TWI491631B - A photohardenable resin and a dispersant using the same - Google Patents

Description

Photocurable resin and dispersant using same

The present invention relates to a novel photocurable resin having a specific structure and a dispersing agent using the same.

In the fields of paints, inks, and the like, various dispersing agents have been used in order to improve the dispersibility of the pigment, improve the storage stability of the coating material, or the gloss of the coating film. For example, Patent Document 1 discloses a dispersant derived from a compound having at least one basic group containing a ring nitrogen, and Patent Document 2 discloses a method comprising a polyisocyanate, an acrylate compound or an epoxy compound. And a dispersing agent of the reaction product obtained by the reaction of the cyclic compound, and Patent Document 3 discloses a photoresist composition for a color filter using a specific dispersion resin as a dispersing agent.

Further, in recent years, the industry has attempted to impart photocurability to the dispersant itself, and to improve compatibility with the photocurable adhesive, photocurability at the time of coating, adhesion to a substrate, and the like. Patent Document 4 discloses a polyurethane curable photocurable coating material, and Patent Document 5 discloses a pigment dispersion obtained by reacting a (meth) acrylate compound with a monoamine compound. However, the coating or dispersing agent is insufficient in photocurability or adhesion.

[Patent Document 1] Japanese Patent Laid-Open No. 4-210220

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-506436

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-300919

[Patent Document 4] Japanese Patent Laid-Open No. Hei 11-80665

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2007-711

An object of the present invention is to provide a dispersant having high dispersibility, high photocurability at the time of coating, and high adhesion to a substrate.

The present invention achieves the above object by providing a photocurable resin which has one or two hydroxyl groups in the same molecule and has a number average molecular weight by adding a diisocyanate compound (A). After 300 to 5000 compounds (B) and a compound (C) having two hydroxyl groups and two ethylenically unsaturated groups in the same molecule, Michael has an active hydrogen and a tertiary amino group in the same molecule. The compound (D) is obtained.

Moreover, the present invention provides a photocurable resin obtained by further esterifying the photocurable resin with a polybasic acid anhydride (E).

Moreover, the present invention achieves the above object by providing a dispersing agent containing the photocurable resin as an active ingredient.

Since the photocurable resin of the present invention has excellent photocurability, the photocurability of the coating film using the photocurable resin as a dispersing agent as an active component and the adhesion to the substrate after photocuring are high.

Hereinafter, the photocurable resin of the present invention and a dispersing agent using the same will be described in detail based on preferred embodiments.

The photocurable resin of the present invention is a p-diisocyanate compound (A) Addition of a compound (B) having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 5,000, and a compound (C) having two hydroxyl groups and two ethylenically unsaturated groups in the same molecule, The compound (D) having an active hydrogen and a tertiary amino group in the same molecule can be added, and if necessary, the polybasic acid anhydride (E) can be esterified.

The diisocyanate compound (A) for obtaining the photocurable resin of the present invention may, for example, be 1,2-ethylidene diisocyanate, 1,4-tetramethylammonium diisocyanate or 1,6-hexa-extension. Methyl diisocyanate, 2,2,4-trimethyl-1,6-hexamethyldiisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12 - an aliphatic diisocyanate such as dodecane diisocyanate or ω,ω'-diisocyanatodipropyl ether; cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane Alkane-1,4-diisocyanate, 2,2-diisocyanato-1-methyl-cyclohexane, 2,6-diisocyanato-1-methyl-cyclohexane, isophor Keto diisocyanate, 2,5-bis-(isocyanatomethyl)-8-methyl-1,4-methyl bridge-decalin, 3,5-bis-(isocyanatomethyl)- 8-methyl-1,4-methyl bridge-decalin, 1,5-bis(isocyanatomethyl)-4,7-methyl bridge-hexahydroindan, 2,5-bis(isocyano Acid methyl)-4,7-methyl bridge-hexahydroindan, 1,6-bis(isocyanatomethyl)-4,7-methyl bridge-hexahydroindan, 2,6-double ( Isocyanatomethyl)-4,7-methyl bridge-hexahydroindan, 1,5-, 2,5-, 1,6- and 2,6-bis(isocyanato)-4,7 - Jiaqiao-Six Hydroquinone, dicyclohexyl-2,4'- and 4,4'-diisocyanate, 2,4- and 2,6-hexahydrotoluene diisocyanate, perhydro-2,4'-diphenylmethane diisocyanate , perhydro-4,4'-diphenylmethane diisocyanate, 4,4'-di(isocyanatocyclohexyl)methane, 3-isocyanato-methyl-3,5,5-trimethyl a cyclic aliphatic diisocyanate such as cyclohexyl isocyanate; ω, ω'-diisocyanato-1,4-diethylbenzene, Benzene diisocyanate, p-phenylene diisocyanate, 4,4'-diisocyanatobiphenyl, 4,4'-diisocyanato-3,3'-dichlorobiphenyl, 4,4'-diiso Cyanate-3,3'-dimethoxybiphenyl, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 4,4'-diisocyanato-3 , 3'-diphenylbiphenyl, 2,4'- and 4,4'-diisocyanato-diphenylmethane, naphthalene-1,5-diisocyanate, 2,4-toluene diisocyanate, 2, 6-toluene-diisocyanate, N,N'-(4,4-dimethyl-3,3'-diisocyanatodiphenyl)uretdione, m-xylene-diisocyanate, diphenylmethane- 2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,4,4'-triisocyanato-diphenyl ether, 4,4',4"-triisocyanate An aromatic diisocyanate such as triphenylmethane or tris(4-isocyanatophenyl) phosphorothioate.

The diisocyanate compound (A) may be used in the form of a modified product such as a carbodiimide modification, an isocyanurate modification or a biuret modification, or a blocked isocyanate blocked by various blocking agents. The form is used.

The diisocyanate compound (A) is preferably toluene diisocyanate, diphenylmethane diisocyanate or isophorone diisocyanate because the obtained photocurable resin has high adsorptivity to a pigment.

The compound (B) having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 5,000 in the same molecule for obtaining the photocurable resin of the present invention may, for example, be a polyether diol or a polyester diol. Polyester polycarbonate diols, polycarbonate diols, polyolefin diols, and those obtained by oxidizing a terminal hydroxy group of one of the compounds with an alkyl group having 1 to 25 carbon atoms, etc. Can also be mixed.

Examples of the polyether glycols include ethylene oxide adducts such as diethylene glycol and triethylene glycol; and propylene oxide additions such as dipropylene glycol and tripropylene glycol. An object; an ethylene oxide and/or propylene oxide adduct of a low molecular polyol, a polytetramethylene glycol, or the like.

Examples of the polyester diols include ester-forming derivatives such as dicarboxylic diols in amounts smaller than the stoichiometric amount thereof, and ester-forming derivatives such as diesters or esters thereof, acid anhydrides, and halides. Alternatively, the lactone or the hydroxycarboxylic acid obtained by subjecting it to hydrolysis and ring-opening is subjected to a direct esterification reaction and/or a transesterification reaction.

Examples of the low molecular weight diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, and 2-methyl-1,3-propanediol. -butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1 , 5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1 ,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-anthracene An aliphatic diol such as an alcohol or 1,10-decanediol; an alicyclic diol such as cyclohexane dimethanol or cyclohexane diol; an aromatic diol such as benzenedimethanol or bis(hydroxyethoxy)benzene .

Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, and antibutene. Diacid, maleic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipate, 3-methyladipate, 3-methylglutaric acid, 2-methyl Aliphatic dicarboxylic acids such as octyl diacid, 3,8-dimethylsebacic acid, 3,7-dimethylsebacic acid, hydrogenated dimer acid, dimer acid, phthalic acid, p-phenylene An aromatic dicarboxylic acid such as formic acid, isophthalic acid or naphthalene dicarboxylic acid; or an alicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid; and as the above ester-forming derivative, Listed as: an acid anhydride of the dicarboxylic acid, a halide such as a dicarboxylic acid chloride, and a methyl ester, an ethyl ester, a propyl ester, an isopropyl ester, a butyl ester, an isobutyl ester, a pentane of the dicarboxylic acid Lower aliphatic esters such as esters, these may also be used in combination.

Examples of the lactones include γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ. - lactones such as butyrolactone.

