms and 2 mol of (meth) acrylic acid.
An esterified product of 1 mol of an alkylene oxide adduct to a dihydric or higher alcohol among the above-mentioned alcohols having 1 to 20 carbon atoms and 2 mol of (meth) acrylic acid; and the above-mentioned alcohol having 1 to 20 carbon atoms. Examples thereof include an esterified product of 1 mol of a lactone adduct to a dihydric or higher alcohol and 2 mol of (meth) acrylic acid.
Further, the above-mentioned monomer (C121) is a compound obtained by reacting the above-mentioned esterified product with a hydroxyl group which has not reacted with (meth) acrylic acid and a carboxylic acid (propionic acid or the like) having 2 to 10 carbon atoms. May be.
Specific examples of the monomer (C121) include 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 2,4-dimethyl. -1,5-Pentanediol di (meth) acrylate, butylethylpropanediol di (meth) acrylate, ethoxylated cyclohexane methanol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligo Ethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) Acrylate, Polypropylene glycol di (meth) acrylate, Oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9 -Nonandiol di (meth) acrylate and PO-modified and EO-modified bisphenol A di (meth) acrylate and the like can be mentioned.

[Trifunctional (meth) acrylic monomer (C122)]
As the above-mentioned monomer (C122),
An esterified product of 1 mol of a trihydric or higher alcohol among the above-mentioned alcohols having 1 to 20 carbon atoms and 3 mol of (meth) acrylic acid;
An esterified product of 1 mol of an alkylene oxide adduct to a trihydric or higher alcohol among the above-mentioned alcohols having 1 to 20 carbon atoms and 3 mol of (meth) acrylic acid; and the above-mentioned alcohol having 1 to 20 carbon atoms. Examples thereof include an esterified product of 1 mol of a lactone adduct to a trihydric or higher alcohol and 3 mol of (meth) acrylic acid.
Further, the above-mentioned monomer (C121) is a compound obtained by reacting the above-mentioned esterified product with a hydroxyl group which has not reacted with (meth) acrylic acid and a carboxylic acid (propionic acid or the like) having 2 to 10 carbon atoms. May be.
Specific examples of the monomer (C122) include trimethylol ethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, alkylene oxide-modified tri (meth) acrylate of trimethylolpropane, and pentaerythritol tri (meth) acrylate. , Dipentaerythritol tri (meth) acrylate, trimethylolpropanetri [(meth) acryloyloxypropyl] ether, sorbitol tri (meth) acrylate, alkylene oxide 1 to 30 mol adduct having 2-3 carbon atoms of pentaerythritol. (Meta) acrylate, ethoxylated glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, etc. Can be mentioned.

[Four-functional or higher (meth) acrylic monomer (C123)]
Examples of the monomer (C123) include a tetrafunctional or higher (meth) acrylic monomer (C1231) and a tetrafunctional or higher urethane (meth) acrylic monomer (C1232).
It is assumed that the tetrafunctional or higher functional (meth) acrylate monomer (C1231) does not contain the tetrafunctional or higher functional urethane (meth) acrylate monomer.

[Four-functional or higher (meth) acrylic monomer (C1231)]
As the above-mentioned monomer (C1231),
An esterified product of 1 mol of a tetravalent or higher alcohol among the above-mentioned alcohols having 1 to 20 carbon atoms and 4 mol or more of (meth) acrylic acid;
An esterified product of 1 mol of an alkylene oxide adduct to an alcohol having a valence of 4 or more among the alcohols having 1 to 20 carbon atoms and 4 mol or more of (meth) acrylic acid; and the alcohol having 1 to 20 carbon atoms. Examples thereof include an esterified product of 1 mol of a lactone adduct to an alcohol having a valence of 4 or more and 4 mol or more of (meth) acrylic acid.
Further, the above-mentioned monomer (C1231) is a compound obtained by reacting the above-mentioned esterified product with a hydroxyl group which has not reacted with (meth) acrylic acid and a carboxylic acid (propionic acid or the like) having 2 to 10 carbon atoms. May be.
Specific examples of the monomer (C1231) include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol propionate. Tetra (meth) acrylate, tetra (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa Examples thereof include (meth) acrylate, sorbitol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

[Urethane (meth) acrylic monomer with 4 or more functionalities (C1232)]
The monomer (C1232) is U-6LPA, UA-1100H, U-15HA, NK-oligo U-15HA [all manufactured by Shin Nakamura Chemical Industry Co., Ltd.]; UN-3320HA, UN-3320HC, UN-3320HS. , UN-904, UN-906S, UN-901T, UN-905, UN-952 [above, manufactured by Negami Kogyo Co., Ltd.]; UA-306H, UA-306T, UA-306I, UA-510H [above, Kyoeisha] Made by Chemical Industry Co., Ltd.], etc., can be obtained from the market.

