TW201241554A - Photocurable resin composition, dry film and cured article thereof, and printed wiring board using the same - Google Patents

Abstract

To provide a photocurable resin composition, a dry film and a cured article obtained therefrom, and a printed wiring board formed by using the dry film and cured article to form cured skin such as a solder resist, by which even a solder resist cured film cured by UV or heat can be peeled off with a basic aqueous solution to allow reuse of a substrate. The photocurable resin composition comprises (A) poly(meth)acrylate which corresponds to the conventionally acting photosensitive component (except for poly(meth)acrylate derived from the compound of formula (1) below), and arbitrary one or a combination of two or more of (B) a carboxylic acid resin, (C) poly(meth)acrylate and (D) epoxy resin which are all derived from the compound of formula (1) below, where R1 is a polyol derivative with (m+1) valence, R2 is any one of CH2, C2H4, C3H6, C4H8, and a substituted or unsubstituted aromatic ring, R3 is a substituted or unsubstituted aromatic ring, m and n are individually an integer greater than 1 and less than 10, and l is an integer of 0 or 1 or more.

Description

201241554 6. TECHNOLOGICAL FIELD OF THE INVENTION [Technical Field] The present invention relates to an alkali-developable photohardening which can be used for reusing a substrate by being peeled off by an aqueous alkali solution even if it is a cured solder resist film after ultraviolet curing and thermal curing. A resin composition, a dry film and a cured product thereof, and a printed wiring board using the same. [Prior Art] At the time of manufacture of a printed wiring board or the like, a solder resist cured film is formed on the surface of the substrate for the purpose of protecting or preventing solder from adhering to the solder portion. In the method of forming a solder resist curing film, there is a method of printing a pattern by screen printing, forming a solder resist curing film by ultraviolet rays or heat curing, or applying a solder resist composition on a surface of the substrate and drying it, The shape of the pattern is exposed, developed, and hardened to form a solder resist hardener. In the step of forming the solder resist cured film, there are occasions such as printing defects such as cracking and bleeding during printing, or incorporation of foreign matter, occurrence of pinholes, and positional misalignment during exposure, but it is caused by such a solder resist. When the defective substrate is formed, the waste substrate is formed, and the formation of the laminated circuit, the formation of the conductor circuit, the opening, the burying, and the like are all in vain, resulting in a decrease in the yield. Therefore, a method of peeling off the solder resist cured film and reusing the substrate has been proposed (for example, Patent Document 1 and the like). Patent Document 1 proposes a solder resist which is hardened by ultraviolet irradiation by using a mixed solution of sodium hydroxide or potassium hydroxide and three kinds of glycol ethers having a chain length of -5 to 201241554 3 to 6 and water as a stripping solution. Stripping, and the substrate can be reused. However, the peeling described in the above Patent Document 1 is effective only for the cured product which is cured by ultraviolet irradiation, and does not peel off the cured product which is hardened by heat. In addition, a peeling liquid which can be peeled off and a substrate can be reused even if it is a cured film of a solder resist after being irradiated with ultraviolet rays or heat-cured (for example, refer to Patent Document 2 and the like). However, in the above Patent Document 2, the peeling liquid The use of an alkali metal hydroxide and an aprotic polar solvent (N-methyl-2-pyrrolidone) imposes a heavy burden on the environment. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The present invention has been made in view of the above-described prior art, and is provided with a solder resist cured film even after ultraviolet curing and heat curing, and may be made of an aqueous alkali solution, for example, 60°. The 5 to 20 wt% aqueous sodium hydroxide solution of C is peeled off for about 10 to 60 minutes, and the photocurable resin-6-201241554 composition and the dry film thereof which can be reused for the substrate can be used. In particular, by using a photocurable resin composition containing a curable component derived from polyester as a main component as a solder resist, a photocurable resin composition of a raw material of a polyester such as terephthalic acid can be recovered from the waste liquid. The object and its dry film are for the purpose. Further, an object of the present invention is to provide a printed wiring board in which a solder resist cured film is peeled off and a substrate is reused by using such a photocurable resin composition and a dry film thereof. [Means for Solving the Problem] In order to achieve the above object, according to the present invention, there is provided a cured film which is cured by ultraviolet rays and heat hardening, and is carried out by using an aqueous alkali solution, for example, a sodium hydroxide aqueous solution of 5 to 20% by weight at 60 ° C. The photocurable resin composition which can be peeled off for about 10 to 60 minutes, and one aspect thereof is provided to contain (A) poly(meth)acrylate (however, the structure shown by the following general formula (1) is contained (B) of a poly(meth)acrylate derived from a compound, (B) a carboxylic acid resin derived from a compound having a structure represented by the following general formula (1), (C) poly(methyl) A photocurable resin composition characterized by one or more of acrylate and (D) epoxy resin. 201241554 【化1】

Wherein R is a (m+l) valence polyol derivative, R2 is a Ch2, C2H4, C3H6, hH8, substituted or unsubstituted aromatic ring, and R3 is a substituted or unsubstituted aromatic ring. m and n are integers of 1 or more and less than 10, and 1 is an integer of 0 or 1 or more.) Suitable examples are the aforementioned carboxylic acid resins (Β), poly(meth)acrylates (C), and epoxy resins. The organic matter in one or two or more kinds of the relative compositions of (D) contains a ratio of 20% by weight or more. Further, the other aspect of the present invention provides (B) a carboxylic acid resin, (C) a poly(meth) acrylate, and (D) derived from a compound having a structure represented by the above general formula (1). One or two or more kinds of the epoxy resins, and the organic material in the composition contains a photocurable resin composition characterized by a ratio of 20% by weight or more. In a suitable aspect, in the above general formula (1), R1 is a trivalent alcohol derived, R2 is a C2H4, and R3 is preferably a benzene ring. In addition, according to the present invention, a photocurable dry film obtained by applying the photocurable resin composition onto a film and drying it, or a cured film of the photocurable resin or the dry film is also provided. A cured product, in particular, a cured product obtained by photohardening on copper or a cured product obtained by photohardening in a shape of a figure. Further, according to the present invention, there is also provided a printed wiring board comprising a cured film obtained by photohardening a composition of the photocurable resin -8-201241554 or a dry film into a shape and thermosetting. [Effects of the Invention] The present inventors have found that the curable resin or compound used in the photocurable resin composition of the present invention is a carboxylic acid resin derived from a compound having the structure represented by the above general formula (1). Since the poly(meth)acrylate or the epoxy resin is derived from polyester, the ester bond as the main skeleton is hydrolyzed by treatment with an aqueous alkali solution, and the carboxyl group and the hydroxyl group generated by the hydrolysis exhibit strong hydrophilicity. The formed cured film becomes peeled off with an aqueous alkali solution. By using this action as a solder resist composition, for example, the curable resin or compound used in the conventional solder resist composition can be used as a novolac type epoxy resin or a novolak type epoxy acrylate, and the main skeleton is not hydrolyzed, and the peeling property is poor. The shortcomings. Therefore, when a defect occurs in the solder resist curing film forming step, the substrate can be reused by peeling off the solder resist of the substrate. Further, unlike the conventional epoxy acrylate-modified resin, a raw material containing no halogen ions can be used. Therefore, it is possible to form a hardened film which is excellent in electrical insulating properties, heat resistance, and dryness to touch without being halogenated. Therefore, the photocurable resin composition of the present invention is suitably used for forming a hardened film such as a solder resist of a printed wiring board or a flexible printed wiring board. Further, the photocurable resin composition of the present invention contains a curable component derived from polyester as a main component, and can recover a raw material of a polyester such as terephthalic acid from a waste liquid of a peeled solder resist, thereby saving resources and environment. The protective surface is extremely useful. -9-201241554 [Best Mode for Carrying Out the Invention] As described above, the photocurable resin composition of one aspect of the present invention is characterized by containing (A) a poly(meth)acrylate which has been conventionally used as a photosensitive component ( However, the ruthenium complex is compounded by a compound having a structure represented by the following general formula (1), except for the poly(meth) acrylate derived from the compound having the structure represented by the following general formula (1). One or two or more kinds of the (B) carboxylic acid resin, (C) poly(meth) acrylate, and (D) epoxy resin are derived. [Chemical 2] (0HirR, Ο 〇n丨 R2

