JPH11199681A - Photopolymerizable composition and formation of curable coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymerizable composition having good curing rate without suffering inhibition of curing due to enzyme, especially a photopolymerizable composition having good curing rate even when used with pigment. SOLUTION: This photopolymerizable composition consists essentially of a cation polymerizable organic substance, an energy beam-sensitive cation polymerization initiator and a compound represented by the formula (Rs are each methyl group or ethyl group which may be the same or different).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable composition and a method for forming a cured coating film, and more particularly to a photopolymerizable composition capable of polymerizing a cationically polymerizable organic substance with an energy ray-sensitive cationic polymerization initiator. And a method for forming a cured coating film using the same.

[0002]

2. Description of the Related Art Polymerization of a cationically polymerizable organic substance with an energy-ray-sensitive cationic polymerization initiator is not affected by oxygen, has a preferable curability, and has been conventionally performed. However, the curing of such a cationically polymerizable organic substance has a problem that the curing speed is low.

[0003] For this reason, a radical polymerizable substance having a high curing rate and an energy ray-sensitive radical polymerization initiator have also been used, but they are susceptible to curing inhibition by oxygen.

[0004] Photosensitizers have also been used, but when the photopolymerizable composition was used together with a pigment, the curing speed was insufficient.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photopolymerizable composition which is not subject to curing inhibition by oxygen and has a good curing rate. It is an object of the present invention to provide a photopolymerizable composition having a high curing rate and a method for forming a cured coating film using the composition.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above object can be achieved by using a specific anthracene compound as a photosensitizer. The invention has been completed.

That is, the photopolymerizable composition of the present invention comprises, as essential components, (1) a cationically polymerizable organic substance,
(2) an energy ray-sensitive cationic polymerization initiator;
(3) The following general formula: (Wherein R may be the same or different and is a methyl group or an ethyl group.).

Further, the photopolymerizable composition is characterized in that the photopolymerizable composition further comprises (4) a pigment.

Further, in the photopolymerizable composition,
(2) 200 of energy ray-sensitive cationic polymerization initiators
A photopolymerizable composition, characterized in that the light-absorbing area in the range of 350 to 450 nm is less than 10% of the total light-absorbing area of the light-absorbing curve in the range of -500 nm.

Further, the photopolymerizable composition is characterized in that at least 40% by weight of the cationically polymerizable composition is an alicyclic epoxy compound having a cyclohexene oxide structure.

Further, the present invention relates to the photopolymerizable composition,
It is applied so as to have a thickness of 00 μm or less.
0.1 mJ / cm of light having a wavelength of 500 nm or more and 500 nm or less
^{The present} invention relates to a method for forming a cured coating film characterized by irradiating ^two or more.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The (1) cationically polymerizable organic substance used in the present invention refers to a compound which undergoes polymerization or cross-linking reaction by an energy ray-sensitive cationic polymerization initiator activated by irradiation with energy rays.

For example, epoxy compounds, cyclic ether compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiroorthoester compounds,
Vinyl compounds and the like, and one or more of these can be used. Among them, epoxy compounds that are easily available and convenient to handle are suitable. As such an epoxy compound, an aromatic epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin and the like are suitable.

Specific examples of the aromatic epoxy resin include a polyhydric phenol having at least one aromatic ring or a polyglycidyl ether of an alkylene oxide adduct thereof, such as bisphenol A and bisphenol F, and furthermore an alkylene oxide. Glycidyl ether, epoxy novolak resin, etc.

Further, specific examples of the alicyclic epoxy resin are obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or a compound containing cyclohexene or cyclopentene ring with an oxidizing agent. And a compound having a vinylcyclohexane oxide structure obtained by epoxidizing a compound having a cyclohexene oxide structure, a compound having a cyclopentene oxide structure, or a compound having a vinylcyclohexane structure with an oxidizing agent.
For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-
Epoxycyclohexyl carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxy Cyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methyl Cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide 4 - vinyl epoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexyl methyl) adipate, 3,4-epoxy-6-methylcyclohexyl carboxylate, methylene bis (3,
4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, epoxyhexahydrophthalate And di-2-ethylhexyl acid.