Among the (meth) acrylic monomers (C12), (C122) and (C1231) are preferable from the viewpoint of curability, and (C1231) is more preferable.
The polyfunctional (meth) acrylic monomer (C12) may be used alone or in combination of two or more.

The molecular weight [Mc] (g / mol) between the cross-linking points of (C12) is preferably 50 to 200 g / mol, more preferably 50 to 150 g / mol, and particularly preferably 55 to 100 g / mol from the viewpoint of curability. Is. The molecular weight [Mc] (g / mol) between the cross-linking points of (C12) can be calculated by the following formula (1).
[Mc] = 1 / {a ₀ x (1 / Mc ₀ ) + a ₁ x (1 / Mc ₁ ) + ...
+ A _i x (1 / Mc _i ) + ... + an x (1 / Mc _n )} ( ₁ )
In the above calculation formula (1), a ₀ , a ₁ , ... _ai , ... an is the weight% of each component (hereinafter abbreviated as each component) of the ( _meth ) acrylic monomer constituting (C12). Represents.
Further, Mc ₀ , Mc ₁ , ... Mc _i , ... Mc _n represent the molecular weight between the cross-linking points for each component.
[Mc _i ] (g / mol) can be calculated by the following formula (2).
[Mc _i ] = Mn / {2 × (n-1)}
In the above calculation formula (2), Mn is the number average molecular weight (g / mol) of each component, and n represents the number of (meth) acryloyl groups possessed by each component (n is 2 or more).

The weight average molecular weight (hereinafter, may be abbreviated as Mw) of the polyfunctional (meth) acrylic monomer (C12) in the present invention is preferably 200 to 50,000 from the viewpoint of curability.
Mw in the present invention is measured by gel permeation chromatography using THF as a solvent and polyoxypropylene glycol as a standard substance. The sample concentration may be 0.25% by weight, the column stationary phase may be one each of TSKgel SuperH2000, TSKgel SuperH3000, and TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected, and the column temperature may be 40 ° C.

As described above, the cationically polymerizable monomer (C2) contains a monomer (C21) represented by the following general formula (1) and / or a monomer (C22) represented by the following general formula (2).

In the general formula (1) and the general formula (2), R ¹ to R ²⁶ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, respectively.

The methylene group in the above-mentioned hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom.
The methylene group in the alkoxy group having 1 to 18 carbon atoms may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom.
Among R ¹ to R ²⁸ , those preferable from the viewpoint of curability include a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 4 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.). , More preferred is a hydrogen atom.

Further, in the general formulas (1) and (2), a to d, f and g are independently integers of 0 to 4. Further, e and h are integers of 1 to 4, and e = h.
Further, in the general formula (1), from the viewpoint of curability, preferable combinations of a, b, c and d are (a = 1, b = 0, c = 1, d = 0), (a = 1, b. = 1, c = 1, d = 0), (a = 1, b = 1, c = 2, d = 0), (a = 1, b = 1, c = 1, d = 1) and (a) = 2, b = 1, c = 2, d = 1), more preferably (a = 1, b = 0, c = 1, d = 0), (a = 1, b = 1, c = 1, d = 0) and (a = 1, b = 1, c = 1, d = 1), and particularly preferably (a = 1, b = 1, c = 1, d = 0).
Further, in the general formula (2), from the viewpoint of curability, preferable combinations of e, f, g and h are (e = 1, f = 1, g = 0, h = 1), (e = 1, f). = 1, g = 1, h = 1) and (e = 1, f = 2, g = 1, h = 1), more preferably (e = 1, f = 1, g = 0, h = 1). 1).

The monomer (C21) represented by the general formula (1) and the monomer (C22) represented by the general formula (2) can be synthesized by the method described in International Publication No. 2014/175129.

Among the epoxy monomers (C2), the compound represented by the compound represented by the general formula (1) is preferable from the viewpoint of curability, and 3a, 4,7,7a-tetrahydro is more preferable. Indendioxide and 1,3a, 4,6a-tetrahydropentarange oxide.
The epoxy monomer (C2) may be used alone or in combination of two or more.

The cationically polymerizable monomer (C2) contains an oxetane monomer (C23) having 5 to 30 carbon atoms and another cationically polymerizable monomer (C24) in addition to the above-mentioned monomer (C21) and the monomer (C22). You may be.

Examples of the oxetane monomer (C23) having 5 to 30 carbon atoms include a monofunctional oxetane monomer (C231), a bifunctional oxetane monomer (C232), and a trifunctional or higher functional oxetane monomer (C233).