Wherein R1 is a (m+1)-valent polyol derivative, R2 is a CH2, C2H4, C3H6, C4H8, substituted or unsubstituted aromatic ring, and r3 is a substituted or unsubstituted aromatic ring. m and η are an integer of 1 or more and less than 10, and 1 is an integer of 〇 or 1 or more.) According to the study of the present inventors, it has been found that when such a photocurable resin composition is used as a solder resist, for example, impregnation 25 °c of 10wt% NaOH for 30 minutes, etc. The general treatment has sufficient alkali resistance, and can be hardened by treatment with 5~20wt% NaOH aqueous solution at 60 °C for about 1~60 minutes. The flux coating film was peeled off, and the inventors of the present invention were completed. Further, according to the study of the present inventors, it was found that (B) a carboxylic acid resin, (C) poly(meth) acrylate, and (D) derived from a compound having the structure represented by the above general formula (1). Epoxy resin, by any! In combination with two or more kinds of -10-201241554 and the organic matter in the relative composition is 20% by weight or more, the (A) poly(meth) acrylate other than the above is not contained (excluding the above general formula (1) The same effect can be obtained by the structure shown or the poly(meth)acrylate derived from the compound having no structure represented by the above general formula (1). However, the (B) carboxylic acid resin, (C) poly(meth) acrylate, and (D) epoxy resin derived from the compound having the structure represented by the above general formula (1) may be used in any one or two kinds. The combination of the above is preferred for the organic matter in the composition to be 80% by weight or less. When the ratio is more than this ratio, the alkali resistance of the hardened coating film is lowered. Further, when (A) poly(meth)acrylate other than the poly(meth)acrylate derived from the compound having the structure represented by the above general formula (1) is contained, the optical characteristics such as sensitivity are improved. advantageous. Hereinafter, each constituent component of the photocurable resin composition of the present invention will be described in detail. First, the (A) poly(meth) acrylate used in the present invention is derived from a compound not represented by the above general formula (1) or a compound not having the structure represented by the above general formula (1). All of the poly(meth) acrylates can be used, not limited to specific polyfunctional (meth) acrylates. Specific examples include polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and para-hydroxyethyl isocyanurate or such ethylene oxide adducts and propylene oxide addition. Polyvalent acrylates such as ε-caprolactone adducts; phenoxy acrylates, bisphenol oxime diacrylates, and ethylene oxide adducts or propylene oxide additions of such phenols Multivalent acrylates; glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, tri-11 - 201241554 methylolpropane triepoxypropyl ether, trisepoxypropyl isocyanurate The polyvalent acrylate of a non-epoxypropyl ether; not limited to the above, for example, direct acylation of a polyhydric alcohol such as a polyether polyol, a polycarbonate diol or a hydroxyl-terminated polybutadiene or a diisocyanate And urethane acrylated acrylates and melamine acrylates, and/or methacrylates corresponding to the above acrylates. Further, in the present specification, (meth) acrylate means a general term for acrylate, methacrylate and the like, and the other similar expressions are also the same. The (B) carboxylic acid resin derived from the compound having the structure represented by the above general formula (1) used in the present invention can be obtained by a compound containing the structure represented by the above general formula (1) and a polybasic acid described later. Or its anhydrate is obtained by reaction. It is preferred to obtain the (a) polyester by depolymerization of a polyol having two or more hydroxyl groups in the molecule (b), or after reacting with (c) a polybasic acid or an anhydride thereof after depolymerization. . The (B) carboxylic acid resin may not have a photosensitive group. In this case, the compound having the structure represented by the above formula (1) and the compound having one or more ethylenically unsaturated groups in the molecule to be described later may be reacted with a polybasic acid or an anhydride thereof. Preferably, the (a) polyester is depolymerized with a polyol having two or more hydroxyl groups in the molecule (b), or after depolymerization, and (d) has one or more ethylenic unsaturation in the molecule. The compound of the group may be reacted with (c) a polybasic acid or an anhydride thereof. The component (d) and the component (c) may be reacted at once or may be reacted one by one. In the case of successive reactions, the reaction sequence may be first reacted with the component (d) and then with the component (c) or reacted with the component first, and then reacted with the components of the group -12-201241554 and (d), but one or more of them are required to be produced. It is preferably a reaction ratio of two or more carboxyl groups. The (C) poly(meth) acrylate derived from the compound having the structure represented by the above general formula (1) used in the present invention may be a compound containing the structure represented by the above general formula (1) and A compound having one or more ethylenically unsaturated groups in a molecule to be described later is reacted with a polybasic acid or an anhydride thereof, and a reactant thereof is obtained by reacting a compound having one or more ethylenically unsaturated groups in the molecule. It is preferred that the (a) polyester is depolymerized with a polyol having two or more hydroxyl groups in the molecule (b), or after depolymerization, and (d) one or more ethylenic unsaturation in the molecule. The compound of the group is reacted or reacted with (c) a polybasic acid or an anhydride thereof, and the reactant thereof is obtained by reacting the compound with (d) a compound having one or more ethylenically unsaturated groups in the molecule. The (D) epoxy resin derived from the compound having the structure represented by the above general formula (1) used in the present invention may be reacted with epichlorohydrin by a compound containing the structure represented by the above general formula (1), or After treatment with a polybasic acid or an anhydride thereof or a monocarboxylic acid having a phenol group, it is obtained by reacting with epichlorohydrin or a compound having a plurality of epoxy groups in the molecule. Preferably, the (a) polyester is depolymerized with a polyol having two or more hydroxyl groups in the molecule (b), and the obtained depolymerized polymer is directly reacted with epichlorohydrin or (c) polybasic acid or It is obtained by reacting an anhydrate or (e) a monocarboxylic acid having a phenol group with an epichlorohydrin or a compound having a plurality of epoxy groups in the (f) molecule. When the polyester is depolymerized, the ratio of the polyester to the polyol having two or more hydroxyl groups in one molecule is a molar number (α) of the repeating unit of the polyester and two or more hydroxyl groups in one molecule. The molar ratio of the polyol (々)-13- 201241554 is preferably in the range of (α)/(/3) = 〇·5~3, preferably 0.8 to 2, and the ratio is less than 0.5. The effect of excessive content, a decrease in the proportion of the aromatic ring derived, and an improvement in heat resistance or chemical resistance are not preferable. On the other hand, when the above ratio is larger than 3, the depolymerized polymer is crystallized and is insoluble in a solvent, which is not preferable. The aforementioned polyester (a) may be various conventional polyesters, such as polyethylene dicarboxylate (PET), polytrimethylene terephthalate, polybutadiene, polyethylene naphthalene Acid esters, polybutylene naphthalate, polymers, and the like. In addition, PET and recycled PET can be recycled from waste materials such as PET bottle waste materials. These PETs which are excellent in environmental protection are washed and washed, and recycled PET is washed and pelletized. The shape of the above polyester is not particularly limited, and it is preferably in the form of a granule. In addition, it is possible to use a polyfunctional alcohol having two or more hydroxyl groups in the molecule (b), and a bifunctional polyol or a trifunctional or higher polyhydric alcohol can be used. It can be used alone or in combination of two or more types. The bifunctional polyol may, for example, be ethylene glycol, 1,3-propane, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylenediethylene glycol or the like. Propylene glycol, 1,3-butanediol, neopentyl glycol, spiro, dioxanediol, adamantanediol, 3-methyl-1,5-pentanediol, octanediol, 1, 6-hexanediol, 1,4-cyclohexanedimethanol, 2-methanediol 1,3, 3-methylpentanediol 1,5, hexamethylene glycol, octane, 9-anthracene Alkanediol, 2,4-diethyl-1,5-pentanediol, bisphenol A phenolic oxirane-modified compound, bisphenol A-like difunctional phenol. The polyester becomes less than the benzene to benzene liquid crystal. Retrievable and/or kneading, monohydric alcohol, diol methyl propylene glycol diguana epoxide-14- 201241554 propane modified compound, bisphenol A ethylene oxide, propylene oxide copolymerization modified compound, Copolymerization of ethylene oxide and propylene oxide is polyether polyol, polycarbonate diol, adamantane diol, polyether diol, polyester diol, polycaprolactone diol (any! 1 such as PLACCEL 205, PLACCEL L205AL, PLACCEL 205U, PLACCEL 208, PLACCEL L208AL, PLACCEL 210, PLACCEL 21 ON, PLACCEL 212, PLACCEL L212AL, PLACCEL 220, PLACCEL 220N, PLACCEL 220NP1, PLACEL L220AL ' PLACCEL 230, PLACCEL 240, PLACCEL 220EB, PLACCEL 220EC All of the above are made by Daicel Chemical Industry Co., Ltd.; trade name), hydroxyl terminated polyalkane diene glycols (such as 1,4-polyisoprenediol, 1,4- and 1,2-polybutyl) Examples of commercially available hydroxy-terminated polyalkene diene diols such as olefinic diols and their hydride-like elastomers, such as Epole (registered trademark; hydrogenated polyisoprene diol, molecular weight 1,860, level Degree of polymerization 26, Idemitsu Kosan Co., Ltd., PIP (polyisoprene diol, molecular weight 2,200, average polymerization degree 34, Idemitsu Kosan Co., Ltd.), Polytail (registered trademark) H (hydrogenated polybutylene) Diene diol, molecular weight 2,200, average polymerization degree 39, manufactured by Mitsubishi Chemical Corporation, R-45HT (polybutane diol, molecular weight 2, 270, average polymerization degree 42, manufactured by Idemitsu Kosan Co., Ltd.). Examples of the trifunctional or higher polyhydric alcohol include glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, and adamantanetriol. Polycaprolactone triol (for example, PLACCEL 3 03, PLACCEL 3 05, PLACCEL 308, PLACCEL 312, PLACCEL L312AL, PLACCEL 320ML, 201241554 PL AC CEL L3 20AL; all of the above are Daicel Chemical Industry Co., Ltd.; trade name), and The aromatic ring may be, for example, an ethylene oxide or a propylene oxide modified product of a trifunctional or higher sulfonium compound, or a heterocyclic ring, such as Theic, manufactured by Shikoku Chemical Industries Co., Ltd. In particular, when trimethylolpropane is used, it is preferable to obtain a non-turbid amorphous material having a semi-solid fluidity when the polymer is depolymerized, and further has high solubility in a solvent. As the above (c) polybasic acid or an anhydride thereof, a conventionally used polybasic acid or an anhydride thereof can be used. Specific examples thereof include aromatic polycarboxylic acids such as anhydrous phthalic acid, isophthalic acid, terephthalic acid, tetrabromo anhydrous phthalic acid, anhydrous methyl nadic acid, and tetrachloro anhydrous phthalic acid, and the like. Anhydrous, hexahydro anhydrous phthalic acid, tetrahydro anhydrous phthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and other alicyclic carboxylic acids and their anhydrates An aliphatic polycarboxylic acid such as maleic anhydride, fumaric acid, succinic anhydride, adipic acid, sebacic acid or sebacic acid, and the anhydrate thereof, anhydrous pyromellitic acid, anhydrous trimellitic acid, methyl ring A trivalent or higher carboxylic acid or the like such as hexene dicarboxylic acid anhydride may be used singly or in combination of two or more kinds. In the above (d), the compound having one or more ethylenically unsaturated groups in the molecule may, for example, be a compound having one carboxyl group and one or more ethylenically unsaturated groups, or a (meth)acryl group having an isocyanate group. a monomer, a compound having one cyclic ether group and one or more ethylenically unsaturated groups, a compound having one hydroxyl group and one or more ethylenically unsaturated groups, or the like, alone or in combination of two or more Used in combination. Examples of the compound having one carboxyl group and one or more ethylenically unsaturated groups include acrylic acid, a dimer of acrylic acid, methacrylic acid, -16-201241554 /3-styrylacrylic acid, mercaptoacrylic acid, and croton. Acid, α-cyano cinnamic acid, cinnamic acid, (meth)acrylic acid caprolactone adduct, and saturated or unsaturated dibasic acid anhydride and half of (meth) acrylate having one hydroxyl group in one molecule Ester compound and the like. For the production of a half ester compound with a hydroxyl group-containing (meth) acrylate, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, three Hydroxymethylpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate', dipentaerythritol penta(meth)acrylate, phenylepoxypropyl (meth)acrylate, and the like. For the preparation of dibasic acid anhydrides of semi-ester compounds, such as succinic anhydride, maleic anhydride, anhydrous phthalic acid, tetrahydro anhydrous phthalic acid, hexahydro phthalic acid, methyl hexahydro phthalic acid, methyl The internal methylenetetrahydro anhydrous phthalic acid or the like may be used singly or in combination of two or more kinds. The (meth)acryl-based monomer having an isocyanate group is not particularly limited as long as it is an isocyanate compound having one isocyanate group and one or more ethylenically unsaturated groups in the i molecule. Specific examples include, for example, (meth) propylene decyloxyethyl isocyanate, (meth) propylene decyloxy ethoxyethyl isocyanate, bis(acryloxymethyl) ethyl isocyanate or the like. The exemplified body or the like may be used alone or in combination of two or more types. For commercial products, "KarenzMOI" (methacryloyloxyethyl isocyanate), "KarenzAOI" (acryloyloxyethoxyethyl isocyanate), "KarenzMOI-EG" (methacrylic acid) "Ethyl ethoxyethyl isocyanate", "Karenz MOI-BM" (Karenz MOI isocyanate block), "Karenz MOI-BP" (Karenz MOI isocyanate block), "KarenzBEI" (1, 1-double (propylene oxyfluoride) Methyl ethyl) ethyl isocyanate is sold by Zhao-17-201241554 and electrician (share). Also, these product names are registered trademarks. Further, a compound having one hydroxyl group and one or more ethylenically unsaturated groups in one molecule, isophorone diisocyanate, methylphenyl diisocyanate, tetramethyl xylene diisocyanate, or hexazone may be used. A semi-carbamate compound of a diisocyanate such as a methyl diisocyanate. In the case of a compound having one cyclic ether group and one or more ethylenically unsaturated groups in one molecule, for example, 2-hydroxyethyl group (A) Acrylate epoxy propyl ether, 2-hydroxypropyl (meth) acrylate epoxy propyl ether, 3-hydroxypropyl (meth) acrylate epoxy propyl ether, 2-hydroxy butyl ( Methyl) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxypentyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl ( Methyl acrylate epoxidized propyl ether, epoxy propyl (meth) acrylate, 3, 4-epoxy cyclohexyl methacrylate, etc. may be used individually or in combination of 2 or more types. The compound having a hydroxyl group and an ethylenically unsaturated group is not particularly limited as long as it has one hydroxyl group and one or more ethylenically unsaturated groups in one molecule. Specific examples thereof include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and trimethylolpropane di (meth) acrylate. A hydroxyalkyl (meth) acrylate such as pentaerythritol tri(meth) acrylate or dipentaerythritol penta (meth) acrylate may be used singly or in combination of two or more kinds. The (meth) propenyl monomer having a functional group reactive with the above-mentioned alcohol or carboxylic acid may be used singly or in combination of two or more kinds. The above (e) monocarboxylic acid having a phenol group may, for example, be 2-hydroxyl-18-201241554, benzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2-amino-3-hydroxyphenyl group. Propionic acid, 3,4-dihydroxyphenylalanine, 3,4,5-trihydroxybenzoic acid, and the like may be used singly or in combination of two or more kinds. In the above (f) compound having a plurality of epoxy groups, such as ADEKAIZER O-130P 'ADEKAIZER 0-1 80A, ADEKAIZER D-32, ADEKAIZER D-55, etc., manufactured by ADEKA Co., Ltd.; jER (registered trademark) 828, jER8 3 4, jER1001, jER1004, Daicel EHPE3150 manufactured by Chemical Industry Co., Ltd., EPICLON (registered trademark) 840 manufactured by DIC Corporation, EPICLON8 50, EPICLON 205, EPICLON205 5, Nippon Steel Chemical Co., Ltd. EPOTOTE (registered trademark) YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664 by The Dow Chemical Company, Araldite607 1 from BASF Japan, Araldite6084, AralditeG Y 2 5 0 ,