Examples of the polyester polycarbonate diol include those obtained by simultaneously reacting a diol, a dicarboxylic acid, and a carbonate compound such as a dialkyl carbonate, an alkylene carbonate, or a diaryl carbonate; A polyester obtained by reacting a pre-synthesized polyester polyol and a polycarbonate polyol with a carbonate compound; or a reaction of pre-synthesized polyester polyol and polycarbonate polyol with a polyol and a polycarboxylic acid; .

Examples of the polycarbonate diols include poly(1,6-exexyl)carbonate and poly(3-methyl-l,5-amylpentyl) carbonate.

Examples of the polyolefin diols include polybutadiene diol, hydrogenated polybutadiene diol, and hydrogenated polyisoprene diol.

The compound (B) having one or two hydroxyl groups in the same molecule is particularly preferably a polyether diol and/or a polyester diol, because the affinity with the solvent is preferable. The dispersibility of the photocurable resin is improved. The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is from 300 to 5,000, preferably from 500 to 3,000.

The compound (C) having two hydroxyl groups and two ethylenically unsaturated groups in the same molecule for obtaining the photocurable resin of the present invention is, for example, An adduct of a difunctional epoxy compound and an unsaturated monobasic acid.

As the difunctional epoxy compound, for example, a diglycidyl ether of a glycol or an alkylene oxide adduct thereof, a diglycidyl ester of a dibasic acid, or a ring containing a cyclohexene ring or a cyclopentene ring can be used. Specific examples of the compound containing epoxycyclohexane or epoxycyclopentane obtained by epoxidizing a compound with an oxidizing agent include the following compounds.

Examples thereof include a bisphenol M type epoxy resin, a bisphenol P type epoxy resin, and a bisphenol diglycidyl ether type epoxy resin such as an epoxy resin represented by the following formula (I); Hydrogenated bisphenol type diglycidyl ether obtained by hydrogenation of diglycidyl ether type epoxy resin; ethylene glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,2-propanediol diglycidyl ether, 1 , 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2, 2 - dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether a glycidyl ether of an aliphatic diol such as 1,4-cyclohexanedimethanol diglycidyl ether; a phenol novolak type epoxy compound, a biphenol novolak type epoxy compound, and a cresol novolak type epoxy compound a novolac type epoxy compound such as a bisphenol A novolac type epoxy compound or a dicyclopentadiene novolac type epoxy compound; 3,4-epoxy-3- 3-cyclohexylidene-3',4'-epoxy-3-methylcyclohexylmethyl ester, 3,4-epoxy-5-methylcyclohexylcarboxylic acid-3',4'-epoxy- 5-methylcyclohexylmethyl ester, 3,4-epoxy-6-methylcyclohexylcarboxylic acid-3',4'-epoxy-6-methylcyclohexylmethyl ester, 3,4-epoxy Cyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester, 1-epoxyethyl- 3,4-epoxycyclohexane, bis(3,4-epoxycyclohexylmethyl) adipate, methyl bis(3,4-epoxycyclohexane), isopropylene Bis(3,4-epoxycyclohexane), dicyclopentadiene dioxide, ethyl bis(3,4-epoxycyclohexylcarboxylate), 1,2-epoxy An alicyclic epoxy compound such as -2-epoxyethylcyclohexane; a dibasic acid such as diglycidyl phthalate, diglycidyl tetrahydrophthalate or glycidyl dimerate a glycidyl ester; a glycidylamine such as N,N-diglycidylaniline; a heterocyclic epoxy compound such as 1,3-diglycidyl-5,5-dimethylhydantoin; a dioxide compound such as cyclopentadiene; a naphthalene type epoxy compound, a triphenylmethane type epoxy compound, a dicyclopentadiene type epoxy compound, or the like.

(wherein M represents a direct bond, an alkylene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group, O, S, SO ₂ , SS, SO, CO, OCO or selected from the following [Chemical 2] In the substituent of the group shown, the above alkylene group may be substituted by a halogen atom, and R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. An oxy group, an alkenyl group having 2 to 5 carbon atoms or a halogen atom, and the alkyl group, the alkoxy group and the alkenyl group may be substituted by a halogen atom, and R ¹ and R ² may be bonded to form a ring structure, n is 0 or an integer from 1 to 10).

(wherein Q and B each independently represent a hydrogen atom, a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or a carbon number of 3 to 10; a cycloalkyl group, Z and E each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkane The group, the alkoxy group and the alkenyl group may also be substituted by a halogen atom, and A and D each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, and the number of carbon atoms which may be substituted by a halogen atom is 6~ An aryl group of 20, an aralkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted by a halogen atom, or a halogen atom, and the alkyl group and the aromatic group The methyl group in the aryl group or the aralkyl group may also be interrupted by an unsaturated bond, -O- or -S-, and A and D may form a ring from each other, D or each other, and A and D, which may be an aromatic ring, R ³ And a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or a halogen atom, and the alkyl group, the alkoxy group and Alkenyl group can also pass halogen atom Generation, p represents a number of 0 to 5, k represents a number of 0 to 5, a represents a number of 0 to 4, d represents a number of 0 to 4).

In the above formula (I), examples of the alkylene group having 1 to 4 carbon atoms represented by M include methylidene, ethylidene, and propylidene. And butylidene or the like; examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group; or a cyclopropenyl group or a ring; A cycloalkenyl group such as a butenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group or a cyclooctenyl group.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, and a third butyl group. Isobutyl group, pentyl group, isopentyl group, third pentyl group and the like; examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, an isopropoxy group, a propoxy group, and the like. Butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, etc.; as an alkenyl group having 2 to 5 carbon atoms, mention may be made of ethylene. Examples of the halogen group include fluorine, chlorine, bromine and iodine. Examples of the halogen atom include a propylene group, an isopropenyl group, a butenyl group, an isobutenyl group and a pentenyl group. Examples of the ring structure in which R ¹ and R ² are bonded to each other include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, and a piperidine ring. 5~7 member rings such as porphyrin ring, lactone ring and indoleamine ring, and condensed rings such as naphthalene ring, anthracene ring, anthracene ring, anthracene ring, indane ring and naphthalene ring.

In the substituent selected from the group represented by the above [Chemical Formula 2], examples of the alkyl group which may be substituted with a phenyl group represented by Q and B and having 1 to 10 carbon atoms include a methyl group and an ethyl group. Propyl, isopropyl, butyl, t-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-amyl, hexyl, heptyl, isoheptyl, third heptyl, An n-octyl group, an isooctyl group, a trioctyl group, a 2-ethylhexyl group, a n-decyl group, a n-decyl group, or the like, as an alkyl group having 1 to 10 carbon atoms which may be substituted with a phenyl group represented by Q and B The oxy group is the same as the exemplified group as the alkoxy group having 1 to 8 carbon atoms represented by R ¹ and R ² , and examples thereof include a decyloxy group and a decyloxy group. Examples of the cycloalkyl group of 3 to 10 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclodecyl group and the like.

The alkyl group having 1 to 10 carbon atoms represented by Z and E may be the same as those exemplified as the alkyl group having 1 to 10 carbon atoms which may be substituted by the phenyl group represented by Q and B. The alkoxy group having 1 to 10 carbon atoms may be the same as those exemplified as the alkoxy group having 1 to 10 carbon atoms which may be substituted by the phenyl group represented by Q and B; The alkenyl group having 2 to 10 carbon atoms is the same as the group exemplified as the alkenyl group having 2 to 5 carbon atoms represented by Q and B, and examples thereof include hexenyl and heptenyl groups. And an octenyl group, a nonenyl group, a decyl group, etc., and a halogen atom is the same as the base exemplified as the halogen atom represented by Q and B.

The alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, represented by A and D, is the same as the group exemplified as the alkyl group having 1 to 10 carbon atoms represented by Q and B. In addition to the alkyl group substituted with a halogen atom, a trifluoromethyl group, a difluoromethyl group, a monofluoromethyl group, a pentafluoroethyl group, a tetrafluoroethyl group, a trifluoroethyl group, a difluoroethyl group, Heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, etc.; as an aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, Listed: phenyl, 1-naphthyl, 2-naphthyl, 1-indenyl, 1-phenanthryl, o-tolyl, m-tolyl, p-tolyl, 3-indenyl, 9-fluorenyl, 1-tetra Hydronaphthyl, 2-tetrahydronaphthyl, 1-dihydroindenyl, 1-dihydroindenyl, 2-indanyl, 4-vinylphenyl, 3-isopropylphenyl, 4-iso Propyl phenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4 -(2-ethylhexyl)phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl , 3,4- Dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-t-butylphenyl, 2,5-di-t-butylphenyl, 2,6-di-t-butylbenzene Base, 2,4-di-t-amylphenyl, 2,5-di-t-pentylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3, 4-dichlorophenyl, 4-trichloromethylphenyl, 4-trifluoromethylphenyl, perfluorophenyl, etc.; as an aralkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom, Illustrative are: benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, phenylallyl, 4-chlorophenylmethyl, benzyloxy, 1-naphthylmethoxy, 2-naphthylmethoxy, 1-fluorenylmethoxy, etc.; as a heterocyclic group which may be substituted by a halogen atom, a pyrrolyl group, a pyridyl group, a pyrimidinyl group, and an anthracene are mentioned. Base Base, piperidinyl, pyranyl, pyrazolyl, tri , pyrrolidinyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, Thiophenyl, benzophenylthio, thiadiazolyl, thiazolyl, benzothiazolyl, Azolyl, benzo Azolyl, isothiazolyl, iso Azolyl, fluorenyl, Pyridyl, Olinyl, thio Lolinyl, 2-pyrrolidone-1-yl, 2-piperidin-1-yl, 2,4-dioxyimidazol-3-yl, 2,4-dioxy The oxazolidin-3-yl group and the like are the same as those exemplified as the halogen atom represented by Q and B.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ³ , an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and a halogen atom are exemplified by the above formula ( The basis of the description in I).

Examples of the ring structure which can be formed by A, D, or A and D include the groups exemplified in the description of the above formula (I).

The above-mentioned difunctional epoxy compound can also be used, and examples thereof include NC-3000, AK-601, GAN, GOT (manufactured by Nippon Kayaku Co., Ltd.), Adeka Resin EP-4000, Adeka Resin EP-4003S, and Adeka Resin. EP-4080, Adeka Resin EP-4085, Adeka Resin EP-4088, Adeka Resin EP-4100, Adeka Resin EP-4900, Adeka Resin ED-505, Adeka Resin ED-506, Adeka Resin KRM-2110, Adeka Resin KRM- 2199, Adeka Resin KRM-2720 (manufactured by Adeka), R-508, R-531, R-710 (manufactured by Mitsui Chemicals, Inc.), Epikote 190P, Epikote 191P, Epikote 604, Epikote 801, Epikote 828, Epikote 871, Epikote 872, Epikote 1031, Epikote RXE15, Epikote YX-4000, Epikote YDE-205, Epikote YDE-305 (made by Japan Epoxy Resins Co., Ltd.), Sumiepoxy ELM-120, Sumiepoxy ELM-434 (manufactured by Sumitomo Chemical Co., Ltd.) ), Denacol EM-150, Denacol EX-201, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-322, Denacol EX-411, Denacol EX-421, Denacol EX- 512, Denacol EX-521, Denacol EX-614, Denacol EX-711, Denacol EX-7 21. Denacol EX-731, Denacol EX-811, Denacol EX-821, Denacol EX-850, Denacol EX-851, Denacol EX- 911 (manufactured by Nagase Chemtex), Epolight 70P, Epolight 200P, Epolight 400P, Epolight 40E, Epolight 100E, Epolight 200E, Epolight 400E, Epolight 80MF, Epolight 100MF, Epolight 1500NP, Epolight 1600, Epolight 3002, Epolight 4000, Epolight FR-1500, Epolight M-1230, Epolight EHDG-L (manufactured by Kyoeisha Chemical Co., Ltd.), SB-20 (manufactured by Okamura Oil Company), Epiclon 720 (manufactured by Dainippon Ink Chemical Co., Ltd.), UVR-6100, UVR-6105, UVR-6110, UVR-6200, UVR-6228 (manufactured by Union Carbide), Celloxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 3000, Epolead HD300, EHPE- 3150, ETHB, Epofriend (manufactured by Daicel Chemical Co., Ltd.), PY-306, 0163, DY-022 (manufactured by Ciba Specialty Chemicals), Sun Tohto ST0000, Epotohto YD-011, Epotohto YD-115, Epotohto YD-127, Epotohto YD-134, Epotohto YD-172, Epotohto YD-6020, Epotohto YD-716, Epotohto YD-7011R, Epotohto YD-901, Epotohto YDPN-638, Epotohto YH-300, Ne Otohto PG-202, Neotohto PG-207 (manufactured by Tohto Kasei Co., Ltd.), Epiol E-100, Epiol E-400, Epiol E-1000, Epiol NPG-100 (manufactured by Nippon Oil Co., Ltd.), bismuth epoxy compound BPF-G , BCF-G, BPEF-G (manufactured by Osaka Gas Co., Ltd.), and the like.

The difunctional epoxy compound is preferably a compound represented by the above formula (I), and more preferably M in the above formula (I) is represented by the above [Chemical Formula 2]. In particular, those represented by the following general formula (II), (III) or (IV), or the oxime epoxy compounds BPF-G, BCF-G, BPEF-G (shown by the following general formula (V)) Osaka Gas Co., Ltd.) is because the dispersibility of the photocurable resin obtained is improved.

(wherein R ¹ , R ² , Q, Z, n and p are the same as those of the above formula (I)).

(wherein R ¹ , R ² and n are the same as the above formula (I)).

(wherein R ¹ , R ² , A, D, a, d and n are the same as in the above formula (I)).

(wherein R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or a halogen atom; The atom, and the alkyl group, the alkoxy group and the alkenyl group may be substituted by a halogen atom, and R ⁴ and R ⁵ may be bonded to form a ring structure, and n is the same as the above formula (I).

In the above formula (V), the alkyl group having 1 to 5 carbon atoms represented by R ⁴ and R ⁵ , the alkoxy group having 1 to 8 carbon atoms, and the carbon number of 2 to 5 are used. Examples of the alkenyl group and the halogen atom include the groups exemplified in the description of the above formula (I).

Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate-maleate, and hydroxyethyl acrylate-maleic acid. Ester, hydroxypropyl methacrylate-maleate, hydroxypropyl acrylate-maleate, dicyclopentadiene-maleate or with 1 carboxyl group and 2 (A) A difunctional (meth) acrylate such as an acrylonitrile group.

The above difunctional (meth) acrylate having one carboxyl group and two (meth) acrylonitrile groups can be, for example, one hydroxyl group and two (meth) propylene groups in one molecule. The difunctional (meth) acrylate of fluorenyl is obtained by reacting with a dibasic acid anhydride or a carboxylic acid.

The difunctional (meth) acrylate having one carboxyl group and two (meth) acrylonitrile groups may, for example, be the following compound No. 1 or No. 2.

As the above unsaturated monobasic acid, acrylic acid or methacrylic acid is preferred because it is easily available.

Examples of the compound (D) having an active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine and N,N-diethyl-1,3. -propylenediamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N, N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N - an aliphatic diamine such as diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine or N,N-dibutyl-1,4-butanediamine; High piper Piper 1,3-bis(4-piperidinyl)propane, 2-methylperazine 2,6-Dimethyl pipe 2,5-Dimethyl pipe , menthane diamine, isophorone diamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminocyclohexane, diaminodicyclohexylmethane, 3,9-double (3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,4-bis(2-amino-2-methylpropyl)per , an alicyclic diamine such as m-diamine, polycyclohexyl polyamine, bis(aminomethyl)bicyclo[2.2.1]heptane or methyl bis(furanmethylamine); diphenylmethane Aromatic aliphatic amines such as amine, dichlorodiphenylmethanediamine, toluenediamine, diethyltoluenediamine, benzidine, phenylenediamine; aromatic aliphatics such as xylylenediamine and tetramethylxylylenediamine Amine; N-methyl pipe N-ethylpipe N-butylperidazole N-octylperidine An alicyclic amine; containing a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an anthracene ring, an indazole ring, a carbazole ring, a benzimidazole ring, a benzotriazole ring, a benzo Nitrogen-containing five-membered ring such as azole ring, benzothiazole ring, benzothiadiazole ring, pyridine ring, hydrazine Ring, pyrimidine ring, three a compound containing a nitrogen-containing heterocyclic ring and a primary amino group such as a ring, a quinoline ring, an acridine ring or an isoquinoline ring, preferably N-methylpiperidyl. N-ethylpiperine The reason for this is that the obtained photocurable resin has improved adsorption property to the pigment.