Specific examples of the aliphatic epoxy resin include a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof, a polyglycidyl ester of an aliphatic long-chain polybasic acid, and an aliphatic long-chain unsaturated hydrocarbon. And glycidyl acrylate or glycidyl methacrylate homopolymer, glycidyl acrylate or glycidyl methacrylate copolymer, and the like. Representative compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, dipentaerthry Glycidyl ethers of polyhydric alcohols such as tall hexaglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Further, polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol and glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids can be mentioned. Can be Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, epoxy stearin Octyl acid, butyl epoxystearate, epoxidized linseed oil, epoxidized polybutadiene, and the like.

Further, among the above epoxy compounds, 1
Those containing two or more epoxy groups in the molecule,
(1) Energy ray-curable cationic polymerizable organic compound 1
It is particularly preferable to use 50% by weight or more of the 00 parts by weight. As the remaining 50% by weight or less, a compound having one epoxy group in one molecule or a cationic polymerizable organic compound other than the epoxy compounds exemplified below can be used. In addition, a mixture of a cationic polymerizable compound other than an epoxy compound and the above-mentioned cyclohexene oxide compound is also preferable.

Specific examples of the cationically polymerizable organic compound other than the epoxy compound which can be used in the present invention include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-methyl -3-hydroxymethyloxetane, 3-ethyl-3
-Hydroxymethyloxetane, 1,4-bis [(3-
Oxetane compounds such as ethyl-3-oxetanylmethoxy) methyl] benzene, tetrahydrofuran, 2,3-
Oxofuran compounds such as dimethyltetrahydrofuran,
Cyclic acetal compounds such as trioxane, 1,3-dioxolan, and 1,3,6-trioxanecyclooctane;
cyclic lactone compounds such as β-propiolactone and ε-caprolactone; thiirane compounds such as ethylene sulfide and thioepichlorohydrin; thietane compounds such as 1,3-propyne sulfide and 3,3-dimethylthiethane; tetrahydrothiophene Cyclic thioether compounds such as derivatives, ethylene glycol divinyl ether, alkyl vinyl ether, 3,4-dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate),
Examples include vinyl compounds such as triethylene glycol divinyl ether, spiro orthoester compounds obtained by reacting epoxy compounds with lactones, ethylenically unsaturated compounds such as vinylcyclohexene, isobutylene and polybutadiene, and derivatives of the above compounds.

In the present invention, as the (1) cationically polymerizable organic compound, one or more of the above-mentioned cationically polymerizable compounds can be used in combination.

Further, particularly preferred (1) in the present invention.
An embodiment of the cationically polymerizable organic substance is an alicyclic epoxy compound having at least two or more epoxy groups in one molecule, and most preferably 40% by weight or more is an alicyclic epoxy resin having a cyclohexene oxide structure. However, the present invention is not limited to this.

The (2) energy ray-sensitive cationic polymerization initiator used in the present invention is a compound capable of releasing a substance which initiates cationic polymerization by irradiation with energy rays. Particularly preferred is Lewis by irradiation. A double salt that is an onium salt that releases an acid, or a derivative thereof. Representative examples of such compounds include salts of cations and anions represented by the general formula [A] ^{m +} [B] ^m- .

[0022] Here, it is preferable ⁺ cation ^{A m} is an onium, and its structure, for example, can be represented by _{^{[(R 1) a Z]}} m +.

Here, R ¹ is an organic group having ¹ to 60 carbon atoms and which may contain any number of atoms other than carbon. a is an integer of 1 to 5. a number of R ¹ are each independently, it may be the same or different. Further, at least one is preferably an organic group having an aromatic ring as described above. Z is S, N, Se, Te, P, As, S
b, Bi, O, I, Br, Cl, F, an atom or an atomic group selected from the group consisting of N = N. Further, when the valence of Z in the cation ^{Am +} is z, it is necessary that the relationship m = az is satisfied.

