JP2002316965A - New anthracene derivative compound, photopolymerizable composition containing the same and method for forming cured coated film by using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new anthracene derivative compound capable of providing a photopolymerizable composition of which the curing is hardly inhibited by an enzyme, and which has a good curing rate, and further to provide the photopolymerizable composition containing the anthracene derivative compound, and a method for forming a cured coated film by using the composition. SOLUTION: This new anthracene derivative compound is represented by the structural formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel anthracene derivative compound, a photopolymerizable composition containing the same, and a method for forming a cured coating film using the composition.

[0002]

2. Description of the Related Art Polymerization of a cationically polymerizable organic substance with an energy-ray-sensitive cationic polymerization initiator has been conventionally performed because of its good curability because it is not affected by oxygen. However, in curing such a cationically polymerizable organic substance, there is 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] Also, Japanese Patent Application Laid-Open No. 11-199681,
JP-A-11-322954, JP-A-2000-34
In 4704 and the like, a photopolymerizable composition using an anthracene derivative compound as a sensitizer has been studied, but it cannot be said that the sensitizing effect has been sufficiently confirmed for all anthracene derivative compounds. There is still a strong need for new compounds that exhibit a sensitizing effect.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems and to provide a novel photopolymerizable composition which is free from curing inhibition by oxygen and has a good curing speed. Anthracene derivative compound, a photopolymerizable composition containing the same, is not subject to curing inhibition by oxygen, and has a good curing speed, and particularly, a good curing speed even when used in combination with a pigment. An object of the present invention is to provide a photopolymerizable composition obtained and a method for forming a cured coating film using the composition.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, succeeded in synthesizing a novel anthracene derivative compound which can achieve the above-mentioned object, and by using the compound, the above-mentioned object was achieved. The present inventors have found that a photopolymerizable composition and a method for forming a cured coating film conforming to the above conditions can be obtained, and the present invention has been completed.

That is, the novel anthracene derivative compound of the present invention has the following structural formula: It is characterized by being represented by

The photopolymerizable composition of the present invention comprises, as essential constituents, (1) a cationically polymerizable organic substance,
(2) an energy ray-sensitive cationic polymerization initiator;
(3) The anthracene derivative compound of the present invention.

The photopolymerizable composition of the present invention can suitably contain (4) a pigment, and (2) an absorbance curve of an energy ray-sensitive cationic polymerization initiator in an absorbance curve.
350-4 for the total absorption area in the range 0-500 nm
The proportion of the light-absorbing area in the range of 50 nm is preferably less than 10%. Furthermore, it is preferable that 40% by weight or more of (1) the cationically polymerizable composition is an alicyclic epoxy compound having a cyclohexene oxide structure.

Further, according to the method for forming a cured coating film of the present invention, the photopolymerizable composition of the present invention is coated on a substrate to a thickness of 200 μm.
After coating to be less than or equal to
It is characterized by irradiating light having a wavelength of 00 nm or less to 0.1 mJ / cm ² or more.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described in detail. First, the photopolymerizable composition of the present invention will be described. The (1) cationically polymerizable organic substance used in the photopolymerizable composition of the present invention refers to a compound that undergoes a polymerization or a cross-linking reaction by an energy ray-sensitive cationic polymerization initiator activated by irradiation with energy rays. .

Such cationically polymerizable organic substances include:
For example, an epoxy compound, a cyclic ether compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiroorthoester compound, a vinyl compound and the like can be mentioned, and one or more of these can be used. Among them, epoxy compounds that are easily available and convenient to handle are suitable, and in particular, aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins can be preferably used.

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, for example, bisphenol A, bisphenol F, and an alkylene oxide. Glycidyl ether of an oxide-added compound, epoxy novolak resin and the like can be mentioned.

Further, specific examples of the alicyclic epoxy resin include a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or a compound containing a cyclohexene or cyclopentene ring, which is epoxidized with an oxidizing agent. Examples thereof include a compound having a cyclohexene oxide structure or a compound having a cyclopentene oxide structure, and a compound having a vinylcyclohexane oxide structure obtained by epoxidizing a compound having a vinylcyclohexane structure with an oxidizing agent. Representative compounds include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1- Methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3- Methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-
(3,4-epoxycyclohexyl-5,5-spiro-
3,4-epoxy) cyclohexane-metadioxane,
Bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexenedionoxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-
6-methylcyclohexylmethyl) adipate, 3,4
-Epoxy-6-methylcyclohexylcarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxy) Rate), dioctyl epoxy hexahydrophthalate, di-epoxy hexahydrophthalate
2-ethylhexyl and the like.

