TW201124800A - Alkali-developable photocurable resin composition, dried film and cured product of the composition, and printed wiring board comprising the dried film or the cured product - Google Patents

Abstract

To provide an alkali-developable photocurable resin composition excellent in developability (particularly in a through-hole part), having high sensitivity and excellent in soldering heat resistance, electroless gold plating resistance, electric insulation and the like, a dry film and cured product of the composition, and a printed wiring board on which a cured coating such as a solder resist is formed with the dry film or cured product. The photocurable resin composition includes: a carboxylic acid resin derived from a compound represented by general formula (1); a compound having a plurality of ethylenically unsaturated groups in one molecule; and a photopolymerization initiator. The carboxylic acid resin is obtained by depolymerizing (a) a polyester with (b) a polyol having a plurality of hydroxyl groups in one molecule, and reacting the resulting product with (c) a saturated or unsaturated polybasic acid or an anhydride thereof. The photocurable resin composition preferably contains a thermocurable component.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition which can be imaged by an aqueous alkali solution, and more particularly to a solder resist for photocuring by ultraviolet exposure or laser exposure. A composition, a dry film and a cured product thereof, and a printed circuit board having a cured film formed using the same. [Prior Art] A solder resist is formed on the surface layer of a substrate on which a circuit is formed in order to protect a circuit of a printed circuit board. The substrate formed by this circuit generally has not only a circuit in the surface layer but also a myriad of holes called through holes. For the manufacture of printed circuit boards, photoresists have been generally used, and dry film type photoresists or liquid photoresists have been developed. In this case, the alkali-developing type photosensitive resin composition using an aqueous alkali solution as a developing liquid is the mainstream, and several components have been proposed in the past (see Patent Documents 1 to 3, etc.). When the solder resist is applied or laminated on the circuit board having the through holes, the solder resist of the via portion flows into the via holes, which is more difficult to develop than other places, and the photoresist removal has a problem. This will lengthen the development time, or investigate the shape of the cone of the spray to remove it, but the increase of the development time will not only reduce the productivity, but also form a thin line pattern of the necessary photoresist, which will also cause excessive imaging liquid attack. The necessary fine shape produces an undercut, which eventually creates a problem that cannot be formed. In recent years, due to the thinness and thinness of electronic components, printed circuit boards have been developed into high-density, multi-layered, and through-hole diameters. The above problem -5 - 201124800 has become serious. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. H-288091 (Patent Document 3) The present invention has been made in view of the above-described prior art, and an object of the present invention is to provide excellent developability (particularly, a through hole portion), high sensitivity, and heat resistance to soldering. An alkali-developable photocurable resin composition which is excellent in properties such as electroless gold plating resistance and electrical insulating properties, and which takes environmental considerations into consideration. Further, an object of the present invention is to provide a dry film and a cured product which are excellent in the above properties obtained by using such a photocurable resin composition, and a hardened film which forms a solder resist or the like by the dry film or cured product. a printed circuit board. [Means for Solving the Problem] In order to achieve the above object, according to the present invention, it is possible to provide a photocurable resin composition having an alkali developability, which is characterized by comprising a compound having a structure represented by the following general formula (1) The carboxylic acid resin to be derived, a compound having a plurality of B-unsaturated unsaturated groups in 1 to 6 to 201124,800, and a photopolymerization initiator.