[Monofunctional oxetane monomer (C231)]
Examples of the monomer (C231) include 3-ethyl-3-hydroxymethyloxetane (trade name "OXT-101", manufactured by Toa Synthetic Co., Ltd.) and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane. (Product name "OXT-212", manufactured by Toa Synthetic Co., Ltd.), 3-Ethyl-3-phenoxymethyloxetane (trade name "OXT-211", manufactured by Toa Synthetic Co., Ltd.), 3-Ethyl-3-Acri Loxymethyloxetane (trade name "OXE-10", manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 3-ethyl-3-methacryloxymethyloxetane (trade name "ETERNACOLL OXMA", manufactured by Ube Kosan Co., Ltd.) are listed. Be done.

[Bifunctional oxetane monomer (C232)]
Examples of the monomer (C232) include polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, and PO-modified bisphenol A-bis (3-ethyl). -3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F Bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene (trade name "OXT-121", manufactured by Toa Synthetic Co., Ltd.), 3 -Ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane (trade name "OXT-221", manufactured by Toa Synthetic Co., Ltd.), 4,4'-bis [3-ethyl-( 3-Oxetane) methoxymethyl] biphenyl (trade name "ETERNACOLL OXBP", manufactured by Ube Kosan Co., Ltd.), di (3-ethyl-3-oxetanyl) methoxyethyl adipic acid (trade name "bisoxetane adipate", Ube Kosan) (Manufactured by Co., Ltd.), bis (3-ethyloxetane-3-ylmethyl) carbonate (trade name "dioxetane carbonate", manufactured by Ube Kosan Co., Ltd.) and bis- (3-ethyl-oxetane-3-ylmethyl) ester of terephthalate. (Product name "OXTP", manufactured by Ube Kosan Co., Ltd.) and the like can be mentioned.

[Trifunctional or higher oxetane monomer (C233)]
Examples of the monomer (C233) include pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexakis (3-ethyl-3). -Oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakiss (3-ethyl) Examples thereof include -3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, and ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether.
Among the oxetane monomers (C23), (C231) and (C232) are preferable from the viewpoint of curability and adhesiveness, and (C231) is more preferable.
The above-mentioned oxetane monomer (C23) may be used alone or in combination of two or more.

Examples of the other cationically polymerizable monomer (C24) include norbornadiene dioxide, dipentenedioxide, vinylcyclohexene dioxide and 5,6-epoxy-4,7-mesano-1-oxaspiro- (2,5) -octane. And so on.

Examples of the colorant (D) include pigments (inorganic pigments, organic pigments, etc.) and dyes conventionally used in paints, inks, and the like.

Examples of the inorganic pigment include chrome yellow, zinc yellow, dark blue, barium sulfate, cadmium red, titanium oxide, zinc flower, red iron oxide, alumina, calcium carbonate, ultramarine, carbon black, graphite and titanium black.

Examples of organic pigments include soluble azo pigments such as β-naphthol, β-oxynaphthoic acid anilide, acetoacetic acid anilide, and pyrazolone, β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetate anilide monoazo, and aceto. Insoluble azo pigments such as anilide disuazo acetate and pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, halogenated copper phthalocyanine blue, sulfonated copper phthalocyanine blue and metal-free phthalocyanine, isosindrinone, quinacridone, dioxandine, perinone and perylene. Polycyclic or heterocyclic compounds can be mentioned.

As a specific example of the dye, as the yellow dye, phenol, naphthol, aniline, pyrazolone, pyridone or aryl or heteryl azo dye having an open chain type active methylene compound as a coupling component, and azomethin having an open chain type active methylene compound as a coupling component. Examples thereof include methine dyes such as dyes, benziliden dyes and monomethine oxonor dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro dyes, nitroso dyes, acridin dyes and acridinone dyes.

Magenta dyes include phenol, naphthol, aniline, pyrazolone, pyridone, pyrazorotriazole, ring-closed active methylene compounds or aryl or heteryl azo dyes having heterocycles (pyrrole, imidazole, thiophene, thiazole, etc.) as coupling components, couplings. Azomethin dyes having pyrazolone or pyrazorotriazole as components, allylidene dyes, styryl dyes, methine dyes such as merocyanine dyes and oxonol dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, naphthoquinone, anthraquinone and anthrapyridone and the like. Examples thereof include condensed polycyclic dyes such as quinone dyes and dioxazine dyes.

Cyan dyes include azomethine dyes such as Indian aniline dyes and Indian phenol dyes, polymethine dyes such as cyanine dyes, oxonoll dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes and anthraquinone dyes. Examples of the coupling component include aryl or heteryl azo dyes (CI Direct Blue 14, etc.) having phenol, naphthol, aniline, pyrolopyrimidinone or pyrorotriadinone, and indigo / thioindigo dyes.
The colorant (D) may be used alone or in combination of two or more.