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 hexaglycidyl ether of tall, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol are exemplified. 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, etc. No. 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 are also included.

In the present invention, one or more compounds of the cationically polymerizable substances listed as (1) the cationically polymerizable organic substance can be used in combination. (1) Of 100 parts by weight of the cationically polymerizable organic substance, one of the above epoxy compounds
Those containing two or more epoxy groups in the molecule are
It is used in an amount of not less than% by weight. In this case, as the remaining component of less than 50% by weight, a compound containing one epoxy group in one molecule or a cationic polymerizable organic substance other than the epoxy compounds exemplified below can be used. Also, a mixture of the above cyclohexene oxide compound and a cationically polymerizable organic substance other than the epoxy compound is suitable.

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, spiroorthoester compounds obtained by the reaction of epoxy compounds with lactones, ethylenically unsaturated compounds such as vinylcyclohexene, isobutylene and polybutadiene, and derivatives of the above compounds.

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 at least 40% by weight 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 according to the present invention is a compound capable of releasing a substance for initiating cationic polymerization by irradiation with energy rays. Or a derivative thereof, which is an onium salt that releases Representative examples of such compounds include salts of cations and anions represented by the following general formula: [A] ^{m +} [B] ^m- .

Here, the cation A ^{m +} is preferably an onium, and its structure can be represented by, for example, the following general formula [(R ¹ ) _a Z] ^{m +} .

Further, 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 of R ¹ is preferably an organic group having an aromatic ring as described above. Z is S, N, Se, Te,
P, As, Sb, Bi, O, I, Br, Cl, F, N =
An atom or atomic group selected from the group consisting of N.
When the valence of Z in the cation A ^{m +} is z, m
= A−z must be satisfied.

The anion B ^m− is preferably a halide complex, and its structure can be represented by, for example, the following general formula [LX _b ] ^m− .

Here, L is a metal or metalloid which is the central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, C
a, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is a halogen. b is an integer of 3 to 7. Further, when the valence of L in the anion B ^m− is p, it is necessary that the relationship m = bp holds.

Specific examples of the anion represented by the general formula [LX _b ] ^m- include tetrafluoroborate (B
F ₄₎ ^-, hexafluorophosphate (PF ₆₎ ^-, hexafluoroantimonate (SbF ₆₎ ^-, hexafluoroarsenate (AsF ₆₎ ^-, hexachloroantimonate (SbCl ₆₎ ^-, and the like.

Further, as the anion B ^m- , those having a structure represented by the following general formula [LX _b-1 (OH)] ^m- can also be preferably used.
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 anion, trinitrobenzene sulfonic acid anion, and the like. Further, as an anion B ^m-
Tetrakis (pentafluorophenyl) borate can also be preferably used.

In the present invention, among such onium salts, the use of an aromatic onium salt is particularly effective. Among them, aromatic halonium salts described in JP-A-50-151997 and JP-A-50-158680, JP-A-50-151997 and JP-A-52-158.
No. 30899, JP-A-56-55420, Group VIA aromatic onium salts described in JP-A-55-125105, etc., Group VA aromatic onium salts described in JP-A-50-158698, JP-A-56-8428, JP-A-56-149402, JP-A-57-1
Preferred are oxosulfoxonium salts described in JP-A-92429 and the like, aromatic diazonium salts described in JP-A-49-17040, and thiobrillium salts described in U.S. Pat. No. 4,139,655. Other preferable examples include an iron / allene complex and an aluminum complex / photolytic silicon compound-based initiator.

Particularly preferred among these aromatic onium salts are those wherein the cation has the following general formula: Or (Wherein, R is a hydrogen atom, a halogen atom, a hydrocarbon group optionally containing an oxygen atom or a halogen atom, or an alkoxy group optionally having a substituent, which may be the same or different, and Ar is A phenyl group in which one or more hydrogen atoms may be substituted) and (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) phenylsulfide-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-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
-([Beta] -hydroxyethoxy) phenyl) sulfonium hexafluorophosphate, 4- (phenylthio) phenyl-di- (4-([beta] -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 hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-hydroxyphenyl) sulfonium Hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenylbis (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-hydroxyphenylmethyl Sulfonium hexafluorophosphate, p-chlorobe Jill-4-hydroxyphenyl methyl sulfonium hexafluoroantimonate, 4-
Acetoxyphenyldimethylsulfonium hexafluorophosphate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, 4-ethoxycarbonyloxyphenyl Dimethylsulfonium hexafluorophosphate, 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, α-naphthylmethyldimethylsulfonium hexafluorophosphate, α-naphthylmethyldimethylsulfonium hexafluoroantimonate, α-naphthylmethyltetramethylenesulfonium hexafluoro Phosphate, α-naphthylmethyltetramethylenesulfonium hexafluoroantimonate, cinnamyldimethylsulfonium hexafluoroantimonate, 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- Examples thereof include cyanopyridinium hexafluorophosphate, N-benzyl-2-cyanopyridinium hexafluoroantimonate, and the like.

