TW201107356A - Photocurable resin and photocurable resin composition - Google Patents

Abstract

Disclosed is a photocurable resin (A) which has a molecular structure represented by general formula (I). Also disclosed is a carboxyl group-containing photocurable resin (A') which is produced by reacting the photocurable resin (A) with an acid anhydride (d). Further disclosed is a photocurable resin composition which comprises the photocurable resin (A) and/or the carboxyl group-containing photocurable resin (A') and a photopolymerization initiator (B) as the essential components. (In the formula, Ac represents a (meth)acryloyloxy group; R1 represents a residue of an epoxy compound (a), which contains an ethylene group produced by the ring opening of an epoxy group in the compound (a); R2 represents a joint part containing a carbonyloxy group or an urethane bond; n represents an integer of 1 to 99; and m represents 0 or 1.)

Description

[Technical Field] The present invention relates to a cured product of a photocurable resin which is excellent in photocurability, heat resistance, adhesion, and flexibility, and a composition containing the same. [Prior Art] Photocurable resins, among others, UV curable resins, are widely used in adhesives, printing inks, various coating agents, etc. from the viewpoint of rapid hardening and energy saving. Further, a photoresist which is mixed with a carboxyl group-containing resin to impart alkali developability is used as a resist for circuit formation for use in a printed circuit board, or as a plating resist, a solder resist, or the like. Others can be used as a color filter or a black matrix or a protective agent for flat display applications. The UV curable resin is generally a polyester acrylate, an epoxy acrylate, a urethane acrylate or the like (for example, refer to Patent Documents 1 to 3). From the viewpoint of rapid hardenability, almost all of them are It is a liquid compound. However, this form of resin is indeed imparted with rapid hardenability, and conversely, there are many problems in the residual properties of many electronic materials such as reflow resistance or heat resistance of solder heat resistance. Further, the quick-setting resin generally has a hardening shrinkage, and the obtained cured product is brittle and has poor adhesion. It is a property that is strongly required for adhesives, printing inks, various coating agents, etc., and it is necessary to develop (meth) which has such heat resistance and adhesion. Acrylate resin. On the other hand, the issue of environmental issues in recent years is being widely discussed -5-201107356. Recently, new materials are attracting attention, not from compounds of petroleum resources, but from natural materials. Among them, the present inventors have noted lactic acid. Lactic acid is not a compound derived from petroleum resources, and fermented lactic acid obtained by fermentation of a natural product can be used. Further, since it has a functional group which can be easily chemically modified, such as a residue or a hydroxyl group, a variety of molecular designs can be made. Further, depending on the molecular design, the proportion of carbon derived from natural materials can be increased, thereby providing a very environmentally friendly material. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent No. 3,446,840 [Patent Document 2] Japanese Patent No. 3 543 409 [Patent Document 3] JP-A-2004- 1-23780 [Problems to be Solved by the Invention] The present invention has been made in view of the above-described circumstances, and an object of the invention is to provide a photocurable resin which is environmentally friendly and has excellent UV curability and heat resistance by using lactic acid as one of the starting materials. a cured product excellent in adhesion and flexibility; and a photocurable resin composition containing the same. [Means for Solving the Problem] In order to achieve the above object, according to the present invention, it is possible to provide a photocurable resin which is characterized in that an epoxy compound (a), lactic acid or polylactic acid-6-201107356 (b), The (meth)acrylic monomer (C) having an acid group or an isocyanate group is obtained by reacting as an essential monomer component, and has a molecular structure represented by the following formula (Ϊ).

The residue of the compound (a) of the vinyl group formed by ring opening of the epoxy group of the compound (a), R2 represents a site containing a carbonyloxy group or a urethane bond; η represents 1 to 99. The integer, m means 〇 or 1). In addition, in the present specification, the term "(meth)acrylic" refers to the term "acrylic", methacrylic, and the like, and relates to (meth)acryloxyl, (meth)acrylic, (a) The base acrylate or other similar performance is also the same.

Among the suitable aspects, the photocurable resin is a structural unit represented by the following formula (11) as an essential repeating unit;

(Π) (wherein Ac represents a (meth)acryloxy group, R2 represents a node site containing a mineral or urethane bond, and fc represents a hydroxyl group or a (meth)acryloxy group, R3 represents a hydrocarbon group having 1 to 10 carbon atoms, n represents an integer of 1 to 99, m represents 〇 or a 1' dotted line indicates a bond with another structural unit). 201107356 In a more suitable aspect, in the above formula (I) or (II), a node having a carbonyloxy group or a urethane bond represented by R2 is represented by the following formula: A2, or the object represented by a3. Ο Η

II I —〇—C—Ν—R4— a1 OH Η Ο a2

II I I II -〇—C—Ν—R5-N—C—〇—〇

II —Ο—C—R7— a3 (In the above formulas, 'R4 represents an alkylene group having 1 to 10 carbon atoms, R5 represents a hydrocarbon group having 1 to 20 carbon atoms, and R6 represents an alkylene group having 1 to 30 carbon atoms. The base and R7 represent a stretching group having a carbon number of 1 to 10. In other suitable embodiments, the photocurable resin has an average of 0.1 to 2.0 (meth) acryloxy groups per molecule of the epoxy compound. In a particularly suitable aspect, the aforementioned epoxy compound (a) is an epoxy resin (a') having two or more epoxy groups in one molecule, and (meth)acrylic acid having an acid group or an isocyanate group. The monomer (c) is a (meth)acrylic acid, and has a molecular structure obtained by reacting a (meth)acrylic acid with a hydroxyl group-containing resin of a reaction product of the epoxy resin (a,) and lactic acid. Among other suitable forms, the aforementioned epoxy compound (a) is an epoxy resin (a') having two or more epoxy groups in one molecule, and (meth)acrylic acid having an acid group or an isocyanate group. The monomer (c) is a (meth) acrylonitrile alkyl isocyanate and has (meth) propyl decyl alkyl isocyanate and the above epoxy resin (a') with lactic acid or polylactic acid (b -8 - 201107356 ) A structure obtained by reacting a hydroxyl group-containing resin of a reaction product. In another suitable aspect, the aforementioned epoxy compound (a) has a molecular structure which is a reaction between an acid anhydride or a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate monomer in one molecule. An epoxy resin (a') having two or more epoxy groups, and the epoxy resin (a') is reacted with a hydroxyl group-containing resin of a reaction product of lactic acid or polylactic acid (b). Further, according to the present invention, there is also provided a photocurable resin containing a carboxyl group, which is obtained by reacting an acid anhydride (d) with the photocurable resin. Further, according to the present invention, there is provided a photocurable resin composition comprising at least one photohardenable selected from the group consisting of the photocurable resin (A) and the carboxyl group-containing photocurable resin (A'). The resin and the photopolymerization initiator (B) are essential components. The carboxyl group-containing photocurable resin (A') other than the carboxyl group-containing photocurable resin (A') or the thermosetting component (D) is further contained in the form of a photocurable resin composition. [Effect of the Invention] The photocurable resin of the present invention is an epoxy compound (a), lactic acid or polylactic acid (b), and a (meth)acrylic acid monomer having an acid group or an isocyanate group (c) As a necessary monomer component reaction, by using lactic acid as one of the starting materials, an environmentally-friendly hardened material can be formed, and at the same time, the structural portion represented by the above formula (I) is used as a necessary repeating unit. It is a cured product which is excellent in UV curability and is excellent in heat resistance, density, and flexibility. [Embodiment] By the reaction of the functional group of the (meth)acrylic monomer (C) having an acid group or an isocyanate group with the reaction of the epoxy compound (a) with lactic acid or polylactic acid (b) The terminal hydroxyl group reacts to easily obtain the photocurable resin of the present invention. In such a manner, the unsaturated double bond of the (meth)acrylic monomer (c) is introduced into a portion away from the main chain of the resin via the lactic acid skeleton, thereby exhibiting excellent photoreactivity while introducing lactic acid. By the skeleton, a cured product having hydrophilicity and adhesion and flexibility can be obtained. Further, depending on the molecular design, the lactic acid content can be greatly increased, and a photocurable resin which is mild to the environment can be obtained. Further, heat resistance can be imparted by selectively reacting an epoxy compound reactive with lactic acid. Further, at this time, a substance which can selectively react with lactic acid to impart heat resistance is easily obtained by using an epoxy resin. Hereinafter, the photocurable resin of the present invention will be specifically described in detail. First, when a polyfunctional cresol novolone type epoxy resin is used as the component (a), lactic acid is used as the component (b), and (meth)acrylic acid is used as the component (c), photohardening as shown by the following formula can be obtained. Resin. -10- 201107356

Rx

Rx = H ^CH3 R8 = H, or COCH=CH2 In addition, when (a) component is polyfunctional cresol monoester, (b) component is lactic acid, and (c) component is used (in the case of an anhydride, the following formula can be obtained) A photohard phenolic epoxy resin methyl acrylate resin is represented.