Further, the anion ^{B m-is} preferably a halide complex, and its structure, for example, can be represented by _[LX ^{b] m-.}

Here, L is a metal or semimetal (Metalloid) which is the central atom of the halide complex.
And B, P, As, Sb, Fe, Sn, Bi, A
1, Ca, In, Ti, Zn, Sc, V, Cr, Mn,
Co or the like. X is halogen. b is an integer of 3 to 7. Further, the valence of L in the anion B ^m− is p
In this case, it is necessary that the relationship m = bp is satisfied.

Specific examples of the anion [LX _b ] ^{m- in} the above general formula include tetrafluoroborate (BF ₄ ) ⁻ , hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , hexafluoro Arsenate (AsF ₆ ) ⁻ , hexachloroantimonate (SbCl ₆ ) ^{− and the} like.

Further, the anion ^{B m-may} be preferably used a structure represented by ^{_{m- [LX b-1 (OH}} )].
L, X and b are the same as above. Other anions that can be used include perchlorate ion (ClO
₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO
₃ ) ⁻ , fluorosulfonic acid ion (FSO ₃ ) ⁻ , toluenesulfonic acid anion, trinitrobenzenesulfonic acid anion and the like.

As the anion ^Bm- , tetrakis (pentafluorophenyl) borate can be preferably used.

In the present invention, it is particularly effective to use an aromatic onium salt among such onium salts.
Among them, JP-A-50-151997 and JP-A-50-1
Aromatic halonium salts described in JP-A-58680, and VIA aromatics described in JP-A-50-151997, JP-A-52-30899, JP-A-56-55420, JP-A-55-125105 and the like. Group onium salt, JP-A-50
A VA-group aromatic onium salt described in JP-A-1558698;
JP-A-56-8428, JP-A-56-149402
And oxosulfoxonium salts described in JP-A-57-192429, aromatic diazonium salts described in JP-A-49-17040, and thiobrillium salts described in U.S. Pat. No. 4,139,655 are preferred. Other preferable examples include an iron / allene complex and an aluminum complex / photolytic silicon compound-based initiator.

Among these aromatic onium salts, particularly preferred are those as cations. Or (Wherein, R represents a hydrogen atom, a halogen atom, or a hydrocarbon group optionally containing an oxygen atom or a halogen atom, or an alkoxy group optionally having a substituent, and Ar represents one or more hydrogen atoms. And a compound represented by the formula: (tolylcumyl) iodonium, bis (tertiarybutylphenyl) iodonium, triphenylsulfonium and the like. For example, 4,4 '
-Bis (di (β-hydroxyethoxy) phenylsulfonio) phenylsulfide-bis-hexafluorophosphate, 4- (4-benzoyl-phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4, 4′-bis (di (β-
Hydroxyethoxy) phenylsulfonio) phenylsulfide-bis-hexafluorophosphate, 4,
4′-bis (di (β-hydroxyethoxy) phenylsulfonio) phenylsulfide-bis-hexafluoroantimonate, 4,4′-bis (difluorophenylsulfonio) phenylsulfide-bis-hexafluorophosphate, 4,4 '-Bis (difluorophenylsulfonio) phenylsulfide-bis-hexafluoroantimonate, 4,4'-bis (phenylsulfonio) phenylsulfide-bis-hexafluorophosphate, 4,4'-bis (phenylsulfonio) Phenyl sulfide-bis-hexafluoroantimonate,
4- (4-benzoylphenylthio) phenyl-di-
(4- (β-hydroxyethoxy) phenyl) sulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4- (4 -Benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (4-
Benzoylphenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-diphenylsulfonium hexafluoroantimonate, 4- (phenylthio)
Phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluorophosphate,
(Phenylthio) phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4- (phenylthio) phenyl-di-
(4-fluorophenyl) sulfonium hexafluorophosphate, 4- (phenylthio) phenyl-di-
(4-fluorophenyl) sulfonium hexafluoroantimonate 4- (phenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (phenylthio)
Phenyl-diphenylsulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluoro Antimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-hydroxyphenyl) sulfonium hexafluorophosphate,
(2-chloro-4-benzoylphenylthio) phenyl bis (4-hydroxyphenyl) sulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, (tolylcumyl) iodonium hexafluorophosphate, (tolylcumyl )
Iodonium hexafluoroantimonate, (tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate, bis (tertiarybutylphenyl) iodonium hexafluorophosphate, bis (tertiarybutylphenyl) iodonium hexafluoroantimonate, bis (tertiarybutylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyldimethylsulfonium hexafluorophosphate, benzyldimethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-
Hydroxyphenylmethylsulfonium hexafluorophosphate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluorophosphate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-
Methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate,
4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, α-naphthylmethyldimethylsulfonium hexafluorophosphate, α-naphthylmethyldimethylsulfonium hexafluoroantimonate, α-naphthylmethyltetramethylenesulfonium hexafluorophosphate, α-naphthylmethyltetra Methylenesulfonium hexafluoroantimonate, cinnamyldimethylsulfonium hexafluorophosphate, cinnamyldimethylsulfonium hexafluoroantimonate, cinnamyltetramethylenesulfonium hexafluorophosphate,
Cinnamyltetramethylenesulfonium hexafluoroantimonate, N- (α-phenylbenzyl) -2-
Cyanopyridinium hexafluorophosphate, N-
(Α-phenylbenzyl) -2-cyanopyridinium hexafluoroantimonate, N-cinnamyl-2-cyanopyridinium hexafluorophosphate, N-cinnamyl-2-cyanopyridinium hexafluoroantimonate, N- (α-naphthylmethyl)- 2-cyanopyridinium hexafluorophosphate, N- (α-
Naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, N-benzyl-2-cyanopyridinium hexafluorophosphate, N-benzyl-2
-Cyanopyridinium hexafluoroantimonate.

