JP2019044153A - Active energy ray-curable composition - Google Patents

Abstract

To provide an active energy ray-curable composition capable of being cured at low energy amount even when a material such as a coloring agent which attenuates or shields an irradiation light exists at high concentration or in the case of a thick film.SOLUTION: There is provided an active energy ray-curable composition (Z) containing a photoradical initiator (A), an acid generator (B), a polyfunctional (meth)acrylate monomer (C1), a bifunctional epoxy monomer (C2) having no ester group, having an alicyclic skeleton and having 5 to 30 carbon atoms and an oxetane monomer having 5 to 30 carbon atoms (C3), a coloring agent (D) and/or a metal oxide powder (E).SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray curable composition.

The so-called UV coating, which cures and coats the surface by light irradiation, is expanding its application range such as coating agents, paints, and printing inks from the viewpoint of its workability (rapid curing) and low VOC (volatile organic compounds). .
Generally, UV coating agents comprise radically polymerizable monomers and photoradical initiators, and, depending on the application, colorants and additives.
The colorant is roughly divided into a pigment and a dye, and is blended to color the coating. The coloring agent has a light absorbing property according to the color, and absorbs a part (or a large part) of the irradiation light used in curing to attenuate the light or shield the irradiation light. Light may not reach the deep part of the coated film.
In order to solve this problem, it has been proposed to use a radically polymerizable compound, a cationically polymerizable compound, and a photopolymerization initiator having a thioxanthone skeleton (see, for example, Patent Document 1).

  However, the invention described in Patent Document 1 uses a radically polymerizable compound, a cationically polymerizable compound, and a photopolymerization initiator having a thioxanthone skeleton, and is improved in that it can be cured with an energy irradiation amount smaller than that of the prior art. However, in the ink composition containing a black pigment such as carbon black which easily absorbs ultraviolet rays, there is a problem that the curability is insufficient or a curing wrinkle or shrinkage occurs.

JP 10-60026 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide low energy even when a substance such as a coloring agent which attenuates or blocks irradiation light is present at a high concentration or in the case of a thick film. It is an object of the present invention to provide an active energy ray curable composition which can be cured in an amount.

The present inventors arrived at the present invention as a result of earnestly examining to achieve the above object.
That is, in the present invention, the photoradical initiator (A), the acid generator (B), the polyfunctional (meth) acrylate monomer (C1), and an ester group-free alicyclic skeleton-containing 5 carbon atoms Active energy ray-curable composition containing at least one bifunctional epoxy monomer (C2), C5 to C30 oxetane monomer (C3), colorant (D) and / or metal oxide powder (E) Article (Z): A cured product of the above-mentioned active energy ray-curable composition (Z).

  The active energy ray curable composition (Z) of the present invention has excellent curability, and the cured product has excellent substrate adhesion. Moreover, the hardened | cured material of the active energy ray curable composition (Z) of this invention is excellent in contamination resistance.

The active energy ray-curable composition (Z) in the present invention has no photo radical initiator (A), acid generator (B), polyfunctional (meth) acrylate monomer (C1), and no ester group. C5-C30 bifunctional epoxy monomer (C2) having an alicyclic skeleton, C5-C30 oxetane monomer (C3), colorant (D) and / or metal oxide powder (E) Contains
In the present invention, the expression "(meth) acrylate" means acrylate and / or methacrylate, and the expression "(meth) acrylic" means acrylic and / or methacryl.

  As a photo radical initiator (A) in this invention, a benzoin compound (A-1), an alkyl phenone compound (A-2), an anthraquinone compound (A-3), a thioxanthone compound (A-4), a ketal compound (A) -5), benzophenone compound (A-6), phosphine oxide compound (A-7), oxime ester compound (A-8) and the like.

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

  As the alkylphenone compound (A-2), acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl- Phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone, 2-hydroxy-1- {4- [4- (2W-hydroxy-2-methyl-propi] Yl) - benzyl] phenyl} -2-methyl - propan-1-one, and the like.

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

  As a thioxanthone compound (A-4), 2,4-diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone etc. are mentioned.

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

  Examples of benzophenone compounds (A-6) include benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone.

  As the phosphine oxide compound (A-7), 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis- (2,6-dimethoxy benzoyl) -2,4,4-trimethyl pentyl phosphine oxide and bis ( 2,4,6-trimethyl benzoyl) -phenyl phosphine oxide etc. are mentioned.

  As the oxime ester compound (A-8), 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime) and ethanone-1- [9-ethyl-6- (2) -Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.

Among the photo radical initiators (A), preferred are the alkylphenone compounds (A-2) and phosphine oxide compounds (A-7) from the viewpoint of curability, and more preferred is the α-hydroxyalkylphenone skeleton A compound having an α-aminoalkylphenone skeleton (above, A-2), and a phosphine oxide compound (A-7) having a benzoyl group.
The photo radical initiator (A) may be used alone or in combination of two or more.

From the viewpoint of curability, the photo radical initiator (A) preferably has a molar absorption coefficient (ε) at a wavelength of 405 nm measured in acetonitrile or methanol of 5 to 1200 ml / g · cm.
As an initiator whose ε is in the above preferable range, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 [ε: 280], 2- (dimethylamino) -2 -[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone [ε: 280], 2-hydroxy-1- {4- [4- (2-hydroxy-) 2-Methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [ε: 7], 2,4,6-trimethylbenzoyldiphenylphosphine oxide [ε: 165] and bis (2,4,6 6-trimethyl benzoyl) -phenyl phosphine oxide [(epsilon): 899] etc. is mentioned.

The acid generator (B) in the present invention means a compound capable of generating an acid by an actinic ray, a radical or heat.
As said acid generator (B), the acid generator etc. which consist of a cation component and an anion component are mentioned.
As an acid generator which consists of a cation component and an anion component, an acid generator (B1) whose cation component is sulfonium, an acid generator (B2) whose cation component is iodonium, etc. are mentioned.

  As an acid generator (B1) whose cation component is sulfonium, the compound etc. which are shown by following General formula (1) or following General formula (2) are mentioned.