Rx

3 L^ORg.

CH2

Rx = Η or CH3 Rg = H, or C0CH=CH2 Further, a polyfunctional epoxy resin is used for the component (a), lactic acid is used for the component (b), and (2-) a cresol-phenolic phenol type is used. -11 - 201107356 In the case of oxyethyl isocyanate, a photocurable resin as shown by the following formula can be obtained. 0

Ri〇=H, ^conhch2ch2ococh=ch2 Further, it is considered that a polyfunctional formazan-type epoxy resin is used for the component (a), a lactic acid is used for the component (b), and a polyisocyanate compound and a component are used for the component (c). The reaction of a (meth) acrylate monomer (for example, isophorone! a reaction of an isochlorite with hydroxyethyl (meth) acrylate) can be obtained as shown in the following formula Photocurable resin.

The number of the 201107356 is less than the number of epoxy groups of the epoxy resin used as the component (a), and can be arbitrarily adjusted depending on the reaction ratio of the component (b) and the component (c) to the component (a). The reaction of the above components (a) to (c) may be carried out by simultaneously using lactic acid or polylactic acid (b) and a (meth)acrylic monomer (c) having an acid group or an isocyanate group together with the epoxy compound (a). The method of the reaction, or the method of first reacting lactic acid or polylactic acid (b) and then reacting the (meth)acrylic monomer (c) having an acid group or an iso-cyanate group . Such a reaction is carried out in the presence or absence of an organic solvent as described later, and in the presence of a polymerization inhibiting agent such as hydroquinone or oxygen, and is usually carried out at about 50 to 150 °C. In this case, a tertiary amine such as triethylamine or a tertiary ammonium salt such as triethylbenzylammonium chloride or an imidazole compound such as 2-ethyl-4-methylimidazole or a phosphorus compound such as triphenylphosphine may be added as necessary. As a catalyst. Further, in the above reaction, the ratio of each component (the ratio of the raw material to be charged) is 0, and the carboxyl group of the lactic acid or polylactic acid (b) becomes 0 with respect to 1 equivalent of the epoxy group of the epoxy compound (a). 2 to 1.1 equivalents, and the total of the hydroxyl group produced by the reaction of the epoxy group of the component (a) with the carboxyl group of the component (b) and the residual hydroxyl group of the lactic acid or the polylactic acid (b) is 1 equivalent, and The acid group or isocyanate group of the (meth)acrylic monomer (C) having an acid group or an isocyanate group is preferably a ratio of 0.05 to 1.0 equivalent. When the carboxyl group of the lactic acid or the polylactic acid (b) is less than 0.2 equivalent to 1 equivalent of the epoxy of the epoxy compound (a), the heat resistance and the adhesion of the object of the present invention are not sufficiently obtained. The effect of the softness improvement is -'13-201107356 Conversely, more than 1.1 equivalents of 'even if used in excess' theoretically only one equivalent will react, so that the number of such compounds remaining in the unreacted state increases, and the physical properties of the cured product are lowered. The main reason 'is not good. The photocurable resin (A) obtained in such a manner is preferably 0.1 to 2.0 equivalents of (meth) propylene oxide based on 1 equivalent of the final epoxy group. Further, the weight average molecular weight of the photocurable resin (A) obtained by the above reaction varies depending on the resin skeleton, and is generally 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the dryness of the touch drying property of the coating film may be poor, and the moisture resistance of the coating film after exposure may be poor, and the film may be reduced during development, and the resolution may be greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 1,500,000, workability is deteriorated and storage stability is poor. Further, the weight average molecular weight can be measured by, for example, GPC or the like under the following conditions. Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation, tj Pipe column: Protection column "Hxl-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + Tosoh "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GELG3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation. Detector: RI (differential refractometer) Measurement conditions:

Column temperature: 40°C -14- 201107356 Developing solvent: tetrahydrofuran flow rate: 1 · 0 m 1 /min In addition, the double bond equivalent of the above photocurable resin (A) is 100 g/eq or more. It is preferably g/equivalent or less. From the viewpoint of improving photocurability, it is preferably from 100 g / equivalent to 600 g / equivalent. Further, from the viewpoint of improving flexibility, it is preferred that the double bond equivalent is 0 to 500 g/eq or more. The epoxy compound (a) used for the synthesis of the photocurable resin (A) may, for example, be 2-hydroxyethyl (meth)acrylate glycidyl ether or 2-hydroxypropyl (meth)acrylate. Glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, (methyl) Ethylene terpene-containing ethylenically unsaturated monomer such as 2-hydroxyl-ol glycidyl acrylate, 6-hydroxyhexyl methacrylate (meth) acrylate or glycidyl (meth) acrylate, bisphenol A Epoxy resin, bisphenol F epoxy resin, bisphenol s type epoxy resin, brominated bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, biphenol epoxy resin, dimethyl a phenolic epoxy resin, a phenol novolak type epoxy resin, a cresol novolac type epoxy resin, a brominated phenol novolak type epoxy resin, a phenolic epoxy resin such as a phenolic epoxy resin such as bisphenol A; Glycidyl ester, diglycidyl hexahydrocarbonate, dimerized acid diglycidyl And other glycidol vinegar compounds; diglycidyl iso-dichlorouric acid vinegar, n, n, n', n'-tetraglycidyl meta-xylene diamine, n, n, n', n'-tetrahydro- 15- 201107356 Glycidylamine compounds such as glyceryl bisaminomethylcyclohexane and N,N-diglycidyl aniline, and alicyclic epoxy resins such as 3,4-epoxycyclohexanecarboxylate, A a conventionally used epoxy compound such as a copolymer of glycidyl acrylate and a copolymer of styrene and methyl methacrylate, a copolymer of glycidyl methacrylate and cyclohexylmaleimide, and the like Epoxy resin. For the lactic acid or the polylactic acid (b), for example, Musashi no lactic acid (registered trademark) F manufactured by Musashino Chemical Research Co., Ltd., or the like can be suitably used. Further, a lactic acid oligomer having a moderately repetitive structure in which lactic acid is dehydrated and condensed between molecules can also be used. (meth)acrylic acid having an acid group (organic acid group) for the (meth)acrylic monomer (c) having an acid group or an isocyanate group used for the synthesis of the photocurable resin (A) The monomer (c-1) and the (meth)acrylic monomer (c-2) having an isocyanate group may be used singly or in combination of two or more. Examples of the acid group-containing (meth)acrylic monomer (c-1) include acrylic acid, methacrylic acid, acrylic anhydride, methacrylic anhydride, crotonic acid, cinnamic acid, vinyl acetate, and sorbic acid. A polylactone (meth) acrylate or a (meth) acrylate 2 polymer which is obtained by reacting ε-butyrolactone with (meth)acrylic acid to elongate a molecule, and these may be used alone or in combination of two or more. The (meth)acrylic monomer (c-2) having an isocyanate group is not particularly affected by the isocyanate compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule. -16- 201107356 To the limit. Specific examples include, for example, (meth)acryloxyethyl isocyanate, (meth)acryloxyethoxyethyl isocyanate, bis(acryloxymethyl)ethyl isocyanate or Such denatured bodies and the like. In the case of commercial products, there are "KARENZ MOI" (methacryloxyethyl isocyanate), "KARENZAOI" (acryloxyethoxyethyl isocyanate), "KARENZ MOI-EG" (methacryl)醯 ethoxyethoxyethyl isocyanate), "KARENZ MOI-BM" (isocyanate block of AREKARENZ MOI), "KARENZ MOI-BP" (isocyanate block of KARENZ MOI), "KARENZ ΒΕΙ" (1 , 1-bis(acryloxymethyl)ethyl isocyanate), sold by Showa Denko Co., Ltd. in the market. In addition, any of these product names are registered trademarks. Further, a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule and a diisocyanate such as isophorone diisocyanate, toluene diisocyanate, tetramethyl xylene diisocyanate or hexamethylene diisocyanate may be used. A semicarbamate compound. These (meth)acrylic monomers (C-2) having an isocyanate group may be used singly or in combination of two or more. Further, by subjecting the hydroxyl group of the photocurable tree obtained in the above manner to the hydroxyl group of the photocurable resin, the acid anhydride (d) is further reacted to introduce a carboxyl group, thereby producing a carboxyl group-containing light soluble in an aqueous alkali solution. Curable resin (A'). In the reaction, the amount of the acid anhydride (d) used is generally 相对. 1 〜 1 · 〇 耳 之 , 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 The acid value of the carboxyl group-containing photocurable resin (A1) is an addition amount of about 20 to 200 mg K 〇 H / g, preferably 50 to 120 mg KOH / g. -17-201107356 The addition of the acid anhydride (d) to the photocurable resin (a) is in the presence or absence of an organic solvent as described later, and in the presence of methylhydroquinone, hydroquinone monomethyl ether, and It is carried out in the presence of a polymerization agent such as a tea phenol or a gallic phenol, and is usually in the range of about 50 to 150. (: carried out. This may be necessary to add a tertiary amine such as triethylamine, a triethylbenzylammonium chloride grade salt, an imidazole compound such as 2-ethyl-4-methylimidazole, a triphenylphosphine compound, or a cycloalkane. A metal salt of an organic acid such as an acid, lauric acid, stearic acid, oleic acid or octenoic acid such as chromium, pin, potassium or sodium may be used as a catalyst. These may be used singly or in combination of two or more. Examples thereof include methyltetrahydrobenzene'tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, and 3,6-endomethylenetetrahydrogen. An alicyclic dianhydride such as phthalic anhydride, methylenetetrahydrophthalic anhydride or tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenylsuccinic acid penta(dodecene) Succinic anhydride, phthalic anhydride, trimellitic acid aliphatic or aromatic dibasic anhydride, or biphenyl tetracarboxylic dianhydride, diphenylcarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane An aliphatic or aromatic tetrabasic acid such as tetracarboxylic dianhydride, coke anhydride or diphenyl ketone tetracarboxylic dianhydride may be used alone or in combination of two or more. In the photocurable tree of the present invention obtained in the above manner and/or the photocurable resin (A') having a carboxyl group, a polymerization initiator (B) may be further added, thereby obtaining the present invention. Photohardenable tree. In the photocurable resin composition of the present invention, the photopolymerization initiator, the photoinitiator, and the sensitizer may be exemplified by phosphorus, lithium, and a catalyst anhydride when the benzene is hydroquinone inhibited. Ethyl formic acid anhydride, anhydride, etc., tetramite dianhydride ί (A acylate for use in photofat group-18-201107356 compound, acetophenone compound, brewing compound, thioxanthone compound, ketal compound, two A phenyl ketone compound, a xanthone compound, etc.. Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Specific examples of the ethyl ketone compound include, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1, 1-Dichloroacetophenone. 0 Specific examples of the hydrazine compound include 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, and 1-chloropurine. Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-di. Examples of the ketal compound include acetophenone dimethyl ketal and decyl dimethyl ketal. Specific examples of the diphenyl ketone compound include, for example, two. Phenyl ketoxime, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzylidene-4'-ethyldiphenyl sulfide, 4-Benzylmercapto-4'-propyldiphenyl sulfide. Others are α-aminoacetophenone-based, mercaptophosphine oxide-based, oxime-ester-based, and specific examples thereof include 2-methyl- 1-[4-(Methylthio)phenyl]-2-morpholinan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butyl Alkan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butene Ketone, hydrazine, hydrazine-dimethylamino acetophenone, etc. Examples of commercially available products include -19-201107356 IRGACURE 907, IRGACURE 369, IRGACURE 379, etc., manufactured by Chiba Japan Co., Ltd. Examples of commercially available products include CGI-325, IRGACURE OXE01, IRGACURE OXE02, and N-1919 manufactured by ADEKA Co., Ltd., manufactured by Chiba Japan Co., Ltd. The initiator may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide. And bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, etc. As a commercial item, Lucirin Tpo' Chiba by BASF Corporation is mentioned. IRGACURE 8 1 9 made by Japan Corporation. The above description discloses a representative photopolymerization initiator, and is not limited as long as it is a radical active species generated by light irradiation or a substance which contributes to the function of the growth species. Further, it does not cause generation of radicals by itself, and a sensitizer which is conventionally known to have a sensitizing effect can be used for the above photopolymerization initiator. The photopolymerization initiator and the sensitizer may be used singly or in combination of two or more. In addition, in order to impart alkali developability to the photocurable resin composition of the present invention, a conventional carboxyl group-containing resin (C) other than the above-mentioned carboxyl group-containing photocurable resin (A') can be used. As a specific example of the carboxyl group-containing resin (C), a compound (any of an oligomer and a polymer) as exemplified below can be suitably used. (1) obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with a compound containing an unsaturated group such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene. Carboxyl containing resin. (2) aliphatic diisocyanate, branched aliphatic diisocyanate, -20- 201107356 alicyclic diisocyanate, aromatic diisocyanate and other diisocyanates and dimethylolpropionic acid, dimethylol butyric acid, etc. Alcohol compound, polycarbonate-based polyol, polyether-based polyol, polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide addition diol, and phenolic hydroxyl group A carboxyl group-containing urethane resin produced by addition polymerization of a diol compound such as a compound having an alcoholic hydroxyl group. (3) Diisocyanate and bisphenol A epoxy resin, hydrogenated bisphenol A oxime epoxy resin, bisphenol F epoxy resin, bisphenol s type epoxy resin, bisphenol phenol epoxy resin, a carboxyl group-containing photosensitive amine group produced by addition polymerization of a (meth) acrylate or a partial acid anhydride denature thereof, a carboxyl group-containing diol compound, and a diol compound of a bifunctional epoxy resin such as a phenol type epoxy resin Formate resin. (4) In the resin synthesis of the above (2) or (3), a compound having a hydroxyl group and one or more (meth)acrylic groups in the molecule, such as a hydroxyalkyl (meth)acrylate, is added. A carboxy-containing photosensitive urethane resin of yttrium acrylate. (5) In the synthesis of the resin of the above (2) or (3), a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added to have one isocyanate group and one or more (methyl) in the molecule. The acrylate-based compound is subjected to a (meth) acrylated carboxyl group-containing photosensitive urethane resin. (6) A carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a polyfunctional (solid) epoxy resin having two or more functional groups to form a dibasic acid anhydride to a hydroxyl group present in a side chain. -21 - 201107356 (7) The (meth)acrylic acid is reacted with a polyfunctional epoxy resin which oxidizes the hydroxyl group of the bifunctional (solid) epoxy resin with epichlorohydrin to form a 2-ary acid anhydride to the reaction. A hydroxyl group-containing photosensitive resin of a hydroxyl group. (8) A carboxyl group-containing polyester resin obtained by adding a dibasic acid anhydride to a first-order hydroxyl group produced by reacting a dicarboxylic acid with a bifunctional oxetane resin. (9) The resin of the above (1) to (8) is further added to a carboxyl group-containing photosensitive resin having a compound of an epoxy group and one or more (meth)acrylic groups in one molecule. In the photocurable resin composition of the present invention, a thermosetting component (D) may be added in order to impart heat resistance. For the thermosetting component used in the present invention, an amine resin such as a melamine resin or a benzoguanamine resin, a block isocyanate compound, a cyclic carbonate compound, a polyfunctional epoxy compound, or a polyfunctional oxetane compound can be used. A thermosetting resin which is conventionally used, such as an episulfide resin or a melamine derivative. It is particularly suitable to have two or more cyclic ether groups and/or cyclic thioether groups (hereinafter abbreviated as cyclic (thio)ether group) thermosetting component (D) in the molecule. The thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is a cyclic ether group having two or more 3, 4 or 5 membered rings in the molecule, or a cyclic sulfur. The compound of any one or two groups of the ether group may, for example, be a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1) having at least two in the molecule. The above compound of an oxetanyl group, that is, a polyfunctional oxetane compound (D-2), a compound having two or more thioether groups in a molecule, -22-201107356 is also an episulfide resin ( D-3) and so on. For the above-mentioned polyfunctional epoxy compound (D-1), for example, JER828, jER834, jER1001, jERl 004' manufactured by Japan Epoxy Resin Co., Ltd., EPICLON 840, EPICLON 850, EPICLON 205, EPICLON 205, manufactured by DIC Corporation, may be mentioned. 5, Dongdu Chemical Company

