JP5259354B2 - Photocurable resin and dispersant using the same - Google Patents

Description

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

  Conventionally, in the fields of paints and inks, various dispersants have been used to improve the dispersibility of pigments and increase the storage stability of paints and the gloss of coating films. For example, Patent Document 1 discloses a dispersant derived from a compound having at least one ring nitrogen-containing basic group, and Patent Document 2 discloses a polyisocyanate, an acrylate compound, an epoxide compound, and a cyclic compound. A dispersant comprising a reaction product obtained by reaction with a compound is disclosed, and Patent Document 3 discloses a color filter resist composition using a specific dispersion resin as a dispersant.

  In recent years, attempts have been made to impart photocurability to the dispersant itself to improve compatibility with the photocurable binder, photocurability at the time of coating, adhesion to the substrate, and the like. Patent Document 4 discloses a polyurethane resin-based photocurable coating agent, and Patent Document 5 discloses a pigment dispersant obtained by reacting a (meth) acrylate compound with a monoamine compound. The coating agent or dispersant was not sufficiently photocurable or adhesive.

JP-A-4-210220 JP 2000-506436 A Japanese Patent Laid-Open No. 10-300909 Japanese Patent Laid-Open No. 11-80665 JP 2007-711 A

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

In the present invention, the diisocyanate compound (A) is a compound (B) having a number average molecular weight of 300 to 5000 having one or two hydroxyl groups in the same molecule, and an adduct of a bifunctional epoxy compound and an unsaturated monobasic acid ( After addition of C), polystyrene-converted weight average molecular weight obtained by Michael addition of diethylamine, diethanolamine, dibutylamine or N-methylpiperazine (D) and measured by SEC (Size Exclusion Chromatography) The above object is achieved by providing a photo-curable resin having a molecular weight of 1000 to 50000 .

  Moreover, this invention provides the photocurable resin obtained by esterifying a polybasic acid anhydride (E) further to the said photocurable resin.

  Moreover, this invention achieves the said objective by providing the dispersing agent which uses the said photocurable resin as an active ingredient.

  Since the photocurable resin of the present invention has excellent photocurability, the dispersant containing the photocurable resin as an active ingredient is applied to the photocured during coating and the substrate after photocuring. High adhesion.

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

The photocurable resin of the present invention is a compound (B) having a number average molecular weight of 300 to 5,000 having one or two hydroxyl groups in the same molecule, a bifunctional epoxy compound and an unsaturated monobasic compound with respect to the diisocyanate compound (A). After the acid adduct (C) is added , any one of diethylamine, diethanolamine, dibutylamine or N-methylpiperazine (D) is Michael-added, and if necessary, polybasic acid anhydride (E) is added. Obtained by esterification.

  Examples of the diisocyanate compound (A) used for obtaining the photocurable resin of the present invention include 1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2 , 4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4, -trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, ω, ω'-diisocyanate dipropyl ether, etc. Aliphatic diisocyanate; cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,2-diisocyanate-1-methyl-cyclohexane, -2,6-diisocyanate -1-methyl-cyclohex Sun, isophorodiisocyanate, 2,5-bis- (isocyanatomethyl) -8-methyl-1,4-methano-decahydronaphthalene, 3,5-bis- (isocyanatomethyl) -8-methyl-1, 4-methano-decahydronaphthalene, 1,5-bis (isocyanatomethyl) -4,7-methano-hexahydroindane, 2,5-bis (isocyanatomethyl) -4,7-methano-hexahydroindane, 1,6-bis (isocyanatomethyl) -4,7-methano-hexahydroindane, 2,6-bis (isocyanatomethyl) -4,7-methano-hexahydroindane, 1,5-, 2,5 -, 1,6- and 2,6-bis (isocyanate) -4,7-methano-hexahydroindane, dicyclohexyl-2,4'- and 4,4'-diiso Anate, 2,4- and 2,6-hexahydrotolylene diisocyanate, perhydro-2,4'-diphenylmethane diisocyanate, perhydro-4,4'-diphenylmethane diisocyanate, 4,4'-di (isocyanatocyclohexyl) -methane Cyclic aliphatic diisocyanates such as 3-isocyanate-methyl-3,5,5-trimethylcyclohexyl isocyanate; ω, ω'-diisocyanate-1,4-diethyl-benzene, 1,3-phenylene diisocyanate, 1 , 4-phenylene diisocyanate, 4,4'-diisocyanate-diphenyl, 4,4'-diisocyanate-3,3'-dichlorodiphenyl, 4,4'-diisocyanate-3,3'-dimethoxy -Diphenyl, 4,4'-diisocyanate-3,3 -Dimethyl-diphenyl, 4,4'-diisocyanate-3,3'-diphenyl-diphenyl, 2,4'- and 4,4'-diisocyanato-diphenylmethane, naphthalene-1,5-diisocyanate, 2, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, N, N '-(4,4-dimethyl-3,3'-diisocyanatodiphenyl) -uretodione, m-xylylene diisocyanate, diphenylmethane-2,4 '-Diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,4,4'-triisocyanate-diphenyl ether, 4,4', 4 "-triisocyanate triphenylmethane, tris (4-isocyanatophenyl)- And aromatic diisocyanates such as thiophosphate.

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

  As the diisocyanate compound (A), tolylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate are preferable because adsorbability of the resulting photocurable resin to the pigment is high.

  Examples of the compound (B) having a number average molecular weight of 300 to 5000 having one or two hydroxyl groups in the same molecule used for obtaining the photocurable resin of the present invention include polyether diols, polyester diols, Examples include polyester polycarbonate diols, polycarbonate diols, polyolefin diols, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms. Also good.

  Examples of the polyether diols include ethylene oxide adducts such as diethylene glycol and triethylene glycol; propylene oxide adducts such as dipropylene glycol and tripropylene glycol; ethylene oxide and / or propylene oxide adducts of low molecular polyols, Examples include polytetramethylene glycol.

  Examples of the polyester diols include low-molecular diols, divalent carboxylic acids in an amount less than the stoichiometric amount, or ester-forming derivatives such as esters, anhydrides, halides, and / or lactones or hydrolyzed derivatives thereof. Examples thereof include those obtained by direct esterification and / or transesterification with a hydroxycarboxylic acid obtained by ring.

  Examples of the low molecular diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 2-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-nonanediol Aliphatic diols such as 1,10-decanediol; cyclohexanedimethanol, alicyclic diols such as cyclohexanediol; xylylene glycol, aromatic glycols such as bishydroxyethoxybenzene.

  Examples of the divalent carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, dodecanedioic acid, and 2-methylsuccinic acid. Acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid Aliphatic dicarboxylic acids such as dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. , Anhydrides of these divalent carboxylic acids, halides such as the divalent carboxylic acid chlorides; Methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, include lower aliphatic esters such as amyl esters, these may also be mixed.

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

  Examples of the polyester polycarbonate diols include those obtained by simultaneously reacting diols, divalent carboxylic acids and carbonate compounds such as dialkyl carbonates, alkylene carbonates, diaryl carbonates, etc., polyester polyols synthesized in advance and polycarbonate polyols reacted with carbonate compounds. And those obtained by reacting polyester polyol and polycarbonate polyol synthesized in advance with polyol and polycarboxylic acid.

  Examples of the polycarbonate diols include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.

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

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

The photocurable resin of the present invention, as the component (C), using a bifunctional epoxy compound and an adduct of an unsaturated monobasic acid.