The particle size of the colorant (D) is preferably 0.01 μm to 2.0 μm, more preferably 0.01 μm to 1.0 μm, as the volume average particle size from the viewpoint of the vividness of the coating film.

Examples of the metal oxide powder (E) include particles containing oxides of Si, Mg, Al, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Sn and Zn.
Specific examples thereof include titanium oxide, aluminum oxide, barium titanate, calcium zirconate, niobium oxide, lead zirconate titanate and the like.
Examples of the shape of the metal oxide powder (E) include spherical particles and needle-shaped particles.
The metal oxide powder (E) may be used alone or in combination of two or more.

From the viewpoint of adhesive strength, the particle size of the metal oxide powder (E) is preferably 0.01 μm to 2.0 μm as a volume average particle size, and more preferably 0.01 μm to 1.0 μm.

The active energy ray-curable composition (Z) for a pressure-sensitive adhesive of the present invention is an additive other than the above-mentioned (A), (B), (C1), (C2), (D) and (E). May be contained.
Examples of other additives include a dispersant (F), a sensitizer (G), a solvent and the like.

The dispersant (F) includes dispersants manufactured by Big Chemie (Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, 182, 184 and 2020 etc.), Ajinomoto Fine Techno Co., Ltd. dispersants (Ajinomoto PB711, PB821, PB814, PN411, PA111, etc.), Lubrizol Co., Ltd. dispersants (Solspurs 5000, 12000, 32000, 33000, 36000, 39000, etc.) and the like. ..
The dispersant (F) may be used alone or in combination of two or more.

Examples of the sensitizer (G) include anthracene, thioxanthone, benzophenone thioxanthone, phenothiazene, perylene and the like.
Among them, anthracene is preferable because it can dramatically improve the photosensitivity when used in combination with a cationic polymerization initiator.
Anthracene sensitizers include diexianthracene (trade name "UVS-1101", manufactured by Kawasaki Kasei Kogyo Co., Ltd.), dipropoxyanthracene (trade name "UVS-1221", manufactured by Kawasaki Kasei Kogyo Co., Ltd.) and Examples thereof include dibutoxyanthracene (trade name "UVS-1331", manufactured by Kawasaki Kasei Kogyo Co., Ltd.).
Among the sensitizers (G), dibutoxyanthracene is preferable from the viewpoint of solubility and curability in various monomers.
The sensitizer (G) may be used alone or in combination of two or more.

From the viewpoint of adhesiveness, the weight ratio of the monomer (C11) is preferably 45 to 95% by weight based on the total weight of the monomer (C1) and the monomer (C2).
From the viewpoint of curability, the weight ratio of the monomer (C12) is preferably 0.1 to 5% by weight based on the total weight of the monomer (C1) and the monomer (C2).
The ratio of the total weight of the monomers (C21) and (C22) is 0.1 to 50% by weight based on the total weight of the monomers (C1) and the monomers (C2) from the viewpoint of curability. Is preferable.

From the viewpoint of curability, the weight ratio of the monomer (C23) is preferably 3 to 50% by weight based on the total weight of the monomer (C1) and the monomer (C2).

The weight ratio of the photoradical initiator (A) is preferably 0.1 to 10% by weight, more preferably, based on the weight of the monomer (C1) from the viewpoint of curability and adhesiveness. Is 0.5 to 5% by weight.

From the viewpoint of curability, the weight ratio of the acid generator (B) is preferably 0.1 to 50% by weight, more preferably 1 to 20% by weight, based on the weight of the monomer (C2). %.

The total weight of the radically polymerizable monomer (C1) and the cationically polymerizable monomer (C2) is preferably 3 to 50% by weight based on the weight of the active energy ray-curable composition (Z) for a pressure-sensitive adhesive. More preferably, it is 5 to 40% by weight.

The ratio of the total weight of the colorant (D) and the metal oxide powder (E) is based on the weight of the active energy ray-curable composition (Z) for a pressure-sensitive adhesive from the viewpoint of colorability and curability. It is preferably 1 to 60% by weight, more preferably 1 to 30% by weight.

The weight ratio of the dispersant (F) is the same as that of the colorant (D) and the metal oxide powder (E) from the viewpoint of dispersibility of the colorant (D) and the metal oxide powder (E). It is preferably 1 to 100% by weight, more preferably 5 to 90% by weight, based on the total weight.