Further, (2) the energy ray-sensitive cationic polymerization initiator may be selected from 200 to 5 in the absorbance curve.
350-450 n for a total absorption area in the range of 00 nm
The effect of the present invention can be obtained most remarkably when the ratio of the light absorption area in the range of m is less than 10%.

Further, (2) 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 (1) cationically polymerizable organic substance. It is preferable that the initiator be used in a part. When the amount of the initiator is too small, the curing is delayed, while when the amount is too large, adverse effects such as brittleness are liable to occur.

The (3) anthracene derivative compound used in the photopolymerizable composition of the present invention has the following structural formula: Is a novel compound of the present invention represented by the formula (1), and when used together with the above (1) and (2), is activated by an energy ray to promote (2) the action of an energy ray-sensitive cationic polymerization initiator. Has a function as a sensitizer.

The anthracene derivative compound of the present invention is a novel compound which has never been isolated before and is the first compound isolated by the present inventors. The synthesis method used by the present inventors is as follows. That is, anthraquinone and cyclohexanone are mixed in an aqueous alkaline solution, and if necessary, a reducing agent such as sodium hydrosulfite is mixed under a nitrogen stream to ripen the mixture.
-Can be obtained by adding phenoxyethoxy bromide and reacting under reflux conditions, and can be obtained by extracting with a solvent such as toluene, or recrystallizing with a solvent such as acetone as necessary.

The (3) anthracene derivative compound of the present invention is an extremely useful compound as a sensitizer capable of providing a photopolymerizable composition which is not subject to curing inhibition by oxygen and has a good curing rate. is there.

(3) The amount of the anthracene derivative compound used is 0.1 to 10 mmol, preferably 0.2 to 4 mmol per 100 g of the cationically polymerizable organic substance.
Should be used. If the amount is outside the above range, it is difficult to obtain the effects of the present invention.

Although not essential in the photopolymerizable composition of the present invention, a radically polymerizable organic substance and an energy-ray-sensitive radical polymerization initiator can be added 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 is preferably contained in one molecule. It is a compound having at least 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 meta (acryl) group are preferred because they are easy to synthesize and obtain, and easy to handle. Specific examples include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and (meth) acrylate esters of alcohols.

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 (meth) acrylates, particularly preferred is an acrylate of an aromatic epoxy resin, and a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, (Meth) acrylate obtained by reacting with acrylic acid. For example, a glycidyl ether obtained by reacting bisphenol A or an alkylene oxide adduct thereof with epichlorohydrin is reacted with (meth) acrylic acid to obtain (meth) acrylate, epoxy novolak resin and (meth) acrylate.
(Meth) acrylate obtained by reacting acrylic acid is exemplified.

Preferred urethane (meth) acrylates are obtained by reacting one or more hydroxyl group-containing polyesters or hydroxyl group-containing polyethers with a hydroxyl group-containing (meth) acrylate and an isocyanate (meth). Acrylates) and (meth) acrylates obtained by reacting hydroxyl group-containing (meth) acrylates 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.

The hydroxyl group-containing polyether is preferably a hydroxyl group-containing polyether 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) acrylate obtained by an esterification reaction between a dihydric alcohol and (meth) acrylic acid is particularly preferable. For example, 2-hydroxyethyl (meth) acrylate is preferable. No.

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.

Preferred polyester (meth) acrylates include hydroxyl-containing polyesters and (meth) acrylates.
Polyester (meth) acrylate obtained by reacting with acrylic acid. Preferred as the hydroxyl group-containing polyester used here are one or two or more polyhydric alcohols and one or two or more monobasic acids,
A hydroxyl group-containing polyester obtained by an esterification reaction with a polybasic acid, and examples of the polyhydric alcohol include the same compounds 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, 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 used herein is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to a polyhydric alcohol. The same can be exemplified. 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,
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.

In the present invention, it is preferred that at least 50 parts by weight of the 100 parts by weight of the radically polymerizable organic substance is a compound having a (meth) acryl group in the molecule.
Further, the content of the radically polymerizable organic substance in the photopolymerizable composition of the present invention is preferably 200 parts by weight or less based on 100 parts by weight of the cationically polymerizable organic substance.
It is particularly preferred that the amount is not more than 00 parts by weight.