In addition, these energy ray-sensitive cationic polymerization initiators may have an initiator whose light-absorbing area in the range of 350 to 450 nm is less than 10% based on the total light-absorbing area of the light-absorbing curve in the range of 200 to 500 nm. When used, the effects of the present invention can be obtained most remarkably.

The amount of the energy ray-sensitive cationic polymerization initiator to be used is 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the cationically polymerizable organic substance. When the amount of the initiator is too small, the curing is slowed down.

(3) The following general formula used in the present invention: (Wherein R may be the same or different and is a methyl group or an ethyl group.) In the composition of the present invention, the compound represented by the formula (2)
It promotes the action of the energy ray-sensitive cationic polymerization initiator, and specifically, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9-ethoxy-10-methoxyanthracene and the like can be used.
Among these compounds, preferred are 9,10-dimethoxyanthracene and 9,10-diethoxyanthracene for ease of synthesis.

(3) The amount of the compound represented by the above general formula is 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight based on 100 parts by weight of the (1) cationically polymerizable organic substance. do it. If the ratio is outside the above range, the effects of the present invention are hardly obtained.

Although not essential for the photopolymerizable resin composition of the present invention, a radically polymerizable organic substance and an energy ray-sensitive radical polymerization initiator can be blended as required.

Here, the radically polymerizable organic substance is a radically polymerizable organic compound which is polymerized or cross-linked by irradiation with energy rays in the presence of an energy ray-sensitive radical polymerization initiator, and preferably has at least one molecule per molecule. It is a compound having one or more unsaturated double bonds.

Examples of such compounds include acrylate compounds, methacrylate compounds, allyl urethane compounds, unsaturated polyester compounds, styrene compounds and the like.

Among such radically polymerizable organic substances, compounds having a meth (acryl) group are preferred because they are easy to synthesize and obtain and easy to handle. For example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and (meth) acrylate esters of alcohols may be mentioned.