In the general formula (1) or (2), each of Ar ^{1 to} Ar ⁷ independently has at least one benzene ring skeleton, and is a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms An alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a nitro group, a carboxyl group, a hydroxyl group, a mercapto group, an amino group, a cyano group, a phenyl group, a naphthyl group 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 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 (1) and the general formula (2) 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 benzene or a residue obtained by removing one or two hydrogen atoms from a heterocyclic compound such as benzofuran, benzothiophene, indole, quinoline or coumarin.
Examples of two benzene rings include naphthalene, biphenyl, fluorene, or dibenzofuran, dibenzothiophene, xanthone, xanthene, thioxanthone, acridine, phenothiazine and thianthrene, and one or two hydrogen atoms. The residue etc. which were remove | excluded are mentioned.
Examples of three benzene rings include residues obtained by removing one or two hydrogen atoms from a heterocyclic compound such as anthracene, phenanthrene, terphenyl, p- (thioxanthylmercapto) benzene and naphthobenzothiophene. Etc.
Examples of the case of having four benzene ring skeletons include naphthacene, pyrene, benzoanthracene, triphenylene and the like, and residues and the like in which one or two hydrogen atoms are removed.

  The halogen atom includes fluorine, chlorine, bromine and iodine, with fluorine and chlorine being preferred.

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

  As said C1-C20 alkyl group, a methyl group, an ethyl group, n- or iso-propyl group, n-, sec- or tert- butyl group, n-, iso- or neo-pentyl group, hexyl Groups, heptyl groups and octyl groups.

  As said C1-C20 alkoxy group, a methoxy group, an ethoxy group, n- or iso-propoxy group, n-, sec- or tert- butoxy group, n-, iso- or neo-pentyloxy group And hexyloxy group, heptyloxy group and octyloxy group.

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

  Examples of the alkylsilyl group having 1 to 20 carbon atoms include trialkylsilyl groups (such as trimethylsilyl and triisopropylsilyl).

As the group (α) to be substituted for Ar ^{1 to} Ar ⁷ described above, halogen atoms, cyano groups, phenyl groups, naphthyl groups, phenoxy groups, phenylthio groups, and those having 1 to 20 carbon atoms are preferable from the viewpoint of acid generation efficiency It is 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, and more preferably a halogen atom, a cyano group, a phenyl group, 1 to 5 carbon atoms 15 alkyl groups, alkoxy groups having 1 to 15 carbon atoms, alkylthio groups having 1 to 15 carbon atoms and acyl groups having 1 to 15 carbon atoms, and halogen atoms and alkyl groups having 1 to 10 carbon atoms are particularly preferred. 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.

From the viewpoint of acid generation efficiency, Ar ^{1 to} Ar ⁴ , Ar ⁶ and Ar ⁷ are preferably phenyl group, p-methylphenyl group, p-methoxyphenyl group, p-tert-butylphenyl group, 2, 4, 6 -Trimethylphenyl group, p- (thioxanthylmercapto) phenyl group and m-chlorophenyl group.

As Ar ⁵ , from the viewpoint of acid generation efficiency, preferably a phenylene group, a 2- or 3-methyl phenylene group, a 2- or 3-methoxy phenylene group, a 2- or 3-butyl phenylene group and a 2- or 3-chlorophenylene It is a group.

In the general formula (1) or (2), ^(X 1) ^- representing a is the anion component ^- and ^(X 2).
As (X ¹ ) ⁻ and (X ² ) ⁻ described above, a halide anion, a hydroxide anion, a thiocyanate anion, a dialkyldithiocarbamate anion having 1 to 4 carbon atoms, a carbonate anion, a hydrogencarbonate anion, a halogen Aliphatic or aromatic carboxy anion which may be substituted (benzoic acid anion, trifluoroacetate anion, perfluoroalkyl acetate anion, phenylglyoxylate anion, etc.), aliphatic or aromatic sulfo which may be substituted by halogen Xyanion (trifluoromethanesulfonate anion, etc.), hexafluoride antimonate anion (SbF ₆ ⁻ ), phosphine anion [hexafluoride phosphine anion (PF ₆ ⁻ ) and trifluoride tris (perfluoroethyl) phosphine anion (PF ₆ ) ₃ (C ₂ F ₅₎ 3 ^_-), etc.] and borate anion (tetraphenyl borate and butyl triphenyl borate anion), and the like.
Among these, from the viewpoint of curing, preferred are phosphine anions, aliphatic sulfoxion ions substituted with halogen and borate anions, more preferably phosphine anions, particularly preferably PF ₆ ⁻ or PF ₃ (C ₂ F _{5) 3} ^- a.

In the general formula (2), A ¹ is an oxygen atom or a sulfur atom. Preferred from the viewpoint of acid generation efficiency is a sulfur atom.

Preferably, triphenylsulfonium, tri-p-tolylsulfonium or [p- (phenylmercapto) phenyl] diphenylsulfonium is included as a cationic component from the viewpoint of acid generation efficiency as an acid generator (B1) in which the cationic component is sulfonium A compound and a compound represented by the following general formula (3) or (4), more preferably a compound having [p- (phenylmercapto) phenyl] diphenyl sulfonium as a cationic component, the following general formula (3) or (4) It is a compound shown by these.
As the acid generator (B1), one type may be used alone, or two or more types may be used in combination.

(X ³ ) ⁻ to (X ⁴ ) ⁻ in the general formula (3) and the general formula (4) represent the above-mentioned anion component, and (X ¹ ) ⁻ or (X ² ) in the general formula (1) or (2) ) ^- it includes the same ones as exemplified as, preferable ones are also same.

  As an acid generator (B2) whose said cation component is iodonium, the compound etc. which are shown by following General formula (5) are mentioned.

In the general formula (5), Ar ^{8 to} Ar ⁹ each independently have at least one benzene ring skeleton and may be an aromatic hydrocarbon group which may be substituted by the above group (α), or It is a heterocyclic group which may be substituted by a group (α).
Ar ^{8 to} Ar ⁹ are monovalent groups.
Ar ^{8 to} Ar ⁹ in the general formula (5) are groups which make the compound represented by the general formula (5) absorb 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 include general formula (1) or general formula (2) The same ones as those exemplified as Ar ^{1 to} Ar ^{7 in} the following can be mentioned, and a preferable one is an aromatic hydrocarbon group substituted by an alkyl group having 1 to 20 carbon atoms.

In the general formula (5), ^(X 5) ^- represents the anion component represented by the general formula (1) or (2) in ^(X 1) ^- or ^(X 2) ^- exemplified ones and the like as And the preferred ones are also the same.