In the above compound containing a nitrogen-containing heteropentacyclic ring and a primary amino group, for example, as a compound containing an imidazole ring and a primary amino group, 1-(3-aminopropyl)imidazole, histidine, 2- Aminoimidazole, 1-(2-aminoethyl)imidazole, etc., as a compound containing a triazole ring and a primary amino group, 3-amino-1,2,4-triazole, 5-(2) -amino-5-chlorophenyl)-3-phenyl-1H-1,2,4-three Azole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino group -1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, and the like.

The amount of the compound (D) having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of from 1 to 100 mgKOH/g, preferably in terms of the amine value of the photocurable resin obtained. The control is in the range of 5 to 95 mgKOH/g. If the amine value is outside the above range, there is a tendency that the dispersibility is lowered.

Examples of the polybasic acid anhydride (E) to be used in order to obtain the photocurable resin of the present invention include succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, and 2,2'- 3,3'-benzophenone tetracarboxylic anhydride, 3,3'-4,4'-benzophenone tetracarboxylic anhydride, ethylene glycol trimellitous anhydride, glyceryl trimellitic anhydride ester, neighbor Phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, acid anhydride, methylic acid anhydride, trialkyltetrahydrophthalic acid Anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydroortylene An acid anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl bicycloheptylene anhydride, and the like. Among these, succinic anhydride, trimellitic anhydride, and hexahydrophthalic anhydride are preferred.

The photocurable resin of the present invention is a hydroxyl group of the compound (B) having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 5,000, based on one isocyanate group of the diisocyanate compound (A). 0.02~0.5, and 2 hydroxyl groups and 2 ethylenically unsaturated groups in the same molecule After the addition of the hydroxyl group of the compound (C) in a ratio of 0.5 to 0.98, the same is true for one of the ethylenically unsaturated groups of the compound (C) having two hydroxyl groups and two ethylenically unsaturated groups in the same molecule. The ratio of the active hydrogen having the active hydrogen to the tertiary amine group (D) in the molecule is 0.01 to 0.4, which is obtained by adding the wheat. Among them, the total of the hydroxyl group of the compound (B) which contributes to the reaction and the hydroxyl group of the compound (C) is the same as the isocyanate group of the compound (A). Further, it is also possible to esterify one of the remaining hydroxyl groups with a ratio of 0.1 to 1.0 of the anhydride structure of the polybasic acid anhydride (E).

The photocurable resin of the present invention has a mass average molecular weight of 1,000 to 50,000 in terms of polystyrene measured by SEC (Size Exclusion Chromatography). When the mass average molecular weight is 1000 or less, dispersibility and dispersion stability are not obtained, and when it is 50,000 or more, solubility is lowered, dispersibility is deteriorated, and control of the reaction is difficult.

In the reaction for obtaining the photocurable resin of the present invention, a usual urethanation catalyst can be used as a catalyst. Examples of the urethanization reaction catalyst include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin thioformate, and cis-butene. Tin-butyltin, dioctyltin thioate, stannous octoate, tin, acetonitrile, iron, iron, etc., triethylamine, pentamethyldiethylenetriamine, pentamethyldipropanetriamine a tertiary amine system such as tetramethylguanidine, triethylenediamine, dimethylperidine Methylethylper ,methyl Porphyrin, dimethylaminoethyl A cyclic amine such as a porphyrin or a dimethylimidazole.

In the reaction for obtaining the photocurable resin of the present invention, a solvent may be appropriately used as needed. Examples of the solvent include methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophor. Ketones such as ketone; ether, two An ether solvent such as an alkane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid Ester solvent such as isopropyl ester or n-butyl acetate; solvent of cellosolve such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, and cellosolve acetate; methanol, ethanol, and different Or an alcohol solvent such as n-propanol, iso- or n-butanol, pentanol or acetol; an ether ester such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate Solvent; BTX (benzen-toluene-xylene, benzene-toluene-xylene) solvent such as benzene, toluene or xylene; aliphatic hydrocarbon solvent such as hexane, heptane, octane or cyclohexane; turpentine, D- Terpene hydrocarbon oil such as limonene or decene; paraffinic solvent such as mineral oil concentrate, Swasol #310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso #100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, three Halogenated aliphatic hydrocarbon solvent such as vinyl chloride, dichloromethane or 1,2-dichloroethane; halogenated aromatic hydrocarbon solvent such as chlorobenzene; N, N-di An aprotic polar solvent such as carbamide, N-methylpyrrolidone or dimethyl hydrazine; carbitol solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, water, etc., such solvents One type or a mixture of two or more types may be used.

The photocurable resin of the present invention can be produced, for example, by the method shown by the following reaction formula [Chemical Formula 9].

First, on the diisocyanate compound (1) as the component (A), the addition is carried out. The compound (2) having one or two hydroxyl groups in the same molecule as the component (B), and the compound (3) having two hydroxyl groups and two ethylenically unsaturated groups in the same molecule as the component (C). The addition reaction of the component (B) and the component (C) to the component (A) can be carried out according to a usual method, and it is preferred to carry out the reaction at 60 to 90 ° C for 1 to 10 hours.

Then, the meth can be added as a compound having active hydrogen and a tertiary amino group in the same molecule as the component (D), for example, an amine (4). The methic acid addition reaction of the component (D) can be carried out according to a usual method, and it is preferred to carry out the reaction at 20 to 50 ° C for 1 to 10 hours.

Then, the polybasic acid anhydride (5) as the component (E) is subjected to an esterification reaction to obtain a compound (6) as a photocurable resin. The esterification reaction of the component (E) can be carried out according to a usual method, and it is preferred to carry out the reaction at 20 to 50 ° C for 1 to 10 hours.

(wherein, X represents a residue of a difunctional epoxy compound, Y represents a residue of a diisocyanate compound, R ¹¹ represents a hydrogen atom or a methyl group, and R ^c and R ^d each independently represent an alkane having 1 to 5 carbon atoms; a aryl group having 6 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and R ^c and R ^d may be bonded to form a ring structure, and R ^a and R ^b each independently represent a hydrogen atom and carbon. An alkyl group having 1 to 5 atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms or a halogen atom. The alkoxy group and the alkenyl group may be substituted by a halogen atom, and R ^a and R ^b may be bonded to each other to form a ring structure, and s and t are each in the range of 0 to 1000, and the sum of s+t is 2 or more)

The photocurable resin of the present invention described above can be used for a wide range of applications such as lithographic inks, gravure inks, inkjet inks, paints, cosmetics, adhesives, conductivity imparting agents, conductive papers, and resin pigments. , electrophotographic materials, fillers, reinforcing agents, coating materials, battery materials, electrode materials, electronic materials, antistatic materials, electromagnetic wave shielding materials, cable semi-conductors, planar heating elements, adsorbents, catalysts, plastics or Rubber modifiers, lubricants, non-linear optical materials, fibers, carbon nanotubes, plating, various recording media, sealants.

Next, a pigment composition using the photocurable resin of the present invention as a dispersing agent will be described.

The photocurable resin of the present invention can be dispersed as a dispersant together with a pigment and a binder resin in a solvent to prepare a pigment composition. In the pigment composition, the content of the photocurable resin as the dispersing agent is preferably from 30 to 90% by mass, more preferably from 40 to 60% by mass, based on the total solid content of the pigment composition.

As the above pigment, for example, the following organic or inorganic pigments can be used: a nitroso compound, a nitro compound, a peroxide, a diperoxide, a compound, a quinoline compound, an anthraquinone compound, a coumarin compound, a phthalocyanine compound, an isoindolinone compound, an isoporphyrin compound, a quinacridone compound, an indolinone compound, a purple ring ketone compound, hydrazine Compound, diketopyrrolopyrrole compound, thioindigo compound, two Compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment, activated carbon, carbon fiber, carbon nanotube, coiled carbon fiber, carbon naphthalene Rice horn, carbon aerogel, fullerene; hydrophobic resin; metal oxides such as chromium oxide, nickel oxide, iron oxide, cerium oxide, titanium oxide, zinc oxide, calcium oxide, potassium oxide, cerium oxide, aluminum oxide, etc. Layered clay mineral, milorie blue, calcium carbonate, magnesium carbonate, cobalt, manganese, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, phosphate green, iron blue, Ultramarine, sky blue, chrome green, emerald green, etc. These pigments may be used singly or in combination of plural kinds.