  Examples of the bifunctional epoxy compound are obtained by epoxidizing a diglycidyl ether of a dihydric alcohol or an alkylene oxide adduct thereof, a diglycidyl ester of a dibasic acid, a cyclohexene ring or a cyclopentene ring-containing compound with an oxidizing agent. Cyclohexene oxide, a cyclopentene oxide-containing compound, or the like can be used, and specific examples include the following compounds.

  That is, bisphenol diglycidyl ether type epoxy resin such as bisphenol M type epoxy resin, bisphenol P type epoxy resin, epoxy resin represented by the following general formula (I); obtained by hydrogenating the bisphenol diglycidyl ether type epoxy resin Hydrogenated bisphenol type diglycidyl ether; ethylene glycol diglycidyl ether, 1,3-propylene glycol diglycidyl ether, 1,2-propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, die Lenglycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, glycidyl ether of aliphatic dihydric alcohols such as 1,4-cyclohexanedimethanol diglycidyl ether; phenol novolac Type epoxy compounds, biphenyl novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolac type epoxy compounds, dicyclopentadiene novolac type epoxy compounds and the like novolac type epoxy compounds; 3,4-epoxy-3-methylcyclohexylmethyl-3 , 4-Epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl -3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4 -Epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, bis (3,4-epoxycyclohexylmethyl) adipate, methylene bis (3,4-epoxycyclohexane), isopropylidenebis (3,4-epoxycyclohexane ), Alicyclic epoxy compounds such as dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), 1,2-epoxy-2-epoxyethylcyclohexane; diglycidyl phthalate Steric, glycidyl esters of dibasic acids such as tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; glycidyl amines such as N, N-diglycidyl aniline; complex such as 1,3-diglycidyl-5,5-dimethylhydantoin Cyclic epoxy compounds; dioxide compounds such as dicyclopentadiene dioxide; naphthalene-type epoxy compounds, triphenylmethane-type epoxy compounds, dicyclopentadiene-type epoxy compounds, and the like.

（式中、Ｍは直接結合、炭素原子数１〜４のアルキリデン基、脂環式炭化水素基、Ｏ、Ｓ、ＳＯ₂、ＳＳ、ＳＯ、ＣＯ、ＯＣＯ又は下記［化２］で表される群から選ばれる置換基を表し、上記アルキリデン基はハロゲン原子で置換されていてもよく、Ｒ¹及びＲ²は、それぞれ独立して、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、該アルキル基、アルコキシ基及びアルケニル基は、ハロゲン原子で置換されていてもよく、Ｒ¹及びＲ²は、連結して環構造を形成していてもよく、ｎは０又は１〜１０の整数である。）

(In the formula, M is represented by a direct bond, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group, O, S, SO ₂ , SS, SO, CO, OCO, or the following [Chemical Formula 2]. Represents a substituent selected from the group, wherein the alkylidene group may be substituted with a halogen atom, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a carbon atom. Represents 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, alkoxy group and alkenyl group may be substituted with a halogen atom, and R ¹ and R ² are And may be linked to form a ring structure, and n is 0 or an integer of 1 to 10.)

（式中、Ｑ及びＢは、それぞれ独立して、水素原子、炭素原子数１〜１０のアルキル基若しくは炭素原子数１〜１０のアルコキシ基で置換されていてもよいフェニル基又は炭素原子数３〜１０のシクロアルキル基を表し、Ｚ及びＥは、それぞれ独立して、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数２〜１０のアルケニル基又はハロゲン原子を表し、該アルキル基、アルコキシ基及びアルケニル基は、ハロゲン原子で置換されていてもよく、Ａ及びＤは、それぞれ独立して、ハロゲン原子で置換されていてもよい炭素原子数１〜１０のアルキル基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリール基、ハロゲン原子で置換されていてもよい炭素原子数７〜２０のアリールアルキル基、ハロゲン原子で置換されていてもよい炭素原子数２〜２０の複素環基又はハロゲン原子を表し、該アルキル基、アリール基、アリールアルキル基中のメチレン基は、不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、Ａ及びＤは、Ａ同士、Ｄ同士又はＡとＤで環を形成していてもよく、その環は芳香環でもよく、Ｒ³は水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、該アルキル基、アルコキシ基及びアルケニル基は、ハロゲン原子で置換されていてもよく、ｐは０〜５の数を表し、ｋは０〜５の数を表し、ａは０〜４の数を表し、ｄは０〜４の数を表す。）

(In the formula, Q and B are each independently a hydrogen atom, a phenyl group which may be substituted with a C 1-10 alkyl group or a C 1-10 alkoxy group or a C 3 carbon atom. Represents a cycloalkyl group having 10 to 10 carbon atoms, and 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. Represents an atom, and the alkyl group, the alkoxy group and the alkenyl group may be substituted with a halogen atom, and A and D each independently have 1 to 10 carbon atoms which may be substituted with a halogen atom. Alkyl groups, aryl groups having 6 to 20 carbon atoms which may be substituted with halogen atoms, arylalkyl groups having 7 to 20 carbon atoms which may be substituted with halogen atoms Represents a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom or a halogen atom, and the methylene group in the alkyl group, aryl group and arylalkyl group is an unsaturated bond, -O- or- A and D may be interrupted by S-, A and D may form a ring between A, D or A and D, the ring may be an aromatic ring, and R ³ is a hydrogen atom, a carbon atom Represents 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, wherein the alkyl group, alkoxy group and alkenyl group are substituted with a halogen atom. And p represents a number from 0 to 5, k represents a number from 0 to 5, a represents a number from 0 to 4, and d represents a number from 0 to 4.)

  In the general formula (I), examples of the alkylidene group having 1 to 4 carbon atoms represented by M include methylidene, ethylidene, propylidene, butylidene, and the like, and examples of the alicyclic hydrocarbon group include cyclopropyl, cyclobutyl, Examples include cycloalkane groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and cycloalkene groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and cyclooctenyl.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹ and R ² include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl and the like. Examples of the alkoxy group having 1 to 8 carbon atoms include methyloxy, ethyloxy, isopropyloxy, propyloxy, butyloxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and the like. Examples of the alkenyl group having 2 to 5 carbon atoms include ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl and the like, and examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the ring structure that R ¹ and R ² may be formed by linking include cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring. Examples thereof include condensed rings such as rings and naphthalene rings, anthracene rings, fluorene rings, acenaphthene rings, indane rings, and tetralin rings.

In the substituent selected from the group represented by [Chemical Formula 2], the alkyl group having 1 to 10 carbon atoms which may be substituted with the phenyl group represented by Q and B includes methyl, ethyl, propyl, Isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n- decyl and the like, and the alkoxy group having 1 to 10 carbon atoms which may be substituted phenyl group represented by Q and B, having 1 to 8 carbon atoms represented by R ¹ and R ² In addition to the same groups as those exemplified as the alkoxy group, nonyloxy, decyloxy and the like can be mentioned, and examples of the cycloalkyl group having 3 to 10 carbon atoms include , Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like.

  Examples of the alkyl group having 1 to 10 carbon atoms represented by Z and E are the same as those exemplified as the alkyl group having 1 to 10 carbon atoms which may be substituted with the phenyl group represented by Q and B. Examples of the alkoxy group having 1 to 10 carbon atoms include the same groups as those exemplified as the alkoxy group having 1 to 10 carbon atoms which may be substituted with the phenyl group represented by Q and B. As the alkenyl group having 2 to 10 carbon atoms, in addition to the groups similar to those exemplified as the alkenyl group having 2 to 5 carbon atoms represented by Q and B, hexenyl, heptenyl, octenyl, nonenyl, decenyl Examples of the halogen atom include the same groups as those exemplified as the halogen atom represented by Q and B.