EPOTOTE YD-011, YD-013, YD-127, YD-128, DER317, D_E.R.331, DER661, DER664 manufactured by Dow Chemical Co., Ltd., ARAL DITE 6 0 7 1 from Chiba Japan, ARALDITE 6084 'ARALDITE GY25 0 > ARALDITE GY260, SUMI-EPOXY ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Industries, AER3 3 0, AER331, AER661, manufactured by Asahi Kasei Kogyo Co., Ltd. AER664, etc. (any of them are trade names) of bisphenol A epoxy resin; Japan Epoxy Resin company's jERYL903, DIC company's EPICLON 152, EPICLON 165, Dongdu Chemical Co., Ltd. Ε Ο Ο T Ο TE YDB - 4 0 0, Ο YDB-5 00, DER542 manufactured by Dow Chemical Co., Ltd., ARALDITE 8011 manufactured by Chiba Japan Co., Ltd., SUMI-EPOXY ESB-400 manufactured by Sumitomo Chemical Industries, Ltd., ESB-700, manufactured by Asahi Kasei Kogyo Co., Ltd. Brominated epoxy resin such as AER711, AER714, etc. (any of which is a trade name); jER152, jER154 manufactured by Japan Epoxy Resin Co., Ltd., DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., and EPICLON N-made by DIC Corporation 73 0, EPICLON N-770 'EP ICLON N-8 65, EPOTOTE YDCN-701, YDCN-704, manufactured by Dongdu Chemical Co., Ltd. AR AL DI TE E CN 1 2 3 5, -23- 201107356 ARALDITE ECN1273 , ARALDITE ECN1299 , ARALDITE XPY307 EPPN-201, EOCN-1025, EOCN-1 020, EOCN-104S, RE-3 06 manufactured by Nippon Kayaku Co., Ltd., SUMI-EPOXY ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Industries Co., Ltd., manufactured by Asahi Kasei Industrial Co., Ltd. A phenol type epoxy resin such as AERECN-23 5, ECN-299, etc. (any one of which is a trade name); EPICLON 8 3 0 manufactured by DIC Corporation, jER807 manufactured by Japan Epoxy Resin Co., Ltd., and EPOTOTE YDF manufactured by Dongdu Chemical Co., Ltd. -170, YDF-175, YDF-2004, ARALDITE XPY3 06 manufactured by Chiba Japan Co., Ltd. (all of which are trade names), bisphenol F-type epoxy resin; EPOTOTE ST-2004, ST-made by Dongdu Chemical Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as 2007, ST-3 000 (trade name); jER604 manufactured by Japan Epoxy Resin Co., Ltd., EPOTOTE YH-434 manufactured by Tosho Kasei Co., Ltd., ARALDITE MY720 manufactured by Chiba Japan Co., Ltd., Sumitomo Chemical Industries Co., Ltd. SUMI-EPOXY ELM-1 20, etc. Glycidylamine type epoxy resin of the product name), allantoic type epoxy resin such as ARALDITE CY-3 50 (trade name) manufactured by Chiba Japan Co., Ltd.; CELLOXIDE 202 manufactured by DAICEL Chemical Industry Co., Ltd., Chiba Japan Aliphatic epoxy resin of ARALDITE CY175, CY179, etc. (all of which are trade names) manufactured by the company; YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T_E.N., EPPN-501, EPPN manufactured by Dow Chemical Co., Ltd. -502, etc. (any of them are trade names) of trishydroxyphenylmethane type epoxy resin; Japan EP〇Xy Resin company's YL-6056, YX-4000, YL-6121 (any one is a trade name Ethylene glycol type or biphenol type epoxy resin or such mixture; -24- 201107356 EBPS-200 manufactured by Nippon Kayaku Co., Ltd., ΕΡΧ-30 manufactured by Asahi Kasei Kogyo Co., Ltd., EXΑ-1 514 manufactured by DIC Corporation ( Product name), such as bisphenol S type epoxy resin; Japan Epoxy Resin company's jER157S (trade name) and other double 酣A 酣 type epoxy resin; Japan Epoxy Resin company made by £11丫[-931, Chiba Japan Company's ARALDITE 163, etc. (any of which is a trade name) of tetraphenol-based Type epoxy resin; ARALDITE PT810 manufactured by Chiba Japan Co., Ltd., TEPIC 0 manufactured by Nissan Chemical Industries Co., Ltd. (all of which are trade names), heterocyclic epoxy resin, and BLEMMER DGT, such as Nippon Oil Co., Ltd. Glyceryl ester resin; tetraglycidyl xylenyl ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-403 manufactured by DIC Corporation, EXA-4750, Epoxy resin containing naphthalene group such as EXA-4700; epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; methacrylic acid such as CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd. Glycidyl ester copolymerization epoxy resin; even copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-denatured polybutadiene rubber derivative (eg DAICEL chemistry) Industrial PB-3 600, etc., CTBN modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Tosho Kasei Co., Ltd.), etc., are not limited by these. These epoxy resins may be used singly or in combination of two or more. Among these, a phenolic epoxy resin, a heterocyclic epoxy resin, a bisphenol A epoxy resin or the like is particularly preferable. The above polyfunctional oxetane compound (D-2) may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(-25) - 201107356 3-Ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl Benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, methacrylic acid (3-methyl-3-oxetanyl) Ester, (3-ethyl-3-oxetanyl) methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, methacrylic acid (3-B Methyl-3-oxetanyl)methyl esters or polyfunctional oxetanes such as such oligomers or copolymers, in addition to oxetane and phenolic resins, poly(p-hydroxybenzene) An ether compound of a resin having a hydroxyl group such as an ethylene), a Cardo type bisphenol, a calixarene, a resorcinol calixarene or a sesquioxane. Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate may, for example, be mentioned. The compound (D-3) having two or more cyclic thioether groups in the molecule may, for example, be bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd., or the like. Further, an episulfide resin obtained by substituting an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom by the same synthesis method may be used. The blending amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is a photocurability with respect to the photocurable resin (A) and/or a carboxyl group-containing light. A range of 5 to 70 parts by mass (preferably 10 to 50 parts by mass) of 100 parts by mass of the resin (A') (preferably in the case of using two or more kinds thereof) is suitable. The thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule does not exceed the above range because the carboxyl group remains in the cured coating film, heat resistance, alkali resistance, electrical insulation Sex is lower, so it is not good. On the other hand, in the case of the above-mentioned range of -26-201107356, since the low molecular weight cyclic (thio)ether group remains in the dried coating film, the strength of the coating film and the like are lowered, which is not preferable. In the case where the above-mentioned thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is used, it is preferred to contain a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-ylimidazole; dicyanodiamide, benzyldimethylamine 4-(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-indole, fluorene-dimethyl An amine compound such as a benzylamine, a hydrazine compound such as diammonium adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine or the like. In addition, as for the commercially available article, for example, 2ΜΖ-Α, 2ΜΖ-ΟΚ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ (any one of which is a brand name of an imidazole compound) manufactured by Shikoku Chemicals Co., Ltd., and San-Apro Co., Ltd. U-CAT (registered trademark) 3 5 03N, U-CAT3 5 02T (trade name of any blocky isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5 002 One is a bicyclic hydrazine compound and a salt thereof). It is not particularly limited as long as it is a substance which promotes a thermosetting catalyst of an epoxy resin or an oxetane compound, or a reaction of an epoxy group and/or an oxetane group with a carboxyl group, It can be used alone or in combination of two or more. In addition, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2 can also be used. ,4-diamino-8-triazine, 2-vinyl-4,6-diamino-3-triazine·isocyanuric acid adduct, 2,4-diamino-6- Alkyl methoxy-ethoxy-6-201107356-S-triazine. An s-triazine derivative such as an isocyanuric acid addition product, which is also suitable as a compound capable of functioning as an adhesion imparting agent The aforementioned thermosetting catalyst is used. The blending amount of the thermosetting catalyst is sufficient in a usual amount, for example, in a group consisting of the photocurable resin (A) and the photocurable resin (A') having a carboxyl group. The photocurable resin or the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is preferably 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts by mass per 100 parts by mass. Parts by mass. In addition to the above-mentioned thermosetting compound, examples of the thermosetting component include an isocyanate compound and a bulk compound thereof, a bismaleimide compound, an oxazine compound, a carbodiimide resin, etc., particularly with a hydroxyl group or a carboxyl group. The selective reaction is preferred, and can be used without particular limitation. Further, in the curable resin composition of the present invention, a compound having one or more ethylenically unsaturated groups in the molecule may be blended. In order to optimize the hardness, flexibility, and the like of the obtained cured product, various substances can be used, and in view of the photocurability, it is two or more in one molecule. Ethylene unsaturated groups are preferred. Examples of such a compound include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, and dipentaerythritol; a polyvalent alcohol such as hydroxyethyl isomeric cyanurate or a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide adduct; phenoxy acrylate, bisphenol A Acrylate and polyvalent acrylic acid such as ethylene oxide adduct or propylene oxide adduct of such phenols -28-201107356 ester; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane a polyvalent acrylate of a glycidyl ether such as triglycidyl ether or triglycidyl isocyanurate; and a melamine acrylate and/or each methacrylate corresponding to the above acrylate. An epoxy acrylate resin which further reacts acrylic acid with a polyfunctional epoxy resin such as a cresol novolac epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate or a di Q isocyanate such as isophorone diisocyanate may be used. An epoxy urethane acrylate compound in which a carbamate compound reacts with a hydroxyl group of the epoxy acrylate resin. The photocurable resin composition of the present invention can be blended with a colorant. As the coloring agent, a conventionally known coloring agent such as black, white, red, blue, green or yellow may be used, and any of a pigment, a dye, and a pigment may be used. However, from the viewpoint of environmental load reduction and impact on the human body, it is preferred that halogen is not contained. The photocurable resin composition of the present invention may be blended in order to increase the physical strength and the like of the coating film. For such a dip, it is possible to use a conventionally used inorganic or organic tanning material, and it is particularly suitable to use barium sulfate, spherical ceria and talc. Further, in order to obtain a white appearance or flame retardancy, a metal hydroxide such as titanium oxide, metal oxide or aluminum hydroxide may be used as the body pigment pigment. The photocurable resin composition of the present invention may further contain a thermal polymerization inhibiting agent or a fine powder which is conventionally used, such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, gallic phenol, phenothiazine, etc., as necessary. Anti-foaming agents such as cerium oxide, organic bentonite, montmorillonite, etc., antifoaming agents and/or homogenizers such as polyfluorene, fluorine, and polymer, imidazole, thiazole, triazole, etc. -29- 201107356 These well-known additives such as decane coupling agents, antioxidants, and rust inhibitors. In addition, in order to dissolve the photocurable resin (A), the carboxyl group-containing photocurable resin (A'), and the photosensitive (meth) acrylate compound, the photocurable resin composition of the present invention is also prepared. The composition is adjusted to a viscosity suitable for the coating method, and an organic solvent can be blended. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, and card. Glycol ethers such as alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dissolved Cellulose acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and other acetates; ethanol, propanol, B Alcohols such as diol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent oil. These organic solvents may be used singly or in the form of a mixture of two or more. Further, the blending amount of the organic solvent may be arbitrarily determined in accordance with the coating method. The photocurable resin composition of the present invention can be adjusted to a viscosity suitable for the coating method by, for example, the above-described organic solvent, and can be applied by a dip coating method, a flow coating method, a roll coating method, a bar coater method, or the like. It is applied to a substrate by a method such as a screen printing method or a curtain coating method. Thereafter, a coating film which is dry to the touch can be formed by drying (pre-drying) the organic solvent contained in the composition at about 60 to 1 Torr (temperature of TC). Alternatively, the above composition may be coated. To -30-201107356, the carrier film is dried and wound in the form of a film to form a dry film. Such a dry film can be formed by adhering to a substrate to form a resin insulating layer. A high-pressure mercury lamp or a metal halide lamp can be easily irradiated with an active energy ray by irradiating an active energy ray to a coating film of the obtained photocurable resin composition, whereby a cured product can be easily obtained. The exposed portion (the portion irradiated with the active energy ray is hardened), and when the obtained photocurable resin composition is patterned, the patterned light is transmitted through the contact or non-contact method. The cover is selectively exposed by active energy rays, or the pattern is directly exposed by a laser direct exposure machine, and is dissolved in a dilute aqueous alkali solution (for example, 0.3 to 3% sodium carbonate). Further, the unexposed portion is developed to form a resist pattern. Further, in the case of the composition containing the thermosetting component (D), for example, it is heated to a temperature of about 140 to 200 ° C to thermally harden it. The thermosetting property of the hydroxyl group of the photocurable resin (A) or the carboxyl group of the carboxyl group-containing photocurable resin Ο (A') and two or more cyclic ether groups and/or cyclic thioether groups in the molecule In the reaction of the component (D), a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed. Further, even when the thermosetting component (D) is not contained, The ethylenically unsaturated bond remaining in an unreacted state during thermal exposure may be thermally radically polymerized by heat treatment, or may be subjected to heat treatment (thermosetting) in order to improve coating film properties or according to purpose and use. In addition to the pre-formed printed circuit board or flexible printed circuit board, paper-phenol resin, paper-epoxy tree-31 - 201107356 grease, glass cloth-epoxy resin, glass-poly Imine, glass cloth / non-woven fabric - Epoxy resin, glass cloth/paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, etc. All grades (FR-4, etc.) copper-clad laminates are used. a polyimide film, a PET film, a glass substrate, a ceramic substrate, a ruthenium wafer, etc. The volatile drying after the photocurable resin composition of the present invention is applied, and a hot air circulation type drying furnace, an IR furnace, or the like can be used. A hot plate, a convection oven, etc. The exposure machine used for the active energy ray irradiation may be a transport type exposure machine that can illuminate an active energy ray, and in the case of pattern formation, a high pressure mercury lamp or a metal may be used. Ultraviolet exposure device for halogen lamps or devices directly depicted (for example, laser direct imaging devices that directly image images with lasers from CAD data from a computer). As far as the active energy ray is concerned, as long as the maximum wavelength of the light used is in the range of 3 5 0 to 4 1 Onm, any of a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gas laser, a solid laser, or a semiconductor laser Anyone can do it. In addition, the amount of exposure varies depending on the film thickness, etc., and generally can be set at 5 to 800 mJ/cm 2 (preferably 1 〇 to 5 00 mJ/cm 2 , more preferably 10 to 3 00 mJ/cm 2 ). Within the scope. In the case of the development method in the case of performing the above-described development, an appropriate method such as a dipping method, a shower method, a spray method, or a brush method may be employed. Further, as the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia or an amine can be used. -32-201107356 [Examples] The following examples and comparative examples are disclosed, and the present invention is specifically described, but the present invention is not limited by the following examples. In addition, the "parts" and "%" mentioned in the following contents are all based on quality unless otherwise specified. Resin Synthesis Example 1 0 In a flask equipped with a thermometer, a stirrer, and a reflux condenser, diethylene glycol monoethyl ether acetate (100 g) and cresol novolac type epoxy resin (made by DIC Co., Ltd., EPICLON N-680) were placed. , softening point 82 ° C, epoxy equivalent 211) 211 g (1.0 m), 90% lactic acid (Musashino Chemical Research Institute Co., Ltd., Musashino lactic acid 90F, purity 90%) 100g (lactic acid is 1.0 m) Two butyl hydroxytoluene 1.5 lg and hydroquinone. 15 g, heated to 100 ° C and uniformly dissolved. Next, 1 · 14 g of triphenylphosphine was placed, and the temperature was raised to 110 ° C while being purged with nitrogen, and the contained hydrazine was removed to the outside of the system at any time, and the reaction was carried out for 1 hr. Next, after the system was replaced with an air atmosphere, 152 g of diethylene glycol monoethyl ether acetate and 2-propenyloxyethyl isocyanate (Karez AOI, manufactured by Showa Denko Co., Ltd.) were placed in the obtained reaction liquid. Molecular weight 141) 148g (1·0 5 mole), the reaction was carried out at 85 ° C for 3 hours, and the peak of the isocyanate group (2270 cm·1) in the solution was confirmed by an infrared spectrophotometer to obtain a solid content acid value of 12.7. A resin solution of mgKOH/g and a solid component of 64.0%. The solid component had a double bond equivalent of 429 and a lactic acid content of 20%. This was used as the resin varnish 1. In addition, 'the obtained photocurable resin red-33-201107356 external absorption spectrum (measured using Fourier transform infrared spectrophotometer FT-IR) is shown in Fig. 1, and the nuclear magnetic resonance spectrum (solvent CDC13, reference substance TMS) (Tetramethyl decane)) is disclosed in Figure 2. Intermediate Synthesis Example 1 (Synthesis of lactic acid oligomer) 90% lactic acid was placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser (Musashino lactic acid 90F, purity 90%, manufactured by Musashino Chemical Research Co., Ltd.) 1 000g (10m of lactic acid), and the temperature is raised to 120 °C while being filled with nitrogen. The dehydrated water produced by dehydration and esterification of the contained water and lactic acid is removed to the outside of the system at the same time, and the reaction is carried out for 11 hours. A resin solution having an acid value of 207 mgKOH/g was obtained. This was used as the lactic acid oligomer intermediate X-1. Resin Synthesis Example 2 In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 147 g of diethylene glycol monoethyl ether acetate and a cresol novolac type epoxy resin (EPICLONN-680, manufactured by DIC Co., Ltd., softening point 82°) were placed. C, epoxy equivalent 211) 211 g (1.0 mol), lactic acid oligomer intermediate (χ-ΐ) 216 g (0.8 mol), acrylic acid 14.4 g (0.2 mol) 'di-tert-butylhydroxytoluene 2.21 g And hydroquinone. 22g, heated to i00 ° C and allowed to dissolve evenly. Next, 1.68 g of triphenylphosphine was placed, and the temperature was raised to 110 ° C in an air atmosphere, and the reaction was carried out for 8 hours. Next, 188 g of diethylene glycol monoethyl ether acetate and 2-propylene methoxyethyl isocyanate (Karez AOI, sub-34-201107356 sub-quantity 141) were placed in the obtained reaction liquid. 106 g (0.75 mol), the reaction was carried out at 85 ° C for 3 hours, and the peak of the isocyanate group (2270 cm·1) in the solution was confirmed by an infrared spectrophotometer to obtain a solid content acid value of 7. 〇mgKOH/g, solid. A resin solution of 62.0% of the composition. The solid component had a double bond equivalent of 5 76 and an lactic acid content of 40%. This was used as the resin varnish 2. Further, the infrared absorption spectrum of the obtained photocurable resin (measured using a Fourier transform infrared spectrophotometer FT-IR) is disclosed in Fig. 3, and the nuclear magnetic resonance 0 spectrum (solvent CDCh, reference material TMS (tetramethyl) The decane)) is disclosed in Figure 4. Resin Synthesis Example 3 In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 100 g of diethylene glycol monoethyl ether acetate and a formaldehyde resin (EPICLON N-680, softened by DIC Co., Ltd.) were placed. Point 82 ° C, epoxy equivalent 21 1 ) 21 lg (1·0 mol), 90% lactic acid (Musashino lactic acid research institute Co., Ltd., Musashino lactic acid 90F, purity 90%) 100g (lactic acid is lo Mohr), dibutyl hydroxytoluene 1.5 lg and hydroquinone 15 g, heated to 100 ° C to dissolve evenly. Next, 1 · 14 g of triphenylphosphine was placed, and the temperature was raised to 11 〇 ° C while being filled with nitrogen, and the contained water was removed to the outside of the system at any time, and the reaction was carried out for 10 hours. After the system was replaced with an air atmosphere, 181 g of diethylene glycol monoethyl ether acetate and 2-propenyloxyethyl isocyanate (Karez AOI, manufactured by Showa Denko Co., Ltd., molecular weight) were placed in the obtained reaction solution. 141) 148 g (1.05 mol) was reacted at 85 ° C for 3 hours, and it was confirmed by infrared spectrophotometry -35 - 201107356 that the peak of the isocyanate group (227 〇 cm_1) in the solution disappeared. Further, 51.7 g (〇.34 mol) of tetrahydrophthalic anhydride was placed, and the reaction was carried out at 110 ° C for 3 hours to obtain a resin solution having a solid content of 49.0 mgKOH/g and a solid component of 64%. The solid component had a double bond equivalent of 477 and a lactic acid content of 18.8%. This was used as the resin varnish 3. Further, the infrared absorption spectrum of the obtained photocurable resin (measured using a Fourier transform infrared spectrophotometer FT-IR) is disclosed in Fig. 5, and the nuclear magnetic resonance spectrum (solvent CDC13, reference material TMS (tetramethyl decane) Fig. 6 〇 resin synthesis example 4 In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 30.8 g of diethylene glycol monoethyl ether acetate and a bisphenol A type epoxy resin (manufactured by DIC Corporation) were placed. EPICLON 850, epoxy equivalent 187) 18 7g (i. 〇mol), 90% lactic acid (Musashino Chemical Research Institute Co., Ltd., Musashino lactic acid 90F, purity 90%) 100g (lactic acid is 1 · 0 mole ), di-tert-butylhydroxytoluene 1.39 g and hydroquinone. 14 g, heated to 90 t and allowed to dissolve uniformly. Next, 1,3-97 g of triphenylphosphine was placed, and the nitrogen gas was poured while raising the temperature to 11 〇 ° C, and the contained water was removed to the outside of the system at any time, and the reverse was carried out for 11 hours. Next, after replacing the system with an air atmosphere, the obtained reaction solution was charged with diethylene glycol monoethyl ether acetate 9 1.2 g and 2-propenyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., KARENZAOI). , molecular weight i41) 141g (l. 〇mole), the reaction was carried out at 85 ° C for 3 hours, and the peak of -36-201107356 isocyanate group (227〇cnT1) in the solution disappeared by an infrared spectrophotometer to obtain a solid component. A resin solution having an acid value of 3.5 mgKOH/g and a solid content of 76.0%. The solid component had a double bond equivalent of 4 18 and a lactic acid content of 22%. Use this as a resin varnish 4 . Further, the infrared absorption spectrum of the obtained photocurable resin (measured using a Fourier transform infrared spectrophotometer FT-IR) is shown in Fig. 7, and the nuclear magnetic resonance spectrum (solvent CDC13, reference material TMS (tetramethyl decane) )) is shown in Figure 8. Indole resin synthesis example 5 In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 30.8 g of diethylene glycol monoethyl ether acetate and a bisphenol A type epoxy resin (made by DIC Co., Ltd., EPICLON 850, epoxy equivalent) were placed. 187) 187g (l. 〇mole), 90% lactic acid (Musashino Chemical Research Institute Co., Ltd., Musashino lactic acid 90F, purity 90%) 1 00g (lactic acid is 1. 〇 Mo ear), two third butyl 1.39 g of hydroxytoluene and 0.14 g of hydroquinone were heated to 90 〇 ° C and uniformly dissolved. Next, 0.97 g of triphenylphosphine was placed, and nitrogen gas was poured while being heated to 110 ° C, and the contained water was removed to the outside of the system at any time, and the reaction was carried out for 11 hours. After the system was replaced with an air atmosphere, 91.2 g of diethylene glycol monoethyl ether acetate and 2-propenyloxyethyl isocyanate (Karez Electric Co., Ltd., KARENZAOI, molecular weight) were placed in the obtained reaction solution. 141) 141 § (1.0 mol), the reaction was carried out at 85 ° C for 3 hours, and it was confirmed by an infrared spectrophotometer that the peak of the isocyanate group (2270 CHT1) in the solution disappeared. Further, 69.9 g (0.46 mol) of tetrahydrophthalic anhydride was placed, and the reaction was carried out at 115 t: for 4 hours, and -37-201107356, a resin solution having a solid content acid value of 57.2 mgKOH/g and a solid content of 80% by weight was obtained. The solid component had a double bond equivalent of 488 and a lactic acid content of 18%. This is used as the resin varnish 5. Further, the infrared absorption spectrum of the obtained photocurable resin (measured using a Fourier transform infrared spectrophotometer FT-IR) is shown in Fig. 9, and the nuclear magnetic resonance spectrum (solvent CDC13, reference material TMS (tetramethyl decane) )) is shown in Figure 10. Resin varnish 60 Using a carboxyl group-containing modified cresol novolac type epoxy acrylate (DICLITEUE-9210, solid content acid value 82.9 mgKOH/g, solid content 62%, double bond equivalent of solid component 361) 1 to 5 and Comparative Examples 1 to 3 The components disclosed in Table 1 were blended and stirred in the ratios disclosed in Table 1 to dissolve them, thereby obtaining a photocurable resin composition. The photocurable resin composition was applied onto a PET film, and Examples 1 to 5 and Comparative Example 1 were dried at 80 ° C for 20 minutes after coating. After coating, the PET film was cured with light. The composition of the resin is adhered to each other, and the composition is sterilized by UV irradiation with a cumulative amount of light of 1 000 mJ/cm 2 to obtain a hardened coating film having a target film thickness of about 15 to 20 μm. -38 - 201107356