As the acid generator (B2) in which the cationic component is iodonium, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2] .1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium 2- (3 tetracyclo [4.4.0.12,5.17,10] dodecanyl) -1,1 Diphenyliodonium salts such as difluoroethanesulfonate, diphenyliodonium N, N'-bis (nonafluoro-n-butanesulfonyl) imidate, diphenyliodonium camphorsulfonate, etc .; bis (4t butylphenyl) Iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) Iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2- (3-tetracyclo [4.4] .0.12,5.17,10] dodecanyl) -1,1-difluoroethane sulfonate, bis (4-t-butylphenyl) iodonium N, N'-bis (nonafluoro-n-butanesulfonyl) imidate, bis (4 -T-Butylphenyl) iodonium camphorsulfonate etc Bis (4-t-butylphenyl) iodonium salt; 4-methylphenyl) {4- (1-methylethyl) phenyl} iodonium hexafluorophosphate, (4-methylphenyl) {4- (2-methylpropyl) phenyl } Iodonium hexafluorophosphate, [bis (4-t-butylphenyl)] iodonium hexafluorophosphate, [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] iodonium hexafluorophosphate , [Bis (4-methoxyphenyl)] iodonium and [bis (4-methoxyphenyl)] iodonium hexafluorophosphate, (4-methylphenyl) {4- (1-methylethyl) phenyl} iodonium tris (pentafluoro) ethyl) Trifluorophosphate, (4-methylphenyl) {4- (2-methylpropyl) phenyl} iodonium tris (pentafluoroethyl) trifluorophosphate, [bis (4-t-butylphenyl)] iodonium tris (pentafluoro) Ethyl) trifluorophosphate, [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] iodonium tris (pentafluoroethyl) trifluorophosphate, [bis (4-methoxyphenyl)] iodonium and Examples include [bis (4-methoxyphenyl)] iodonium tris (pentafluoroethyl) trifluorophosphate and the like. (4-Methylphenyl) {4- (1-methylethyl) phenyl} iodonium, (4-methylphenyl) {4- (2-methylpropyl) phenyl} iodonium, [bis] are preferred from the viewpoint of acid generation efficiency. (4-t-butylphenyl) iodonium, [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] iodonium, [bis (4-methoxyphenyl)] iodonium and [bis (4- (phenylphenyl)] iodonium; It is a compound having methoxyphenyl)] iodonium as a cation component, more preferably (4-methylphenyl) {4- (1-methylethyl) phenyl} iodonium, (4-methylphenyl) {4- (2-methyl) Propyl) phenyl} iodonium and [bis (4-t-butylphenyl)] iodonium .
The acid generator wherein the cationic component is iodonium can generate an acid by thermal decomposition by heat of reaction or chemical decomposition by redox reaction with radical species, in addition to light. The generated acid immediately reacts with the epoxy monomer, and cationic polymerization proceeds. The heat of reaction generated in association with the cationic polymerization further promotes the cationic polymerization in an autocatalytic manner.
As the acid generator (B2), one type may be used alone, or two or more types may be used in combination.

  Among these acid generators (B), preferred are acid generators (B2) in which the cationic component is iodonium from the viewpoint of curability.

  Examples of the polyfunctional (meth) acrylate monomer (C1) include bifunctional (meth) acrylate monomer (C11), trifunctional (meth) acrylate monomer (C12) and tetrafunctional or higher (meth) acrylate monomer (C13). Be

  As said monomer (C11), bifunctional (meth) acrylate monomer (C111), bifunctional urethane (meth) acrylate monomer (C112), and bifunctional polyester (meth) acrylate monomer (C113) are mentioned.

[Bifunctional (meth) acrylate monomer (C111)],
As the monomer monomer (C111), 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1 5, 5-Pentanediol di (meth) acrylate, butylethylpropanediol di (meth) acrylate, ethoxylated cyclohexanemethanol 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, neopentyl glycol dihydroxypivalate di (meth) acrylate Ethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di ( Examples include meta) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and propoxylated ethoxylated bisphenol A di (meth) acrylate.

[Bifunctional urethane (meth) acrylate monomer (C112)]
The monomer (C112) is not particularly limited as long as it is a compound obtained by reacting a (meth) acrylic acid having a hydroxyl group with an isocyanate, for example, a hydroxyl group per equivalent of a compound having two isocyanate groups. These compounds can be obtained by reacting in the presence of a metal-based compound (such as a tin compound and a bismuth compound) using as a catalyst 2 equivalents of (meth) acrylic acid having

It does not specifically limit as an isocyanate used as a raw material of said monomer (C112), An isophorone diisocyanate, 2, 4- tolylene diisocyanate, 2, 6- tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate , Tris (isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate and 1,6,10-undecanetriisocyanate And the like.
Moreover, as said isocyanate, the chain extension obtained by reaction of a polyol (Ethylene glycol, glycerol, sorbitol, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol etc.) and excess isocyanate It is also possible to use the isocyanate compounds mentioned.

  The (meth) acrylate having a hydroxyl group as a raw material of the monomer (C112) is not particularly limited, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate And 2-hydroxybutyl (meth) acrylate, and mono (meth) acrylate of a dihydric alcohol such as polyethylene glycol.

[Bifunctional polyester (meth) acrylate monomer (C113)]
The monomer (C113) is obtained by esterifying the hydroxyl group of a polyester oligomer having a hydroxyl group at the end obtained by condensation of a polycarboxylic acid and a polyol with (meth) acrylic acid, or adding an alkylene oxide to a polycarboxylic acid The terminal hydroxyl group of the resulting oligomer can be obtained by esterification with (meth) acrylic acid.

  As a polyol which is a structural unit of the said monomer (C113), alkylene glycol (Ethylene glycol, 1, 2- propylene glycol, 1, 3- propylene glycol, 1, 4- butanediol, neopentyl glycol, 1, 4) -Butenediol, 1,5-pentanediol and 1,6-hexanediol etc., alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol etc.), alicyclic Diols (1,4-cyclohexanedimethanol and hydrogenated bisphenol A, etc.), bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.), bisphenol alkylene Kisaido (ethylene oxide, propylene oxide and butylene oxide, etc.) adducts (average addition molar number 2 to 8) and glycerin.