In the above pigment composition, the content of the pigment is preferably from 10 to 80% by mass, more preferably from 30 to 70% by mass, based on the total of the solid content contained in the pigment composition.

A commercially available product can also be used as the above pigment. As a commercial item, pigment red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122 is mentioned, for example. , 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; pigment green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

The binder resin is not particularly limited, and a commonly used binder such as an ink, a paint, a coating material, or a solder resist can be used. As such a binder resin, for example, a photocurable resin other than the photocurable resin of the present invention, a thermosetting resin, an alkali-soluble resin, an acrylic resin, a soluble nylon and a polymer latex, a melamine resin, and a phenol resin can be used. , epoxy resin, diallyl phthalate resin, petroleum resin, maleic acid resin, phenol resin, acid alcohol resin, polyoxynoxy resin, fluorocarbon resin, by ring (alicyclic or a natural polymeric material such as polyurethane, gelatin, casein, starch, cellulose derivative, alginic acid obtained from the reaction of an aromatic) isocyanate with a polyhydric alcohol, polyvinyl butyral, polyvinylpyrrolidone, Polyvinyl alcohol, polyolefin, polyvinyl chloride, styrene copolymer, polystyrene, polycarbonate, polyamide, polyester, and the like.

In the above pigment composition, the content of the above binder resin is preferably from 1 to 70% by mass based on the total solid content of the pigment composition. Good is 3~30% by mass.

The solvent is not particularly limited as long as it is a solvent capable of dispersing the above-mentioned respective components, and for example, a solvent which is used in the reaction for obtaining the photocurable resin can be used. These solvents may be used alone or in combination of two or more. Mixed solvent.

The pigment composition is preferably prepared in such a manner that the content of the solvent is as follows, and the total solid content contained in the pigment composition is 0.1 to 30% by mass.

A photopolymerization initiator can be used in the above pigment composition.

As the photopolymerization initiator, a previously known compound can be used, and examples thereof include: benzamidine peroxide, 2,2'-azobisisobutyronitrile, benzophenone, phenylbiphenyl ketone, and 1 -hydroxy-1-benzimidylcyclohexane, benzoin, benzoin dimethyl ketal, 1-benzyl-1-dimethylamino-1-(4'- Polinylbenzylidene)propane, 2- Lolinyl-2-(4'-methylindenyl) benzhydrylpropane, 9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Isopropyl-9-oxosulfur Diethyl-9-oxosulfur , ethyl hydrazine, 4-benzylidene-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzylidene propane, 2-hydroxy-2-(4'-iso Propyl)benzhydrylpropane, 4-butylbenzylidenetrichloromethane, 4-phenoxybenzhydryldichloromethane, methyl benzylidenecarboxylate, 1,7-bis (9' -Acridine)heptane, 9-n-butyl-3,6-bis (2'- Olinoisobutyl) carbazole, 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, p-methoxyphenyl-2,4-bis(trichloromethyl)-all three 2-methyl-4,6-bis(trichloromethyl)-all three , 2-phenyl-4,6-bis(trichloromethyl)-all three 2-naphthyl-4,6-bis(trichloromethyl)-all three , 2-(p-butoxystyryl)--three , 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4- Diazole, 9-phenyl acridine, 9,10-dimethylbenzophenone , benzophenone/micilone, hexaarylbiimidazole/mercaptobenzimidazole, 9-oxosulfur /amine, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, and Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2001-233842, Japanese Patent Laid-Open A compound described in JP-A-2006-97141, JP-A No. 2006-516246, Japanese Patent No. 3860170, Japanese Patent No. 3798008, and WO2006/018973. Among these, a compound represented by the following formula (a) or (c) is preferred.

(wherein R ⁷¹ , R ⁷² and R ⁷³ each independently represent R, OR, COR, SR, CONRR' or CN, and R and R' represent an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, It may be substituted by a halogen atom and/or a heterocyclic group, wherein the alkyl group of the alkyl group and the aralkyl group may also be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond, and R and R ' may also form a ring together, R ⁷⁴ represents a halogen atom or an alkyl group, R ⁷⁵ represents a hydrogen atom, a halogen atom, an alkyl group or a substituent represented by the following formula (b), and g is an integer of 0 to 4, when When g is 2 or more, a plurality of R ⁷⁴ may be different bases).

(wherein ring M represents a cycloalkyl ring, an aromatic ring or a heterocyclic ring, R ⁷⁶ represents a halogen atom or an alkyl group, Y ⁷¹ represents an oxygen atom, a sulfur atom or a selenium atom, and Z ⁷¹ represents a carbon atom number of 1 to 5 Alkyl, h represents an integer from 0 to 4, and when h is 2 or more, a plurality of X ⁷³ may be different bases).

(wherein R ⁶ and R ⁷ each independently represent R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , CONR ²² R ²³ or CN, and R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom and have 1 carbon atom; An alkyl group of ~20, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, an alkyl group, an aryl group or an aralkyl group And the hydrogen atom of the heterocyclic group may further be OR ³¹ , COR ³¹ , SR ³¹ , NR ³² R ³³ , CONR ³² R ³³ , -NR ³² -OR ³³ , -NCOR ³² -OCOR ³³ , -C(=N- OR ³¹ )-R ³² , -C(=N-OCOR ³¹ )-R ³² , CN, halogen atom, -CR ³¹ =CR ³² R ³³ , -CO-CR ³¹ =CR ³² R ³³ , carboxy or epoxy group Substituting, R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and the methyl group of the alkyl group of the substituent represented by the above R ²¹ , R ²² , R ²³ , R ³¹ , R ³² and R ³³ may be an unsaturated bond, The ether bond, the thioether bond, the ester bond, the thioester bond, the guanamine bond or the urethane bond is interrupted 1 to 5 times, and the alkyl group of the above substituent May be a branched side chains, may also be cyclic alkyl terminal group of the above-described substituents may be an unsaturated bond, and, R ²² and R ^23, and R ³² and R ³³ may together form a ring, respectively, and .R ³ R ⁴ independently represents R ²¹ , OR ²¹ , SR ²¹ , COR ²¹ , CONR ²² R ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , CN, a halogen atom or The hydroxyl group, a and b are each independently 0 to 4. X ¹ represents a direct bond or CO, and X ² represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁴¹ R ⁴² , CO, NR ⁴³ or RR ⁴⁴ , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , CONR ²² R ²³ or CN, and R ⁸ may be bonded to one carbon atom of the adjacent benzene ring via -X ² - A ring structure is formed, or R ⁸ and R ⁹ may together form a ring, and R ⁴¹ , R ⁴³ and R ⁴⁴ are each independently, and may form a ring together with any of the adjacent benzene rings).

Further, an ethylenically unsaturated monomer, a chain transfer agent, a surfactant, or the like may be used in combination in the above pigment composition.

Examples of the ethylenically unsaturated bond monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isodecyl acrylate, and acrylic acid. Stearyl ester, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, methacrylic acid-2- Hydroxyethyl ester, 2-hydroxypropyl methacrylate, butyl methacrylate, third butyl methacrylate, cyclohexyl methacrylate, trishydroxyl Methyl propane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate, and the like.

Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, and N-(2-mercaptopropylpropane). Glycosyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)aminemethylmercapto]propionic acid, 3-[N-(2-mercaptoethyl)amino]propyl Acid, N-(3-mercaptopropyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl(4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, nonylphenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto a mercapto compound such as -3-hydroxypyridine, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate) or pentaerythritol tetrakis(3-mercaptopropionate), which is oxidized. The obtained disulfide compound, an iodide compound such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid or 3-iodopropanesulfonic acid.