The epoxy (meth) acrylate is, for example, an acrylate obtained by reacting a conventionally known aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like with (meth) acrylic acid. It is. Among these epoxy acrylates, particularly preferred is an acrylate of an aromatic epoxy resin, in which a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof is reacted with (meth) acrylic acid. (Meta) obtained by reacting
Acrylate. For example, glycidyl ether obtained by reacting bisphenol A or an alkylene oxide adduct thereof with epichlorohydrin,
(Meth) acrylate obtained by reacting with (meth) acrylic acid, and (meth) acrylate obtained by reacting epoxy novolak resin with (meth) acrylic acid are exemplified. Preferred as urethane (meth) acrylates are (meth) acrylates obtained by reacting one or more hydroxyl-containing polyesters or hydroxyl-containing polyethers with hydroxyl-containing (meth) acrylates and isocyanates, (Meth) acrylates obtained by reacting the contained (meth) acrylic acid ester with isocyanates.

Preferred as the hydroxyl group-containing polyester used here is a hydroxyl group-containing polyester obtained by reacting one or more polyhydric alcohols with one or more polybasic acids, Examples of the aliphatic polyhydric alcohol include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol,
Neopentyl glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol and the like can be mentioned. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, trimellitic acid and the like.

Preferred as the hydroxyl group-containing polyether are hydroxyl group-containing polyethers obtained by adding one or more alkylene oxides to a polyhydric alcohol. The same thing can be illustrated. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide.

Preferred as the hydroxyl group-containing (meth) acrylic acid ester are hydroxyl group-containing (meth) acrylic acid esters obtained by an esterification reaction between a polyhydric alcohol and (meth) acrylic acid. The same compounds as those described above can be exemplified.

Among such hydroxyl group-containing (meth) acrylic acids, a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction between a dihydric alcohol and (meth) acrylic acid is particularly preferred, for example, 2-hydroxyethyl (meth) acrylic acid. A) acrylate.

As the isocyanate, a compound having at least one isocyanate group in a molecule is preferable, and isocyanates such as tolylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
Valent isocyanate compounds are particularly preferred.

The preferred polyester (meth) acrylate is a polyester (meth) obtained by reacting a hydroxyl group-containing polyester with (meth) acrylic acid.
Acrylate. Preferred as the hydroxyl group-containing polyester used here is a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols with one or more monobasic acids or polybasic acids. As the polyhydric alcohol, those similar to the aforementioned compounds can be exemplified. Examples of the monobasic acid include formic acid, acetic acid, butyric acid, and benzoic acid.
Examples of polybasic acids include adipic acid, terephthalic acid,
Examples include phthalic anhydride and trimellitic acid.

Preferred as the polyether (meth) acrylate is a polyether (meth) acrylate obtained by reacting a hydroxyl group-containing polyether with meth (acrylic) acid. Preferred as the hydroxyl group-containing polyether to be used here is one of polyhydric alcohols.
A hydroxyl-containing polyether obtained by adding one or more alkylene oxides,
Examples of the polyhydric alcohol include the same compounds as those described above. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide.

Preferred as (meth) acrylic acid esters of alcohols are aromatic or aliphatic alcohols having at least one hydroxyl group in the molecule, and an alkylene oxide adduct thereof reacted with (meth) acrylic acid. (Meth) acrylate obtained by, for example, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, Stearyl (meth) acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) acrylate, benzyl (meth) acrylate, 1,3-butanediol di (meth)
Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified tri Examples include methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate. One or more of these radically polymerizable organic substances can be used in combination according to desired performance.

It is preferable that 50 parts by weight or more of the radical polymerizable organic compound is a compound having a (meth) acryl group in the molecule.

The content of the radically polymerizable organic substance in the present invention is preferably at most 200 parts by weight, particularly preferably at most 100 parts by weight, based on 100 parts by weight of the cationically polymerizable organic substance.

Here, the energy ray-sensitive radical polymerization initiator is a compound capable of initiating radical polymerization by energy irradiation, and is a ketone-based compound such as an acetophenone-based compound, a benzyl-based compound, a benzophenone-based compound, and a thioxanthone-based compound. Compounds are preferred.

Examples of the acetophenone-based compound include, for example, diethoxyacetophenone, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenyl Ethane
1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin-n-butyl ether, benzoin isobutyl ether and the like.

Examples of the benzyl compound include benzyl, anisyl and the like.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and the like. No.

Examples of the thioxanthone compounds include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

One or more of these energy ray-sensitive radical polymerization initiators can be used in combination according to the desired performance.