  Examples of the alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom represented by A and D are the same as those exemplified as the alkyl group having 1 to 10 carbon atoms represented by Q and B. In addition to groups, those substituted with halogen atoms include trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl , Tetrafluoropropyl, trifluoropropyl, perfluorobutyl and the like. Examples of the aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom include phenyl, 1-naphthyl, 2-naphthyl, 1- Anthryl, 1-phenanthryl, o-tolyl, -Tolyl, p-tolyl, 3-fluorenyl, 9-fluorenyl, 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, 1-acenaphthenyl, 1-indanyl, 2-indanyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropyl Phenyl, 4-butylphenyl, 4-isobutylphenyl, 4-t-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-butylphenyl, 2 4-di-t-pentylphenyl, 2,5-di-t-amylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-trichloromethylphenyl, 4-tri Examples of the arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, and the like. Examples include a styryl, cinnamyl, 4-chlorophenylmethyl, benzyloxy group, 1-naphthylmethoxy group, 2-naphthylmethoxy group, 1-anthrylmethoxy, and the like, and examples of the heterocyclic group optionally substituted with a halogen atom include Pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazi , Piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl , Isoxazolyl, indolyl, urolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine -3-yl and the like, and examples of the halogen atom include the same groups as those exemplified as the halogen atom represented by Q and B.

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

  Examples of the ring structure that may be formed between A, D, or A and D include the groups exemplified in the description of the general formula (I).

  A commercially available thing can also be used as said bifunctional epoxy compound, for example, NC-3000, AK-601, GAN, GOT (made by Nippon Kayaku Co., Ltd.), Adeka Resin EP-4000, Adeka Resin EP-4003S, 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, manufactured by Adeka Resin KRM-2720 (Adeka Resin KRM-2720A ), R-508, R-531, R-710 (Mitsui Chemicals), Epicoat 190P, Epicoat 191P, Epicoat 604, Epicoat 801, Epicoat 828, Epicoat 871, Epicoat 8 2, Epicoat 1031, Epicoat RXE15, Epicoat YX-4000, Epicoat YDE-205, Epicoat YDE-305 (manufactured by Japan Epoxy Resin Co., Ltd.), Sumiepoxy ELM-120, Sumiepoxy ELM-434 (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-512, Denacol EX-512, Denacol EX-521 , Denacol EX-614, Denacol EX-711, Denacol EX-721, Denacol EX-731, Denacol EX-811, Denacol EX-821, Denacol EX-850, Denaco Le EX-851, Denacol EX-911 (manufactured by Nagase ChemteX Corporation), Epolite 70P, Epolite 200P, Epolite 400P, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 80MF, Epolite 100MF, Epolite 1500NP, Epolite 1500 , Epolite 3002, Epolite 4000, Epolite FR-1500, Epolite M-1230, Epolite EHDG-L (manufactured by Kyoeisha Chemical Co., Ltd.), SB-20 (manufactured by Okamura Oil Co., Ltd.), Epiklon 720 (manufactured by Dainippon Ink Chemical Co., Ltd.), UVR -6100, UVR-6105, UVR-6110, UVR-6200, UVR-6228 (manufactured by Union Carbide), Celoxide 2021, Celoxide 2021P, Celoxai 2081, Celoxide 2083, Celoxide 2085, Celoxide 3000, Epolide HD300, EHPE-3150, ETHB, Epoblend (Daicel Chemicals), PY-306, 0163, DY-022 (Ciba Specialty Chemicals), Santo Tote ST0000, Epototo YD-011, Epototo YD-115, Epototo YD-127, Epototo YD-134, Epototo YD-172, Epototo YD-6020, Epototo YD-716, Epototo YD-7011R, Epototo YD-901, Epoto YDP 638, Epototo YH-300, Neototo PG-202, Neototo PG-207 (manufactured by Toto Kasei), Epiol E-100, Epiol E-400, Epiol E-10 0, (manufactured by NOF Corporation) EPIOL NPG-100, fluorene epoxy compound BPF-G, BCF-G, BPEF-G (manufactured by Osaka Gas Co., Ltd.).

  As the bifunctional epoxy compound, a compound represented by the above general formula (I) is preferable. In the above general formula (I), M is represented by the above [Chemical Formula 2], particularly the following general formula (II), Light obtained from (III) or (IV), represented by the following general formula (V), or fluorene-based epoxy compounds BPF-G, BCF-G, BPEF-G (manufactured by Osaka Gas Co., Ltd.) It is more preferable because the dispersibility of the curable resin is improved.

（式中、Ｒ¹、Ｒ²、Ｑ、Ｚ、ｎ及びｐは、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , Q, Z, n and p are the same as those in the general formula (I).)

（式中、Ｒ¹、Ｒ²及びｎは、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² and n are the same as those in the general formula (I).)

（式中、Ｒ¹、Ｒ²、Ａ、Ｄ、ａ、ｄ及びｎは、上記一般式（Ｉ）と同じである。）

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

（式中、Ｒ⁴及びＲ⁵は、それぞれ独立して、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、該アルキル基、アルコキシ基及びアルケニル基は、ハロゲン原子で置換されていてもよく、Ｒ⁴及びＲ⁵は、連結して環構造を形成していてもよく、ｎは、上記一般式（Ｉ）と同じである。）

(Wherein R ⁴ and R ⁵ are each independently 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) Represents an atom, and the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, R ⁴ and R ⁵ may be linked to form a ring structure, Same as formula (I).)

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

  Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, dicyclo Examples thereof include pentadiene malate or a bifunctional (meth) acrylate having one carboxyl group and two (meth) acryloyl groups.

  The bifunctional (meth) acrylate having one carboxyl group and two (meth) acryloyl groups is, for example, a bifunctional (meta) having one hydroxyl group and two (meth) acryloyl groups in one molecule. ) It can be obtained by reacting an acrylate with a dibasic acid anhydride or a carboxylic acid.

  Examples of the bifunctional (meth) acrylate having one carboxyl group and two (meth) acryloyl groups include the following compound Nos. 1 or No. 2 can be mentioned.

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

The photocurable resin of the present invention, as the component (D), using diethylamine, diethanolamine, either of dibutylamine or N- methylpiperazine.

Introduction amount of the above SL component (D) is preferably controlled to a range of 1~100mgKOH / g Amine Value of the resulting photocurable resin, it is more preferable to control the range of 5~95mgKOH / g. When the amine value is out of the above range, the dispersion ability tends to be lowered.

  As the polybasic acid anhydride (E) used as necessary to obtain the photocurable resin of the present invention, succinic acid anhydride, maleic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride 2,2'-3,3'-benzophenone tetracarboxylic acid anhydride, 3,3'-4,4'-benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimelli Tate, phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2, 5-Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarbo Acid anhydride, trialkyl tetrahydrophthalic anhydride - maleic acid adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid. Among these, succinic anhydride, trimellitic anhydride and hexahydrophthalic anhydride are preferable.

The photocurable resin of the present invention has a hydroxyl group of a compound (B) having a number average molecular weight of 300 to 5,000 having one or two hydroxyl groups in the same molecule with respect to one isocyanate group of the diisocyanate compound (A). after hydroxyl group was added in 0.5 to 0.98 or a ratio of 02 to 0.5 pieces and bifunctional epoxy compound and an unsaturated adduct of a monobasic acid (C), bifunctional epoxy compounds and unsaturated mono A ratio of 0.01 to 0.4 active hydrogen of either (D) of diethylamine, diethanolamine, dibutylamine or N-methylpiperazine per one ethylenically unsaturated group of the adduct of basic acid (C) Can be obtained by adding Michael. However, the total of the hydroxyl group of the compound (B) and the hydroxyl group of the compound (C) contributing to the reaction is the same as the isocyanate group of the compound (A). Furthermore, the polybasic acid anhydride (E) can be esterified at a ratio of 0.1 to 1.0 with respect to one remaining hydroxyl group.