  Examples of the polycarboxylic acid which is a constituent unit of the monomer (C113) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sevantic acid, Azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, isooctenylsuccinic acid, n-octylsuccinic acid, isooctylsuccinic acid and aconite Acids and anhydrides or lower alkyl esters of these acids and the like can be mentioned.

[Trifunctional (meth) acrylate monomer (C12)]
As the monomer (C12), trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, alkylene oxide modified tri (meth) acrylate of trimethylolpropane, pentaerythritol tri (meth) acrylate, dipenta Erythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, sorbitol tri (meth) acrylate, tri (2 to 30 moles of a C2-C3 alkylene oxide adduct of pentaerythritol, tri (tri) Meta) acrylate, ethoxylated glycerin tri (meth) acrylate, propionic acid dipentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri Acrylate and the like ethoxylated isocyanuric acid triacrylate.

[A tetrafunctional or higher (meth) acrylate monomer (C13)]
Examples of the monomer (C13) include tetrafunctional or higher (meth) acrylate monomers (C131) and tetrafunctional or higher urethane (meth) acrylate monomers (C132).

[Tetrafunctional or higher (meth) acrylate monomer (C131)]
Examples of the monomer (C131) include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and propionate dipentaerythritol tetra (meth) ) Acrylate, tetra (meth) acrylate of 1 to 11 moles adduct of C 2 -C 3 alkylene oxide of pentaerythritol, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, sorbitol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate and the like can be mentioned.

[Tetrafunctional or higher urethane (meth) acrylate monomer (C132)]
The above-mentioned monomer (C132) is U-6LPA, UA-1100H, U-15HA (above, Shin-Nakamura Chemical Co., Ltd. product), UN-3320HA, UN-3320HC, UN-3320HS, UN-904, UN- 906S, UN-901T, UN-905, UN-952 (above, made by Negami Kogyo Co., Ltd.), UA-306H, UA-306T, UA-306I, UA-510H (above, made by Kyoeisha Chemical Co., Ltd.), etc. It can be obtained from the market.

The (meth) acrylate monomer (C1) preferably has a high radical polymerization rate and a large reaction heat. If the radical polymerization rate is high, even small amounts of radical species can be cured. In addition, when the heat of reaction is large, the cationic polymerization reaction can be catalyzed, thereby accelerating the curing. Therefore, it is desirable that the (meth) acrylate monomer (C1) has a high functional group density.
In addition, when a substance such as coloring agent (D) and / or metal oxide powder (E) is present at a high concentration, light does not reach the deep part, so curing occurs only near the surface and in the deep part (internal) Hardening is difficult. When the deep part (inner part) is uncured, the adhesion at the interface between the base and the resin is lowered, so that the base adhesion is lowered.
Among the above-mentioned (meth) acrylate monomers (C1), preferred from the above-mentioned viewpoints (curability, adhesion to a substrate and stain resistance) are (C12) and (C13), and more preferred is (C131) ).
The above-mentioned polyfunctional (meth) acrylate monomers (C1) may be used alone or in combination of two or more.

The weight average molecular weight (hereinafter sometimes abbreviated as Mw) of the polyfunctional (meth) acrylate monomer (C1) 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 Corp.) connected, and the column temperature may be 40 ° C.

  As a C5-C30 bifunctional epoxy monomer (C2) which does not have an ester group and has an alicyclic skeleton, norbornadiene dioxide, dipentene dioxide, vinylcyclohexene dioxide, 5, 6-epoxy-4, 7 -Mesano-1-oxaspiro- (2,5) -octane, limonene dioxide, a compound represented by the following general formula (6), a compound represented by the following general formula (7), and the like.

In the general formula (6) and the general formula ^(7), R 1 ^{to R 26} each represent a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group having 1 to 18 carbon atoms having 1 to 18 carbon atoms.

The carbon atom in the said C1-C18 hydrocarbon group may be substituted by the oxygen atom, and the hydrogen atom may be substituted by the halogen atom.
The carbon atom in the said C1-C18 alkoxy group may be substituted by the oxygen atom, and the hydrogen atom may be substituted by the halogen atom.
Among R ^{1 to} R ²⁶ , hydrogen atoms, halogen atoms and hydrocarbon groups having 1 to 4 carbon atoms (such as methyl, ethyl, propyl and butyl groups) are preferable from the viewpoint of curability, more preferably Is a hydrogen atom.

Further, in the general formula (6) and the general formula (7), a to h are each independently an integer of 0 to 4.
Further, in the general formula (6), from the viewpoint of curability, the combination of a, b, c and d is preferably (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) or a = 2, b = 1, c = 2, d = 1), and more preferably (a = 1, b = 0, c = 1, d = 0), (a = 1, b = 1, c) = 1, d = 0) or (a = 1, b = 1, c = 1, d = 1), particularly preferably (a = 1, b = 1, c = 1, d = 0) .
Further, in the general formula (7), from the viewpoint of curability, a combination of e, f, g and h is preferably (e = 1, f = 1, g = 0, h = 1), (e = 1, f = 1, g = 1, h = 1) or (e = 1, f = 2, g = 1, h = 1), more preferably (e = 1, f = 1, g = 0, h = 1).

As a compound represented by General formula (6), 3a, 4, 7, 7a- tetrahydro indendi oxide etc. are mentioned.
As a compound represented by General formula (7), a dicyclopentadiene dioxide etc. are mentioned.

  The compounds represented by the general formula (6) and the compounds represented by the general formula (7) can be synthesized by the method described in WO 2014/175129, and the like.

  In cationic polymerization with an epoxy compound, it is desirable that the epoxy monomer has a high functional group density and does not have a highly polar group such as an ester group, a urethane group, a urea group, or an amino group. If the functional group density is high, the initiation reaction rate will be high, and if it does not have a highly polar group, chain transfer reaction will be difficult to occur.

The functional group density [x] (mmol / g) of the epoxy monomer can be calculated by the following formula (1).
[X] = (a ₀ × c ₀ / M ₀ + a ₁ × c ₁ / M ₁ +...
+ A _i × c _i / M _i +... + A _n × c _n / M _n ) × 10 (1)
In the above formula (1), a ₀ , a ₁ ,... A _i ,... A _n represent the weight percentage of each component of the epoxy group-containing compound constituting the epoxy monomer (hereinafter abbreviated as each component), c _{0 , c 1, ··· c i,} ··· c n is the number of epoxy groups in the _{components, M 0, M 1, ···} M i, ··· M n , the molecular weight of each component Represent.