The energy-sensitive radical polymerization initiator as described above is used in an amount of 0.04
The content is 5 to 10% by weight, preferably 0.1 to 10% by weight. If it exceeds this range, it is difficult to obtain a cured product having sufficient strength, and if it is below this range, the resin may not be sufficiently cured.

The photopolymerizable composition of the present invention, in which the radical polymerizable organic substance and the energy ray-sensitive radical polymerization initiator are blended, has a higher curing rate when irradiated with energy rays than in the case where these are not blended. Rising and preferred.

Further, the photopolymerizable resin composition of the present invention includes:
Although not essential, an organic compound having two or more hydroxyl groups in one molecule can be blended as necessary. For example, two molecules per molecule of a polyhydric alcohol, a hydroxyl group-containing polyether, a hydroxyl group-containing polyester, a polyhydric phenol, etc.
By blending an organic compound having at least two hydroxyl groups, the mechanical strength of the cured coating film can be increased.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and the like.

The hydroxyl group-containing polyether is a compound obtained by adding one or more alkylene oxides to one or more polyhydric alcohols or phenols. Examples of the polyhydric alcohol used for this include ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, 1,3-butanediol, 1,4-butanediol. , 1,6-hexanediol and the like. Examples of the polyhydric phenol include bisphenol A, bisphenol F, phenol novolak resin, and cresol novolak resin. Examples of the alkylene oxide include butylene oxide, propylene oxide, and ethylene oxide.

The hydroxyl group-containing polyester is a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols or polyphenols with one or more monobasic acids or polybasic acids. And a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols or phenols with one or more lactones. Examples of the polyhydric alcohol and the polyhydric phenol include the same as those described above. Examples of the monobasic acid include formic acid, acetic acid, butyric acid, and benzoic acid. Examples of the polybasic acid include adipic acid, terephthalic acid, trimellitic acid and the like. Lactones include β-propiolactone, γ-butyrolactone, ε-caprolactone, and the like.

The polyhydric phenol is a compound containing two or more hydroxyl groups per molecule directly bonded to an aromatic ring,
The same as those described above can be used.

In the present invention, a thermoplastic polymer compound, a filler, a heat-sensitive cationic polymerization initiator, a coloring agent, a leveling agent, an antifoaming agent, a thickening agent may be used as long as the effects of the present invention are not impaired. Various resin additives such as a flame retardant, an antioxidant, and a stabilizer can be used in combination within a range of ordinary use.

The photopolymerizable composition of the present invention can be used for various applications, for example, coating materials, coating materials (paints) containing pigments and dyes such as paints, printing inks, negative photoresists, adhesives It can be used as a material.