  In the photocurable resin of the present invention, the weight average molecular weight in terms of polystyrene measured by SEC (Size Exclusion Chromatography) is 1000 to 50000. When the mass average molecular weight is 1000 or less, dispersibility and dispersion stability cannot be obtained. When the mass average molecular weight is 50000 or more, the solubility is lowered, and the dispersibility is inferior and the reaction is difficult to control.

  In the reaction for obtaining the photocurable resin of the present invention, a normal urethanization reaction catalyst can be used as a catalyst. Examples of the urethanization reaction catalyst include tin series such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin thiocarboxylate, dibutyltin maleate, dioctyltin thiocarboxylate, stannous octoate, Iron such as iron acetylacetonate and ferric chloride, tertiary amine such as triethylamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine and tetramethylguanidine, triethylenediamine, dimethylpiperazine, methylethylpiperazine, methylmorpholine, dimethyl Examples thereof include cyclic amines such as aminoethylmorpholine and dimethylimidazole.

  In the reaction for obtaining the photocurable resin of the present invention, a solvent can be appropriately used as necessary. Examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, Ether solvents such as 1,2-diethoxyethane, dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate; ethylene glycol monomethyl ether, ethylene glycol Cellosolve solvents such as monoethyl ether, propylene glycol monomethyl ether acetate, cellosolve acetate; methanol, ethanol, iso- or n-propanol, iso- Is an alcohol solvent such as n-butanol, amyl alcohol, and acetone alcohol; an ether ester solvent such as ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, and propylene glycol methyl acetate; a BTX solvent such as benzene, toluene, and xylene; Aliphatic hydrocarbon solvents such as heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 ( Paraffin solvents such as Exxon Chemical Co., Ltd .; Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; Halogens such as chlorobenzene Aromatic hydrocarbon solvents; aprotic polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, water, etc. These solvents can be used as one or a mixture of two or more.

The photocurable resin of the present invention can be produced by, for example, a method represented by the following reaction formula [Chemical 9].
First, the diisocyanate compound (1) which is the component (A), the compound (2) which is the component (B), the compound (2) which has one or two hydroxyl groups in the same molecule, and the bifunctional epoxy compound which is the component (C) And an adduct (3) of an unsaturated monobasic acid . The addition reaction of the component (B) and the component (C) to the component (A) can be performed according to a conventional method, but is preferably performed at 60 to 90 ° C. for 1 to 10 hours.
Next, Michael (4), which is component (D), diethylamine, diethanolamine, dibutylamine or N-methylpiperazine is added. The Michael addition reaction of component (D) can be carried out according to a conventional method, but is preferably performed at 20 to 50 ° C. for 1 to 10 hours.
Subsequently, the polybasic acid anhydride (5) which is the component (E) is esterified to obtain a compound (6) which is a photocurable resin. The esterification reaction of component (E) can be carried out according to a conventional method, but is preferably carried out at 20 to 50 ° C. for 1 to 10 hours.

（式中、Ｘは二官能エポキシ化合物の残基を表し、Ｙはジイソシアネート化合物の残基を表し、Ｒ¹¹は水素原子又はメチル基を表し、Ｒ^c及びＲ^dは、それぞれ独立して、炭素原子数１〜５のアルキル基、炭素原子数６〜２０のアリール基又は炭素原子数２〜２０の複素環基を表し、Ｒ^c及びＲ^dは連結して環構造を形成していてもよく、Ｒ^a及びＲ^bは、それぞれ独立して、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基、炭素原子数６〜２０のアリール基又はハロゲン原子を表し、該アルキル基、アルコキシ基及びアルケニル基は、ハロゲン原子で置換されていてもよく、Ｒ^a及びＲ^bは連結して環構造を形成していてもよく、ｓ及びｔは、それぞれ０〜１０００の数であり、ｓ＋ｔの和は２以上である。）

(In the formula, X represents a residue of a bifunctional 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 carbon. Represents an alkyl group having 1 to 5 atoms, an 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 linked to form a ring structure. , R ^a and R ^b are each independently 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 6 carbon atoms. Represents an aryl group or a halogen atom of ˜20, the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and R ^a and R ^b may be linked to form a ring structure; , S and t are each a number from 0 to 1000; (The sum of s + t is 2 or more.)

The photo-curable resin of the present invention described above includes various inks such as offset ink, gravure ink, inkjet ink, paint, cosmetics, adhesive, conductivity imparting agent, conductive paper, resin pigment, electrophotographic material, filler. , Reinforcing agent, coating material, battery material, electrode material, electronic material, antistatic material, electromagnetic wave shielding material, cable semi-conductor, planar heating element, adsorbent, catalyst, plastic or rubber modifier, lubricant, It can be used for a wide range of applications such as nonlinear optical materials, fibers, carbon nanotubes, plating, various recording media, and sealants.

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

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

Examples of the pigment include nitroso compounds, nitro compounds, peroxides, diperoxides, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthanthrones. Compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment, activated carbon, carbon fiber , Carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; hydrophobic resin; chromium oxide, nickel oxide, iron oxide, iridium oxide, acid Metal oxides such as titanium, zinc oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay minerals, miloli blue, calcium carbonate, magnesium carbonate, cobalt-based, manganese-based, talc, kaolin, ferrocyanide, various metal sulfates Organic or inorganic pigments such as sulfide, selenide, phosphate ultramarine blue, bitumen, ultramarine, cerulean blue, pyridiane, emerald green and the like can be used. These pigments can be used alone or in combination.
In the pigment composition, the content of the pigment is preferably 10 to 80% by mass, and more preferably 30 to 70% by mass in the total solid content in the pigment composition.

  A commercial item can also be used as said pigment. Examples of commercially available products include Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 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, 13, 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 Bull-15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 etc. are mentioned.

The binder resin is not particularly limited, and binders usually used for inks, paints, coating materials, solder resists and the like can be used. Examples of such a binder resin include 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, a phenol resin, and an epoxy. Resin, diallyl phthalate resin, petroleum resin, maleic acid resin, phenol resin, alkyd resin, silicone resin, fluororesin, polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol, gelatin, casein, starch , Cellulose derivatives, natural polymer materials such as alginic acid, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl alcohol, polyolefin, polyvinyl chloride, styrene copolymer, polystyrene, polycarbonate, polyamide, polyester, etc. .
In the pigment composition, the content of the binder resin is preferably 1 to 70% by mass and more preferably 3 to 30% by mass in the total solid content in the pigment composition.

The solvent is not particularly limited as long as it is a solvent that can disperse each of the above-mentioned components. For example, those exemplified as the solvent in the reaction for obtaining the photocurable resin can be used. Can be used as one or two or more mixed solvents.
In the pigment composition, the content of the solvent may be adjusted so that the total solid content in the pigment composition is 0.1 to 30% by mass.

  A photopolymerization initiator can be used for the pigment composition.