On the other hand, the above-mentioned energy ray-sensitive radical polymerization initiator is a compound capable of initiating radical polymerization by energy irradiation, and is a ketone such as an acetophenone compound, a benzyl compound, a benzophenone compound or a thioxanthone compound. A system compound can be suitably used.

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 compound 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 amount of the energy-sensitive radical polymerization initiator is 0.05 to 10% by weight, preferably 0.1 to 10% by weight, based on the radically polymerizable organic substance. If it exceeds this range, it is difficult to obtain a cured product having sufficient strength, while if it is below this range, the resin may not be sufficiently cured.

The photopolymerizable composition of the present invention in which the above-mentioned radically polymerizable organic substance and the energy ray-sensitive radical polymerization initiator are blended has a further increased curing rate when irradiated with energy rays as compared with the case where these are not blended. ,preferable.

In the photopolymerizable composition of the present invention, although not essential, an organic compound having two or more hydroxyl groups in one molecule can be blended as required.
That is, for example, polyhydric alcohols, hydroxyl-containing polyethers, hydroxyl-containing polyesters, polyhydric phenols, etc.
By blending an organic compound having two or more hydroxyl groups in one molecule, 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 phenols 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 having two or more hydroxyl groups directly bonded to an aromatic ring in one molecule.
The same as those described above can be used.

Further, in the present invention, a thermoplastic polymer compound, a filler, a heat-sensitive cationic polymerization initiator, a coloring agent, a leveling agent, a defoaming agent, Various resin additives such as a thickener, 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 in 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 inorganic pigments and organic pigments can be used as the pigment.For example, as the inorganic pigment, barite,
Precipitated barium sulfate, chalk, precipitated calcium carbonate, 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, zinc molybdate, lead molybdate, antimony dioxide, antimony pentoxide, water Extender pigments such as magnesium oxide, aluminum hydroxide, red phosphorus, titanium white, zinc white, lithopone, zinc sulfide, lead white, basic lead sulfate, zircon oxide, antimony white, tin oxide,
White pigments such as lead zinc white, lead silicate, tungsten white, Patchonson white, manganese white, carbon black,
Black pigments such as graphite, iron black, silica black, chrome black, bone charcoal, and vegetable charcoal; gray pigments such as zinc dust, lead suboxide, silicon carbide, and slate powder; and red, red, red, cadmium red, Cadmium mercury red, molybdenum red, cuprous oxide, antimony red, chromium tin red, iodine red, ferrocyan copper,
Red pigments such as mercury chromate, uranium red, ultramarine red, and cobalt red; brown pigments such as amber, siena, manganese peroxide tea, copper tea, and ferrocyan copper; and graphite, zinc chromate, cadmium yellow, and lead cyanamide , Synthetic orca,
Titanium yellow, antimony yellow, barium yellow, strontium yellow, stone yellow, mineral yellow, calcium chromate, siderin yellow, turner yellow, nickel yellow, aureoline, cadmium chromate, tin sulfide, tungsten yellow, vanadium yellow, mercury yellow, iodine Yellow pigments such as 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, Shere green, Bremen green ,
Kasselmann green, Brown Schwaig green, Genter green,
Green pigments such as Bolly Green, Copper Phosphate, Chromium Phosphate, Iron Green, Mars Green, Navy Blue, Ultramarine Blue, Cobalt Blue, Cerulean Blue, Manganese Blue, Molybdenum Blue, Tungsten Blue, Egyptian Blue, Rock Ultramarine, Lime Blue, Blue pigments such as copper sulfide, copper borate, copper phosphate, and antimony blue; purple pigments such as manganese purple, dark cobalt purple, thin cobalt purple, mars purple, tin purple, chromium chloride, and ultramarine blue; aluminum powder; Other inorganic pigments such as copper powder, copper alloy powder, and pearl pigment can be used.

Examples of the organic pigment include insoluble azo, azo lake, fanal, metal complex salt, phthalocyanine, quinacridone, dioxazine and the like.

Examples of dyes include nitroso dyes, nitro dyes, azo dyes, anthraquinone dyes, indigo dyes, sulfur dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, azine dyes, thiazine dyes, and oxazine dyes. Dyes, acridine dyes, thiazole dyes and the like. 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 position selectivity is required for polymerization and curing of the photopolymerizable composition of the present invention,
A laser beam with good light-collecting properties (especially an oscillation wavelength of 300 nm
To 450 nm). When positional selectivity is not required, a mercury lamp or the like is economical and preferable.