As the surfactant, a fluorine-based surfactant such as a perfluoroalkyl phosphate or a perfluoroalkyl carboxylate, or an anionic system such as an alkali metal salt of a higher fatty acid, an alkyl sulfonate or an alkyl sulfate can be used. Surfactant, cationic surfactant such as higher amine hydrohalide, quaternary ammonium salt, polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride Such as nonionic surfactants, amphoteric surfactants, surfactants such as polyoxo-based surfactants, these may also be used in combination.

It is also possible to further use a thermoplastic organic polymer in the above pigment composition to improve the properties of the cured product. As the thermoplastic organic polymer, for example, Listed: polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-A Methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polypropylene decylamine, saturated polyester, and the like.

It may also be used in combination with the above pigment composition: viscosity adjuster, pH adjuster, surface tension adjuster, thickener, thixotropic imparting agent, leveling agent, antifoaming agent, adhesion imparting agent, anisole , hydroquinone, catechol, tert-butylcatechol, thiophene Isothermal polymerization inhibitor, catalyst, lubricant, plasticizer, adhesion improver, filler, decane coupling agent, chelating agent, humectant, penetrant, mold inhibitor, rust inhibitor, preservative, anti-drying agent , quick-drying agents, fixatives, antioxidants, UV absorbers, heat stabilizers, flame retardants, lubricants, processing aids, anti-caking agents, electrolytes, catalysts, other dispersants, etc.

As a method of dispersing or pulverizing the above pigment by using the photocurable resin of the present invention as a dispersing agent, a mortar, a bead mill, a plastic mill, a ball mill, a vibrating ball mill, a roll mill, a rod mill, and a can be used. Mill, cone mill, high-amplitude ball mill, pin mill, hammer mill, knife hammer mill, grinder, jet mill, back jet mill, spiral jet mill, jet miller , micronizer, nanomizer, Majac mill, micro atomizer, micron mill, rotary cutter, impact A method such as a pulverizing mill, a compression shearing mill, a Henkel mixer, or the like.

The above pigment resin composition can be printed, immersed, etc. by a spin coater, a slit coater, a roll coater, a curtain coater, and the like. It is applied to support substrates such as metal, paper, and plastic. Further, the pigment resin composition may be temporarily applied to a support substrate such as a film, and then transferred to another support substrate, and the application method is not limited.

The photocurable resin of the present invention can also be used as a coating material or an adhesive, a molding material, or the like. In the case of use as a coating material or an adhesive, a composition containing a photocurable resin is applied onto a substrate, and then cured by irradiation with light. Moreover, when it is used as a molding material, the photocurable resin flows into the mold which has a space part, and it irradiates light, and it hardens it. As the light source for the active light used for curing, a light having a wavelength of 240 to 410 nm can be used, and for example, an ultrahigh pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, a metal halide lamp, or the like can be used. The irradiation conditions such as the amount of irradiation of the active light and the irradiation time can be appropriately set depending on the photocurable resin to be used and the use.

[Examples]

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

[Example 1] Production of Photocurable Resin No. 1

Into a four-liter four-necked flask equipped with a stirring device, a nitrogen gas introduction tube, a reflux cooling tube, and a thermometer, 75.0 g of a bisphenol fluorene type epoxy resin (epoxy equivalent: 231) as a difunctional epoxy compound was added as an unsaturated layer. 23.8 g of monobasic acid, 0.273 g of 2,6-di-t-butyl-p-cresol, 0.585 g of tetrabutylammonium chloride and 65.9 g of propylene glycol-1-monomethyl ether-2-acetate at 90 ° C The mixture was stirred for 1 hour, then stirred at 100 ° C for 1 hour, then at 110 ° C for 1 hour, and then at 120 ° C for 14 hours to prepare a component (C). cold To the room temperature, 55.6 g of polyethylene glycol monomethyl ether (Uniox M-1000 manufactured by NOF Corporation) having a number average molecular weight of 1,000 as a component (B) was added as a component (B). 28.6 g of 4-toluene diisocyanate, 0.182 g of dibutyltin dilaurate, and 206 g of propylene glycol-1-monomethyl ether-2-acetate were stirred at 70 ° C for 2 hours. Further, 3.57 g of diethylamine as the component (D) was added thereto, and the mixture was stirred at room temperature for 2 hours, and 1.63 g of succinic anhydride as the component (E) was added thereto, and the mixture was stirred at 40 ° C for 5 hours. A photocurable resin No. 1 (Mw=11500, Mn=5300, and an amine value (solid content) of 15 mgKOH/g in the form of a propylene glycol-1-monomethyl ether-2-acetate solution. The acid value (solid content) was 5 mgKOH/g).

In addition, the photocurable resin No. 1 has a structure in which one of the isocyanate groups of the component (A) is added in a ratio of 0.17 of the hydroxyl group of the component (B) and 0.83 of the hydroxyl group of the component (C). After the formation, one of the ethylenically unsaturated groups of the component (C) is added with a ratio of 0.15 of the active hydrogen of the component (D), and one of the remaining hydroxyl groups is a polybasic acid anhydride (E). The structure of the anhydride structure is 0.1 in a ratio of esterification.

[Example 2] Production of Photocurable Resin No. 2 <Step 1> Synthesis of 1,1-bis(4-hydroxyphenyl)indane

Under a nitrogen atmosphere, 200 g of 1-indanone and 855 g of phenol were added to a 2-liter four-necked flask equipped with a stirring device, a nitrogen introduction tube, a reflux cooling tube and a thermometer, and slowly dripped at a temperature of 40 ° C or lower. 59.4 g of sulfuric acid was added, followed by 16.1 g of 3-mercaptopropionic acid. After the dropwise addition, the mixture was stirred at 55 ° C for 20 hours, and then 300 g of ethyl acetate and 50.4 g of a 48% by mass aqueous sodium hydroxide solution were added for neutralization, and the precipitated crystals were filtered to obtain 224 g of a crude product. Make this thick The product was dissolved in 1450 g of ethyl acetate, and washed with 500 g of a 5 mass% aqueous ammonium acetate solution until the pH of the organic layer reached 4 to 5. Then, 50 g of anhydrous magnesium sulfate was added to the organic layer obtained by liquid separation and dried. The solvent was distilled off, and 400 g of toluene was added for crystallization. The obtained crystals were dispersed and washed with toluene, and then vacuum dried at 40 ° C to obtain 135 g of 1,1-bis(4-hydroxyphenyl)indane (yield 29.5%) in white crystals.

<Step 2> Synthesis of 1,1-bis[4-(2,3-epoxypropoxy)phenyl]indane

To a four-liter four-necked flask equipped with a stirring device, a nitrogen gas introduction tube, a reflux cooling tube, and a thermometer under nitrogen atmosphere, the 1,1-bis(4-hydroxyphenyl)indole obtained in the step 1 was 29.2 g. And 142 g of epichlorohydrin, then 0.412 g of benzyltriethylammonium chloride was added and stirred at 74 ° C for 14 hours. Then, the temperature was lowered to 60 ° C, and 16.1 g of a 48% by mass aqueous sodium hydroxide solution was added dropwise under a reduced pressure of 13,000 Pa, and then the epichlorohydrin which azeotroped with water was returned to the system while stirring for 2.5 hours. At the time when the azeotropy of water disappeared, the temperature was gradually lowered while decompressing, and then epichlorohydrin was distilled off at 120 ° C for 2 hours. After returning to normal pressure, 205 g of toluene was added and washed three times. To the organic layer obtained by the separation of oil and water, 3.99 g of a 48% by mass aqueous sodium hydroxide solution, 0.412 g of benzyltriethylammonium chloride and 0.870 g of water were added, followed by stirring at 80 ° C for 2.5 hours. After cooling to room temperature, 0.692 g of a 10% by mass aqueous sodium dihydrogen phosphate solution was added for neutralization, and water washing was performed three times. The obtained organic layer was separated by filtration of oil and water using celite, and the solvent was distilled away to obtain 36.6 g of 1,1-bis[4-(2,3-epoxypropoxy)phenyl group as a pale yellow viscous material. Indane (yield 92%, epoxy equivalent of 212).