  As the photopolymerization initiator, conventionally known compounds can be used. For example, benzoyl peroxide, 2,2′-azobisisobutyronitrile, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1- Benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholy-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro -4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- ( '-Isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2 '-Morpholinoisobutyroyl) carbazole, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, p-methoxyphenyl-2,4-bis (trichloromethyl) -s- Triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-butoxystyryl) -s-triazine, 2- (p-butoxystyryl) ) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine, bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, as well as JP 2000-80068, JP 2001-233842, JP 2005-97141, JP 2006-516246, JP 3860170. No. 3, Japanese Patent No. 3798008, and compounds described in WO 2006/018873. Among these, the compound represented by the following general formula (a) or (c) is preferable.

（式中、Ｒ⁷¹、Ｒ⁷²及びＲ⁷³は、それぞれ独立して、Ｒ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’又はＣＮを表し、Ｒ及びＲ’は、アルキル基、アリール基、アリールアルキル基又は複素環基を表し、これらはハロゲン原子及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアリールアルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよく、また、Ｒ及びＲ’は一緒になって環を形成していてもよく、Ｒ⁷⁴は、ハロゲン原子又はアルキル基を表し、Ｒ⁷⁵は、水素原子、ハロゲン原子、アルキル基又は下記一般式（ｂ）で表される置換基を表し、ｇは０〜４の整数であり、ｇが２以上の時、複数のＲ⁷⁴は異なる基でもよい。）

(Wherein R ⁷¹ , R ⁷² and R ⁷³ each independently represents R, OR, COR, SR, CONRR ′ or CN, and R and R ′ are an alkyl group, an aryl group, an arylalkyl group or Represents a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, of which the alkylene part of the alkyl group and arylalkyl group is an unsaturated bond, ether bond, thioether bond, ester bond R and R ′ may be combined together to form a ring, 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 general formula (b) is represented, g is an integer of 0 to 4, and when g is 2 or more, a plurality of R ⁷⁴ may be different groups.

（式中、環Ｍはシクロアルカン環、芳香環又は複素環を表し、Ｒ⁷⁶はハロゲン原子又はアルキル基を表し、Ｙ⁷¹は酸素原子、硫黄原子又はセレン原子を表し、Ｚ⁷¹は炭素原子数１〜５のアルキレン基を表し、ｈは０〜４の整数であり、ｈが２以上の時、複数のＸ⁷³は異なる基でもよい。）

(In the formula, ring M represents a cycloalkane 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 the number of carbon atoms. 1 represents an alkylene group of 1 to 5, h is an integer of 0 to 4, and when h is 2 or more, the plurality of X ⁷³ may be different groups.

（式中、Ｒ⁶及びＲ⁷は、それぞれ独立して、Ｒ²¹、ＯＲ²¹、ＣＯＲ²¹、ＳＲ²¹、ＣＯＮＲ²²Ｒ²³又はＣＮを表し、Ｒ²¹、Ｒ²²及びＲ²³は、それぞれ独立して、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、アルキル基、アリール基、アリールアルキル基及び複素環基の水素原子は、更にＯＲ³¹、ＣＯＲ³¹、ＳＲ³¹、ＮＲ³²Ｒ³³、ＣＯＮＲ³²Ｒ³³、−ＮＲ³²−ＯＲ³³、−ＮＣＯＲ³²−ＯＣＯＲ³³、−Ｃ（＝Ｎ−ＯＲ³¹）−Ｒ³²、−Ｃ（＝Ｎ−ＯＣＯＲ³¹）−Ｒ³²、ＣＮ、ハロゲン原子、−ＣＲ³¹＝ＣＲ³²Ｒ³³、−ＣＯ−ＣＲ³¹＝ＣＲ³²Ｒ³³、カルボキシル基又はエポキシ基で置換されていてもよく、Ｒ³¹、Ｒ³²及びＲ³³は、それぞれ独立して、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、上記Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ³¹、Ｒ³²及びＲ³³で表される置換基のアルキレン部分のメチレン基は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合又はウレタン結合により１〜５回中断されていてもよく、上記置換基のアルキル部分は分岐側鎖があってもよく、環状アルキルであってもよく、上記置換基のアルキル末端は不飽和結合であってもよく、また、Ｒ²²とＲ²³及びＲ³²とＲ³³は、それぞれ一緒になって環を形成していてもよい。Ｒ³及びＲ⁴は、それぞれ独立して、Ｒ²¹、ＯＲ²¹、ＳＲ²¹、ＣＯＲ²¹、ＣＯＮＲ²²Ｒ²³、ＮＲ²²ＣＯＲ²¹、ＯＣＯＲ²¹、ＣＯＯＲ²¹、ＳＣＯＲ²¹、ＯＣＳＲ²¹、ＣＯＳＲ²¹、ＣＳＯＲ²¹、ＣＮ、ハロゲン原子又は水酸基を表し、ａ及びｂは、それぞれ独立して、０〜４である。Ｘ¹は、直接結合又はＣＯを表し、Ｘ²は、酸素原子、硫黄原子、セレン原子、ＣＲ⁴¹Ｒ⁴²、ＣＯ、ＮＲ⁴³又はＰＲ⁴⁴を表し、Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³及びＲ⁴⁴は、それぞれ独立して、Ｒ²¹、ＯＲ²¹、ＣＯＲ²¹、ＳＲ²¹、ＣＯＮＲ²²Ｒ²³又はＣＮを表し、Ｒ⁸は、−Ｘ²−を介して隣接するベンゼン環の炭素原子の１つと結合して環構造を形成していてもよく、あるいはＲ⁸とＲ⁹が一緒になって環を形成していてもよく、Ｒ⁴¹、Ｒ⁴³及びＲ⁴⁴は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成していてもよい。）

(In the formula, 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 are each independently A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, Group, aryl group, arylalkyl group and heterocyclic group are further represented by 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 , optionally substituted with a carboxyl group or an epoxy group, R ³¹ , R ³² and R ³³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. The methylene group of the alkylene part of the substituent represented by the formula 2 to 20 and represented by R ²¹ , R ²² , R ²³ , R ³¹ , R ³² and R ³³ is an unsaturated bond, an ether bond, It may be interrupted 1 to 5 times by a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and the alkyl part of the substituent may have a branched side chain or a cyclic alkyl, The alkyl terminal of the substituent may be an unsaturated bond, and R ²² and R ²³ and R ³² and R ³³ may be combined to form a ring, R ³ and R ^4. Are each independently 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, halogen atom or hydroxyl group, a and b are Each independently represents 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 PR ⁴⁴ . , R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represents R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , CONR ²² R ²³ or CN, and R ⁸ represents —X ² — May be bonded to one of the adjacent carbon atoms of the benzene ring to form a ring structure, or R ⁸ and R ⁹ may be combined to form a ring, and R ⁴¹ , R ⁴³ and R ⁴⁴ are each independently a one benzene ring adjacent one It may form a ring turned. )

  The pigment composition may further contain an ethylenically unsaturated monomer, a chain transfer agent, a surfactant, and the like.

  Examples of the ethylenically unsaturated bond monomer include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, N-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic acid Methoxyethyl, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Tertiary butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, penta Risuri tall 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, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) 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, mercapto Enol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Mercapto compounds such as pionate), disulfide compounds obtained by oxidizing the mercapto compound, iodinated alkyls such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Compounds.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

  By using a thermoplastic organic polymer in the pigment composition, the properties of the cured product can be improved. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester.