OH

(wherein R1 represents a (m + l)-valent polyol derivative, and 1 and 11 are 1 or more, and an integer of less than 10 '1 is 0 or 1 or more is an integer less than 10, and R2 is CH2. Any of C2H4, C3H6, C4H8, a substituted or unsubstituted aromatic ring (particularly a benzene ring or a naphthalene ring), and R3 means a substituted or unsubstituted aromatic ring (particularly a benzene ring or a naphthalene ring). In a preferred embodiment, the carboxylic acid resin is obtained by depolymerizing (a) a polyhydric alcohol having a plurality of hydroxyl groups in the (b) 1 molecule, or after (s) a saturated or unsaturated polybasic acid or The result of its anhydride reaction. In this case, it is preferred that the polyol (b) having a plurality of groups in the above-mentioned one molecule is at least diamethylene methacrylate or/and polycarbonate diol. More preferably, the photocurable resin composition further contains a thermosetting component, more preferably a mercapto group-containing resin (but does not include a carboxyl group-containing resin derived from a compound having a structure represented by the above general formula (1)), More preferably, it contains a coloring agent. Such a photocurable resin composition, particularly a photocurable * thermosetting resin composition containing a thermosetting component, is suitably used as a solder resist. Further, according to the present invention, it is possible to provide a photocurable dry film obtained by applying the photocurable resin composition onto a film and dried, and hardening the photocurable resin composition or the dry film. A cured product obtained by photohardening on copper or photohardened into a pattern of 201124800. Further, according to the present invention, there is provided a printed circuit board which is characterized in that the photocurable resin composition or the dry film is photohardened into a pattern and then thermally cured. [Effect of the Invention] The photocurable resin composition of the present invention contains a carboxylic acid resin derived from a compound having a structure represented by the above general formula (1), and particularly contains a polyester having a plurality of hydroxyl groups in one molecule. The polyol obtained by the above-mentioned general formula (1) obtained by depolymerization of a polyol, and a carboxylic acid resin obtained by reacting with a saturated or unsaturated polybasic acid or an anhydride thereof as a development aid can form alkali developability. In particular, it is excellent in the development of through holes, and is excellent in solder heat resistance, electroless gold plating resistance, moisture resistance, electrical insulation, and the like. Therefore, the photocurable resin composition of the present invention is suitable for forming a hard coat film such as a solder resist of a printed circuit board or a flexible printed circuit board. [Embodiment of the Invention] The photocurable resin composition of the present invention is characterized in that a carboxylic acid resin containing a compound having a structure represented by the above general formula (1) as a developing aid is used. In the case of the present inventors, the carboxylic acid resin derived from the compound having the structure represented by the above general formula (1) is obtained, and the obtained photocurable resin composition is excellent in developability of the dried coating film. When the carboxylic acid resin was not contained in the above-mentioned -8-201124800, it was found that the through-holes were excellent in developability, and the soldering resistance was excellent in electroless gold plating resistance, moisture resistance, electrical insulation, and the like. The carboxylic acid resin is a carboxyl group-containing tree obtained by depolymerizing (a) a polyester having (b) a plurality of hydroxy groups of a hydroxyl group, or a reaction of a saturated or unsaturated polybasic acid or an anhydride thereof. Excellent imaging. In particular, by changing the balance between the component (a) and the (b) molar, it becomes an oligomer having both a carboxyl group and a hydroxyl group. Since the oligomer of the hydroxyl group and the carboxyl group is used, the development property can be improved more than when the conventional carboxyl group is used. Further, the oligomer obtained by using the trifunctional polyol in the component (b) may have a multi-branched structure, which is also an important reason for improvement. In addition, when a typical carboxylic acid resin olefin-acrylic acid copolymer (trade name: manufactured by JONCRYL 68, J Polymer Co., Ltd.) or trimellitic acid of a low molecular weight carboxylic acid is used, the development of the via hole is improved, but instead The apparent imageability of the surface is increased, and the image is dull. The performance of the solder resist at this time is poor in electrical characteristics. This is unexpected. The polyester (a) for the synthesis of the compound having the structure of the above formula (!) as the raw material of the carboxylic acid resin may be a conventional polyester, for example, polyethylene terephthalate or polyphenylene terephthalate. Ester, polybutylene terephthalate, polyethylene terephthalate, polybutylene diester, 4, dihydroxy bisphenol and