BPE-900: bisphenol A epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) TMPTA: Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.) IRGACURE 184 : 1-hydroxyl ring Hexyl phenyl ketone (manufactured by Chiba Japan Co., Ltd.) [Table i] Composition (parts by mass) Example Comparative Example 1 2 3 4 5 1 2 3 Resin varnish 1 78 Resin varnish 2 81 Resin varnish 3 78 Resin varnish 4 66 Resin varnish 5 63 PNA-127 71 BPE-900 50 TMPTA 50 IRGACURE 184 1 1 1 1 1 1 1 1 PNA-127 : Phenolic novolac type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd.) 70% solid state : The hardened coating film after UV irradiation Q was peeled off from the PET film for the purpose of confirming the obtained cured state, and the softness and the ease of rupture were evaluated. After UV irradiation, it was evaluated as 〇 for a soft film that did not break, and X for a significant rupture. Friction test:

For the purpose of testing the hardenability of the cured product, a rubbing test for the hardened material rubbing was performed 50 times using a waste cloth containing acetone. Those who did not dissolve on the surface were judged to be sufficiently hardened and rated as 〇; those who observed slight dissolution on the surface were evaluated as X-39-201107356 Heat resistance test: Each hardened coating film was placed in a hot air circulating drying oven at 200 ° C, and heated 3 minutes. After heating, it was taken out, and the trace of the melt was visually observed to carry out a heat resistance test. The melting 'variant' was rated as 〇 at all, and some were confirmed to have melting, and the changer was rated as X. The results of the above tests are summarized and disclosed in Table 2. [Table 2] Characteristic Example Comparative Example 1 2 3 4 5 1 2 3 State of hardened coating film 〇〇〇〇〇〇〇X Friction test 〇〇〇〇〇〇X 〇Heat resistance test 〇X 〇XXXX 〇 As a result of the results disclosed in Table 2, it is apparent that the cured product obtained by curing the photocurable resin composition of the present invention has a tendency to be cured from the state of the cured coating film, the friction test, and the heat resistance test. Ester acrylate and epoxy acrylate have the same hardenability and heat resistance. Further, since lactic acid is used as a raw material, a photocurable resin composition which is mild to the environment can be provided by increasing the proportion of carbon derived from nature. Examples 6 to 12 and Comparative Examples 4 and 5 The above-mentioned resin varnish 1 to 6 ' was blended in the ratio disclosed in Table 3 'after mixing with a mixer, and then kneaded by a three-roll mill to prepare an alkali-developing type photosensitive property. Resin composition. -40- 201107356