  In the above pigment composition, if necessary, a viscosity modifier, a pH adjuster, a surface tension modifier, a thickener, a thixotropic agent, a leveling agent, an antifoaming agent, an adhesion promoter, anisole, hydroquinone, Thermal polymerization inhibitors such as pyrocatechol, tert-butylcatechol, phenothiazine, catalysts, lubricants, plasticizers, adhesion promoters, fillers, silane coupling agents, chelating agents, moisturizers, penetrants, antifungal agents, rust prevention Agent, preservative, anti-drying agent, quick-drying agent, fixing agent, antioxidant, UV absorber, heat stabilizer, flame retardant, lubricant, processing aid, anti-blocking agent, electrolyte, catalyst, other dispersants, etc. Can be used in combination.

  The method of dispersing or pulverizing the pigment using the photocurable resin of the present invention as a dispersant includes mortar, bead mill, plast mill, ball mill, vibration ball mill, roller mill, rod mill, tube mill, conical mill, high swing ball mill, pin Die mill, Hammer mill, Knife hammer mill, Attrition mill, Jet mill, Counter jet mill, Spiral jet mill, Jet mizer, Micronizer, Nanomizer, Macjack mill, Micro atomizer, Micron mill, Rotary cutter, Impact grinding mold mill And a method using a compression shear type mill, a Henschel mixer and the like.

  The pigment resin composition is applied onto a support substrate such as metal, paper, or plastic by a known means such as a spin coater, slit coater, roll coater, curtain coater, various printing, or dipping. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  The photocurable resin of the present invention can also be used as a paint, an adhesive, a molding material or the like. When used as a paint or an adhesive, a composition containing a photocurable resin is applied to a substrate and then cured by irradiation with light. Moreover, when using as a molding material, photocurable resin is poured into the type | mold which has a space part, and light is then irradiated and hardened. As a light source of active light used for curing, a light source that emits light having a wavelength of 240 to 410 nm can be used. For example, an ultrahigh pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, a metal halide lamp Etc. can be used. Irradiation conditions such as the irradiation amount of the active light and the irradiation time can be appropriately set according to the photocurable resin used and the application.

  EXAMPLES Hereinafter, although an Example and an evaluation example are given and this invention is demonstrated further in detail, this invention is not restrict | limited to these Examples.

[Example 1] Photocurable resin No. 1 Production of 1 Into a 1 L four-necked flask equipped with a stirrer, a nitrogen introduction tube, a reflux condenser, and a thermometer, 75.0 g of a bisphenolfluorene type epoxy resin (epoxy equivalent 231) as a bifunctional epoxy compound, unsaturated monobasic acid 23.8 g of acrylic 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, (C) component was manufactured by stirring at 90 ° C. for 1 hour, at 100 ° C. for 1 hour, at 110 ° C. for 1 hour and at 120 ° C. for 14 hours. After cooling to room temperature, 55.6 g of polyethylene glycol monomethyl ether having a number average molecular weight of 1000 (NOF M-1000 manufactured by NOF Corporation) as component (B), 2,4-tolylene diisocyanate 28 as component (A) .6 g, dibutyltin dilaurate 0.182 g and propylene glycol-1-monomethyl ether-2-acetate 206 g were added and stirred at 70 ° C. for 2 hours. Further, the mixture was cooled to room temperature, 3.57 g of diethylamine was added as component (D) and stirred at room temperature for 2 hours. 1.63 g of succinic anhydride was added as component (E) and stirred at 40 ° C. for 5 hours, and then propylene glycol. -1-monomethyl ether-2-acetate solution as a target, photocurable resin No. 1 (Mw = 11500, Mn = 5300, amine value (solid content) 15 mgKOH / g, acid value (solid content) 5 mgKOH / g).
In addition, photocurable resin No. 1 is obtained by adding 0.17 hydroxyl groups of the component (B) and 0.83 hydroxyl groups of the component (C) to one isocyanate group of the component (A), and then adding the component (C). The active hydrogen of component (D) is added by Michael at a ratio of 0.15 to one ethylenically unsaturated group, and the acid of polybasic acid anhydride (E) is added to one remaining hydroxyl group. The anhydride structure has a structure esterified at a ratio of 0.1.

[Example 2] Photocurable resin No. 2 <Step 1> Synthesis of 1,1-bis (4-hydroxyphenyl) indane In a 2 L four-necked flask equipped with a stirrer, a nitrogen introduction tube, a reflux condenser, and a thermometer, 1- 200 g of indanone and 855 g of phenol were charged, and 59.4 g of sulfuric acid was added dropwise slowly at 40 ° C. or lower, followed by 16.1 g of 3-mercaptopropionic acid. After dropping, the mixture was stirred at 55 ° C. for 20 hours, neutralized by adding 300 g of ethyl acetate and 50.4 g of 48 mass% sodium hydroxide aqueous solution, and the precipitated crystals were filtered to obtain 224 g of a crude product. This crude product was dissolved in 1450 g of ethyl acetate, washed with 500 g of 5% by mass aqueous ammonium acetate solution until the organic layer had a pH of 4 to 5, and 50 g of anhydrous magnesium sulfate was added to the separated organic layer 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 vacuum dried at 40 ° C. to obtain 135 g of 1,1-bis (4-hydroxyphenyl) indane as white crystals (yield 29.5%).

<Step 2> Synthesis of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane Into a 2 L four-necked flask equipped with a stirrer, nitrogen introduction tube, reflux condenser and thermometer, nitrogen was added. Under the atmosphere, 29.2 g of 1,1-bis (4-hydroxyphenyl) indane obtained in Step 1 and 142 g of epichlorohydrin were added, 0.412 g of benzyltriethylammonium chloride was added, and the mixture was stirred at 74 ° C. for 14 hours. Subsequently, the temperature was lowered to 60 ° C., 16.1 g of a 48 mass% sodium hydroxide aqueous solution was added dropwise under a reduced pressure of 13000 Pa, and the mixture was stirred for 2.5 hours while returning epichlorohydrin azeotropic with water into the system. . When water azeotropy disappeared, the pressure was gradually reduced while raising the temperature, and epichlorohydrin was distilled off at 120 ° C. for 2 hours. The pressure was returned to normal pressure, and 205 g of toluene was added and washed with water three times. To the organic layer separated into oil and water were added 3.99 g of a 48% by mass aqueous sodium hydroxide solution, 0.412 g of benzyltriethylammonium chloride and 0.870 g of water, and the mixture was stirred at 80 ° C. for 2.5 hours. The mixture was cooled to room temperature, neutralized by adding 0.692 g of a 10% by mass aqueous sodium dihydrogen phosphate solution, and washed with water three times. The organic layer obtained by oil-water separation was filtered through celite, the solvent was distilled off, and 36.6 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane was converted to a pale yellow viscous product. Obtained as a preparation (yield 92%, epoxy equivalent 212).

<Step 3> Photocurable resin No. Production of 2 Into a 500 mL four-necked flask equipped with a stirrer, a nitrogen introduction tube, a reflux condenser, and a thermometer, 1,1-bis [4- (2,3- Epoxypropyloxy) phenyl] indane 30.0 g, 10.4 g acrylic acid as unsaturated monobasic acid, 0.120 g 2,6-di-t-butyl-p-cresol, 0.256 g tetrabutylammonium chloride and propylene glycol Component (C) was prepared by charging 26.9 g of -1-monomethyl ether-2-acetate and stirring at 90 ° C. for 1 hour, 105 ° C. for 1 hour and 120 ° C. for 17 hours. Cooled to room temperature, 22.9 g of commercially available polypropylene glycol monomethyl ether having a number average molecular weight of 1000 as component (B), 12.0 g of 4,4′-diphenylmethane diisocyanate as component (A), 0.076 g of dibutyltin dilaurate and propylene 65.3 g of glycol-1-monomethyl ether-2-acetate was added and stirred at 70 ° C. for 2 hours. Further, the mixture was cooled to room temperature, 2.83 g of diethanolamine was added as component (D) and stirred at room temperature for 2 hours, 5.39 g of succinic anhydride was added as component (E), and the mixture was stirred at 40 ° C. for 5 hours. -1-monomethyl ether-2-acetate solution as a target, photocurable resin No. 2 (Mw = 5400, Mn = 3100, amine value (solid content) 20 mgKOH / g, acid value (solid content) 40 mgKOH / g).
In addition, photocurable resin No. (2) is the addition of 0.24 hydroxyl groups of component (B) and 0.76 hydroxyl groups of component (C) to one isocyanate group of component (A), and then component (C) The active hydrogen of component (D) is added by Michael at a ratio of 0.19 to one ethylenically unsaturated group, and the acid of polybasic acid anhydride (E) is added to one remaining hydroxyl group. The anhydride structure has a structure esterified at a ratio of 0.81.