liquid crystal polyester of terephthalic acid and p-hydroxybenzene polycondensate. For example, there are those in which the residue of the p ET bottle, the film, and other PET products is pulverized, the recycled polyester which has been collected and washed, and the like, which have been washed and formed into granulated heat. c) The fat, because of the composition of the benzophenone hns ο η with the above-mentioned imaging property of the acid resin, can not be obtained after the appearance is not)), the well-known PET for the p-naphthoic acid for PET thin waste return can be -9- 201124800 Market acquisition. The polyol (b) having a plurality of hydroxyl groups in one molecule can be used without any particular limitation. The bifunctional polyols are, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butanediol, neopentyl glycol. , spiro (ethylene) glycol (SPG), dioxanediol (Dog), adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, hexane Alcohol, 1,4-cyclohexanedimethanol, 2-methylpropanediol, 1,3,3-methylpentanediol, 1,5-hexanediol, octanediol, 9-nonanediol, 2, 4-Diethyl-1,5-pentanediol, an ethylene oxide-modified compound of a difunctional phenol such as bisphenol A, a propylene oxide-modified compound such as a bisphenol A difunctional phenol, such as bisphenol Ethylene oxide of bisphenol of A, propylene oxide copolymerization modified compound, copolymerized polyether polyol of ethylene oxide and propylene oxide, polycarbonate diol, adamantane diol, polyether a diol, a polyester diol, a hydroxyl terminated polyalkylene diol, (for example, 1,4-polyisoprene diol, 1,4- and 1,2-polybutadiene diol, and the like) The elastomer of the hydrogen additive). Commercially available products such as the above-mentioned hydroxyl-terminated polyalkylene diene glycol are Epol (manufactured by Idemitsu Petrochemical Co., Ltd., argonized polyisoprene diol, molecular weight 1,860, average degree of coincidence 26), PIP ( Idemitsu Petrochemical Co., Ltd., polyisoprene diol, molecular weight 2,200, average degree of overlap 34), polyether HA (manufactured by Mitsubishi Chemical Corporation, hydrogenated polybutadiene diol, molecular weight 2,200, average degree of coincidence 39), 11 -45111' (manufactured by Idemitsu Petrochemical Co., Ltd., polybutadiene diol, molecular weight 2,270, average degree of overlap 42). The trifunctional or higher polyhydric alcohol is, for example, glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, sorbitol, pentane-10-201124800 tetraterpene, ~dimethylolpropane, two Pentaerythritol, tripentaerythritol, diamond glycol, etc., and such ethylene oxide or propylene oxide modified compounds. Further, the polyhydric alcohol having an aromatic ring is, for example, a epoxide compound or a propylene oxide-modified compound having a phenol compound having three or more functional groups, and a compound having a heterocyclic ring, for example, Theic, manufactured by Shikoku Chemical Industries Co., Ltd. These polyols can be used singly or in combination of two or more. In the case of the above, the trifunctional polyol represented by the trihydroxydecylpropane can be obtained as a non-turbid substance when forming a depolymerized polymer, and is preferable in terms of solubility in a solvent. Therefore, it is preferable that the above-mentioned polyol has trimethylpropane and/or a derivative thereof as an essential component, and particularly preferably, the polyol contains 50 mol% or more of trimethylolpropane and/or Or its derivatives. Further, in order to promote the aforementioned depolymerization, a depolymerization catalyst can be used. The depolymerization catalyst is, for example, monobutyltin hydroxide, dibutyltin oxide, monobutyltin-2-ethylhexanoate, dibutyltin dilaurate, stannous oxide, tin acetate, zinc acetate, manganese acetate, cobalt acetate. Calcium acetate, lead acetate, antimony trioxide, tetrabutyl titanate, tetraisopropyl titanate, and the like. The amount of the polymerization catalyst to be used is usually from 0.005 to 5 parts by mass, particularly preferably from 0.05 to 3 parts by mass, based on 100 parts by mass of the total of the polyester (a) and the polyol (b). Inside. As the saturated or unsaturated polybasic acid or the acid anhydride (c) for synthesizing the above carboxylic acid resin, a conventionally known polybasic acid or an anhydride thereof can be used. Specific examples include aromatic polycarboxylic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrabromophthalic anhydride, hymic acid anhydride, and tetrachlorophthalic anhydride, and An alicyclic carboxylic acid such as an acid anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride-11 - 201124800, 1,4-cyclohexanedicarboxylic acid or 1,3-cyclohexanedicarboxylic acid An aliphatic polycarboxylic acid such as an acid anhydride, maleic anhydride, fumaric acid, succinic anhydride, adipic acid, sebacic acid or sebacic acid, and an anhydride thereof, pyromellitic anhydride, trimellitic anhydride, methylcyclohexene dicarboxylic anhydride A trifunctional or higher carboxylic acid or the like. The ratio of the aforementioned polyester (a) to the polyol (b) at the time of depolymerization is the molar number (A1) of the repeating unit with respect to the polyester, and the molar ratio (81) of the polyol is (eight 1). / (81) = 0.3 to 5, preferably