<Step 3> Manufacture of Photocurable Resin No. 2

To a 500 mL four-necked flask equipped with a stirring device, a nitrogen gas introduction tube, a reflux cooling tube, and a thermometer, 1,1-bis[4-(2,3-) obtained in the second step as a difunctional epoxy compound was added. 30.0 g of epoxycyclopropoxy)phenyl]indene, 10.4 g of acrylic acid as unsaturated monobasic acid, 0.120 g of 2,6-di-t-butyl-p-cresol, 0.256 g of tetrabutylammonium chloride, and propylene glycol 26.9 g of 1-methylol-2-acetate was stirred at 90 ° C for 1 hour, then at 105 ° C for 1 hour, and then at 120 ° C for 17 hours to prepare a component (C). 22.9 g of a polypropylene glycol monomethyl ether having a number average molecular weight of 1,000 as a component (B) and 12.0 g of 4,4'-diphenylmethane diisocyanate as a component (A) were added thereto. 0.076 g of dibutyltin laurate and 65.3 g of propylene glycol-1-monomethyl ether-2-acetate were then stirred at 70 ° C for 2 hours. Further, 2.83 g of diethanolamine as the component (D) was added thereto, and the mixture was stirred at room temperature for 2 hours, and 5.39 g of succinic anhydride as the component (E) was added thereto, and the mixture was stirred at 40 ° C for 5 hours. The photocurable resin No. 2 of the target product was obtained in the form of a propylene glycol-1-monomethyl ether-2-acetate solution (Mw = 5400, Mn = 3100, and the amine value (solid content) was 20 mgKOH/g, acid The value (solid content) was 40 mgKOH/g).

In addition, the photocurable resin No. 2 has a structure in which one of the isocyanate groups of the component (A) is added in a ratio of 0.24 of the hydroxyl group of the component (B) and 0.76 of the hydroxyl group of the component (C). After the formation, one of the ethylenically unsaturated groups of the component (C) is added with a ratio of 0.19 of the active hydrogen of the component (D), and further, a polybasic acid anhydride is used for one of the remaining hydroxyl groups. E) The structure of the anhydride structure is 0.81 to make it esterified.

[Example 3] Production of Photocurable Resin No. 3

To a 500 mL four-necked flask equipped with a stirring device, a nitrogen inlet tube, a reflux cooling tube and a thermometer, 1,1-bis[4-(2,3-epoxypropoxy) as a difunctional epoxy compound was added. Phenyl]-1-(4-biphenylyl)-1-cyclohexylmethane (epoxy equivalent: 279) 33.0 g, 6.22 g of acrylic acid as unsaturated monobasic acid, 2,6-di-t-butyl group 0.082 g of cresol, 0.153 g of tetrabutylammonium chloride and 10.5 g of propylene glycol-1-monomethyl ether-2-acetate were stirred at 90 ° C for 1 hour, then at 100 ° C for 1 hour, then at 110 The mixture was stirred at ° C for 1 hour and then at 120 ° C for 17 hours to prepare a component (C). To the room temperature, 16.9 g of a monomethyl ether of a commercially available ethylene glycol/propylene glycol copolymer having a number average molecular weight of 1,000 as a component (B), and isophorone diisocyanate as a component (A) of 8.34 g were added. There were 0.055 g of dibutyltin dilaurate and 62.9 g of propylene glycol-1-monomethyl ether-2-acetate, followed by stirring at 70 ° C for 2 hours. Further, after cooling to room temperature, N-methylperazine as a component (D) was added. 0.986 g and stirring at room temperature for 2 hours, adding 1.50 g of tetrahydrophthalic anhydride as the component (E), and stirring at 40 ° C for 5 hours, followed by propylene glycol-1-monomethyl ether-2-B A photocurable resin No. 3 (Mw = 13400, Mn = 6500, an amine value (solid content)) of 20 mgKOH/g, and an acid value (solid content) of 10 mgKOH/g) was obtained in the form of an acid ester solution. .

In addition, the photocurable resin No. 3 has a structure in which one of the isocyanate groups of the component (A) is added in a ratio of 0.23 of the hydroxyl group of the component (B) and 0.77 of the hydroxyl group of the component (C). After the formation, one of the ethylenically unsaturated groups of the component (C) is added with a ratio of 0.08 of the active hydrogen of the component (D), and one of the remaining hydroxyl groups is a polybasic acid anhydride (E). The structure of the anhydride structure of 0.16 is esterified.

[Example 4] Production of Photocurable Resin No. 4

Into a four-liter four-necked flask equipped with a stirring device, a nitrogen gas introduction tube, a reflux cooling tube, and a thermometer, 75.0 g of a bisphenol A type epoxy resin (epoxy equivalent: 186) as a difunctional epoxy compound was added as a Saturated monobasic acid 29.6, 2,6-di-t-butyl-p-cresol 0.321 g, tetrabutylammonium chloride 0.728 g and propylene glycol-1-monomethyl ether-2-acetate 69.8 g at 120 ° C The mixture was stirred for 16 hours to prepare a component (C). 69.7 g of a monomethyl ether of a commercially available ethylene glycol/propylene glycol copolymer having a number average molecular weight of 2000 as a component (B), and 2,4-toluene diisocyanate 26.0 as a component (A) were added to the room temperature. g, 0.201 g of dibutyltin dilaurate and 231 g of propylene glycol-1-monomethyl ether-2-acetate were then stirred at 70 ° C for 2 hours. Further, after cooling to room temperature, N-methylperazine as a component (D) was added. 3.59 g and stirring at room temperature for 2 hours to obtain a photocurable resin No. 4 (Mw=9500, Mn=5200, in the form of a propylene glycol-1-monomethyl ether-2-acetate solution, The amine value (solid content) was 20 mgKOH/g, and the acid value (solid content) was 0 mgKOH/g).

In addition, the photocurable resin No. 4 has a structure in which one of the isocyanate groups of the component (A) is added in a ratio of 0.12 of the hydroxyl group of the component (B) and 0.88 of the hydroxyl group of the component (C). After the formation, the structure was obtained by adding a ratio of the ethylenic unsaturated group of the component (C) to the ratio of 0.09 of the active hydrogen of the component (D).

[Example 5] Production of Photocurable Resin No. 5

To a 500-mL four-necked flask equipped with a stirring device, a nitrogen gas introduction tube, a reflux cooling tube, and a thermometer, 50 g of a tetramethylbiphenyl type epoxy resin (epoxy equivalent: 194) as a difunctional epoxy compound was added. 18.9 g of acrylic acid as an unsaturated monobasic acid, 0.209 g of 2,6-di-t-butyl-p-cresol, 0.465 g of tetrabutylammonium chloride, and 46.0 g of propylene glycol-1-monomethyl ether-2-acetate. The mixture was stirred at 90 ° C for 1 hour, then at 100 ° C for 1 hour, then at 110 ° C for 1 hour, and then at 120 ° C for 17 hours to prepare a component (C). After cooling to room temperature, 32.7 g of a 5 mol addition product of caprolactone of 2-hydroxyethyl acrylate which is commercially available as a component (B), and 15.7 g of 2, 4-toluene diisocyanate as (A) component were added. 0.118 g of dibutyltin laurate and 130 g of propylene glycol-1-monomethyl ether-2-acetate were then stirred at 70 ° C for 2 hours. Further, after cooling to room temperature, N-methylperazine as a component (D) was added. 6.30 g and stirred at room temperature for 2 hours to obtain a photocurable resin No. 5 of the target product in the form of a propylene glycol-1-monomethyl ether-2-acetate solution (Mw=4700, Mn=2700, The amine value (solid content) was 60 mgKOH/g, and the acid value (solid content) was 0 mgKOH/g).

In addition, the photocurable resin No. 5 has a structure in which one of the isocyanate groups of the component (A) is added in a ratio of 0.27 of the hydroxyl group of the component (B) and 0.73 of the hydroxyl group of the component (C). After the formation, the structure of the wheat-based unsaturated group of the component (C) and the active hydrogen of the component (D) were 0.24.