[Example 3] Photocurable resin no. 3. Preparation of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] as a bifunctional epoxy compound in a 500 mL four-necked flask equipped with a stirrer, a nitrogen inlet tube, a reflux condenser, and a thermometer -1- (4-biphenylyl) -1-cyclohexylmethane (epoxy equivalent 279) 33.0 g, acrylic acid 6.22 g as unsaturated monobasic acid, 2,6-di-t-butyl-p-cresol 0.082 g , 0.153 g of tetrabutylammonium chloride and 10.5 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour and 120 ° C. for 17 hours. (C) component was manufactured. Cooled to room temperature, 16.9 g of a commercially available ethylene glycol / propylene glycol copolymer having a number average molecular weight of 1000 as component (B), 8.34 g of isophorone diisocyanate as component (A), 0.055 g of dibutyltin dilaurate And 62.9 g of propylene glycol-1-monomethyl ether-2-acetate was added and stirred at 70 ° C. for 2 hours. The mixture was further cooled to room temperature, 0.986 g of N-methylpiperazine was added as component (D) and stirred at room temperature for 2 hours, 1.50 g of tetrahydrophthalic anhydride was added as component (E), and stirred at 40 ° C. for 5 hours. Thereafter, as a propylene glycol-1-monomethyl ether-2-acetate solution, a target photocurable resin No. 3 (Mw = 13400, Mn = 6500, amine value (solid content) 20 mgKOH / g, acid value (solid content) 10 mgKOH / g).
In addition, photocurable resin No. 3 is obtained by adding 0.23 hydroxyl groups of the component (B) and 0.77 hydroxyl groups of the component (C) to one isocyanate group of the component (A), and then adding the component (C). The active hydrogen of component (D) is Michael-added at a ratio of 0.08 to one ethylenically unsaturated group, and the acid of polybasic acid anhydride (E) is added to one remaining hydroxyl group. The anhydride structure has a structure esterified at a ratio of 0.16.

[Example 4] Photocurable resin no. Production of 4 Into a 1 L four-necked flask equipped with a stirrer, a nitrogen inlet tube, a reflux condenser, and a thermometer, 75.0 g of bisphenol A type epoxy resin (epoxy equivalent 186) as a bifunctional epoxy compound, unsaturated monobasic acid As an acrylic 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, (C) component was manufactured by stirring at 0 degreeC for 16 hours. After cooling to room temperature, 69.7 g of a commercially available ethylene glycol / propylene glycol copolymer having a number average molecular weight of 2000 as component (B), 26.0 g of 2,4-tolylene diisocyanate as component (A), dibutyltin 0.201 g of dilaurate and 231 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 70 ° C. for 2 hours. Further, the mixture was cooled to room temperature, 3.59 g of N-methylpiperazine was added as a component (D), and the mixture was stirred at room temperature for 2 hours, and the target photocurable resin No. was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. . 4 (Mw = 9500, Mn = 5200, amine value (solid content) 20 mgKOH / g, acid value (solid content) 0 mgKOH / g).
In addition, photocurable resin No. 4 is obtained by adding 0.12 hydroxyl groups of the component (B) and 0.88 hydroxyl groups of the component (C) to one isocyanate group of the component (A), and then adding the component (C). The active hydrogen of component (D) is Michael-added at a ratio of 0.09 to one ethylenically unsaturated group.

[Example 5] Photocurable resin no. Production of 5 In a 500 mL four-necked flask equipped with a stirrer, a nitrogen inlet tube, a reflux condenser, and a thermometer, 50 g of tetramethylbiphenyl type epoxy resin (epoxy equivalent 194) as a bifunctional epoxy compound, as an unsaturated monobasic acid Acrylic acid 18.9 g, 2,6-di-t-butyl-p-cresol 0.209 g, tetrabutylammonium chloride 0.465 g and propylene glycol-1-monomethyl ether-2-acetate 46.0 g were charged at 90 ° C. The mixture was stirred for 1 hour at 100 ° C for 1 hour, 110 ° C for 1 hour, and 120 ° C for 17 hours to prepare component (C). After cooling to room temperature, 32.7 g of a commercially available 2-hydroxyethyl acrylate caprolactone 5 mol adduct as component (B), 15.7 g of 2,4-tolylene diisocyanate as component (A), 0.118 g of dibutyltin dilaurate and 130 g of propylene glycol-1-monomethyl ether-2-acetate was added and stirred at 70 ° C. for 2 hours. Further, the mixture was cooled to room temperature, 6.30 g of N-methylpiperazine was added as component (D), and the mixture was stirred at room temperature for 2 hours, and the target photocurable resin No. was obtained as a propylene glycol-1-monomethyl ether-2-acetate solution. . 5 (Mw = 4700, Mn = 2700, amine value (solid content) 60 mgKOH / g, acid value (solid content) 0 mgKOH / g).
In addition, photocurable resin No. 5 is obtained by adding 0.27 hydroxyl groups of the component (B) and 0.73 hydroxyl groups of the component (C) to one isocyanate group of the component (A), and then adding the component (C). The active hydrogen of component (D) is Michael-added at a ratio of 0.24 to one ethylenically unsaturated group.

[Example 6] Photocurable resin No. 6 Production of 6 Into a 1 L four-necked flask equipped with a stirrer, nitrogen introduction tube, reflux condenser and thermometer, 30.0 g of binaphthol type epoxy resin (epoxy equivalent 199) as a bifunctional epoxy compound, as unsaturated monobasic acid Charged 11.1 g of acrylic acid, 0.124 g of 2,6-di-t-butyl-p-cresol, 0.272 g of tetrabutylammonium chloride and 27.4 g of propylene glycol-1-monomethyl ether-2-acetate, 120 ° C. And stirred for 16 hours to prepare component (C). After cooling to room temperature, 19.6 g of a commercially available ethylene glycol / propylene glycol copolymer having a number average molecular weight of 1000 as component (B), 17.6 g of 4,4′-diphenylmethane diisocyanate as component (A), 0.078 g of dibutyltin dilaurate and 118 g of propylene glycol-1-monomethyl ether-2-acetate were added and stirred at 70 ° C. for 2 hours. Further, the mixture was cooled to room temperature, 3.62 g of dibutylamine was added as component (D) and stirred at room temperature for 2 hours, and 2.10 g of hexahydrophthalic anhydride was added as component (E) and stirred at 40 ° C. for 5 hours. Photocurable resin No. 1 which is the target product as a propylene glycol-1-monomethyl ether-2-acetate solution. 6 (Mw = 22000, Mn = 8200, amine value (solid content) 20 mgKOH / g, acid value (solid content) 10 mgKOH / g).
In addition, photocurable resin No. 6 is obtained by adding 0.14 hydroxyl groups of the component (B) and 0.86 hydroxyl groups of the component (C) to one isocyanate group of the component (A) and then adding the component (C). The active hydrogen of component (D) is added by Michael at a ratio of 0.19 to one ethylenically unsaturated group, and the acid of polybasic acid anhydride (E) is added to one remaining hydroxyl group. The anhydride structure has a structure esterified at a ratio of 0.46.