Among the above-mentioned epoxy monomers (C2), preferred are the compounds represented by the general formula (6) and the compounds represented by the general formula (7) from the viewpoints of curability, adhesion to a substrate and stain resistance. And more preferably 3a, 4,7,7a-tetrahydroindendioxide, 1,3a, 4,6a-tetrahydropentadioxide, dicyclopentadiene dioxide and 1-methyldicyclopentadiene dioxide.
The epoxy monomers (C2) may be used alone or in combination of two or more.

  As a C5-C30 oxetane monomer (C3), a monofunctional oxetane monomer (C31), a bifunctional oxetane monomer (C32), a trifunctional or more than trifunctional oxetane monomer (C33), etc. are mentioned.

[Monofunctional oxetane monomer (C31)]
Examples of (C31) include 3-ethyl-3-hydroxymethyl oxetane (trade name “OXT-101”, manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (product Name "OXT-212", manufactured by Toagosei Co., Ltd., 3-ethyl-3-phenoxymethyl oxetane (trade name "OXT-211", manufactured by Toagosei Co., Ltd.), 3-ethyl-3-cyclohexoxymethyl Oxetane (trade name "OXT-213", manufactured by Toagosei Co., Ltd.), 3-ethyl-3-acryloxymethyl oxetane (trade name "OXE-10", manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 3-ethyl -3- methacryloxymethyl oxetane (trade name "ETERNACOLL OXMA", manufactured by Ube Industries, Ltd.) and the like.

[Bifunctional oxetane monomer (C32)]
Examples of (C32) include polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (hereinafter sometimes abbreviated as EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether Propylene oxide (hereinafter sometimes abbreviated as 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-oxetanyl methoxy) ) Methyl] benzene (brand name "OX “-121”, manufactured by Toagosei Co., Ltd., 3-ethyl-3 {[(3-ethyloxetan-3-yl) methoxy] methyl} oxetane (trade name “OXT-221”, manufactured by Toagosei Co., Ltd.) 4,4'-bis [3-ethyl- (3-oxetanyl) methoxymethyl] biphenyl (trade name "ETERNACOLL OXBP", manufactured by Ube Industries, Ltd.), di (3-ethyl-3-oxetanyl) methoxyethyl adipine Acid (trade name "bis adipate oxetane", manufactured by Ube Industries, Ltd.), bis (3-ethyl oxetane-3-ylmethyl) carbonate (trade name "dioxetane carbonate", manufactured by Ube Industries, Ltd.) and bis terephthalate -(3-ethyl-oxetan-3-ylmethyl) ester (brand name "OXTP", Ube Industries, Ltd. product) etc. are mentioned.

[Trifunctional or higher oxetane monomer (C33)]
As (C33) above, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanyl) Methyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexakis (3-ethyl-3) -Oxetanylmethyl) ether, caprolactone modified with dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-o Setanirumechiru) ether and the like.
In the cationic polymerization by the ring opening reaction, it is desirable that the monomer be used in combination with an epoxy monomer and an oxetane monomer. Epoxy monomers have a high initiation reaction rate, but a low growth reaction rate and a high chain transfer reaction rate. The oxetane monomer has a very low initiation reaction rate, but a high growth reaction rate and a low chain transfer reaction rate. Therefore, by using an epoxy monomer and an oxetane monomer in combination, it is possible to dramatically increase the cationic polymerization rate by the ring-opening reaction, and the polymerization proceeds even with a small amount of acid. Therefore, it is desirable that the oxetane monomer have a high functional group density.
Among the oxetane monomers (C3), preferred are (C31) and (C32) from the viewpoints of curability, adhesion to a substrate, and stain resistance, and more preferred is (C32).
The above-mentioned oxetane monomers (C3) may be used alone or in combination of two or more.

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

  Examples of the inorganic pigment include yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc oxide, bengala, alumina, calcium carbonate, ultramarine blue, carbon black, graphite and titanium black.

  Examples of organic pigments include soluble azo pigments such as β-naphthol, β-hydroxynaphthoic acid anilide, acetoacetic acid anilide and pyrazolone, β-naphthol, β-oxynaphthoic acid, β-oxynaphthoic acid anilide, acetoacetic acid anilide monoazo and acetoacetate Insoluble azo pigments such as anilide anilide disazo and pyrazolone, phthalocyanine pigments such as copper phthalocyanine blue, copper phthalocyanine blue halide, sulfonated copper phthalocyanine blue, metal free phthalocyanine, etc Polycyclic or heterocyclic compounds may be mentioned.

  Specific examples of the dye include, as a yellow dye, an aryl or heterylazo dye having phenol, naphthol, aniline, pyrazolone, pyridone or an open chain active methylene compound as a coupling component, and an azomethine dye having an open chain active methylene compound as a coupling component And methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; quinophthalone dyes, nitro, nitroso dyes, acridine dyes, acridinone dyes and the like.

  As magenta dyes, aryl or heterylazo dyes having phenol, naphthol, aniline, pyrazolone, pyridone, pyrazolotriazole, ring-closing active methylene compounds or heterocyclic rings (such as pyrrole, imidazole, thiophene and thiazole) as coupling components, coupling Azomethine dyes, arylidene dyes, styryl dyes, merocyanine dyes and methine dyes such as oxonol dyes having pyrazolone or pyrazolotriazole as components, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, naphthoquinones, anthraquinones and anthrapyridones, etc. And condensed polycyclic dyes such as dioxazine dyes.

As cyan dyes, azomethine dyes such as indoaniline dyes and indophenol dyes, polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, anthraquinone dyes And aryl or heterylazo dyes (such as CI Direct Blue 14) having phenol, naphthol, aniline, pyrrolopyrimidinone or pyrrolotriazinone as coupling components, 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, and more preferably 0.01 μm to 1.0 μm, as an average particle size from the viewpoint of the sharpness of the coating film.

The active energy ray curable composition (Z) of the present invention can be used for forming a green sheet and forming an electrode layer of a ceramic electronic component by containing the metal oxide powder (E).
As the metal oxide powder (E), Si, Mg, Al, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Sn, except for those mentioned as the above-mentioned colorant (D) The particle | grains containing the oxide of Zn are mentioned.
Specific examples thereof include aluminum oxide, barium titanate, calcium zirconate, niobium oxide and lead zirconate titanate.
Examples of the shape of the metal oxide powder (E) include spherical particles and needle-like particles.
The metal oxide powder (E) may be used alone or in combination of two or more.