Araldite GY260, SUMI- EPOXY ESA-01 1 manufactured by Sumitomo Chemical Industries Co., Ltd., ESA-0 14, ELA-1 15, ELA-128, AER330, AER331, AER661, AER664, etc., manufactured by Asahi Kasei Kogyo Co., Ltd. Name) bisphenol A type epoxy resin; jERYL903 manufactured by Mitsubishi Chemical Corporation' EPICLON 1 52 manufactured by DIC Corporation, EPICLON 1 65, EPOTOTEYDB-400, YDB-500, and The Dow Chemical Company, manufactured by Nippon Steel Chemical Co., Ltd. D. E. R · 5 4 2. Araldite 8011 manufactured by BASF Jap an, SUMI-EPOXY ESB-400 manufactured by Sumitomo Chemical Industries, ESB-7000, AER711, AER714 manufactured by Asahi Kasei Kogyo Co., Ltd. ( Brominated epoxy resin of the trade name; three 201241554 jER152, jER154 manufactured by Ryo Chemical Co., Ltd., DEN431, DEN43 manufactured by The Dow Chemical Company, EPICLONN-7 30 manufactured by DIC Corporation, EPICLONN-770, EPICLONN- 865, EPOTOTEYDCN-701, YDCN-704 manufactured by Nippon Steel Chemical Co., Ltd., A ra 1 dite E CN 1 2 3 5 manufactured by BASF Japan, Araldite ECN 1 273, Araldite ECN 1 299, Araldite XPY307, E manufactured by Nippon Kayaku Co., Ltd. P PN (registered trademark) -1, EOCN (registered trademark) -1025, EOCN-1 020, EOCN-104S, RE-3 06, NC-3000, SUMI- EPOXY ESCN-195X, ESCN- manufactured by Sumitomo Chemical Industries, Ltd. 220, AERECN-23 5, ECN-299, etc. (all trade names) made of Asahi Kasei Industrial Co., Ltd.; EPICLON 83 made by DIC Corporation, jER8 07 made by Mitsubishi Chemical Corporation, manufactured by Nippon Steel Chemical Co., Ltd. EPOTOTEYDF-170, YDF-175, YDF-2004, BASFJapan

Ara丨diteXPY3 06 (all are brand name) double 酣F type epoxy resin; Epoxy Chemical Co., Ltd. EPOTOTEST-2004, ST-2007 'ST-3000 (product name) and other hydrogenated bisphenol A type epoxy resin : JER604 manufactured by Mitsubishi Chemical Corporation, EPOTOTEYH-434 manufactured by Nippon Steel Chemical Co., Ltd., Araldite MY720 manufactured by BASF Japan, and SUMI- EPOXY ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (all trade names) Epoxy resin; Acetone epoxide type epoxy resin such as Ara丨dite CY_3 5 0 (trade name) manufactured by BASF JaPan Co., Ltd.: Celloxide (registered trademark) 202 1 manufactured by Daicel Chemical Industry Co., Ltd., manufactured by BASF Japan

Araldite CY175, CY179, etc. (all trade names) alicyclic epoxy resin YL-933, manufactured by Mitsubishi Chemical Corporation, TEN, EPPN-501, EPPN-5 02, etc., manufactured by The Dow Chemical Company -20-201241554 Name) trihydroxyphenylmethane type epoxy resin; bis-6 phenol type or bisphenol type epoxy resin such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation or their like Mixture; EBPS-200 manufactured by Nippon Kasei Co., Ltd., EPX-30 manufactured by ADEKA Co., Ltd., bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by DIC Corporation, jER157S (trade name) manufactured by Mitsubishi Chemical Corporation, etc. Bisphenol A novolac type epoxy resin; jERYL-931 manufactured by Mitsubishi Chemical Corporation, Araldite 1 63 manufactured by BASF Japan Co., Ltd. (all trade name), Tetraphenylolethane type epoxy resin; Araldite PT810 (trade name) manufactured by BASF Japan Co., Ltd. Heterocyclic epoxy resin such as TEPIC (registered trademark) manufactured by Nissan Chemical Industries Co., Ltd.; diepoxypropyl phthalate resin such as DMG made by Sakamoto Oil Co., Ltd. ZX- 1063 and other four Epoxypropyl xylenol ethane resin, Enagen-based epoxy resin such as ESN-190, ESN-3 60 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Corporation; Epoxy resin with dicyclopentadiene skeleton such as HP-72〇0 and HP-7200H manufactured by the company; epoxy methacrylate copolymerized epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd. Further copolymerized epoxy resin of cyclohexylmaleimide and epoxypropyl methacrylate; epoxy modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industry Co., Ltd.), CTBN Modified epoxy resin (for example, YR-1〇2 and YR-45 0 manufactured by Nippon Steel Chemical Co., Ltd.), etc., but is not limited thereto. Among these, an epoxy resin which does not use epichlorohydrin in the epoxidation process or which has a high purity and a small amount of residual chlorine is preferred from the viewpoint of halogen-free. These epoxy resins may be used alone or in combination of two or more. -21 - 201241554 In order to promote the aforementioned depolymerization, a depolymerization catalyst can be used. Depolymerization catalyst, such as monobutyltin hydroxide, dibutyltin oxide, monobutyltin-2-ethylhexanoate, dibutyltin dilaurate, stannous oxide, tin acetate, zinc acetate, manganese acetate, acetic acid Cobalt, calcium acetate, lead acetate, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate, and the like. The amount of the depolymerization catalyst used is in the range of 0.005 to 5 parts by mass, preferably 0.05 to 3 parts by mass, based on the total amount of the polyester and the polyol, and the photopolymerization used in the present invention. In terms of the initiator, it is preferred to use at least one selected from the group consisting of an oxime ester-based photopolymerization initiator, an aminoethylbenzene-based photopolymerization initiator, and a fluorenylphosphine oxide-based photopolymerization initiator. A photopolymerization initiator. For the oxime ester-based photopolymerization initiator, for example, CGI-3 25 manufactured by BASF Japan Co., Ltd., IRGACURE (registered trademark) OXE01, IRGACURE OXE02, N-1919 manufactured by ADEKA Co., Ltd., NCI-831, and the like can be exemplified. Further, a photopolymerization initiator having two oxime ester groups in the molecule may be used. Specifically, for example, an oxime ester compound having a carbazole structure represented by the following general formula may be used.

-22- 201241554 (wherein X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms), an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, carbon) Alkoxy groups of 1 to 8 or more, substituted with an alkylamino group or a dialkylamino group having an alkyl group having 1 to 8 carbon atoms, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, An alkoxy group having 1 to 8 carbon atoms, an amine group, or an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, and each of Y and Z is a hydrogen atom and having a carbon number of 1 to 17 An alkyl group, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amine group, having a carbon number) a substituted alkylamino group or a dialkylamino group of an alkyl group of 1 to 8 or a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amine group, having carbon Alkylamino or dialkylamino group of an alkyl group of 1 to 8 is substituted, fluorenyl, pyridyl, benzofuranyl, benzothienyl, Ar is a bond, or a carbon number of 1 to 1 〇 Alkyl, vinyl, phenyl, phenyl, pyridyl, naphthyl, thienyl, thiol, a thienyl group, a furfuryl group, a 2,5-pyrrole-diyl group, a 4,4'-fluorenyl-diyl group, a 4,2'-styrene-diyl group, and p is an integer of 〇 or 1. In particular, the above general formula In the case where X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, P is ruthenium, Ar is a bond, or a phenyl group, a naphthyl group, a thienyl group or a thienyl group is preferred. The amount of such an oxime ester photopolymerization initiator is preferably 0.02 to 10% by weight based on the total amount of the composition. When the amount is less than 2% by weight, the light hardening property on the copper is insufficient, and the coating film properties such as chemical resistance are lowered in addition to the peeling of the coating film. On the other hand, when it exceeds 1 〇wt%, light absorption on the surface of the coating film becomes intense, and deep hardenability tends to decrease. -23- 201241554 The aforementioned α-aminoethenyl photopolymerization initiator is specifically, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone- 1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4- Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoethyl benzene, and the like. For commercial products, such as IRGACURE 907, IRGACURE 3 69, IRGACURE 3 79 manufactured by BASF Japan. The above fluorenyl phosphine oxide-based photopolymerization initiator is specifically, for example, 2,4,6-trimethylbenzimidium diphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene). )-Phenylphosphine oxide, bis(2,6-dimethoxybenzhydrazide)-2,4,4-trimethyl-pentylphosphine oxide, and the like. For the commercial products, such as Lucirin TPO manufactured by BASF Co., Ltd., IRGACURE 819 manufactured by BASF Japan Co., Ltd., etc., the amount of the α-aminoethylbenzene-based photopolymerization initiator and the mercaptophosphine oxide-based photopolymerization initiator are It is preferred that the total amount of the composition is 0.5 to 15% by weight. When the amount is less than 0.5% by weight, the photocurability of copper is insufficient, and the coating film properties such as chemical resistance are deteriorated in addition to peeling of the coating film. On the other hand, when it exceeds 15 wt%, the effect of reducing the outgas is not obtained, and further, the light absorption on the surface of the coating film is intense, and the deep hardenability tends to be lowered. Other photopolymerization initiators, photoinitiating aids, and sensitizers which are suitable for use in the photocurable resin composition of the present invention include, for example, a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxanthone compound. A ketal compound, a benzophenone compound, a tertiary amine compound, and a xanthone compound. Specific examples of the benzoin compound include benzoin, -24-201241554 benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Specific examples of the acetaminophen compound include acetophenone, 2,2-dimethoxy-2-phenylethyl benzene, and 2,2-diethoxy-2-phenyl ethene benzene. 1,1-dichloroacetamidine and the like. Specific examples of the ruthenium compound include 2-methylindole, 2-ethylanthracene, 2-t-butylhydrazine, and chloranthene. Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4·diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropyl. Thioxanthone and the like. Specific examples of the ketal compound include etidinol ketal and benzyl dimethyl ketal. Specific examples of the benzophenone compound include benzophenone, 4-benzoic acid diphenyl sulfide, 4-benzhydrazyl-4'-methyldiphenyl sulfide, and 4-benzene. Formazan-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide, and the like. Specific examples of the tertiary amine compound include, for example, an ethanolamine compound and a compound having a dialkylaminobenzene structure, and commercially available 4,4'-dimethylaminobenzophenone (Japanese) Cao Da (share) system Nisso