[Evaluation Examples 1 to 6]
Photocurable resin No. obtained in Examples 1-6. 1-No. Evaluation of 6 was performed as follows.
<Dispersibility evaluation>
With respect to 10 g of the pigment shown in [Table 1], the photocurable resin Nos. Obtained in Examples 1 to 6 above. 1-No. 6 (in terms of solid content) was added in an amount of 7.5 g, and 32.5 g of propylene glycol-1-monomethyl ether-2-acetate was further added. The mass of the obtained dispersion was 50 g. After premixing with a stirrer, dispersion treatment was performed for 15 minutes in the range of 20 to 45 ° C. with a planetary stirrer. As beads, 50 g of 0.1 mmφ zirconia beads were added. The beads and the dispersion liquid were separated by a filter, and the pigment composition No. 1-No. 6 were obtained respectively.
Dispersibility evaluation was performed by observing dispersibility visually. A sample obtained by uniformly dispersing to obtain a slurry solution was indicated by ○, and a product obtained by agglomeration and sedimentation or by gelation was indicated by ×. The results are shown in [Table 1].
<Photocurability evaluation>
The coating solution was adjusted by the following composition, and the obtained coating solution was applied to an aluminum substrate with a bar coater to a thickness of about 1 μm. After drying at 70 ° C. for 15 minutes, exposure was performed using an ultra-high pressure mercury lamp as a light source with a spectral irradiation device CT-25CP manufactured by JASCO Corporation, followed by immersion in methyl ethyl ketone for 30 seconds and rinsing with xylene to obtain a spectral sensitivity at 365 nm. It was measured. For the sensitivity, the minimum curing energy required for curing at 365 nm was determined from the number of cured film steps remaining on the aluminum plate and the amount of emitted light at 365 nm. The results are shown in [Table 1].
(Combination)
Pigment composition No. 1-No. 6 50.00 parts polyether acrylate (Shin Nakamura Chemical "A-400") 3.80 parts polyurethane acrylate (Negami Kogyo "UN-9000 PEP") 1.90 parts photopolymerization initiator (Ciba Special) "Irg-907" manufactured by Tea Chemicals)
1.10 parts leveling agent ("BYK-323" manufactured by Big Chemie) 0.01 parts propylene glycol-1-monomethyl ether-2-acetate 43.19 parts <Adhesion evaluation>
Each of the coating solutions prepared above was applied to a PET film (A4300 manufactured by Toyobo Co., Ltd.) with a bar coater to a thickness of about 1 μm. After drying at 70 ° C. for 15 minutes, an ultraviolet ray was irradiated using a conveyor type ultraviolet ray irradiator to obtain 180 mJ / cm ² to obtain a coated product. Adhesion is applied with a cellophane adhesive tape manufactured by Nichiban Co., Ltd., and the degree of peeling is visually observed. What peeled most was set as x. The results are shown in [Table 1].

[Comparative Evaluation Examples 1 to 3]
The above-mentioned photocurable resin No. 1-No. Except not adding 3, operation similar to the said evaluation examples 1-3 was performed. The results are shown in [Table 1].

[Comparative Evaluation Examples 4 to 7]
The above-mentioned photocurable resin No. 4-No. The same operations as in Evaluation Examples 4 to 6 were performed except that the commercially available dispersant shown in [Table 1] was added instead of 6. The results are shown in [Table 1].

  From the results of [Table 1], the following is clear. The pigment composition using the photocurable resin of the present invention has the same dispersibility as the pigment composition using a commercially available dispersant. In addition, the coating liquid obtained from the pigment composition using the photocurable resin of the present invention is more photocurable at the time of coating than the coating liquid obtained from the pigment composition using a commercially available dispersant. And the adhesiveness to the base material after photocuring is high.

Claims (8)

To the diisocyanate compound (A), a compound (B) having a number average molecular weight of 300 to 5000 having one or two hydroxyl groups in the same molecule and an adduct (C) of a bifunctional epoxy compound and an unsaturated monobasic acid are added. Then , any one of diethylamine, diethanolamine, dibutylamine, or N-methylpiperazine (D) is added by Michael , and the weight average molecular weight in terms of polystyrene measured by SEC (Size Exclusion Chromatography) is 1,000 to 50,000. A photo-curing resin. It said difunctional epoxy compound is represented by the following general formula (I) is a compound represented by Claim 1, wherein the photocurable resin.

(In the formula, M is represented by a direct bond, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group, O, S, SO ₂ , SS, SO, CO, OCO, or the following [Chemical Formula 2]. Represents a substituent selected from the group, wherein the alkylidene group may be substituted with a halogen atom, and R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a carbon atom. Represents 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, alkoxy group and alkenyl group may be substituted with a halogen atom, and R ¹ and R ² are And may be linked to form a ring structure, and n is 0 or an integer of 1 to 10.)

(In the formula, Q and B are each independently a hydrogen atom, a phenyl group which may be substituted with a C 1-10 alkyl group or a C 1-10 alkoxy group or a C 3 carbon atom. Represents a cycloalkyl group having 10 to 10 carbon atoms, and 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. Represents an atom, and the alkyl group, the alkoxy group and the alkenyl group may be substituted with a halogen atom, and A and D each independently have 1 to 10 carbon atoms which may be substituted with a halogen atom. Alkyl groups, aryl groups having 6 to 20 carbon atoms which may be substituted with halogen atoms, arylalkyl groups having 7 to 20 carbon atoms which may be substituted with halogen atoms Represents a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom or a halogen atom, and the methylene group in the alkyl group, aryl group and arylalkyl group is an unsaturated bond, -O- or- A and D may be interrupted by S-, A and D may form a ring between A, D or A and D, the ring may be an aromatic ring, and R ³ is a hydrogen atom, a carbon atom Represents 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, wherein the alkyl group, alkoxy group and alkenyl group are substituted with a halogen atom. And p represents a number from 0 to 5, k represents a number from 0 to 5, a represents a number from 0 to 4, and d represents a number from 0 to 4.) Said difunctional epoxy compound is represented by the following general formula (II) is a compound represented by Claim 1, wherein the photocurable resin.

(In the formula, R ¹ , R ² , Q, Z, n and p are the same as those in the general formula (I).) Said difunctional epoxy compound is represented by the following general formula (III) is a compound represented by Claim 1, wherein the photocurable resin.

(In the formula, R ¹ , R ² and n are the same as those in the general formula (I).) It said difunctional epoxy compound is represented by the following general formula (IV) is a compound represented by Claim 1, wherein the photocurable resin.

(In the formula, R ¹ , R ² , A, D, a, d and n are the same as those in the general formula (I).) It said difunctional epoxy compound is represented by the following general formula (V) is a compound represented by Claim 1, wherein the photocurable resin.

(Wherein R ⁴ and R ⁵ are each independently 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) Represents an atom, and the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, R ⁴ and R ⁵ may be linked to form a ring structure, Same as formula (I).) Claim 1 photocurable resin according to any one of 6, further multi salt Motosan anhydride (E) esterified allowed to obtained photocurable resin. Dispersing agent comprising as an active ingredient the photocurable resin according to any one of claims 1-7.