Next, the method for forming a cured coating film of the present invention will be described. First, the photopolymerizable composition of the present invention is applied to a substrate so as to have a thickness of 200 μm or less, preferably 100 μm or less. 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 resin,
Examples include synthetic resin base materials such as epoxy resins, polyamide resins, polyurethane resins, polyurea resins, and polycarbonate resins, 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. When light having a wavelength shorter than the above range has poor transmittance to the photopolymerizable composition (particularly, when a pigment or a dye is contained).
And may not be cured sufficiently. On the other hand, if the wavelength is longer than the above range, 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 range, the energy ray-sensitive cationic polymerization initiator may not be sufficiently activated, and as a result, the photopolymerizable composition may not be sufficiently cured.

[0069]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments. [Example 1] Anthraquinone 10.4 g, water 150 m
l, cyclohexanone 100 ml, sodium hydroxide 1
5 g was placed in a four-necked flask, and the inside of the system was replaced with nitrogen gas, and then 10 g of sodium hydrosulfite was charged. The system turned red. After continuing the reaction at room temperature for 2 hours, 30.2 g of 2-phenoxyethoxybromide was added, and the mixture was refluxed for 24 hours. After cooling, toluene 400m
The product was extracted with 1 and recrystallized from acetone to obtain a product as pale yellow crystals (yield: 85%). The analytical values of the product are shown below. Melting point ^{145 ℃ · 1 H-NMR δ4.4-4.6,8H} , methylene Deruta6.9-7.5,14H, aromatic Deruta8.3-8.5,4H, aromatic-elemental analysis (C ₃₀ H ₂₆ O ₄ ) Calculation C: 79.98, H: 5.82, O: 14.
21 Observed C: 79.94, H: 5.83, O: 14.
23 From the above results, the product has the following structural formula: It was identified as the compound represented by.

Example 2 A photopolymerizable composition having the composition shown in Tables 1 and 2 below was prepared and evaluated as follows. The results obtained are shown in Tables 1 and 2 below. 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 by a high-pressure mercury lamp having a height of 15 cm. Then, the number of times until the base was seen was measured.

[0072]

[Table 1]

[0073]

[Table 2]

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 Emissions polymerization initiator 4: 4,4'-bis (diphenyl sulfonyl O) phenyl sulfide - bis - hexafluoroantimonate sensitizer 1: structural formula obtained in Example 1, 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)

[0075]

As described above, according to the present invention, there is provided a novel anthracene derivative compound which is not subject to curing inhibition by oxygen and can provide a photopolymerizable composition having a favorable curing rate. The photopolymerizable composition of the present invention obtained by containing the anthracene derivative compound is not subject to curing inhibition by oxygen, has a good curing speed, and is particularly used together with a pigment. However, a good curing speed can be obtained. Further, by using such a photopolymerizable composition of the present invention, a cured coating film forming method capable of obtaining a cured coating film at a favorable curing rate is realized.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/028 G03F 7/028 7/029 7/029 7/26 501 7/26 501 F term (reference) 2H025 AA00 AB20 AC01 AD01 BD03 CA00 CA17 CA48 2H096 AA30 BA01 BA20 EA02 4H006 AA01 AB92 GP03 4J005 AA01 AA02 AA06 AA08 AA09 BA00 BB02 4J036 AB07 AB09 AB10 AD01 AD08 AF01 AG01 AJ01 AJ12 AJ11 AJ11 AJ12 AJ12 AJ12 AJ12 AJ12 AJ12 AJ12 AJ12 AJ02 HA02 HA03 JA01 JA06 JA09 JA15

Claims (6)

[Claims] 1. The following structural formula: A novel anthracene derivative compound represented by the formula: 2. An essential component comprising (1) a cationically polymerizable organic substance, (2) an energy ray-sensitive cationic polymerization initiator, and (3) an anthracene derivative compound according to claim 1. A photopolymerizable composition comprising: 3. The photopolymerizable composition according to claim 2, which contains (4) a pigment. 4. The ratio of the light-absorbing area in the range of 350 to 450 nm to the total light-absorbing area in the range of 200 to 500 nm in the absorbance curve of the energy ray-sensitive cationic polymerization initiator is less than 10%. Or the photopolymerizable composition according to 3. 5. (1) 4 of the cationically polymerizable composition
The photopolymerizable composition according to any one of claims 2 to 4, wherein 0% by weight or more is an alicyclic epoxy compound having a cyclohexene oxide structure. 6. After coating the photopolymerizable composition according to any one of claims 2 to 5 on a substrate so as to have a thickness of 200 μm or less, a wavelength of 350 nm or more and 500 nm or less is applied to the application surface. A method for forming a cured coating film, which comprises irradiating light of 0.1 mJ / cm ² or more.