CureMABP), 4,4 '-diethylaminobenzophenone (EADOGA YA CHEMICAL EAB), etc. Dialkylaminobenzophenone, 7-(diethylamino)-4- Methyl-2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin) and the like, dialkylamine-based coumarin compound, 4-dimethyl Ethyl benzoic acid ethyl (Kayacure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), 2-methylamino benzoic acid ethyl (international Bio--25- 201241554

Quantacure DMB manufactured by Synthetics, 4-dimethylamino benzoic acid (η-butoxy) vinegar (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylamino benzoic acid isoamylethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (Esolol 5 07 manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (HODO GAYA CHEMICAL (share) EAB) and so on. Among the above photopolymerization initiators, photoinitiating aids and sensitizers, a thioxanthone compound and a tertiary amine compound are preferred. In particular, the thioxanthone-containing compound is preferred from the viewpoint of deep hardenability. Among them, a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone or 2-chlorothioxanone 2,4-diisopropylthioxanthone is used. Preferably, the amount of such a thioxanthone compound is preferably 15% by weight or less based on the total amount of the composition. When the amount of the thioxanthone compound is more than 15% by weight, the thick film hardenability is lowered and the product cost is increased. More preferably, it is 1 〇 wt% or less. Further, in terms of the tertiary amine compound, a compound having a dialkylaminobenzene structure, wherein a dialkylamine benzophenone compound and a dialkylamine having a maximum absorption wavelength of from 3 to 450 nm are used. The coumarin compound and the coumarin ketone are particularly preferred. In the case of the aforementioned dialkylaminobenzophenone compound, the toxicity of 4,4'-diethylaminobenzophenone is also low. The dialkylamine-based coumarin compound has a maximum absorption wavelength of 3 50 to 41 Onm and an ultraviolet field, and the colorless transparent photosensitive composition can provide coloring of the color of the coloring pigment itself by using a coloring pigment more than ever. Solder mask film. In particular, the laser light of 7-( -26- 201241554 diethylamino)-4 -methyl-2H-1-benzopyran-on Onm has an excellent sensitizing effect. The amount of such a tertiary amine compound is preferably from 0.1 to 15% by weight. The third-stage amine-based shirt has a tendency to be insufficiently sensitized when it is 0% by weight. The dry solder resist coating film of the tertiary amine compound tends to be strong and the deep-hardenability is lowered. For other photopolymerization initiators, IRGACURE3 89, IRGACURE784, etc. are also suitable. These photopolymerization initiators, photoinitiating aids, and mixtures of two or more types are used. Such a photopolymerization initiator, a photoinitiator, and 100 parts by mass of the relative poly(meth)acrylate are 35. When it exceeds 35 parts by mass, there is a tendency to wait for light absorption. Further, these photopolymerization initiators and photoinitiating aids have a specific wavelength, and the sensitivity is lowered depending on the occasion. However, these are not just for the sensitivity of the composition. It is necessary to absorb light of a specific wavelength as necessary, so that the shape and opening of the resist are changed to be vertical, and the processing precision of the line width or the opening diameter can be improved. In the photocurable resin composition of the present invention, a conventionally used ketone such as N-phenylacetic acid, thiophenoxyacetic acid or mercaptothiazole as a chain transfer agent is added to a wavelength of 400 to a total of 3 The match is not up to the limit. More than 15 wt%, the light absorption of the surface of the BASF Japan company sensitizer, alone or with the total mass of the sensitizer below the sclerosing property of the good, and the sensitizer is enhanced by the absorption of UV absorbers The purpose is to make the surface photoreactive cone-like and inverse-conical shape the same as the sensitivity to enhance glycine and phenoxy. Chain transfer agent -27- 201241554 A chain transfer with a carboxyl group such as mercapto succinic acid, thioglycolic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and its derivatives a chain transfer agent having a hydroxyl group such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; Alkyl mercaptan, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanethiol, 4-methyl Phenyl mercaptan, dodecyl alcohol, propane thiol, butane thiol, pentane thiol, 1-inchin thiol, cyclopentane thiol, cyclohexane thiol, thioglycerol, 4, 4 - thiodiphenylthiol, etc. Further, a heterocyclic compound having a mercapto group function as a chain transfer agent may, for example, be mercapto-4-butyrolactone (alias: 2-mercapto-4-r-butene) Ester), 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butane lactone, 2-oxime 4-butylidene, N-methoxy-2-mercapto-4-butylidene, N-ethoxy-2-mercapto-4-butylidene, N-A Base-2-mercapto-4-butylidene, N-ethyl-2-mercapto-4-butylidene, N-(2-methoxy)ethyl-2-mercapto-4- Butane amide, N-(2-ethoxy)ethyl-2-mercapto-4-butylidene, 2-mercapto-5-valerolactone, 2-mercapto-5-pentalone Amine, N-methyl-2-mercapto-5-pentalinamide, N-ethyl-2-mercapto-5-pentalinamide, N-(2-methoxy)ethyl-2- Mercapto-5-valeroinamide, N-(2-ethoxy)ethyl-2-mercapto-5-valeroinamide, 2-mercapto-6-hexylamine, etc. a heterocyclic compound having a mercapto group which does not impair the developability chain transfer agent of the photocurable resin composition, with mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1, 2,4- Triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole is preferred. These chain transfer agents may be used alone or in combination. Further, in the photocurable resin composition of the present invention, a photopolymerizable resin containing a carboxyl group may be added for the purpose of improving photosensitivity, developability, heat resistance, and electrical properties. The weight average molecular weight of the photosensitive resin of a carboxyl group varies depending on the resin skeleton, but one It is preferably 2,000 to 1 50,000, and further preferably in the range of 5,000 to 100,000. The weight average molecular weight is less than 2,000, and the coating film has poor adhesion properties, poor moisture resistance of the coating film after exposure, and film formation during development. On the other hand, when the weight average molecular weight exceeds 1,500, the developability is remarkably deteriorated, and the storage stability is poor. The conjugated amount of the carboxyl group-containing photosensitive resin is the total amount of the composition. A range of 50% by weight or less, preferably 10% to 40% by weight is preferred. All of the above-mentioned carboxyl group-containing photosensitive resins can be used in combination of one type or two or more types. In the photocurable resin composition of the present invention, a thermosetting component can be used in order to impart heat resistance. As the thermosetting component used in the present invention, an amine resin such as a melamine resin or a benzoguanamine resin, a blocked isocyanate compound, a cyclic carbonate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, or a ring can be used. A conventional thermosetting resin such as an oxysulfide resin, a melamine derivative, a bismaleimide, an oxazine compound, an oxazoline compound, or a carbodiimide compound. In particular, a thermosetting component having a plurality of cyclic ether groups and/or cyclic thioether groups (hereinafter referred to as "cyclic (thio)ether group)" in the molecule is particularly preferable. The thermosetting property of a plurality of cyclic (thio)ether groups in such a molecule is a cyclic ether group having a complex number of 3, 4 or 5 membered rings or a cyclic thioether group in the molecule. Any one of the compounds of the two types, for example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, or a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxygen heterocycle. A butane compound or a compound having a plurality of thioether groups in the molecule, that is, an epoxy sulfide resin. Examples of the polyfunctional epoxy compound include epoxidized vegetable oils such as ADEKAIZER O-130P, ADEKAIZER O-180A, ADEKAIZER D-32, and ADEKAIZER D-55 manufactured by ADEKA Co., Ltd.; jER (registered trademark) 828 manufactured by Mitsubishi Chemical Corporation. , JER834, jERlOOl, jER1004, EHPE3150 manufactured by Daicel Chemical Industry Co., Ltd., EPICLON (registered trademark) 840 manufactured by DIC Corporation, EPICLON85 0, EPICLON 205, EPICLON205 5, EPOTOTE (registered trademark) YD manufactured by Nippon Steel Chemical Co., Ltd. -011, YD-013, YD-127, YD-128 'The DER317, DER331, DER661, DER664 by the Dow Chemical Company, Araldite607 1 of the BASF Japan company, Araldite6084, AralditeG Y2 5 0,