The weight ratio of the sensitizer (G) is preferably 0.1 to 10% by weight based on the total weight of the monomers (C1) and the monomers (C2) from the viewpoint of curability. It is preferably 0.5 to 5% by weight.

The method for producing the active energy ray-curable composition (Z) for a pressure-sensitive adhesive of the present invention is not particularly limited.
For example, the photo-radical initiator (A), the acid generator (B), the monomer (C1), the monomer (C2), the colorant (D) and / or the above. Metal oxide powder (E), and if necessary, the dispersant (F) and the sensitizer (G) are mixed in a temperature range of 20 to 40 ° C. with a known mechanical stirrer. And a method using a magnetic stirrer or the like) to uniformly mix the mixture.

The active energy ray-curable composition (Z) for a pressure-sensitive adhesive of the present invention can be obtained as a cured product by irradiating with an active energy ray (active light of 360 nm to 830 nm or the like).
Heating may be performed for the purpose of diffusing the acid generated from the acid generator during and / or after irradiation with the active light beam.
The heating temperature is preferably 30 ° C. to 200 ° C., more preferably 35 ° C. to 150 ° C., and particularly preferably 40 ° C. to 120 ° C.

The method for applying the active energy ray-curable composition (Z) for a pressure-sensitive adhesive of the present invention to a substrate is not particularly limited, and a known and commonly used coating method can be used. Specifically, for example, gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, comma coater, direct coater, fountain die coater, T die coater, roll coater and gravure. Examples thereof include a coating method using a coating device (coater) such as a coater.
Among these, a roll coater and a comma coater are preferable.

Examples of the active energy rays include ionizing radiation (α rays, β rays, γ rays, neutron rays, electron beams, etc.), ultraviolet rays, and the like. Above all, ultraviolet rays are preferable.
Further, the device for irradiating the active energy ray (active energy ray irradiating device) is not particularly limited, and a known and commonly used active energy ray irradiating device can be used. Examples of the active energy ray irradiating device include a lamp for generating ultraviolet rays (UV lamp) and an EB (electron beam) irradiating device.
As the UV lamp, a high-pressure discharge lamp (metal halide lamp, high-pressure mercury lamp, etc.), a low-pressure discharge lamp (chemical lamp, black light lamp, fluorescent lamp for insect trapping, etc.) and the like are preferable.

The illuminance of the active energy rays (particularly ultraviolet rays) irradiated to form the cured product of the present invention is not particularly limited, but is preferably 1 to 20 mW / cm ² , and more preferably 1 to 15 mW / cm ² .
The above-mentioned activation energy ray irradiation is not particularly limited, but a separator (peeling liner) or the like may be attached to the surface of the applied pressure-sensitive adhesive of the present invention for the purpose of blocking oxygen.
As the separator, a known and commonly used release paper or the like can be used. The separator can be formed by a known and commonly used method. Further, the thickness of the separator is not particularly limited.

The active energy ray-curable composition (Z) for a pressure-sensitive adhesive of the present invention is extremely useful as a pressure-sensitive adhesive for bonding optical members and the like because it can cure a thick film at a high colorant concentration even with a small amount of energy. ..

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the following examples, parts represent parts by weight and% represents% by weight.

Production Example 1: Production of acid generator (B1-1) {compound represented by chemical formula (8)} While stirring 12.1 parts of diphenyl sulfoxide, 9.3 parts of diphenyl sulfide and 43.0 parts of methanesulfonic acid. To this, 7.9 parts of anhydrous acetic acid was added dropwise, and the mixture was reacted at 40 to 50 ° C. for 5 hours, then cooled to room temperature (about 25 ° C.), and the reaction solution was subjected to 20% tris (pentafluoroethyl) trifluorophosphate. It was poured into 121 parts of a potassium aqueous solution and stirred at room temperature for 1 hour to precipitate a yellow viscous oil. This oil is extracted with ethyl acetate, the organic layer is washed with water several times, the solvent is distilled off from the organic layer, toluene is added to the obtained residue to dissolve it, and then hexane is added to add hexane at 10 ° C. After stirring for 1 hour, the mixture was allowed to stand. After 1 hour, the solution was separated into two layers, so the upper layer was removed by liquid separation. Hexane was added to the residue and mixed well at room temperature to precipitate pale yellow crystals. This was separated by filtration and dried under reduced pressure to obtain 48 parts of the target acid generator (B1-1).