Among them, when used as a coating material containing a pigment or a dye, the effects of the present invention are most remarkably exhibited. The pigments and dyes that can be used in the present invention are not particularly limited, and as the pigments, either inorganic pigments or organic pigments can be used.For example, as the inorganic pigment, barite, precipitated barium sulfate, chalk, precipitated calcium carbonate can be used. , Chalk, clay, abrasive powder, talc, diatomaceous earth, silica white, alumina white, gypsum, satin white, gloss white, bentonite, calcium silicate, precipitated magnesium carbonate, aluminum silicate, calcium leadate, calcium molybdate, molybdenum Pigments such as zinc oxide, lead molybdate, antimony dioxide, antimony pentoxide, magnesium hydroxide, aluminum hydroxide, and red phosphorus, titanium white, zinc white, lithopone, zinc sulfide, lead white, basic lead sulfate, and oxidation Zircon, antimony white, tin oxide, lead zinc white, lead silicate, White pigments such as Gusten White, Patchonson White, and Manganese White; black pigments such as carbon black, graphite, iron black, silica black, chrome black, bone charcoal, and vegetable charcoal; zinc powder, lead suboxide, silicon carbide, Gray pigments such as slate powder, red iron, red lead, vermilion, cadmium red, cadmium mercury red, molybdenum red, cuprous oxide, antimony red, chrome tin red, iodine red, ferrocyan copper, mercury chromate, uranium red, Red pigments such as red ultramarine, cobalt red, and brown pigments such as amber, siena, manganese peroxide tea, copper tea, ferrocyan copper, and graphite, zinc chromate, cadmium yellow, lead cyanamide, synthetic oak, titanium yellow, Antimony yellow, barium yellow, strontium yellow, ore, mineral yellow, calcium chromate, siderin yellow, turner yellow, nickel yellow, aureoline Chromic acid cadmium, tin sulfide, tungsten yellow,
Yellow pigments such as vanadium yellow, mercury yellow, lead iodide, thallium yellow, lead arsenite, chromium lead, chromium lead oxide, viridian, zinc green, cobalt green, emerald green, manganese green, Egyptian green, patina, malachite Green, Scheele green, Bremen green, Kasselmann green, Brown Schwaig green,
Green pigments such as Genter green, Bolly green, copper phosphate, chromium phosphate, iron green, Mars green, etc., navy blue, ultramarine, cobalt blue, cerulean blue, manganese blue, molybdenum blue, tungsten blue, Egyptian blue, rock ultramarine, Blue pigments such as lime blue, copper sulfide, copper borate, copper phosphate, and antimony blue; manganese purple, dark cobalt purple, light cobalt purple, and mars purple;
Other examples include purple pigments such as tin violet, chromium chloride, and ultramarine blue, and other inorganic pigments such as aluminum powder, copper powder, copper alloy powder, and pearl pigment.

Examples of the organic pigment include insoluble azo, azo lake, fanal, metal complex salt, phthalocyanine, quinacridones, dioxazines and the like. As the dye, nitroso dye, nitro dye, azo dye, anthraquinone dye, indigo dye, sulfur dye, diphenylmethane dye, triphenylmethane dye, xanthene dye, azine dye, thiazine dye, oxazine dye, Acridine dyes, thiazole dyes and the like can be mentioned. Among these pigments and dyes, particularly preferred ones do not contain a nitrogen atom. Those containing a nitrogen atom may reduce the rate of cationic polymerization.

The photopolymerizable composition of the present invention is polymerized and cured by irradiation with active energy rays. Examples of the active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies, and ultraviolet rays are the most economical and preferable. Examples of the ultraviolet light source include an ultraviolet laser, a mercury lamp, particularly a (ultra) high pressure mercury lamp, a xenon lamp, an alkali metal lamp, and a commercially available electrodeless lamp (for example, a V bulb (trade name) manufactured by Fusion, a D bulb (trade name) ))and so on. When the position selectivity is necessary for polymerization and curing of the photopolymerizable composition of the present invention,
A laser beam with good light-gathering properties (especially an oscillation wavelength of 300 nm
To 450 nm). If the position selectivity is not so high, a mercury lamp or the like is economical and preferable.

Hereinafter, the method for forming a cured coating film of the present invention will be described. First, the photopolymerizable composition of the present invention described above, 200μm or less, preferably 100μm
It is applied to have the following thickness. The substrate that can be used here is not particularly limited. For example, iron, copper, aluminum, a metal substrate such as stainless steel, wood, paper, a fibrous substrate such as cloth, a poly-α-olefin resin, a polyester resin Examples thereof include synthetic resin base materials such as resin, epoxy resin, polyamide resin, polyurethane resin, polyurea resin, and polycarbonate resin, and inorganic base materials such as glass, mortar, and rock. If the thickness of the coating film exceeds the above, curing to a deep portion tends to be insufficient.

Next, 3 to the applied photopolymerizable composition
Light having a wavelength of 50 nm or more and 500 nm or less is 0.1 mJ /
Light having a wavelength of not less than cm ² , preferably not less than 350 nm and not more than 450 nm is irradiated at 1 mJ / cm ² or more. In the case of light having a shorter wavelength than the above, there is a case where the transmittance is not good for the photopolymerizable composition (particularly, a case where a pigment or a dye is contained).
It may not be cured sufficiently. Conversely, with light having a longer wavelength than the above, the energy ray-sensitive cationic polymerization initiator may not be sufficiently activated, and as a result, the photopolymerizable composition may not be sufficiently cured. Further, even with light having an energy amount less than the above, the energy ray-sensitive cationic polymerization initiator may not be sufficiently activated, and as a result, the photopolymerizable composition may not be sufficiently cured.