Araldite GY260, SUMI- EPOXY ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Industries Co., Ltd., A. E. R. 330, A. E. R. 331, A. E. R. 661, A. E. R. 664 (E-brand name) bisphenol A type epoxy resin; JERYL903 manufactured by Mitsubishi Chemical Corporation 'EPICLON 152' EPICLON 165' manufactured by DIC Corporation EPOTEYDB-400, YDB-5 00, The, manufactured by Nippon Steel Chemical Co., Ltd. D. by Dow Chemical Company E. R. 542, BASFJapan Company -30- 201241554 Araldite801 1. SUMI-EPOXY ESB-400, E S B - 700, manufactured by Sumitomo Chemical Industries Co., Ltd., A. E. R. 711, A_E. R. Brominated epoxy resin of 714 et al. (both trade names); jER152, jER154, manufactured by Mitsubishi Chemical Corporation, D manufactured by The Dow Chemical Company. E. N. 43 1. D. E. N·43 8. EPICLONN-730, EPICLONN-770, EPIC L ONN - 8 6 5 manufactured by DIC Corporation, EPOTOTEYDCN-701, YDCN-704 manufactured by Nippon Steel Chemical Co., Ltd., A r al dite E CN manufactured by BASF Japan 1 2 3 5, A ra 1 dite ECN 1 2 7 3 , AralditeECN 1 299, Araldite XPY3 07, EPPN-201, EOCN-1 025, EOCN- 1 020, EOCN-104S, RE-306, manufactured by Nippon Kayaku Co., Ltd. NC-3000, SUMI- EPOXY ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Industries Co., Ltd., manufactured by Asahi Kasei Kogyo Co., Ltd. E. R. ECN-235, ECN-299, etc. (all trade names), novolak-type epoxy resin; EPICLON 83 0 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, EPOTOTEY DF-1 70, YDF-175 manufactured by Nippon Steel Chemical Co., Ltd. YDF-2004, AralditeXP Y3 06 manufactured by BASF Japan, etc. (both trade names) bisphenol F-type epoxy resin; EPOTOTEST-2004, ST-2007, ST-3 000 (trade name), etc. manufactured by Nippon Steel Chemical Co., Ltd. Hydrogenated bisphenol A type epoxy resin; jER6 04 manufactured by Mitsubishi Chemical Corporation, EPOTOTEYH-43 4 manufactured by Nippon Steel Chemical Co., Ltd., AralditeMY720 manufactured by BASF Japan, and SUMI- EPOXY ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. Epoxypropylamine type epoxy resin of the product name; Erythroquinone type epoxy resin such as Araldite CY-3 50 (trade name) manufactured by BASF Japan Co., Ltd.; Celloxide manufactured by Daicel Chemical Industry Co., Ltd. (Login-31 - 201241554 Standard) 2021, alicyclic epoxy resin of Araldite CY175, CY179, etc. (both trade names) manufactured by BASF Japan Co., Ltd.; ¥1^93, manufactured by Mitsubishi Chemical Corporation, T., manufactured by The Dow Chemical Company. E. N. , EPPN-501, EPPN-5 02, etc. (all trade names) of trihydroxyphenylmethane type epoxy resin: YL-605 6, manufactured by Mitsubishi Chemical Corporation, YX-4000, YL-6121 (all trade names) Dimethylphenol type or bisphenol type epoxy resin or a mixture thereof; EBPS-200 manufactured by Sakamoto Chemical Co., Ltd., EPX-30 manufactured by ADEKA Co., Ltd., and EXA-15 14 (trade name) manufactured by DIC Corporation Epoxy resin; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; JERYL-931 manufactured by Mitsubishi Chemical Corporation, and Aralditel 63 manufactured by BASF Japan Co., Ltd. (all trade names) Tetra phenylolethane type Epoxy resin; Araldite PT810 manufactured by BASF Japan Co., Ltd., TEPIC manufactured by Nissan Chemical Industries Co., Ltd. (all trade names), heterocyclic epoxy resin: Dimethyl propyl benzoate, etc., manufactured by Nippon Oil Co., Ltd. Formate resin; tetradecyl propyl xylenol ethane resin such as ZX-1063 manufactured by Nippon Steel Chemical Co., Ltd.; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA- manufactured by DIC Corporation 4750, EXA-4700 and other naphthalene-containing epoxy resins; HP-7200, H made by DIC Epoxy resin with dicyclopentadiene skeleton such as P-7200H; epoxy methacrylate copolymerized epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd.; further cyclohexylmalayiya Copolymerized epoxy resin of amine and glycidyl methacrylate: epoxy modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industry Co., Ltd.), CTBN modified epoxy resin (for example, new YR-102, YR-4 50, etc. manufactured by Nippon Steel Chemical Co., Ltd., etc., but are not limited thereto. These rings -32- 201241554 Oxygen resins may be used singly or in combination of two or more. In particular, EHPE3150, PB-3600, and Celloxide 2021 (all manufactured by Daicel Chemical Co., Ltd.) are preferred because the epoxide-modified compound of the peracetic acid method is free from impurities of a halogen ion. In addition, epoxidized vegetable oils such as ADEKAIZER D-32, ADEKAIZER D-55, ADEKAIZER O-130P, and ADEKAIZER O-180A (all manufactured by ADEKA) are also preferably halogen-free. In the above polyfunctional oxetane compound, in addition to bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy) )methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanyl) Oxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl)methacrylate, (3-A Poly-3-oxo-butyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or polyfunctional such as oligomers or copolymers Examples of the oxetane include, for example, oxetane and novolak resins, poly(p-hydroxystyrene), Car do type bisphenols, calixarene, cup-resorcinol aromatic hydrocarbons, and the like. An etherified product of a resin having a hydroxyl group such as sesquioxanes or the like. Other examples thereof include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate. The compound having a plurality of cyclic thioether groups in the above-mentioned molecule may, for example, be a bisphenol A type epoxy sulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Further, an epoxy-sulfide-33-201241554 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 amount of the hot hard component having a plurality of cyclic (thio)ether groups in the above molecule is preferably 1 equivalent of the carboxyl group in the composition, more preferably 〇 equivalent, more preferably 0. 8~2. A range of 0 equivalents. The amount of the thermosetting component having a cyclic (thio)ether group in the molecule is less than 0. 6. The residual carboxyl group in the solder resist film is not good because of heat resistance, alkali resistance, and electric power. On the other hand, more than 2. In the case of 5 equivalents, the amount of the cyclic (thio)ether group remaining in the dried coating film is not good. Further, as another thermosetting component, a compound having an isocyanate group or a blocked isocyanate group in one molecule can be added. In the case of having a plurality of isocyanate groups or blocked isocyanate groups, for example, a polyisocyanate compound having a complex isocyanate group in one molecule, or a compound having a plurality of block acid ester groups in one molecule, That is, a blocked isocyanate compound or the like. As the polyisocyanate compound, for example, an aromatic cyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of polyisocyanates such as 4,4'-diphenylmethane diester, 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate| 1,5-diisocyanate, 〇-二Tolyl diisocyanate, m-dimethyl isocyanate and 2,4-tolyl dimer. Examples of aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanide diisocyanate, trimethyl hexamethylene diisocyanate, methyl bis(cyclohexyl isocyanate) and isophor Keto diisocyanate. Chemical formation • 6 ～ 2 · 5 The number of complexes such as the low-molecularity of the complex number, such as a compound with a complex number, a compound of an isocyanuric polyisocyanate, a specific acid of naphthalene-phenyl Ester, 4,4-aliphatic ring-34- 201241554 Specific examples of polyisocyanates such as bicycloheptane triisocyanate. And an adduct of an isocyanate compound, a burette form, and an isocyanurate body as exemplified above. The blocked isocyanate group contained in the above-mentioned blocked isocyanate compound is a group which is inactivated by the reaction of an isocyanate group and a block agent. Upon heating to a specific temperature, the blocker dissociates to form an isocyanate group. In the case of such a blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent can be used. Examples of the isocyanate compound which can be reacted with the block agent include an isocyanurate type, a biuret type, and an addition type. As the isocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate are as exemplified above. In the above isocyanate block agent, for example, a phenolic blocker such as phenol, cresol, xylenol, chlorophenol or ethylphenol; ε-caprolactam, δ-valeroinamide, r-butyrolactam And /S-propionalamine and other internal amide-blocking agents; active methylene blockers such as ethyl acetate and acetonitrile; methanol, ethanol, propanol, butanol, and amyl alcohol , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, Alcohol blocker such as butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; formaldehyde oxime, acetaldehyde oxime, acetamidine, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine, ring Anthracene blocker such as hexane oxime; alcohol blocker such as butyl alcohol, hexyl alcohol, t-butyl alcohol, thiophenol, methyl thiophenol, or B-35-201241554 thiophenol; An amide amine blocker such as guanamine or benzoguanamine; a quinone imine blocker such as succinimide succinate or succinimide; guanamine, aniline, butylamine, dibutylamine, etc. Amine blocker; imidazole, 2-ethylimidazole Imidazole-based blocking agent; methylene imine and propylene imine extension block alkylene amine, and the like. The above-mentioned blocked isocyanate compound may be a commercially available product such as Sumijuir (registered trademark) BL-3175, BL-4165, BL-1100, BL-1 265, Desmodur (registered trademark) TPLS-2957, TPLS-2062, TPLS-2078. TPLS-2117, Desmosome21 70, Desmosome 2265 (above, Sumitomo Bayeramide Co., Ltd., trade name), C〇r〇nate (registered trademark) 2512, Coronate 2513, Coronate 2 5 20 (above, 曰 聚 polyamine Formate, product name), B-830, B-815, B-846, B-870, B-874, B-882 (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name), TPA-B80E, 1 7B-60PX, E402-B80T (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name), and the like. Further, Sumijuir BL-3175 and BL-4265 were obtained by using methyl ethyl hydrazine as a block agent. The compound having a plurality of isocyanate groups or blocked isocyanate groups in the above-mentioned one molecule may be used singly or in combination of two or more kinds. The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in such a molecule is from 1 to 50% by weight, more preferably from 2 to 40% by weight based on the total amount of the composition. When the aforementioned matching amount is less than 1 wt%, it is not preferable to obtain sufficient toughness of the coating film. On the other hand, when the amount exceeds 50% by weight, the preservation stability is not improved. Further, other thermosetting components include, for example, a melamine derivative, a -36-201241554 benzoguanamine derivative, and the like. For example, there are a methylol melamine compound, a hydroxymethylbenzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, and the like. Further, an alkoxymethylated melamine compound, an alkoxymethylated benzoguanamine compound, an alkoxymethylated glycoluril compound, and an alkoxymethylated urea compound can be obtained by using a respective methylol group The hydroxymethyl group of a melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, and a methylol urea compound is converted into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and may, for example, be a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group or a butoxymethyl group. Especially in the body or the environment, the concentration of formaldehyde is 0. More than 2% of the melamine derivative is preferred. Such commercial products, such as Cymel (registered trademark) 300, the same 301, the same 3 03, the same 370, the same 325, the same 327, the same 701, the same 266, the same 267, the same 238, the same 1141, the same 272, the same 202, the same 1156, the same 1158, the same 1123, the same 1170, the same 1174, the same UFR65, the same 300 (above, Mitsui-Cyanamid (share) system), NIKALAC (registered trademark) Mx-750, the same Mx-0 3 2 Same as Mx-270, same Mx-280, same Mx-290, same Mx-706, same Mx-70 8, same Mx-40, same Mx-31, same Ms-11, same Mw-30, same Mw-30HM , with Mw-390, the same Mw-100LM, the same MW-750LM, (above, (share) three and chemical system). The above thermosetting component may be used singly or in combination of two or more. When a thermosetting component having a plurality of cyclic (thio)ether groups in the above molecule is used, it is preferred to contain a thermosetting catalyst. Such thermosetting catalysts, such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano Ethyl-2-phenyl-37- 201241554 imidazole, imidazole derivatives such as 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethyl Amine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-di An amine compound such as methylbenzylamine, an anthracene acid adipate or a phosphonium azelate or the like: a phosphorus compound such as triphenylphosphine, etc. Further, as a commercially available person, for example, Shikoku Chemical Industry Co., Ltd. 2MZ-A '2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (trade name of imidazole-based compound), U-CAT (registered trademark) manufactured by San-apro Co., Ltd. 3 5 03N, U-CAT3 502T A trade name of a blocked isocyanate compound of a base amine, DBU, DBN, U-CATSA102, U-CAT5002 (all bicyclic hydrazine compound and a salt thereof). It is not particularly limited thereto, and may be a thermosetting catalyst of an epoxy resin or an oxetane compound, or a reaction capable of promoting an epoxy group and/or an oxetanyl group and a carboxyl group, either alone or in combination. More than one kind of mixture is used. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-ethylene-2 can also be used. , 4-diamino-S-triazine, 2-ethylene-4,6-diamino-S-triazine. Iso- cyanuric acid adduct, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine. The S-triazine derivative such as an isomeric cyanuric acid addition product is preferably used for the compound having the function of the adhesion imparting agent and the above-mentioned thermosetting catalyst. The ratio of the amount of the thermosetting catalyst to the usual amount is sufficient, for example, 100 parts by mass of the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule, preferably 0. 1 to 20 parts by mass, more preferably 0. 5~ 15. 0 parts by mass The photocurable resin composition of the present invention can be used in combination with a coloring agent. In the case of the colorant -38-201241554, a conventional coloring agent such as red, blue, green or yellow may be used, and any of a pigment, a dye, and a pigment may be used. However, it is preferable that halogen is not contained in view of a reduction in environmental load and a human influence. Red coloring agent: As a red coloring agent, there are monoazo, diazo, Azo Lake, benzimidone, anthraquinone, diketopyrrole, condensed azo, anthraquinone, quinophthalone Etc., for example, the following color index can be attached (C.  I.  ; The Society of Dyers and Colourists Issued) Numbered Single Azo System: P i gme nt Red 1 , 2 , 3, 4,5 ,6 ·,8,9, 12, 14,15 ,16 ,17, 21 - 22,23 ,3 1 ,32, 1 1 2,1 1 4, 146, 147, 151 ' 170, 184 , 187, 188, 193, 210, 245 , 25 3, 25 8, 266, 267, 268 , 269 ° Diazo: Pigment Red 3 7,38,41. Single Azo Lake Series: Pigment Red 48 : 1 , 48 : 2 , 48 : 3 , 48 : 4 , 49 : 1 , 49 : 2 , 50 : 1 , 52 : 1 > 52 : 2 > 53 : 1 , 53 : 2 , 57 : 1 , 58 : 4 , 63 : 1 , 63 : 2 , 64 : 1 , 68 . Phenimide series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208. Philippine: Solvent Red 135, Solvent Red 179, Pigment Red 12 3' Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224 ° -39- 201241554卩it slightly slightly: Pigment Red 254, Pigment Red 2 5 5 ' Pigment Red 264, Pigment Red 270, Pigment Red 272 · Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 ' Pigment Red 242.恵醌 Department: P igment R ed 1 6 8 , P igment R ed 1 7 7 , Pigment Red 216 , Solvent Red 149 , Solvent Red 150 , Solvent Red 52 , S o 1 ve nt Re d 2 0 7 〇 V V ketone Line: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207 ' Pigment Red 209. Blue coloring agent: As a blue coloring agent, there are a phthalocyanine-based or an anthraquinone-based, and the pigment system is classified into a compound of Pigment. Specifically, the following may be mentioned: Pigment Blue 15, Pigment Blue 15 : 1, Pigment Blue 15 : 2, Pigment Blue 15:3, Pigment Blue 15: 4' Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60. For dye systems, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 and more. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used. -40- 201241554 Green Colorant: For green colorants, there are also phthalocyanine, lanthanide and phenanthrene. In particular, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 2 0 can be used. , Solvent Green 28, etc. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used. Yellow coloring agent: Examples of the yellow coloring agent include a monoazo type, a diazo type, a condensed azo type, a benzimidone type, an isoindolinone type, an anthraquinone type, and the like, and specific examples thereof include the following. Lanthanum: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Y e 11 o w 1 4 7 , P i g m e n t Y e 11 o w 1 9 9 , P i g m e n t Y e 11 o w 2 0 2 . Iso-P-pyrroline ketone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185 ° condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Y e 11 ow 1 5 5, P igment Y e 11 ow 1 6 6 , P igment Y e 11 ow 1 8 0. Benzimidone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154 ' Pigment Yellow 156 ' Pigment Yellow 175, Pigment Yellow 181. Monoazo system: Pigment Yellow 1,2,3,4,5,6,9, -41 - 201241554 10, 12, 61 -62 > 62 :1, 65,73,74, 75 , 97 , 100 f 104, 105, 1 11, 116, 167, 168, 169, 182, 183° Diazo: Pigment Yello w 1 2,1 3,1 4 ,1 6,1 7 ,5 5 9 63 , 81 , 83 , , 87, 126, 127, 152, 170, 172 * 174, 176, 188, 198. For the purpose of adjusting other colors, you can also add colorants such as purple, orange, brown > black. Specific examples, such as Pigment Violet 19, 23, 29 ' 32 ' 36, 38, 42 , Solvent Violet 13, 36, C. I. Pigment Orange 1 C. I. Pigment Orange 5, C. I. Pigment Orange 13 C. I. Pigment Orange 14, C. I. Pigment Orange 16 , C .  