Production Example 2: Production of acid generator (B2-1) {compound represented by chemical formula (9)}

Toluene [manufactured by Tokyo Chemical Industry Co., Ltd.] 6.5 parts, isopropylbenzene [manufactured by Tokyo Kasei Co., Ltd.] 8.1 parts, potassium iodide [manufactured by Tokyo Chemical Industry Co., Ltd.] 5.4 parts and acetic anhydride 20 The portion was dissolved in 70 parts of acetic acid, cooled to 10 ° C., and a mixed solution of 12 parts of concentrated sulfuric acid and 15 parts of acetic acid was added dropwise over 1 hour while maintaining the temperature at 10 ± 2 ° C. The temperature was raised to 25 ° C. and the mixture was stirred for 24 hours. Then, 50 parts of diethyl ether was added to the reaction solution, washed with water three times, and the diethyl ether was distilled off under reduced pressure. An aqueous solution prepared by dissolving 118 parts of potassium trifluorophosphate (pentafluoroethyl) in 100 parts of water was added to the residue, and the mixture was stirred at 25 ° C. for 20 hours. Then, 500 parts of ethyl acetate was added to the reaction solution, washed with water three times, and the organic solvent was distilled off under reduced pressure to obtain 5.0 parts of the target acid generator (B2-1).

Production Example 3: Production of 3a, 4,7,7a-Tetrahydroinden Dioxide (C21-1) 3a, 4,7,7a-Tetrahydroinden in a SUS reaction vessel equipped with a cooling tube, a stirrer, and a thermometer [ Made by Tokyo Kasei Kogyo Co., Ltd.] 120 parts and 480 parts of ethyl acetate were charged, and 1,270 parts of an ethyl acetate solution having a peracetic acid concentration of 30% was added dropwise over 3 hours. The reaction temperature was adjusted to be maintained at 30 ° C. during the dropping. After completion of the dropping, the reaction temperature was kept at 30 ° C. for 3 hours to complete the epoxidation reaction. After cooling the reaction solution to room temperature, 1200 g of a 20% aqueous sodium hydroxide solution was added, the mixture was stirred for 1 hour, allowed to stand for 30 minutes, and the solution was separated to remove unreacted peracetic acid and acetic acid as a compound product. After distilling ethyl acetate using a distillation apparatus, 152 parts of 3a, 4,7,7a-tetrahydroindendioxide (C21-1) was obtained.

Production Example 4: Production of Dicyclopentadiene Dioxide (C22-1) 132 parts of dicyclopentadiene [manufactured by Tokyo Kasei Kogyo Co., Ltd.], ethyl acetate 480 in a glass reaction vessel equipped with a cooling tube, agitator, and a thermometer. Parts were charged, and 1,270 parts of an ethyl acetate solution having a peracetic acid concentration of 30% was added dropwise over 3 hours. The reaction temperature was adjusted to be maintained at 30 ° C. during the dropping. After completion of the dropping, the reaction temperature was kept at 30 ° C. for 3 hours to complete the epoxidation reaction. After cooling the reaction solution to room temperature, 1200 g of a 20% aqueous sodium hydroxide solution was added, and the mixture was stirred for 1 hour, allowed to stand for 30 minutes, and separated to remove unreacted peracetic acid and acetic acid of multiple organisms. After distilling ethyl acetate using a distillation apparatus, 164 parts of dicyclopentadiene dioxide (C22-1) was obtained.

<Examples 1 to 61, Comparative Examples 1 to 4>
(A) to (F) shown in Tables 1 to 3 are collectively blended according to the blending composition (part) shown in Tables 1 to 3, stirred with a disperser until uniformly dispersed, and Examples 1 to 1 to 3. The active energy ray-curable composition (Z) for a pressure-sensitive adhesive of 61 and the comparative active energy ray-curable composition of Comparative Examples 1 to 4 were obtained.

The active energy ray-curable composition (Z) for a pressure-sensitive adhesive of Examples 1 to 61 and the comparative active energy ray-curable composition of Comparative Examples 1 to 4 were evaluated according to the following evaluation methods. The evaluation results are shown in Tables 1 to 3.

(1) Measurement of gelation fraction [evaluation of curability]
[Method for producing cured product for evaluation of gelation fraction]
Each active energy ray-curable composition is 500 μm using a baker type applicator on a PET film [trade name: MRF50, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., thickness: 50 μm] whose surface has been mold-released. It was applied so as to have the coating thickness of, and a coating film was formed. By laminating and adhering another release PET film similar to the above on this coating film, release films are arranged above and below the coating film of the active energy ray-curable composition and laminated in a sandwich shape ( Sealed). Then, at room temperature, using a black light [trade name: FL20SBL, manufactured by Sankyo Electric Co., Ltd.], UV (wavelength: 365 nm) with an illuminance of 5 mW / cm ² is irradiated (integrated light amount: 500 mJ / cm ² ). , A cured product for evaluation was obtained.