[0070]

Next, the present invention will be described based on embodiments. Photopolymerizable compositions having the composition shown in Tables 1 to 3 below were prepared and evaluated as follows. Table 1 below shows the obtained results.
Also described in 3. Tack free time: No. on aluminum coated paper No. 6 bar coater (applied thickness: about 10 μm) or No. 6 Each of the photopolymerizable compositions was applied using a 60 bar coater (applied thickness: about 90 μm), irradiated with light at various line speeds using a high-pressure mercury lamp having a height of 15 cm, and then measured for the time (sec) until the tackiness disappeared. did. The irradiation dose (at 365 nm) at each line speed is as follows. ^{25m / min: 8mJ / cm 2} 20m / min: 10mJ / cm 2 15m / min: 13mJ / cm 2 10m / min: 20mJ / cm 2

MEK Love Test: N on aluminum coated paper
o. Each of the photopolymerizable compositions was applied with a bar coater of No. 6 and irradiated with light at a line speed of 10 m / min using a high-pressure mercury lamp having a height of 15 cm. The number of times to see was measured.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

Epoxy resin 1: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Epoxy resin 2: 1,4-butanediol diglycidyl ether Epoxy resin 3: phenol novolak resin (epoxy equivalent 190) Photocation Polymerization initiator 1: 4,4′-bis (di (β-hydroxyethoxy) phenylsulfonio) phenylsulfide-bis-hexafluorophosphate Photocationic polymerization initiator 2: 4- (4-benzoyl-phenylthio) phenyl- Di- (4-fluorophenyl) sulfonium hexafluorophosphate Photocationic polymerization initiator 3: 4- (2-chloro-4-benzoyl-phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate Optical click Polymerization initiator 4: 4,4'-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate Photocationic polymerization initiator 5: 4,4'-bis (diphenylsulfonio) phenyl sulfide-bis- Hexafluoroantimonate Sensitizer 1: 9,10-diethoxyanthracene Sensitizer 2: 9,10-dimethoxyanthracene Acrylic resin: dipentaerythritol hexaacrylate Photo-radical polymerization initiator: 2-hydroxy-2-methyl-
1-phenylpropan-1-one polyol: ε-caprolactone adduct of trimethylolpropane (average molecular weight 300)

[0076]

As described above, in the photopolymerizable composition of the present invention, by using a specific anthracene compound as a photosensitizer, curing is not inhibited by oxygen and the curing speed is reduced. Good, especially when used with a pigment, a good curing rate can be obtained.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C09D 11/00 C09D 11/00 163/00 163/00 G03F 7/031 G03F 7/031 // C08L 63/00 C08L 63/00 C09J 163 / 00 C09J 163/00

Claims (5)

[Claims] 1. Indispensable constituent components (1) a cationically polymerizable organic substance, (2) an energy ray-sensitive cationic polymerization initiator, and (3) a general formula represented by the following formula: (Wherein R may be the same or different and is a methyl group or an ethyl group.) A photopolymerizable composition comprising a compound represented by the formula: 2. The photopolymerizable composition according to claim 1, further comprising (4) a pigment. (3) The absorption area in the range of 350 to 450 nm is less than 10% with respect to the total absorption area of the absorption curve in the range of 200 to 500 nm of the energy ray-sensitive cationic polymerization initiator. The photopolymerizable composition according to claim 1. 4. (1) 4 of the cationically polymerizable composition
The photopolymerizable composition according to any one of claims 1 to 3, wherein 0% by weight or more is an alicyclic epoxy compound having a cyclohexene oxide structure. 5. A photopolymerizable composition according to any one of claims 1 to 4, which is applied on a substrate so as to have a thickness of 200 μm or less.
A method for forming a cured coating film, which comprises irradiating light having a wavelength of not more than nm to 0.1 mJ / cm ² or more.