I.  P i gment Orange 17 , C. I. Pigment Orange 24, C. I. Pigment Orange 34, C.  I.  P i gment Orange 36 > C. I. Pigment Orange 38 ' C · I · Pi gment Orange 40 , C. I. Pigment Orange 4 3, C.  I. Pi gment Orange 46, C. I. Pigment Orange 49 ' C · I.  Pi gm ent Orange 5 1 , C. I. Pigment Orange 6 1 , C. I. Pigment Orange 63 C. I. Pigment Orange 6 4 , C .  I.  P i g m e n t Orange 7 1 , C. I. Pigment Orange 73 ' C .  I.  P i gment Brown 23 C. I. Pigment Brown 25 ' C. I. Pigment Black 1, C. I. Pigment B1 a c k 7 and so on. The proportion of the above-mentioned coloring agent is not particularly limited, and is preferably 5 w t % or less, more preferably 0 · 1 to 3 w % % in the solid content of the composition. The photocurable resin composition of the present invention can be used in combination with a material for the purpose of improving the physical strength of the coating film, etc., as needed. In terms of such materials, although conventional inorganic or organic tanning materials can be used, barium sulfate, spherical ceria and talc are particularly suitable for use. 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 amount of the mashing material is preferably 75 wt% or less, more preferably 0. A ratio of 1 to 60% by weight. When the amount of the compound is more than 7 5 wt% of the total amount of the composition, the viscosity of the insulating composition becomes high, coating, formability is lowered, and the cured product becomes brittle. Further, the photocurable resin composition of the present invention can be used in the synthesis of a resin used in the present invention, preparation of a composition, or adjustment of viscosity applied to a substrate or a carrier film, and an organic solvent can be used. Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, and carbitol , glycol ketones such as methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate , butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, methyl 2-hydroxyisobutyrate, etc.; ethanol Alcohols such as propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and petroleum-soluble petroleum spirit. Such an organic solvent may be used singly or in combination of two or more. -43- 201241554 The photocurable resin composition of the present invention can be further used in combination with conventional thermal polymerization inhibitors, fine powdered cerium oxide, organic bentonite, montmorillonite, and the like which are conventionally used as tackifiers and ketones. A conventional additive such as an antifoaming agent and/or a coating agent such as a fluorine-based or a polymer-based compound, a decane coupling agent such as an imidazole-based compound, a thiazole-based or a triazole-based compound, an antioxidant, and a rust preventive agent. The photocurable resin composition of the present invention can be adjusted, for example, to a viscosity suitable for the coating method, and the dip coating method, the shower coating method, the roll coating method, the bar coating method, or the screen printing on the substrate. The method is applied by a method such as a curtain coating method, and the organic solvent contained in the composition is volatilized (temporarily dried) at a temperature of about 60 to 100 ° C to form a non-adhesive coating film. Further, by applying the above composition to a carrier film and drying the film as a film winder, the resin insulating layer can be formed. Thereafter, by contact (or non-contact), through the patterned mask, selectively direct exposure of the active energy line with an exposure or laser direct exposure machine, so that the unexposed portion is a dilute aqueous solution ( For example 0. A 3 to 3 wt% aqueous solution of sodium carbonate was developed to form a resist pattern. Further, in the case of a composition containing a thermosetting component, for example, by heat-heating to a temperature of about 140 to 180 ° C, the carboxyl group of the carboxyl group-containing resin or the carboxyl group-containing photosensitive resin has a carboxyl group and a molecule. The thermosetting component of a plurality of cyclic ether groups and/or cyclic thioether groups is reacted to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. . In addition, in the case where the thermosetting component is not contained, the ethylenically unsaturated bond of the photocurable component remaining in the unreacted state upon exposure by heat treatment undergoes thermal radical polymerization, and the coating film property is improved, so that the purpose is Use can be -44 - 201241554 heat treatment (thermal hardening). In the above substrate, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimine, glass can be used in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance. Cloth/non-fibrous cloth-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, polyimide films, PET films, glass substrates, ceramic substrates, wafer boards, and the like. The volatilization drying which is carried out after applying the photocurable resin composition of the present invention can be carried out by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a heat source having a vapor-heated air method to be used in the dryer) The hot air convection contact method and the manner in which the nozzle is blown to the support) are performed. After the photocurable resin composition of the present invention is applied and evaporated to dryness, the obtained coating film is exposed (irradiation of active energy rays). The exposed portion of the coating film (the portion irradiated with the active energy ray) is hardened. For the exposure machine to be used for the active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device that uses a direct laser to draw an image with CAD data from a computer), an exposure machine equipped with a metal halide lamp, and a (super) device can be used. An exposure machine using a high-pressure mercury lamp, an exposure machine equipped with a mercury short-arc lamp, or a direct drawing device using an ultraviolet lamp such as an (ultra) high-pressure mercury lamp. For the active energy line, laser light having a maximum wavelength in the range of 350 to 410 nm can be used, which can be a gas laser or a solid laser. Further, although the exposure amount varies depending on the film thickness or the like, it is usually in the range of -45 to 201241554 of 5 to 800 mJ/cm2, preferably 5 to 500 mJ/cm2. As the direct drawing device, for example, a product manufactured by Orbotech Co., Ltd., PENTAX Corporation, or the like can be used, and any device capable of generating laser light having a maximum wavelength of 350 to 41 Onm can be used. In the above development method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. The developing solution can use potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, and amine. An aqueous solution such as an alkali. The photocurable resin composition of the present invention may be formed by applying a solder resist to a film such as polyethylene terephthalate and drying it, in addition to a method of directly applying a liquid to a substrate. The dry film form of the layer is used. The case where the curable resin composition of the present invention is used as a dry film is as follows. The dry film is a structure having a sequentially laminated carrier film, a solder resist layer, and a peelable protective film which is used as necessary. The solder resist layer is such that the alkali-developable photocurable resin composition is about 10 to 150 μm in a carrier film or a protective film by a knife coater, a lip coater, a notch coater, a film coater or the like. The thickness is uniformly coated and dried to form. After the solder resist layer is formed on the carrier film, the protective film is laminated thereon, or the solder resist layer is formed on the protective film, and the laminate is laminated to the carrier film to obtain a dry film. For the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μηα can be used. In terms of a protective film, a polyethylene film, a polypropylene film, or the like can be used, but the adhesion to the solder resist layer is smaller than that of the carrier film. It is better. A protective film (permanent protective film) is formed on a printed wiring board using a dry film -46-201241554, the protective film is peeled off, the solder resist layer is superposed on the substrate on which the circuit is formed, and laminated and formed using a laminator or the like. A solder resist layer is formed on the substrate having the circuit. The formed solder resist layer is exposed, developed, and heat-cured in the same manner as described above to form a cured coating film. The carrier film may be peeled off at any point before or after exposure. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the examples described below. In addition, the following "parts" and "%" are quality benchmarks unless otherwise specified. (B-1) Carboxylic acid resin synthesis example 1 A PET sheet (Mitsubishi Chemical Co., Ltd.: Novapex, IV) was placed in a 1000 mL four-neck round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube.値1. 1) 3 84 parts, after making the inside of the flask into a nitrogen atmosphere. Immerse in a salt bath heated to 300 °C. The PET dissolves and begins to stir while adding dibutyltin oxide. 6 copies. Next, 134 parts of trimethylolpropane which was dissolved at 130 ° C in advance was added in a small amount in such a manner that the PET was not cured. During this period, the agitation speed was increased to 150 rpm during the viscosity reduction phase. Subsequently, the oil bath was heated to 240 ° C in advance by a salt bath, and the internal temperature of the flask was maintained at 220 ° C ± 10 ° C for 5 hours. Next, 51 parts of the reactant was placed in a 1000 mL four-necked flask equipped with a stirrer, an air introduction tube, a fractionation tube, and a cooling tube, and 81 parts of acrylic acid and -47-201241554 p-toluenesulfonic acid were added. 4 parts, p-methoxyphenol oxime. 8 parts of methyl isobutyl ketone 2 1 2 parts and toluene 11 2 parts were stirred and uniformly dissolved, and then immersed in an oil bath heated to 1 15 ° C ± 5 ° C for a specific period of time. After the completion of the reaction, the acid value of the reaction liquid was measured, and an aqueous alkali equivalent of an acid equivalent was placed in a flask to be stirred and neutralized. Next, saline (20 wt%) was added and stirred. Thereafter, the solution was transferred to a separatory funnel, and the same amount of methyl ethyl ketone as the reaction liquid was added, and the aqueous phase was discarded. The oil phase was washed twice with saline (5 wt%) and the aqueous phase was discarded. Further, the oil phase was washed twice with a small amount of tap water, and the aqueous phase was discarded. Next, the reaction solution was transferred to a beaker, and the oil phase was stirred with hexane in a beaker, and the supernatant was discarded after standing. Finally, it was concentrated by an evaporator to obtain a PET-containing acrylate resin. Next, 50 parts of PET-containing acrylate resin and 27 parts of carbitol acetate were placed in a 300 mL four-neck round bottom flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and the inside of the flask was placed in a nitrogen atmosphere. Immerse in an oil bath heated to 80 °C ± 5 °C. Next, make triphenylphosphine 0. 8 parts with methoxyphenol 0. 4 parts. The carbitol acetate solution dissolved in 10 parts of carbitol acetate was slowly dropped, and 20 parts of tetrahydro anhydrous phthalic acid was divided into 2 parts. The reaction was carried out for 10 hours in 5 hours, and the resin solution of the carboxyl group-containing acrylate having a solid content of 65%, a solid content of 128 mgKOH/g, and a chlorine concentration of 20 ppm or less was obtained. This resin solution is referred to as B-1. (B-2) Carboxylic Acid Synthesis Example 2 In a 500 mL four-neck round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, 62 parts of 1,3-propanediol and trishydroxymethyl- 48- 201241554 Propane 7. 8 parts, dibutyltin oxide 0. 77 parts, isophthalic acid 40. 6 parts, PET film (Mitsubishi Chemical Co., Ltd.: Novapex, IV値1. 1) 64 parts, after making the inside of the flask into a nitrogen atmosphere. Immerse in an oil bath heated to 1300 °C. The contents were dissolved and heated to 180 °C. Subsequently, the temperature was raised to 23 5 ° C, and the reaction was continued for 1 hour. After 1 hour, PET tablets were added in sequence (Mitsubishi Chemical Co., Ltd.: Novapex, IV値1. 1) 128 parts with isophthalic acid 81. After 3 parts, the reaction was continued for 14 hours until it became a transparent liquid. Next, the internal temperature of the flask was maintained at 200 ° C, stirring was started, and 96 parts of trimellitic acid was added thereto to dissolve. After that, the reaction was continued for 8 hours. Next, the flask was cooled to ll ° ° C, and triphenylphosphine was added. 02 parts, methoxyphenol 0. 51 parts, carbitol acetate 287. 7 parts and stir. After continuous stirring, 51 parts of glycidyl methacrylate was added and reacted for 6 hours. Thus, a varnish containing a carboxyl group-containing photosensitive compound having a solid content of 65% and a solid content of 90 mgKOH/g was obtained. Hereinafter, the resin solution is referred to as B-2 (B-3) carboxylic acid resin Synthesis Example 3, and a 500 mL four-neck round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube was placed, and a PET sheet was added. (Mitsubishi Chemical Co., Ltd.: Novapex, IV値1. 1) 192 parts, after making the inside of the flask into a nitrogen atmosphere. .  Immerse in a salt bath heated to 300 °C. The PET dissolves and begins to stir while adding dibutyltin oxide. 6 copies. Next, 134 parts of trimethylolpropane which was previously dissolved at 130 ° C was added in small portions in such a manner that the PET was not cured. During this period, the agitation speed was increased to -49 - 201241554 150 rpm during the viscosity reduction phase. Subsequently, the oil bath was heated to 240 ° C in advance by a salt bath, and the inner temperature of the flask was maintained at 220 ° C ± 10 ° C for 5 hours, and then cooled to room temperature. Next, add tetrahydro anhydrous phthalic acid (THPA) 12 1. 6 parts, 240 parts of carbitol acetate, after the inside of the flask was made into a nitrogen atmosphere. Immerse in an oil bath warmed to 125 ± 5 °C. The stirring was started slowly, and the reaction was carried out for 3 hours to obtain a carboxylic acid resin having a nonvolatile content of 65%, a solid content of acid of 103 mgKOH/g, and a chlorine concentration of 20 ppm or less. This resin solution is referred to as B-3. Synthesis Example of Photosensitive Resin Containing Carboxyl Group To 600 parts of diethylene glycol monoethyl ether acetate, o-cresol novolac type epoxy resin (made by DIC Corporation, EPICLON N-695 'softening point 95 ° C, Epoxy equivalent 214, the average number of functional groups 7. 6) 1070 parts (epoxypropyl number (total number of aromatic rings): 5.00 moles), 360 parts of acrylic acid (5. 0 molar), and hydroquinone 1. 5 parts, heated and stirred at 1 ° C, and dissolved evenly. Next, adding triphenylphosphine 4. 3 parts, after heating at 1 10 °C for 2 hours, the temperature was raised to 120 ° C, and the reaction was further carried out for 12 hours. In the obtained reaction liquid, 415 parts of aromatic hydrocarbon (Solvessol 50) and tetrahydroanhydrobenzene were added. Formic acid 456. 0 copies (3. 0 mol), the reaction was carried out for 4 hours at 1 l ° C, and after cooling, a resin solution having a solid content of 65%, a solid content of 89 mg K〇H/g, and a chlorine concentration of 40 0 ppm was obtained. This resin solution is referred to as R-1. (C) Synthesis Example of Polyester Acrylate In a 500-neck round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, 192 parts of PET sheets were added (Mitsubishi Chemical Co., Ltd. -50-201241554: Novapex (trade name), after making the inside of the flask into a nitrogen atmosphere. Immersion in a salt bath heated to 30 (TC). The PET sheet was dissolved and stirring was started while adding dibutyltin oxide. 65 copies. Next, 134 parts of trimethylolpropane dissolved in advance at 130 ° C was added in small portions in such a manner that the PET was not cured. During this period, the agitation speed was increased to 15 O rpm during the viscosity reduction phase. Subsequently, the salt bath was exchanged for an oil bath which was previously heated to 240 ° C, and the internal temperature of the flask was maintained at 220 ° C ± 1 ° C for 5 hours. The reactants are yellow transparent at room temperature and soft and sticky. To the obtained reactant 1 〇 0 parts, 74 parts of toluene 37 parts of 'methyl isobutyl ketone was added and mixed. Next, 65 parts of acrylic acid, 1.94 parts of p-toluenesulfonic acid, and p-methoxyphenol 0. For 26 hours, the reaction was carried out at 110 ° C for 100 hours, and cooled to room temperature. The acid value of the obtained reaction liquid was measured, and an aqueous alkali solution of an acid amount was added to the flask, followed by stirring and neutralization. Next, 50 parts of saline was added and stirred. Thereafter, the solution was transferred to a separatory funnel, and the aqueous phase was discarded, and the oil phase was washed twice with 100 parts of a 5 wt% NaCl solution. After washing, the solvent was partially distilled off by an evaporator to obtain a nonvolatile matter of 100%. The obtained reactant was in the form of a soft, brownish transparent liquid at room temperature. This resin solution is referred to as C-1 〇 (D-1) epoxy resin Synthesis Example 1 A 500 mL four-neck round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube was added to a PET sheet ( Mitsubishi Chemical Co., Ltd.: -51 - 201241554