[Table 3] Composition: Comparative Example (parts by mass) 6 7 8 9 10 11 12 4 5 Resin varnish 161 161 161 32 161 161 161 161 Resin varnish 1 31 Resin varnish 2 32 Resin varnish 3 31 156 156 Resin varnish 4 26 Resin varnish 5 25 Compound (C-1,1 20 20 ΡΝΑ-127 29 Photopolymerization initiator (Β-1/2 15 15 15 15 15 15 15 15 15 Photopolymerization initiator (B-2)·3 1 1 1 1 1 1 1 1 1 Colorant (E-1) M 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Polyoxygenated defoamer 3 3 3 3 3 3 3 3 3 3 Thermally hardening component 37.5 37.5 37.5 37.5 37.5 37.5 37.5 37.5 37.5 Organic solvent (F-2,6 10 10 10 10 10 10 10 10 10 10 *1 : Dipentaerythritol pentaacrylate (DPHA: manufactured by Nippon Kayaku Co., Ltd.) *2 : 2-methyl-1-( 4-methylthiophenyl)-2-morpholine propyl _1 RIRA IRGAGURE9〇7 : chibaJapan prepared company) test *3 : 2,4-diethyl thioxanthone (KAYACUREDETX-S: Nippon Chemical Company system)) *4 · CI Pigment Blue 15 : 3 *5 : DURANATETPA-B8〇E (Solid ingredients made by Asahi Kasei Chemicals Co., Ltd. 8〇*6 : Aromatic organic solvent (IPZOL) E 150 Idemitsu Kogyo Co., Ltd.) · ° Performance evaluation: &lt;Optimum exposure amount&gt; By the screen printing method, the above-mentioned Examples 6 to 12 are good &amp; ^, and the second Han tt is compared with the examples 4 and 5 The resin composition was applied onto a glass substrate and dried in a @ &amp; 8 〇〇c hot air circulating drying oven for 30 minutes. After drying, an exposure apparatus equipped with a high pressure mercury lamp was used, and the stage exposure meter Γ ^ L1 was u fell, Mep Tablet ) _ -41 - 201107356 (Kodak No.2 ) Exposure, after exposure (30 ° C, 〇. 2MPa, lwt% sodium carbonate aqueous solution) for 60 seconds, in the residual stage exposure When the pattern of the table is 7 steps, the optimum exposure amount is determined. <Development property> The above-described Examples 6 to 12 and Comparative Example 4 were formed by a screen printing method so that the film thickness became about 25 μm. The photosensitive resin composition of 5 was applied onto a glass substrate, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, development was carried out by using a 1 wt% aqueous sodium carbonate solution, and the time until the dried coating film was removed was measured by a code table. Characteristic test: The photosensitive resin compositions of the above examples and comparative examples were applied onto a glass substrate by a screen printing method to have a film thickness of about 20 μm, and dried in a hot air circulating drying oven at 80 °C. 60 minutes. After drying, exposure was carried out at an optimum exposure amount, and a 1 w t% sodium carbonate aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 0.2 MPa for 60 seconds to obtain a photosensitive pattern. Thereafter, it was cured by heating at 150 ° C for 60 minutes. The following characteristics were evaluated for the obtained hardened coating film. &lt;Adhesiveness&gt; The cured coating film formed on the glass substrate by the above method is cross-cut to have a checkerboard shape according to the usual method, and then, after the peeling test is performed using the cellophane adhesive tape, the checkerboard is used. The number of residues in the grid is evaluated by the following benchmarks -42 - 201107356. 〇: The number of remaining checkers is 70 or more and 100 or less. △: The number of remaining checkers is 30 or more and less than 70 X: The number of remaining checkers is 0 or more and less than 30 &lt;Flexibility&gt; In the method, the glass was removed, and the hardened coating film formed on the PET of about 40 μm was peeled off, and the softness and the brittleness were evaluated. The softness of the obtained cured film was evaluated as 〇, and it was evaluated as X with hard brittleness and no softness. The results of the foregoing tests are summarized and disclosed in Table 4. [Table 4]