in the range of 0.5 to 4.5. When the above ratio is less than 0.3, the polyol is excessively contained, the proportion of the aromatic ring derived from the polyester is decreased, and the dryness of the touch, the heat resistance to soldering, or the electrical properties are deteriorated when the solder resist is formed. On the other hand, when the above ratio is more than 5, it is almost a crystallized product derived from polyester, and these are insoluble in a solvent, which is not preferable. Further, the reaction ratio (input ratio) of the above-mentioned saturated or unsaturated polybasic acid or its anhydride (c) with respect to the produced polyol is 0.1 mol per part of the produced polyol, preferably (c) ~3 mole range. The acid value of the carboxylic acid resin is preferably in the range of 10 to 200 mgKOH/g, more preferably 20 to 120 mgKOH/g. When the acid value of the carboxylic acid resin is less than 10 mg KOH/g, the effect of improving the developability is not obtained. Further, when it is higher than 200 mgKOH/g, not only the through holes but also the surface are imaged, so that the appearance is not good, and the electricity is not good. Insulation also deteriorates. The carboxylic acid resin has a weight average molecular weight of from 600 to 50,000, preferably from 700 to 20,000. When the weight average molecular weight is less than 600, the dryness (non-stick property) of the coating film may be poor, the moisture resistance of the coating film after exposure may be poor, and the film may be reduced during development, and the resolution may be greatly lowered. Weight -12- 201124800 When the average molecular weight exceeds 5,000, the developing properties are sometimes significantly deteriorated, and the storage stability is poor. The amount of the carboxylic acid resin to be added is 5 to 80% by mass, preferably 5 to 60% by mass based on the solid content of the composition, and is sensitive to the carboxyl group-containing resin and/or the carboxyl group-containing resin when used in combination with a carboxyl group-containing resin described below. 100 parts by mass of the resin (the total amount thereof when two or more kinds are used, the same applies hereinafter) is 5 to 200 parts by mass, preferably 10 to 100 parts by mass. When the amount of the carboxylic acid resin is more than the above range, not only the through holes but also the surface are developed, so that the appearance is poor and the electrical insulating properties are also deteriorated. The compound having a plurality of ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with an active energy ray, so that the carboxyl group-containing resin described later is insolubilized in an alkaline aqueous solution, or contributes to insolubilization. By. Such a compound is, for example, a diacrylate of a glycol of ethylene glycol, methoxybutylene glycol, polyethylene glycol, propylene glycol or the like; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, trishydroxyl a polyol such as a polyisocyanurate or a polyacrylate such as an ethylene oxide adduct or a propylene oxide adduct; phenoxy acrylate, bisphenol A diacrylate, and the like a polyacrylate of a phenolic ethylene oxide adduct or a propylene oxide adduct; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl a polyacrylate of a glycidyl ether such as isocyanurate; and a melamine acrylate; and/or a methacrylate corresponding to the above acrylate. Further, for example, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as a cresol novolac type epoxy resin with acrylic acid, or a hydroxyl group of an epoxy propylene-13-201124800 acid ester resin and pentaerythritol triacrylate or the like An epoxy urethane acrylate compound obtained by reacting a hydroxy acrylate with an ethyl melamine compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin does not deteriorate the dryness of the touch and improves the photocurability. The compounding amount of the compound having a plurality of ethylenically unsaturated groups in the molecule is from 1 to 70% by mass, preferably from 5 to 60% by mass, based on the solid content of the composition, as compared with the case where the carboxyl group-containing resin described later is used. The ratio of the carboxyl group-containing resin and/or the carboxyl group-containing photosensitive resin is from 5 to 100 parts by mass, more preferably from 5 to 70 parts by mass, per 100 parts by mass. When the compounding amount of the above compound is less than the above range, photocurability is lowered, and alkali formation after irradiation with an active energy ray causes difficulty in pattern formation, which is not preferable. When it exceeds the above range, the solubility in the aqueous alkali solution is lowered, and the coating film becomes brittle, which is not preferable. The photopolymerization initiator is preferably an α-aminobenzene having an oxime ester photopolymerization initiator selected from the group represented by the following general formula (II) and having the following formula (III) One or more kinds of photopolymerization initiators in the group consisting of an ethyl ketone photopolymerization initiator or a sulfhydryl phosphine-based photopolymerization initiator having a group represented by the following formula (IV). —Ci=N—Ο—C—R5