Novapex, IV値1.1) 192 parts, after the inside of the flask was made into a nitrogen atmosphere. Immerse in a salt bath heated to 300 °C. The PET was dissolved and stirring was started while adding dibutyltin oxide. 65 parts. Next, a small amount of 13 parts of trimethylolpropane dissolved in TC (TC) was added in a small amount so as not to solidify the PET. During this period, the stirring speed was increased to 150 rpm in the viscosity reduction stage. The salt bath was exchanged for an oil bath which was previously heated to 240 ° C, and the internal temperature of the flask was maintained at 220 ° C ± 10 t: after 5 hours of reaction, it was cooled to room temperature. 200 parts of the polymerized polymer thus obtained was added thereto. A 500 mL four-neck round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube was placed in a nitrogen atmosphere in the flask, and immersed in an oil bath heated to 145 ° C ± 5 ° C. The stirring was started at about 30. After a minute, 8 3 parts of tetrahydro-anhydrous phthalic acid was added and stirring was continued. Thus, a carboxylic acid resin having an acid value of 12 mg KOH/g was obtained. Then, 40 parts of the carboxylic acid resin was added to a mixer, a nitrogen introduction tube, and cooling. In a 500 mL four-neck round bottom separable flask, 60 parts of YD-825GS (manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent I85 g/eq., chlorine concentration: 160 ppm) was further added to prepare a nitrogen atmosphere in the flask. Let the oil bath rise slowly. After the contents are dissolved, the oil bath is heated. The reaction was continued to 1 to 10 ° C ± 5 ° C to obtain an epoxidized resin having an epoxy equivalent of 421 g/eq. and a chlorine concentration of 93 ppm. This was called epoxy resin D-1. (D-2) ring Oxygen Resin Synthesis Example 2 In a 500-neck round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, a PET sheet (manufactured by Mitsubishi Chemical Corporation: Novapex, IV値1.1) was added in 192 portions. After the inside of the flask was made into a nitrogen atmosphere, -52- 201241554 was immersed in a salt bath heated to 300 ° C. The PET was dissolved and stirring was started. At the same time, 1.6 parts of dibutyltin oxide was added. Then, it was dissolved at 130 ° C in advance. 104 parts of neopentyl glycol was added in small portions in such a manner that the PET was not cured. During this period, the stirring speed was increased to 150 rpm in the viscosity reduction stage. Then, the salt bath was exchanged for an oil bath which was previously heated to 240 ° C. The reaction temperature was maintained at 220 ° C ± 10 ° C for 5 hours, and then cooled to room temperature. The 18 parts of the polymer obtained in this manner was added to a mixer, a nitrogen introduction tube, and a cooling tube. In a 500 mL four-neck round bottom separable flask, after the flask was placed in a nitrogen atmosphere, helium-hydroxyl was added. 11 parts of benzoic acid and 0.5 part of dibutyltin oxide, the inside of the flask is made into a nitrogen atmosphere. It takes about 4 to 6 hours to slowly heat the hot water bath to 20 CTC to remove the condensed water, and the acid value is lowered when the acid value is sufficiently lowered. In the oil bath, the contents of the flask were taken out to obtain a phenol resin. Then, 45.1 parts of the phenol resin was added to a 500 mL four-neck round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube, and YD- was further added. 66.3 parts of 825GS (manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent: 185 g/eq·, chlorine concentration: 160 ppm), and the inside of the flask was made into a nitrogen atmosphere. The oil bath was gradually warmed up, and after the contents were dissolved, the oil bath was heated to 110 ° C ± 5 ° C to continue the reaction to obtain an epoxidized resin having an epoxy equivalent of 447 g/eq. and a chlorine concentration of 95 ppm. This is called epoxy resin D-2. Examples 1 to 14 and Comparative Examples 1 to 2 Using the resins of the respective Synthesis Examples, the various components shown in Table 1 below were combined with the ratios (mass parts) shown in Table 1, and the mixture was premixed with a mixer. The kneading was carried out to prepare a photosensitive resin composition for a solder resist. -53-201241554 [Table 1] Composition Example Comparative Example (parts by mass) 2 3 4 5 6 7 8 9 10 11 12 13 14 1 2 B-1 77 77 77 30 (B> Carboxylic Acid Resin B-2 77 B -3 77 77 77 77 77 Photosensitive resin containing carboxyl group R-1 77 154 154 77 77 77 154 154 123 154 154 77 154 154 (C) Polyester acrylate C-1 80 80 20 (A) Poly (A Qin C*1 30 30 30 30 30 30 30 30 30 30 enoate*2 30 30 30 30 30 30 Photopolymerization initiator ♦3 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 *4 10 D -1 30 25 30 25 (D) Epoxy Resin D-2 30 25 25 30 *5 25 25 25 25 25 25 25 25 25 25 Hardening Catalyst *6 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Colorant*7 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 *8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 barium sulfate *9 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Anthrone defoamer*10 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Solvent*11 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Remarks Dipentaerythritol hexaacrylate: UA-4200 manufactured by Nippon Kayaku Co., Ltd.: urethane acrylate acrylate IRGACURE 907 manufactured by Shin-Nakamura Chemical Co., Ltd.: IRGACURE 389 manufactured by BASF Japan: RE manufactured by BASF Japan -306 : melamine CIPigment Blue 15 : 3 CIPigment Yellow 147 Barium Sulfate (B-30 Chemicals) *1〇: KS-66 : Shin-Etsuketone (Shares)*11 : Dipropylene glycol monomethyl acid _ -54 - 201241554 Performance evaluation: <from polyester compound content rate> The content of the compound derived from the above general formula (1) in the compositions of the foregoing examples and comparative examples (in the organic component) is shown in Table 2. <Optimum exposure amount> After the circuit pattern substrate having a copper thickness of 35 μm was subjected to buFF ROLL honing, and then washed with water and dried, the photosensitive resin composition of the above examples and comparative examples was completely coated by screen printing. The cloth was dried in a hot air circulating drying oven at 80 ° C for 60 minutes. After drying, using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), the film was exposed by a step plate (Kodak No. 2) and developed (30 ° C, 0.2 MPa, 1 wt% Na 2 C 3 aqueous solution) for 60 seconds. The optimum exposure amount is obtained when the remaining step plate pattern is 7 segments. <Developability> The photosensitive resin composition of the above-mentioned Examples and Comparative Examples was applied to a copper-clad substrate by a screen printing method so that the film thickness after drying was about 25 μm, and was applied at 80 ° C. The hot air circulating drying oven was dried for 30 minutes. After drying, development was carried out with a 1 wt% Na2CO3 aqueous solution, and the time until the dried coating film was removed was measured by a horse watch. <Touch Drying> Each of the photosensitive resin compositions of the above-described Examples and Comparative Examples was subjected to full-screen coating on a patterned copper foil substrate by screen printing, and hot air at 80 - 55 - 201241554 ° C The circulating drying oven was dried for 30 minutes and cooled to room temperature. The PET film was pressed against the substrate, and thereafter, the film attachment state at the time of peeling negative film (negative fi 1 m) was evaluated. The judgment criteria are as follows. ◎: When the film was peeled off, there was no resistance at all, and no trace was left on the coating film. 〇 〇: When the film was peeled off, there was no resistance at all, but the coating film left a little trace. △: When the film was peeled off, there was only a slight resistance, and the coating film left a little trace β X: When the film was peeled off, there was resistance and the coating film clearly left marks. <Resolving property> The circuit pattern substrate having a line/space of 3 0 0/3 0 0 μηι and a copper thickness of 3 5 μη was honed by BUFF ROLL, washed with water, and dried by the screen printing method. The photosensitive resin composition of the comparative example and the drying method were dried in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, exposure was carried out using an exposure apparatus equipped with a high-pressure mercury lamp. The exposure pattern uses a spacer to draw a negative film of 20/30/40/50/60/70/80/90/1 00μιη. The exposure amount is an active energy ray that illuminates the optimum exposure amount of the photosensitive resin composition. After the exposure, an aqueous solution of 1 wt% Na2CO3 at 30 ° C was developed by spraying at a pressure of 2 MPa for 60 seconds, and heat curing at 150 ° C for 60 minutes was carried out to obtain a cured coating film. Using the obtained solder resist, the minimum residual line of the cured coating film of the photosensitive resin composition was adjusted to an optical microscope of 200 times to obtain the resolution. -56-201241554 < Halogen-containing amount> The resin solution obtained in each of the above Synthesis Examples was mixed with the various components shown in Table 1 in the ratio (parts by mass) shown in Table 1, and premixed with a stirrer. The three rolls were kneaded to prepare a photosensitive resin composition. The content of the halogen ion impurity (the total of the chlorine and the bromine) is quantified by using the JAPCA-compliant bottle combustion treatment ion chromatography in the obtained photosensitive resin composition. When the halogen ion concentration is 20 ppm or less (quantitative limit), it is indicated as "-". The results are shown in Table 2. Characteristic test: The compositions of the above respective Examples and Comparative Examples were subjected to full-coating on a patterned copper foil substrate by screen printing, and dried at 80 ° C for 30 minutes to be cooled to room temperature. On the substrate, an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp) was used to expose the solder resist pattern at an optimum exposure amount, and an aqueous solution of 1 wt% Na2C03 at 30 ° C was developed under the conditions of a spray pressure of 2 MPa for 60 seconds. Resistive pattern. The substrate was irradiated with ultraviolet light under the conditions of a cumulative exposure amount of 1 000 mJ/cm 2 in a UV conveyor belt furnace, and then heat-cured at 150 ° C for 60 minutes. The following characteristics were evaluated on the obtained printed substrate (evaluation substrate). <Welding heat resistance> The evaluation substrate coated with the rosin-based flux was immersed in a solder bath set at 2 60 ° C in advance, and the flux was washed with a modified alcohol to visually evaluate the expansion of the resist layer. Stripped. The judgment criteria are as follows. -57- 201241554 ◎: No peeling occurred even after immersion for 1 〇 second for 6 times or more. 〇: No peeling occurred even if it was immersed for 1 〇 for 3 times or more. △: immersed for 10 seconds and repeated three times or more with a slight peeling. χ : After immersion for 10 seconds, the resist layer was expanded and peeled off within 3 times. <Alkali resistance> The evaluation substrate was immersed in a 10 wt% aqueous NaOH solution at room temperature for 30 minutes, and the dissolution of the infiltration or the coating film was evaluated, and the peeling was further confirmed by a peeling test. The judgment criteria are as follows. 〇: No penetration, dissolution, or peeling. △: A little infiltration, dissolution, or peeling was confirmed. X: A large amount of infiltration, dissolution, or peeling was confirmed. <Peelability> The evaluation substrate was immersed in a 10 wt% aqueous NaOH solution at 60 ° C to evaluate whether or not the solder resist layer was peeled off from the substrate. The evaluation criteria are as follows. ◎: It can be peeled off by immersion for 15 minutes. 〇: It can be peeled off by dipping for 30 minutes. △ : After immersion for 60 minutes, a small amount of residue was confirmed. X : Cannot be peeled off. <Electrochromic resistance> The evaluation electrode substrate was produced under the above conditions using a comb-shaped electrode pattern having a line/space of 50/50 μm instead of the copper foil substrate, and the comb-shaped electrode was at 1 2 1 ° C, -58-201241554 97 A bias voltage of DC 30 V was applied under heating and humidification conditions of %RH, and the degree of discoloration of the coating film around the electrode after 100 hours was evaluated. The judgment criteria are as follows. 〇: No discoloration of the film. △: Only a small amount of discoloration of the coating film was confirmed. X : There is discoloration of the coating film. <Dry film production> Each of the photosensitive resin compositions for the solder resists of Example 1 and Comparative Example 1 was appropriately diluted with methyl ethyl ketone, and then coated with a coater to have a film thickness of 30 μm after drying. The PET film (FB-50: 16 μm) manufactured by Toray was dried at 40 to 100 ° C to obtain a dry film. <Production of Substrate> After the substrate on which the circuit was formed was subjected to polishing wheel honing, the dry film produced by the above method was vacuum laminator (MVLP-5® manufactured by Nihon Seiki Co., Ltd.) with a pressurization degree: 0.8 MPa. Heat lamination was carried out under conditions of 70 ° C, 1 minute, and a degree of vacuum of 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer. The obtained substrate was subjected to the following tests for the optimum exposure amount, developability, resolution, solder heat resistance, alkali resistance, peelability, and electrode discoloration resistance in the same manner as in the above evaluation method. The evaluation results are shown in Table 2. -59- 201241554 I Table 21 Characteristic Examples Comparative Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 2 Solder resist form (D: dry film, L·: 雠) L 0 LLLLLLLLLLLLLL 0 L from polyester Compound content rate (%> 21.9 26.0 22.8 43.9 32.9 32.9 54.8 21.9 26.0 22.8 8.6 8.1 11.0 21.9 0 0 0.0 Final exposure (m J/cm 2 ) 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 developability (seconds) 15 15 25 25 15 15 25 15 25 25 25 20 25 30 15 25 25 20 Touch dryness 〇一〇〇0 〇〇〇〇〇〇〇〇〇〇0 One resolution (μηι) 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 Halogen content (ppm) 581 495 174 493 98 98 10 581 495 m 636 615 186 581 66 9 669 Solder heat resistance ◎ ◎ ◎ ◎ ◎ @ ◎ ◎ ◎ ◎ ◎ ◎ @ @ ◎ ◎ ◎ ◎ 耐 耐 耐 ◎ ◎ ◎ ◎ ◎ ◎ ◎ © © ◎ ◎ 〇厶Λ ◎ XXX electrode discoloration resistance △ △ Δ 〇 △ 〇〇 〇 △ Δ 〇 Δ Δ 〇 Δ Δ Δ Δ From the results shown in Table 2 above, it is understood that the use of the present invention does not contain polyester compounds (carboxylic acid resins, poly(meth)acrylates, and epoxy resins). In Comparative Examples 1 and 2 of the photocurable resin composition, the solder resist layer could not be peeled off from the substrate by immersion treatment with a 10 wt% NaOH aqueous solution impregnated at 60 ° C. In contrast, the inventive examples 1 to 14 of the present invention The photocurable resin composition has both general alkali resistance and peeling property in an aqueous alkali solution, and when used as a solder resist, it can be used only by a printed wiring board which is usually discarded due to a defect in the solder resist forming step. The solder resist hardening film is peeled off and washed to reuse the substrate. -60-