[Example 6] Production of Photocurable Resin No. 6

To a 1 L four-necked flask equipped with a stirrer, a nitrogen gas introduction tube, a reflux cooling tube, and a thermometer, 3,7 g of a binaphthol type epoxy resin (epoxy equivalent weight: 199) as a difunctional epoxy compound was added as an unsaturated one. Acidic acrylic acid 11.1g, 2,6-di-t-butyl-p-cresol 0.124g, tetrabutylammonium chloride 0.272 g and 27.4 g of propylene glycol-1-monomethyl ether-2-acetate were stirred at 120 ° C for 16 hours to obtain a component (C). After cooling to room temperature, 19.6 g of a monomethyl ether of a commercially available ethylene glycol/propylene glycol copolymer having a number average molecular weight of 1,000 as a component (B), and 4,4'-diphenylmethane as a component (A) were added. 17.6 g of diisocyanate, 0.078 g of dibutyltin dilaurate, and 118 g of propylene glycol-1-monomethyl ether-2-acetate were then stirred at 70 ° C for 2 hours. Further, after cooling to room temperature, 3.62 g of dibutylamine as the component (D) was added, and the mixture was stirred at room temperature for 2 hours, and 2.10 g of hexahydrophthalic anhydride as the component (E) was added thereto at 40 ° C. After stirring for 5 hours, a photocurable resin No. 6 (Mw = 22,000, Mn = 8200, amine value (solid content)) of the target was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. It is 20 mgKOH/g, and the acid value (solid content) is 10 mgKOH/g).

In addition, the photocurable resin No. 6 has a structure in which one of the isocyanate groups of the component (A) is added in a ratio of 0.14 of the hydroxyl group of the component (B) and 0.86 of the hydroxyl group of the component (C). After the formation, one of the ethylenically unsaturated groups of the component (C) is added with a ratio of 0.19 of the active hydrogen of the component (D), and one of the remaining hydroxyl groups is a polybasic acid anhydride (E). The structure of the anhydride structure of 0.46 is esterified.

[Evaluation Examples 1 to 6]

The photocurable resins No. 1 to No. 6 obtained in Examples 1 to 6 were evaluated in the following manner.

<Dispersibility evaluation>

7.5 g of each of the photocurable resins No. 1 to No. 6 (solid content conversion) obtained in the above Examples 1 to 6 were added to 10 g of the pigments shown in [Table 1]. Further, 32.5 g of propylene glycol-1-monomethyl ether-2-acetate was added. The mass of the dispersion obtained was 50 g. After premixing by a stirrer, dispersion treatment was carried out for 15 minutes in a range of 20 to 45 ° C using a planetary stirring device. As the beads, 50 g of 0.1 mm Φ zirconia beads was added. The beads and the dispersion were separated by a filter to obtain pigment compositions No. 1 to No. 6, respectively.

The evaluation of dispersibility was carried out by visually observing the dispersibility. When the slurry solution was uniformly dispersed to obtain a slurry solution, it was judged as ○, and aggregation or gelation was determined to be ×. The results are shown in [Table 1].

<Photocurability evaluation>

The coating liquid was prepared according to the following composition, and the obtained coating liquid was applied onto an aluminum substrate by a bar coater to a thickness of about 1 μm. After drying at 70 ° C for 15 minutes, the spectroscopic irradiation device CT-25CP manufactured by JASCO Corporation was used, and an ultrahigh pressure mercury lamp was used as a light source for exposure, followed by immersion in methyl ethyl ketone for 30 seconds, followed by rinsing with xylene. The spectroscopic sensitivity at 365 nm was measured. The sensitivity is determined by the number of cured film layers remaining on the aluminum plate and the amount of light emitted at 365 nm to obtain the minimum hardening energy required for curing at 365 nm. The results are shown in [Table 1].

(composition)

<Adhesion evaluation>

The coating liquid prepared above was applied to a PET (polyethylene terephthalate) film (A4300 manufactured by Toyobo Co., Ltd.) to a thickness of about 1 μm by a bar coater. After drying at 70 ° C for 15 minutes, the coating material was obtained by irradiating ultraviolet rays with a conveyor belt type ultraviolet irradiation machine at 180 mJ/cm ² . The adhesiveness was adhered to the transparent adhesive tape manufactured by Nichiban Co., Ltd., and the peeling was visually observed. The peeling-off was almost judged as ○, and the peeling of a part of the coating film was judged as Δ, which was large. Part of the film peeling was judged as ×. The results are shown in [Table 1].

[Comparative Evaluation Example 1~3]

The same operations as in the above evaluation examples 1 to 3 were carried out except that the photocurable resins No. 1 to No. 3 described above were not added. The results are shown in [Table 1].

[Comparative Evaluation Example 4~7]

The same operations as in the above evaluation examples 4 to 6 were carried out, except that the commercially available dispersing agent shown in [Table 1] was added instead of the photocurable resins No. 4 to No. 6 described above. The results are shown in [Table 1].

According to the results of [Table 1], the following items can be clarified. The pigment composition using the photocurable resin of the present invention has dispersibility equivalent to that of a pigment composition using a commercially available dispersant. Further, the coating liquid obtained by using the pigment composition of the photocurable resin of the present invention has photocurability and photohardening at the time of coating with a coating liquid obtained by using a pigment composition of a commercially available dispersant. The adhesion to the substrate is higher afterwards.

Claims (10)

A photocurable resin obtained by adding a di-isocyanate compound (A) to a compound (B) having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 5,000 and having two hydroxyl groups in the same molecule. After the compound (C) with 2 ethylenically unsaturated groups, the wheat may be added to diethylamine, diethanolamine, dibutylamine or N-methylpiperidone. The winner of either (D). The photocurable resin according to claim 1, wherein the compound (C) having two hydroxyl groups and two ethylenically unsaturated groups in the same molecule is an adduct of a difunctional epoxy compound and (meth)acrylic acid. The photocurable resin according to claim 2, wherein the difunctional epoxy compound is a compound represented by the following formula (I): (wherein M represents a direct bond, an alkylene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group, O, S, SO ₂ , SS, SO, CO, OCO or selected from the following [Chemical 2] In the substituent of the group shown, the above alkylene group may be substituted by a halogen atom, and R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. An oxy group, an alkenyl group having 2 to 5 carbon atoms or a halogen atom, and the alkyl group, the alkoxy group and the alkenyl group may be substituted by a halogen atom, and R ¹ and R ² may be bonded to form a ring structure, n is 0 or an integer from 1 to 10). (wherein Q and B each independently represent a hydrogen atom, a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or a carbon number of 3 to 10; a cycloalkyl group, Z and E each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkane The group, the alkoxy group and the alkenyl group may also be substituted by a halogen atom, and A and D each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, and the number of carbon atoms which may be substituted by a halogen atom is 6~ An aryl group of 20, an aralkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted by a halogen atom, or a halogen atom, and the alkyl group and the aromatic group The methyl group in the aryl group or the aralkyl group may also be interrupted by an unsaturated bond, -O- or -S-, and A and D may form a ring from each other, D, or A and D, and the ring may be an aromatic ring, R ³ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or a halogen atom, and the alkyl group or alkoxy group And alkenyl groups can also pass halogen atoms Generation, p represents a number of 0 to 5, k represents a number of 0 to 5, a represents a number of 0 to 4, d represents a number of 0 to 4). The photocurable resin according to claim 2 or 3, wherein the difunctional epoxy compound is a compound represented by the following formula (II): (wherein R ¹ , R ² , Q, Z, n and p are the same as those of the above formula (I)). The photocurable resin according to claim 2 or 3, wherein the difunctional epoxy compound is a compound represented by the following formula (III): (wherein R ¹ , R ² and n are the same as the above formula (I)). The photocurable resin according to claim 2 or 3, wherein the difunctional epoxy compound is a compound represented by the following formula (IV): (wherein R ¹ , R ² , A, D, a, d and n are the same as in the above formula (I)). The photocurable resin according to claim 2, wherein the difunctional epoxy compound is a compound represented by the following formula (V): (wherein R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or a halogen atom; The atom, and the alkyl group, the alkoxy group and the alkenyl group may be substituted by a halogen atom, and R ⁴ and R ⁵ may be bonded to form a ring structure, and n is the same as the above formula (I). The photocurable resin according to any one of claims 1 to 3 or 7, which has a mass average molecular weight of from 1,000 to 50,000 in terms of polystyrene measured by SEC (Size Exclusion Chromatography). A photocurable resin obtained by further esterifying a photocurable resin according to any one of claims 1 to 3 or 7 with a polybasic acid anhydride (E). A dispersing agent which is an active ingredient of the photocurable resin according to any one of claims 1 to 9.