  The particle size of the metal oxide powder (E) is preferably 0.01 μm to 2.0 μm as an average particle size, more preferably 0.01 μm to 1.0 μm, from the viewpoint of dielectric constant.

The active energy ray-curable composition (Z) of the present invention contains other additives in addition to the components (A), (B), (C1), (C2), (C3), (D) and (E). It may contain an agent.
Other additives include dispersant (F), sensitizer (G), solvent and the like.

As a dispersing agent (F), the dispersing agent (Anti-Terra-U, Disperbyk-101,106,110,161,162,164,167,168,170,174,182,184 or the product made by BIC Chemie company or 2020 etc.), Ajinomoto Fine Techno Co., Ltd. dispersants (Adisper PB711, PB821, PB814, PN411 and PA111 etc.), Lubrizol Co., Ltd. dispersants (Solspase 5000, 12000, 32000, 33000, 36000 and 39000 etc.).
The dispersant (F) may be used alone or in combination of two or more.

As the sensitizer (G) in the present invention, anthracene, thioxanthone, benzophenone thioxanthone, phenothiazine, perylene and the like can be mentioned.
Among them, anthracene is preferable because it can dramatically improve the photosensitivity by using it in combination with a cationic polymerization initiator.
As a sensitizer for anthracene, it is possible to use diexianthracene (trade name “UVS-1101”, manufactured by Kawasaki Kasei Kogyo Co., Ltd.), dipropoxy anthracene (trade name “UVS-1221”, manufactured by Kawasaki Kasei Kogyo Co., Ltd.), Dibutoxyanthracene (trade name "UVS-1331" manufactured by Kawasaki Kasei Kogyo Co., Ltd.) can be mentioned.
Among the sensitizers (G), dibutoxyanthracene is preferred from the viewpoint of solubility and curability.
As the sensitizer (G), one type may be used alone, or two or more types may be used in combination.

The weight ratio of the monomer (C1) is preferably 29 to 95% by weight based on the total weight of the monomer (C1), the monomer (C2) and the monomer (C3) from the viewpoint of curability. More preferably, it is 50 to 90% by weight, and particularly preferably 50 to 75% by weight.
The weight ratio of the monomer (C2) is preferably 1 to 30% by weight based on the total weight of the monomer (C1), the monomer (C2) and the monomer (C3) from the viewpoint of curability. More preferably, it is 1 to 10% by weight.
The weight ratio of the monomer (C3) is preferably 4 to 70% by weight based on the total weight of the monomer (C1), the monomer (C2) and the monomer (C3) from the viewpoint of curability. More preferably, it is 5 to 50% by weight, and particularly preferably 20 to 50% by weight.

  The weight ratio of the photo radical initiator (A) is preferably 1 to 30% by weight, more preferably 5 to 20% by weight based on the weight of the monomer (C1) from the viewpoint of curability. is there.

  The weight ratio of the acid generator (B) is preferably 1 to 30% by weight based on the total weight of the monomer (C2) and the monomer (C3) from the viewpoint of curability, more preferably Is 5 to 20% by weight.

  The proportion of the total weight of the colorant (D) and the metal oxide powder (E) is preferably based on the weight of the active energy ray-curable composition (Z) from the viewpoint of colorability and mechanical properties. Is 1 to 60% by weight, more preferably 1 to 30% by weight.

  The weight ratio of the dispersant (F) is determined by using the colorant (D) and the metal oxide powder (E) from the viewpoint of the dispersibility of the colorant (D) and the metal oxide powder (E). It is preferably 1 to 90% by weight, more preferably 5 to 80% by weight, based on the total weight.

  The weight ratio of the sensitizer (G) is preferably 0.1 based on the total weight of the monomer (C1), the monomer (C2) and the monomer (C3) from the viewpoint of curability. It is 10 wt%, more preferably 0.5 to 5 wt%.

The method for producing the active energy ray-curable composition (Z) 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 monomer (C3), and the color Agent (D) and / or the above-mentioned metal oxide powder (E), and, if necessary, the above-mentioned dispersant (F) and sensitizer (G) in a temperature range of 20 to 80 ° C. It can manufacture by mixing uniformly by using the mechanical mixing method (The method of using a mechanical stirrer, a magnetic stirrer, etc.).

The active energy ray-curable composition (Z) of the present invention can be photocured by irradiation with actinic rays of 360 nm to 830 nm, and therefore, other than high pressure mercury lamps generally used, super high pressure mercury lamps, metal halide lamps and high power Metal halide lamps and the like (latest trends in UV / EB curing technology, edited by Rad Tech Research Association, CMC Publishing, p. 138, 2006) can be used.
Heating may be performed in order to diffuse the acid generated from the acid generator during and / or after irradiation with actinic radiation.
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.

  As a method of applying the active energy ray-curable composition (Z) of the present invention to a substrate, known coating methods (spin coat, roll coat, spray coat etc.) and known printing methods (lithography, carton printing, Metal printing, offset printing, screen printing, gravure printing, etc. can be applied. Further, the present invention can also be applied to the application of an ink jet method in which fine droplets are continuously discharged.

  The active energy ray-curable composition (Z) of the present invention is capable of thick film curing with a small amount of energy and high colorant concentration, so it can be used as a coating agent, ink (UV printing ink, UV inkjet printing ink, etc.), paint, It is extremely useful as a material for producing adhesives and ceramic electronic components.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Production Example 1: Production of Acid Generator (B1-2) {Compound Represented by Chemical Formula (8)} 12.1 parts by weight of diphenyl sulfoxide, 9.3 parts by weight of diphenyl sulfide and 43.0 parts by weight of methanesulfonic acid While stirring, 7.9 parts by weight of acetic anhydride is added dropwise thereto, reacted at 40 to 50 ° C. for 5 hours, cooled to room temperature (about 25 ° C.), and this reaction solution is 20% by weight of tris (pentafluoro) The mixture was poured into 121 parts by weight of an aqueous solution of (ethyl) potassium trifluoroborate, and stirred at room temperature for 1 hour to precipitate a yellow viscous oil. The oil is extracted with ethyl acetate, and the organic layer is washed with water several times, and then the solvent is distilled off from the organic layer, and toluene is added to the obtained residue to dissolve it, and then hexane is added to the residue. After stirring for 1 hour, the mixture was allowed to stand. After 1 hour, the solution separated into two layers, so the upper layer was removed by separation. Hexane was added to the residue and mixed well at room temperature to precipitate pale yellow crystals. The resultant was separated by filtration and dried under reduced pressure to obtain 48 parts by weight of the target acid generator (B1-2).