Claims (1)

201241554 VII. Patent application scope: 1. A photocurable resin composition characterized by containing (A) a poly(meth)acrylate (however, a compound having a structure represented by the following general formula (1)) (B) a carboxylic acid resin, (C) a poly(meth) acrylate derived from a compound having a structure represented by the following general formula (1), and a derivatized poly(meth) acrylate) (D) Either one or more of epoxy resins, [Chemical 1] Wherein R 1 is a (m+1)-valent polyol derivative, R 2 is a CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , a substituted or unsubstituted aromatic ring, and r 3 is a substituted or unsubstituted aromatic ring. m and η are 1 or more, an integer less than 1 ,, and 1 is 0 or an integer of 1 or more). 2. The photocurable resin composition according to claim 1, wherein the organic compound in the composition contains the carboxylic acid resin (B) and the poly(methyl) propylene succinate in a ratio of 2% by weight or more. Any one or two or more of C) and epoxy resin (D). A photocurable resin composition containing (B) a carboxyl group derived from a compound having a structure represented by the following formula (1) in an amount of 20% by weight or more or more with respect to the organic matter in the composition. Any one or two or more of an acid resin, (C) poly(meth)acrylate, and (D) epoxy resin, -61 - 201241554 [Chem. 2] (wherein R1 is (m+l) valence polyol derivative, r2焉(:3& 'C4HS, substituted or unsubstituted aromatic ring 2 or unsubstituted aromatic ring, 1!1 and η are (1) The integer '1 is 〇 or an integer of 1 or more.) 4. A photocurable dry film which is obtained by thinning g of the photocurable resin composition according to any one of the above. The cured product is obtained by applying the photocurable resin composition of the above-mentioned item 1 or the photocurable resin film obtained by drying and drying the photocurable resin film to the photocurable dry I shape. The sheet is characterized in that the photocurable resin composition described in any one of the above, or the light-hardened 4 obtained by coating and drying the composition of the former station on the film is formed into a shape and then thermally cured. Hardened film. CH2, C2H4, any, R3 is taken as t, less than 10, and the request item 1~3 is coated and dried in any one of the following: The resin composition is hardened in the enamel film as a graphic item 1 ~3 in: Photocurable resin, dry film hard -62- 201241554 Four designated representative map: (1) The representative picture is: None (2) The symbol of the symbol of this representative figure is simple: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None