-14- 201124800

(wherein R is a hydrogen atom, a phenyl group (which may also be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a tooth atom), and an alkyl group having 1 to 2 carbon atoms (may also be passed through 1) The above hydroxyl group may be substituted, and one or more oxygen atoms may be present in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzhydryl group (may also be An alkyl group having a carbon number of 1 to 6 or a phenyl group), and R5 is an alkyl group having a phenyl group (which may also be substituted by an alkyl group having a carbon number id, a phenyl group or a halogen atom) or a carbon number of 1 to 20 ( It may be substituted by one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or benzamidine. a group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), and R6 and R7 each independently represent an alkyl group or an aralkyl group having 1 to 12 carbon atoms, and R8 and R9 each independently represent hydrogen, An alkyl group having 1 to 6 carbon atoms or two cyclic alkyl ether groups bonded thereto, and R1() and R11 are a linear or branched alkyl group, a cyclohexyl group, and a ring each independently representing a carbon number of 1 to 10. A pentyl group, an aryl group, or a halogen atom, an alkyl group or an alkoxy group The substituted aryl group, but one of R1() and R11 may also represent an R-C(=〇)- group (wherein R is a hydrocarbon group having 1 to 2 carbon atoms). The above-mentioned oxime ester photopolymerization initiator having a group represented by the general formula (Π) is preferably 2-(ethyl oxyiminomethyl) thioxanthone-9 represented by the following formula (V). a ketone, a compound represented by the following general formula (VI), and a compound represented by the following general formula (VII). -15- 201124800 onnc s N:

CH ο cyo

Η3 C \)/

R

(VI R12 (wherein R12 represents a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 12~12, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamidine group, and a carbon number of 2 to 12) a mercapto group or an alkoxycarbonyl group having 2 to 12 carbon atoms (when the number of carbon atoms of the alkyl group constituting the alkoxy group is 2 or more, the 'alkyl group may be substituted with one or more hydroxyl groups, and the middle of the alkyl chain may be Having more than one oxygen atom) or phenoxycarbonyl group, R13 and R14 each independently represent a phenyl group (may also be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and have a carbon number of 1 to 20 The alkyl group (which may be substituted by one or more merid groups, and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, and an alkane having 2 to 20 carbon atoms. Or benzylidene group (may also be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group), R stomach represents a hydrogen atom, a phenyl group (may also be an alkyl group having 1 to 6 carbon atoms, benzene ^ M (substituted by f), an alkyl group having 1 to 20 carbon atoms (may also have one or more oxygen atoms in the middle of the β 'alkyl chain through one or more hydroxyl groups. 16 - 201124800 ), carbon number 5 ~8 cycloalkyl, carbon number 2-20 alkane Group or a benzoyl group (that may also be substituted by alkyl or phenyl of 1~6 carbon atoms)). R19 R18

(R22)q (wherein R16, R17 and R22 each independently represent an alkyl group having 1 to 12 carbon atoms, and R18' R19, R2Q and R21 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; It means 0, S or NH, and p and q each represent an integer of 〇~5, respectively. Among the above-mentioned oxime ester-based photopolymerization initiators, 2-(ethyloxyiminomethyl)thioxanthone-9-one represented by the above general formula (V) and the formula (VI) are more preferred. Compound. Commercially available products are CGI- 3 2 5 manufactured by Cib a Japan Co., Ltd., Irgacure Ο X E 0 1 , Irg a cu r e Ο X E 0 2, A D E K A Company, N -1 9 1 9 and the like. These oxime ester photopolymerization initiators may be used alone or in combination of two or more. The α-aminoacetophenone-based photopolymerization initiator having the general formula (ΙΠ) represents, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-indolyl-acetone- 1, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2·(dimethylamino)-2-[(4-methylbenzene Methyl]-1-[4-(4- morpholinyl)phenyl]-1 -butanone, hydrazine, hydrazine-dimethylaminoacetophenone and the like. Commercial products such as lrgacure 907, Irgacure 3 69, ε: -17- 201124800, manufactured by Ciba Japan Co., Ltd.