[Evaluation method]
Each evaluation cured product was cut into a flat rectangular shape having a size of 50 mm × 25 mm to prepare _a test piece, and the weight W1 of the prepared test piece was measured. After immersing the test piece in ethyl acetate at 23 ° C. for 24 hours, the test piece was taken out from ethyl acetate using a 200 mesh stainless mesh and dried under the condition of 110 ° C. for 1 hour. The weight W ₂ of the test piece after drying was measured, and the gelation fraction was calculated by the following formula.

Gelling fraction (% by weight) = 100 x (W ₂ -W ₀ ) / (W ₁ -W ₀ )
[In the formula, W ₀ represents the weight of the PET film in the cured product for evaluation (for two films of 50 mm × 25 mm × 50 μm); W ₁ represents the weight of the test piece before immersion; W ₂ represents immersion. It represents the weight of the test piece after it has been dried. ]
The curability was evaluated by the gelation fraction measured by the above method, and evaluated according to the following criteria.
<Evaluation criteria>
☆: 80% or more ◎: 50% or more and less than 80% 〇: 20% or more and less than 50% △: 1% or more and less than 20% ×: less than 1%

(2) Measurement of peeling adhesive strength [evaluation of adhesiveness]
[Method of producing a cured product for evaluation of peeling adhesive strength]
Each active energy ray-curable composition is applied to a steel plate made of stainless steel SUS304, and a PET film having a width of 25 mm [trade name: Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., thickness: 100 μm] is applied from above using a pressure-bonding roller. It was applied to a coating thickness of 500 μm to form a coating film. Then, at room temperature, using a black light [trade name: FL20SBL, manufactured by Sankyo Electric Co., Ltd.], UV (wavelength: 365 nm) with an illuminance of 5 mW / cm ² is irradiated (integrated light amount: 500 mJ / cm ² ). , A cured product for evaluation was obtained.
The above cured product was evaluated according to the following evaluation method.

[Evaluation method]
According to the method of JIS Z 0237: 2009 10.4.1, a steel plate made of stainless SUS304 was regarded as a test plate and a PET film was regarded as a tape, and the test was performed.
Specifically, after leaving the cured product for evaluation in an environment of 23 ° C. and 50% humidity for 24 hours, a universal tensile compression tester [product name "TG-1kN", manufactured by Minebea Co., Ltd.] is used. The peeling adhesive force [N / 25 mm] was measured under the conditions of a tensile speed of 300 mm / min and a peeling angle of 180 °.
The adhesiveness was evaluated by the peel strength measured by the above method, and evaluated according to the following criteria.
<Evaluation criteria>
⊚: 10 or more 〇: 5 or more and less than 10 Δ: 1 or more and less than 5 ×: 1 or less

The abbreviations in Tables 1 to 3 are as follows.
<Photoradical initiator (A)>
(A-1): Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [trade name "IRGACURE 819", manufactured by BASF Japan Ltd., pK _b : 24, ε: 899]
(A-2): 2,4,6-trimethylbenzoyldiphenylphosphine oxide [trade name "IRGACURE TPO", manufactured by BASF Japan Ltd., pK _b : 13, ε: 165]
(A-3): 1-Hydroxycyclohexylphenyl ketone [trade name "IRGACURE"
184 ”, manufactured by BASF Japan Ltd., pK _b : 17, ε: 0]

<Acid generator (B)>
(B2-2): (4-Methylphenyl) [4- (2-Methylpropyl) phenyl] Iodonium Hexafluorophosphet [Product name "IRGACURE 250", manufactured by BASF Japan Ltd.

<Monofunctional (meth) acrylic monomer (C11)>
(C11-1), BA: n-butyl acrylate [trade name "butyl acrylate", manufactured by Mitsubishi Chemical Corporation, Mw: 128]
(C11-2), 2EHA: 2-ethylhexyl acrylate [trade name "-2-ethylhexyl acrylate", manufactured by Mitsubishi Chemical Corporation, Mw: 184]
(C11-3), AA: Acrylic acid [Product name "Acrylic acid", manufactured by Mitsubishi Chemical Corporation, Mw: 72]
<Polyfunctional (meth) acrylic monomer (C12)>
(C12-1), TMP-A: Trimethylolpropane triacrylate [trade name "Viscoat # 295", manufactured by Osaka Organic Chemical Industry Co., Ltd., Mw; 296]
(C12-2), DPHA: Dipentaerythritol hexaacrylate [Product name "Neomer DA-600", manufactured by Sanyo Chemical Industries, Ltd., Mw: 524]