Production Example 2: Production of Acid Generator (B2-1) {Compound Represented by Chemical Formula (9)}

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

Production Example 3: Production of 3a, 4,7,7a-tetrahydro indendioxide (C2-1) In a SUS reaction vessel equipped with a cooling pipe, a stirring device, and a thermometer, 3a, 4,7,7a-tetrahydroindene [ 120 parts by weight of Tokyo Chemical Industry Co., Ltd. and 480 parts by weight of ethyl acetate were charged, and 1,270 parts by weight of an ethyl acetate solution having a peracetic acid concentration of 30% by weight was added dropwise over 3 hours. The reaction temperature was adjusted to maintain 30 ° C. during the addition. After completion of the dropwise addition, the reaction temperature was maintained at 30 ° C. for 3 hours to complete the epoxidation reaction. After cooling the reaction solution to room temperature, 1200 parts by weight of a 20 wt% aqueous sodium hydroxide solution is added, stirred for 1 hour, allowed to stand for 30 minutes, and separated to separate unreacted peracetic acid and acetic acid by-product Removed. After distilling off ethyl acetate using a distillation apparatus, 152 parts by weight of 3a, 4, 7, 7a-tetrahydro indendioxide (C2-1) was obtained.

Production Example 4: Production of dicyclopentadiene dioxide (C2-2) 132 parts by weight of dicyclopentadiene [manufactured by Tokyo Chemical Industry Co., Ltd.] in a glass reaction vessel equipped with a cooling pipe, a stirrer, and a thermometer, ethyl acetate 480 parts by weight was charged, and 1,270 parts by weight of an ethyl acetate solution having a peracetic acid concentration of 30% by weight was dropped over 3 hours. The reaction temperature was adjusted to maintain 30 ° C. during the addition. After completion of the dropwise addition, the reaction temperature was maintained at 30 ° C. for 3 hours to complete the epoxidation reaction. After cooling the reaction solution to room temperature, 1200 parts by weight of a 20 wt% aqueous sodium hydroxide solution is added, stirred for 1 hour, allowed to stand for 30 minutes, and separated to separate unreacted peracetic acid and acetic acid by-product Removed. After distilling off ethyl acetate using a distillation apparatus, 164 parts by weight of dicyclopentadiene dioxide (C2-2) was obtained.

<Examples 1 to 45, Comparative Examples 1 to 5>
(A) to (G) listed in Table 1 are compounded according to the blending composition (parts by weight) listed in Table 1 and uniformly mixed at 20 ° C., using an Ultra Disperser manufactured by Yamato Scientific Co., Ltd. The active energy ray-curable composition (Z) of Examples 1 to 45 and the comparative active energy ray-curable composition of Comparative Examples 1 to 5 were stirred at a circumferential speed of 23 m / s (rotational speed: 10,000 rpm). Obtained.

Next, using an applicator, a 100 μm-thick PET film (trade name “Cosmo Shine A4300”, Toyobo Co., Ltd. product) which has been subjected to surface treatment for each active energy ray curable composition (Z) obtained. The coating was applied so that the film thickness after curing was 30 μm, and the solvent was dried by heating at 80 ° C. for 1 minute using a normal air drier (manufactured by Tabai Espec Corp.). It was cured at an exposure amount of 500 mJ / cm ² with a belt conveyor type UV irradiation apparatus (“ECS-151U” manufactured by I-Graphics Co., Ltd.) under an air atmosphere and at room temperature to obtain a cured product for evaluation.
The cured product was evaluated according to the following evaluation methods (1) to (3). The evaluation results are shown in Tables 1 and 2.

<Evaluation method>
(1) Coating film appearance and finger touch test [Evaluation of curability]
The cured product for evaluation was evaluated for curability by visual observation and finger touch, and was evaluated according to the following criteria.
<Evaluation criteria>
:: no curing wrinkles, no tackiness ○: curing wrinkles but no tackiness Δ: at least 1 part cures but tackiness ×: not cured

(2) Adhesion to substrate [Evaluation of adhesion to substrate]
According to JIS K 5600-5-6, the cured product for evaluation is cross-cut into 2 mm × 2 mm grids (10 × 10 = 100 squares), an adhesive tape is stuck on this, and peeled off, 100 squares The number of squares in close contact without peeling was counted visually and evaluated according to the following criteria.
<Evaluation criteria>
:: 100/100
○: 99/100 to 90/100
:: 89/100 to 50/100
X: 49/100 to 0/100

(3) Contamination resistance A black, blue, red Magic Ink (registered trademark) large-sized [made by Terasai Chemical Industry Co., Ltd.] is used to draw a straight line 4-5 cm in length and store in a constant temperature room at 23 ° C for 24 hours did. Subsequently, a solvent in which petroleum benzine and ethanol were mixed in equal parts by mass was sufficiently impregnated into the absorbent cotton, and the drawn straight line was wiped once while being compressed. At this time, the state of the ink remaining in the coating film was evaluated as contamination.
◎: No trace ○: There is a trace, but the shape of the original line can not be determined.
Fair: There is a thin trace, and the shape of the original line can be determined.
X: There is clearly a trace left.

The abbreviations in Tables 1 and 2 are as follows.
<Photo radical initiator (A)>
(A-1): bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide [trade name “IRGACURE 819”, manufactured by BASF Corp., ε: 899]
(A-2): 2,4,6-trimethyl benzoyl diphenyl phosphine oxide [brand name "IRGACURE TPO", BASF Co., Ltd. product, (epsilon): 165]
(A-3): 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [trade name "IRGACURE 127" “BASF Co., Ltd., ε: 7”
(A-4): 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone [trade name “IRGACURE 379 EG”, BASF Co., Ltd., ε: 280]

<Acid Generator (B)>
(B1-1): Diphenyl 4-thiophenoxyphenylsulfonium hexafluorophosphate (trade name "CPI-110P", manufactured by San Apro Co., Ltd.)
(B1-2): Diphenyl 4-thiophenoxyphenylsulfonium tris (pentafluoroethyl) trifluorophosphate (B2-1): 4-methylphenyl-4- (1-methylethyl) phenyliodonium tri (pentafluoroethyl) ) Trifluorophosphate (B2-2): 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate [trade name "IRGACURE 250", manufactured by BASF Corp.]