Characteristic Example Comparative Example 6 7 8 9 10 11 12 4 5 High-pressure mercury lamp exposure (mJ/cm2) 150 150 150 110 100 150 150 150 150 Development (seconds) 20 18 15 10 8 20 17 28 40 Sex 〇〇〇Δ 〇〇〇X 〇bend 〇〇〇X 〇〇〇XX

From the results disclosed in the above Table 4, it is apparent that the cured product obtained by curing the photocurable resin composition of the present invention has superior characteristics as compared with the conventional polyester acrylate or epoxy acrylate. . Further, it has been surprisingly found that the resin into which the lactic acid skeleton is introduced does not significantly deteriorate the developability as compared with Comparative Example 4 and Comparative Example 5. This is considered to be due to the introduction of the lactic acid -43-201107356 skeleton to improve the hydrophilicity. Further, it has been found that a cured coating film having excellent photoreactivity, adhesion, and flexibility can be obtained. Further, depending on the molecular design, it is possible to obtain a photocurable resin which can greatly increase the lactic acid content and is mild to the environment. [Industrial Applicability] The photocurable resin and the photocurable resin composition containing the same according to the present invention can be used for various adhesives, printing inks, coating agents, particularly photoresists, or can be advantageously used. A resistor for forming a circuit, a plating resist, and a solder resist for use as a printed circuit board are used. Others can also be used for color filters or black matrices for planar displays, protective agents, and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows an IR spectrum pattern of a photocurable resin produced in Resin Synthesis Example 1. Fig. 2 is a graph showing the nuclear magnetic resonance spectrum of the photocurable resin produced in Synthesis Example 1 of TfC resin.

Fig. 3 shows an IR spectrum pattern of the photocurable resin produced in Resin Synthesis Example 2. Fig. 4 shows a nuclear magnetic resonance spectrum pattern of the photocurable resin produced in Resin Synthesis Example 2. Fig. 5 shows an IR spectrum pattern of the photocurable resin produced in Resin Synthesis Example 3. Fig. 6 is a graph showing the resonance spectrum of the nuclear magnetic -44-201107356 of the photocurable resin produced in Resin Synthesis Example 3. Fig. 7 shows an IR spectrum pattern of the photocurable resin produced in Resin Synthesis Example 4. Fig. 8 is a view showing a nuclear magnetic resonance spectrum pattern of a photocurable resin produced in Resin Synthesis Example 4. Fig. 9 shows an IR spectrum pattern of the photocurable resin produced in Resin Synthesis Example 5. Fig. 10 shows a nuclear magnetic resonance spectrum pattern of a photocurable resin produced in Resin Synthesis Example 5. 〇 -45-

Claims (1)

201107356 VII. Patent application scope: 1. A photocurable resin characterized by having a molecular structure represented by the following general formula (1), which is an epoxy compound (a), lactic acid or polylactic acid (b), And reacting a (meth)acrylic monomer (c) having an acid group or an isocyanate group as an essential monomer component, (wherein Ac represents a (meth)acryloxy group, Ri represents a residue of the compound (&amp;) of a vinyl group formed by ring opening of an epoxy group of the epoxy compound (a), and R2 represents a carbonyl group. The oxy or urethane-bonded node site, n represents an integer from 1 to 99, and m represents 0 or 1). (2) The photocurable resin according to the first aspect of the invention, wherein the photocurable resin is a structural unit represented by the following general formula (II) as an essential repeating unit. (wherein, Ac represents a (meth)acryloxy group, R2 represents a carbonyloxy group or a urethane-bonded moiety, fc represents a hydroxyl group or a (meth)acryloxy group, and R3 represents a carbon. The hydrocarbon group of the atomic number 1 to 10 'n represents an integer of 1 to 99, m represents 〇 or 丨, and the dotted line represents a bond with another structural unit). 3. The photocurable resin according to claim 1, wherein the node having a carbonyloxy group or a urethane bond represented by the aforementioned 201107356 R2 is a formula a, a2, or a3 The list is not, Ο Η II I — Ο一C一Ν—R4— —Ο—C—N—R5—N—C—Ο R— a — a — — — — — — — — — The hydrocarbon group of 1 to 20, R6 represents an alkylene group having 1 to 30 carbon atoms, and R7 represents an alkylene group having 1 to 10 carbon atoms. 4. The photocurable resin according to claim 1, wherein the photocurable resin has an average of 0.1 to 2.0 (meth) acryloxy groups per molecule of the epoxy compound. 5. The photocurable resin according to claim 1, wherein the epoxy compound (a) is an epoxy resin (a') having two or more epoxy groups in one molecule, and has an acid group or an isocyanate. The (meth)acrylic monomer (c) is a (meth)acrylic acid, and the photocurable resin has a reaction product of (meth)acrylic acid and the epoxy resin (a') and lactic acid. The molecular structure obtained by the reaction of the hydroxyl group-containing resin. 6. The photocurable resin according to claim 1, wherein the epoxy compound (a) is an epoxy resin (a') having two or more epoxy groups in one molecule, and has an acid group or an isocyanate. The (meth)acrylic monomer (c) is a (meth)acrylonitrile alkyl isocyanate, and the photocurable resin has a (meth) acrylonitrile alkyl isocyanate and -47-201107356 A structure obtained by reacting an epoxy resin (a1) with lactic acid or polylactic acid (b) to react with a hydroxyl group-containing resin. 7. The photocurable resin according to claim 1, wherein the epoxy compound (a) has two or more epoxy epoxy resins (a') in one molecule, and the photocurable resin has Molecular structure obtained by reacting an acid anhydride or a cyanate compound with a hydroxyl group-containing (meth) acrylate monomer and a reaction of the epoxy resin (a1) with lactic acid or polylactic acid (b) to form a hydroxyl group-containing resin . 8. A photocurable resin containing a carboxyl group, which is characterized in that an acid d) is reacted with a photocurable resin according to claim 1 of the patent application, and a photocurable resin composition is characterized in that 'At least one photohardenable selected from the group consisting of photocurable resins according to any one of claims 1 to 7 (a photo-curable resin containing a carboxyl group in item 8 of A Patent Application No. 8) The resin and photopolymerization initiation Β are essential components. A photocurable resin composition according to claim 9 of the invention, which further comprises the carboxyl group-containing photocurable resin (Α') as another carboxyl group-containing resin (C). 1 1 The photocurable tree of the ninth or tenth aspect of the patent application's further includes a thermosetting component (D). a polyaminant of the foregoing group, an anhydride (former), and a constituent (object, external composition -48-