<Epoxy monomer (C2)>
(Ratio C2-1), 2021P: 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate [trade name "Selokiside 2021P", manufactured by Daicel Corporation]
<Oxetane Monomer (C23)>
(C23-1), DOX: 3-Ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane [trade name "OXT-221", manufactured by Toagosei Co., Ltd., 12 carbon atoms]
(C23-2), XDO: 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene [trade name "OXT-121", manufactured by Toagosei Co., Ltd., 20 carbon atoms]
(C23-3), EHOX: 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane [trade name "OXT-212", manufactured by Toagosei Co., Ltd., 14 carbon atoms]

<Colorant (D)>
(D-1), [Special Black 250]: Carbon black with an average primary particle diameter of 56 nm [Product "Special Black 250", manufactured by Degussa]
<Metal oxide powder (E)>
(E-1), [PF-726]: Titanium oxide particles with an average primary particle diameter of 240 nm [trade name "PF-736", manufactured by Ishihara Sangyo Co., Ltd.]
<Dispersant (F)>
(F-1), [Solspec 32000]: Polymer dispersant (acid value: 15 mgKO)
H / g, weight average molecular weight: 3,900) [Product name "Solspec 32000", manufactured by Lubrizol]
(F-2), [Solspec 36000]: Polymer dispersant (acid value: 45 mgKO)
H / g, amine value: 0 mgKOH / g, weight average molecular weight of about 50,000) [Product name "Solspec 36000", manufactured by Lubrizol]

From the results of Tables 1 to 3, the active energy ray-curable composition (Z) for a pressure-sensitive adhesive of the present invention is excellent in curability as compared with the comparative active energy ray-curable composition of Comparative Example. I understand.
Further, the cured product of the active energy ray-curable composition (Z) for a pressure-sensitive adhesive of the present invention is excellent in adhesiveness as compared with the cured product of the comparative active energy ray-curable composition of Comparative Example. It can be seen that the deep curability is also sufficient.

The active energy ray-curable composition (Z) for a pressure-sensitive adhesive of the present invention contains a colorant and / or a metal oxide, but is curable when irradiated with active energy rays even in the case of a thick film. A cured product that is excellently cured and has excellent adhesion to a substrate is extremely useful as an adhesive for bonding optical members and the like.

Claims (7)

Photoradic initiator (A), acid generator (B), radically polymerizable monomer (C1), cationically polymerizable monomer (C2), colorant (D) and / or metal oxide powder (E). An active energy ray-curable composition for a pressure-sensitive adhesive containing the above, wherein the radically polymerizable monomer (C1) is a monofunctional (meth) acrylic monomer (C11) and a polyfunctional (meth) acrylic monomer (C12). For a pressure-sensitive adhesive, wherein the cationically polymerizable monomer (C2) contains a monomer (C21) represented by the general formula (1) and / or a monomer (C22) represented by the general formula (2). Active energy ray-curable composition (Z).

[In the general formulas (1) and (2), R ¹ to R ²⁶ are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms; The methylene group in the hydrocarbon group having 1 to 18 carbon atoms may be substituted with an oxygen atom, and the hydrogen atom may be substituted with a halogen atom; methylene in the alkoxy group having 1 to 18 carbon atoms. The group may be substituted with an oxygen atom and the hydrogen atom may be substituted with a halogen atom; a to d, f and g are independently integers of 0 to 4; e and h are 1 It is an integer of ~ 4 and e = h. ] The acid generator (B) is an acid generator composed of a cation component and an anion component, the cation component is sulfonium or iodonium, and the anion component is PF ₆ ^- or PF ₃ (C ₂ F ₅ ⁾ _3- . The active energy ray-curable composition for a pressure-sensitive adhesive according to claim 1. The active energy ray-curable composition for a pressure-sensitive adhesive according to claim 1 or 2, wherein the cationically polymerizable monomer (C2) further contains an oxetane monomer (C23) having 5 to 30 carbon atoms. Based on the total weight of the monomer (C1) and the monomer (C2), the weight ratio of the monomer (C11) is 45 to 95% by weight, and the weight ratio of the monomer (C12) is 0.1 to 5% by weight. %, And the active energy ray curability for a pressure-sensitive adhesive according to any one of claims 1 to 3, wherein the ratio of the total weight of the monomer (C21) and the monomer (C22) is 0.1 to 50% by weight. Composition. The active energy ray for an adhesive according to any one of claims 1 to 4, wherein the weight ratio of the acid generator (B) is 0.1 to 50% by weight based on the weight of the monomer (C2). Curable composition. The active energy for a pressure-sensitive adhesive according to any one of claims 1 to 5, wherein the weight ratio of the photoradical initiator (A) is 0.1 to 10% by weight based on the weight of the monomer (C1). Radical curable composition. A cured product obtained by curing the active energy ray-curable composition for an adhesive according to any one of claims 1 to 6.