<(Meth) acrylate monomer (C1)>
(C1-1): pentaerythritol tetraacrylate [trade name “NEOMER EA-300”, Sanyo Chemical Industries, Ltd., Mw: 352]
(C1-2): dipentaerythritol pentaacrylate [trade name "Neomer DA-600", Sanyo Chemical Industries, Ltd., Mw: 524]
(C1-3): Ethoxylated (4) Pentaerythritol tetraacrylate [trade name "SR494", manufactured by Sartomer Corporation]
(C1-4): Ditrimethylolpropane tetraacrylate (trade name "AD-TMP", manufactured by Shin-Nakamura Chemical Co., Ltd.)
<Epoxy monomer (C2)>
(C2-3): limonene dioxide [trade name "LDO", manufactured by Sakai Chemical Industry Co., Ltd.]
(C2-4): vinylcyclohexene dioxide [trade name "vinylcyclohexene dioxide", manufactured by Sigma-Aldrich Inc.]
(Ratio C2-1): 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (trade name "Ceroxide 2021 P", manufactured by Daicel Corporation)
(Ratio C2-2): 1,6-hexanediol diglycidyl ether [trade name "Denacol Ex-212", Nagase ChemteX Co., Ltd. product]
<Oxetane Monomer (C3)>
(C3-1): 3-ethyl-3 {[(3-ethyl oxetan-3-yl) methoxy] methyl} oxetane [trade name "OXT-221", manufactured by Toagosei Co., Ltd.]
(C3-2): 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene [trade name “OXT-121”, manufactured by Toagosei Co., Ltd.]
(C3-3): 3-ethyl-3-hydroxymethyl oxetane [trade name "OXT-101", manufactured by Toagosei Co., Ltd.]
(C3-4): 3-ethyl-3-phenoxymethyl oxetane [trade name "OXT-211", manufactured by Toagosei Co., Ltd.]

<Colorant (D)>
(D-1): carbon black having an average primary particle diameter of 56 nm (product "Special Black 250", manufactured by Degussa Co., Ltd.)
(D-2): MEK dispersion of carbon black having an average primary particle diameter of 150 nm [Product “MHI Black # 273, manufactured by Mikuni Dye Co., Ltd., solid content concentration: 18% by weight]
<Metal oxide powder (E)>
(E-1): Titanium oxide particles having an average primary particle diameter of 240 nm (trade name "PF-736", manufactured by Ishihara Sangyo Co., Ltd.)
<Dispersing agent (F)>
(F-1): polymeric dispersant (acid value: 15 mg KOH / g, weight average molecular weight: 3, 900) [trade name "Solsperse 32000", manufactured by Lubrizol Corporation]
(F-2): Polymeric dispersant (acid value: 45 mg KOH / g, amine value: 0 mg KOH / g, weight average molecular weight about 50,000) [trade name "Solsperse 36000", manufactured by Lubrizol Corporation]
<Sensitizer (G)>
(G-1): 9, 10-dibutoxyanthracene [Product side "Antracure UVS-1331", manufactured by Kawasaki Kasei Kogyo Co., Ltd.]

From the results of Tables 1 and 2, the active energy ray-curable composition (Z) of the present invention is excellent in the curability as compared with the comparative active energy ray-curable composition of the comparative example.
In addition, the cured product of the active energy ray curable composition (Z) of the present invention is excellent in substrate adhesion as compared to the cured product of the comparative active energy ray curable composition of the comparative example, and the deep portion It is understood that the curability is also sufficient. Moreover, it turns out that it is excellent also in contamination resistance.
The mechanism of the stain resistance is the same as that of the super water repellent performance (Lotus effect) exhibited by the lotus leaf, in which the coating film surface of the cured product of the active energy ray curable composition of the present invention has a fine uneven structure. It is estimated that the effect is manifested.
The fine concavo-convex structure is due to the volume contraction rate difference due to the curing rate difference between the coating surface and the inside of the coating. In the ordinary method, the difference in curing speed is large, and a coarse uneven structure is formed, so the Lotus effect is not expressed. On the other hand, in the active energy ray curable composition of the present invention, it is estimated that the curing speed difference is small, and a fine uneven structure ideal to show the Lotus effect can be formed.

The active energy ray curable composition (Z) of the present invention contains a colorant and / or a metal oxide, but even in the case of a thick film, it has excellent curability at the time of active energy ray irradiation, A cured product obtained by curing is extremely useful as a material for producing coating agents, inks (UV printing inks and UV inkjet printing inks, etc.), paints, adhesives and ceramic electronic parts since it is excellent in substrate adhesion. .

Claims (7)

  Photoradical initiator (A), acid generator (B), polyfunctional (meth) acrylate monomer (C1), and a bifunctional epoxy resin having no ester group and an alicyclic skeleton and having 5 to 30 carbon atoms Active energy ray curable composition (Z) containing a monomer (C2), a C5-C30 oxetane monomer (C3), a coloring agent (D), and / or metal oxide powder (E). The acid generator (B) is an acid generator comprising 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 according to claim 1, which is   The weight ratio of the polyfunctional (meth) acrylate monomer (C1) is 29 to 30 based on the total weight of the polyfunctional (meth) acrylate monomer (C1), the bifunctional epoxy monomer (C2) and the oxetane monomer (C3) It is 95 weight%, the weight ratio of said bifunctional epoxy monomer (C2) is 1 to 30 weight%, and the weight ratio of said oxetane monomer (C3) is 4 to 70 weight%. Active energy ray curable composition.   The active energy according to any one of claims 1 to 3, wherein the proportion by weight of the photo radical initiator (A) is 1 to 30% by weight based on the weight of the polyfunctional (meth) acrylate monomer (C1). Radiation curable composition.   The weight ratio of the acid generator (B) is 1 to 30% by weight based on the total weight of the bifunctional epoxy monomer (C2) and the oxetane monomer (C3). Active energy ray curable composition as described.   The coating agent containing the active energy ray curable composition of any one of Claims 1-5. A cured product of the active energy ray curable composition according to any one of claims 1 to 6.