Irgacure 3 79 and so on. The above-mentioned mercaptophosphine oxide-based photopolymerization initiator having a group represented by the general formula (IV), for example, 2,4,6-trimethylbenzimidium diphenylphosphine oxide, bis(2,4,6- Trimethyl benzamidine)-phenylphosphine oxide, bis(;2,6-dimethoxybenzhydrazide)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lucirin TPO manufactured by BASF Corporation and Irgacure 819 manufactured by Ciba Japan. The amount of the photopolymerization initiator to be added is 0.01 to 20% by mass in the solid content of the composition, preferably 〇.5 to 1% by mass, and is relative to the carboxyl group-containing resin when used in the case of the carboxyl group-containing resin described later. And/or the carboxyl group-containing photosensitive resin 1 part by mass ' is 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass. When the amount of the photopolymerization initiator is less than the above range, the photocurability on copper is insufficient. The film properties such as peeling of the coating film or chemical resistance are lowered, which is not preferable. In addition, when the content is more than the above range, the light absorption of the surface of the solder resist film of the photopolymerization initiator tends to be fast, and the deep hardenability tends to be lowered, which is not preferable. The amount of the oxime ester-based photopolymerization initiator having a group represented by the formula (II) is preferably 0.01 to 20 parts by mass, more preferably 〇.〇1 to 5, based on 100 parts by mass of the carboxyl group-containing resin to be described later. The range of parts by mass. Other photopolymerization initiators, photoinitiating aids, and sensitizers which are suitable for the photocurable resin composition of the present invention, for example, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, Examples of ketal compounds, benzoin compounds, benzoin methyl ether, benzoin ethyl ether . -18 - 201124800 Specific examples of acetophenone compounds are acetophenone, 2,2-dimethoxy. Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1 Specific examples of the -dichlorophenylhydrazine compound are 2-methylhydrazine, 2-ethylhydrazine tert-butylphosphonium, and 1-chlorohydrazine. Specific examples of the thioxanthone compound are 2,4-dimethylthioxanthone, 2:ethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone. Specific examples of the ketal compound are acetophenone dimethyl ketal and benzyl ketal. Specific examples of the benzophenone compound are benzophenone, 4-benzylidene sulfide, 4-benzoyl-4'-methyldiphenyl sulfide, and 4-phenylene ethylbenzene disulfide. , 4-benzylidene-4'-propyldiphenyl sulfide. Specific examples of the tertiary amine compound are an ethanolamine compound, a compound having a diaminobenzene structure, such as 4,4'-dimethylaminobenzophenone, Nissocure MABP, manufactured by Soda Co., Ltd., 4,4'-diethyl Dialkylaminodiphenyl 7-(diethylamino)-4-methyl-2H-1-benzopyran-2·one, such as arylaminodione (EAB, manufactured by Hodogaya Chemical Co., Ltd.) a 4-alkylamino group-containing coumarin-containing 4-dimethylaminobenzoic acid ethyl ester (Kay a cure manufactured by Nippon Kayaku Co., Ltd.), such as 7-(diyl)-4-methylcoumarin Ethyl 2-dimethylaminobenzoate (Quantacure DMB, manufactured by International Synthetics Co., Ltd.), 4-dimethylamino acid (n-butoxy)acetic acid (International Bio-Synthetics, Quantacure BEA), p-dimethyl Kayacure DMBI), 4-aminomethyl benzene 2-acetophenone, 2-2-4-didimethyldiphenyl 4,-alkyl (anthracene benzene) Methyl ketone, ethylamine, EPA Bio-benzoic acid ester (formic acid-19- 201124800 2-ethylhexyl ester (Esolol 507 manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (保土谷化学公The above compound is preferably a thioxanthone compound and a tertiary amine compound. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep hardenability, and preferably 2 thereof. Thiophenone compounds such as 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. The amount of the ketone compound to be added is preferably 5% by mass or less, preferably 5% by mass or less based on the solid content of the composition, and is sensitive to the carboxyl group-containing resin and/or carboxyl group-containing resin when used in a carboxyl group-containing resin to be described later. The resin is used in an amount of 1 part by mass, preferably 20 parts by mass or less, more preferably 10 parts by mass or less. When the amount of the thioxanthone compound is too large, the thick film hardenability is lowered, resulting in an increase in the cost of the product, which is not preferable. " The tertiary amine compound is preferably a compound having a dialkylaminobenzene structure, wherein a dialkylamine benzophenone compound and a dialkylamine having a maximum absorption wavelength of 550 to 4 1 Onm are particularly preferred. a coumarin compound. The dialkylaminobenzophenone compound is 4,4'-di Amino benzophenone is preferably low in toxicity, and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 41 Onm has a maximum absorption wavelength in an ultraviolet region, so that coloration is small, and of course, colorless and transparent The photosensitive composition uses a coloring pigment to provide a colored solder resist film reflecting the color of the coloring pigment itself, particularly 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one It is preferable that the laser light having a wavelength of 4 00 to 41 Onm exhibits an excellent sensitizing effect. The compounding amount of the tertiary amine compound is 0.1 to 20 parts by mass, more preferably oi to ι by mass, relative to the solid content of the composition, in the range of -20 to 201124800, and relative to the carboxyl group-containing resin when used in combination with the resin. And/or 100 parts by mass of the carboxyl group, preferably 0.1 to 20 parts by mass, more preferably 0.1 to ratio. When the amount of the tertiary amine compound is less than the above range, the effect of sufficiently sensitizing the effect is obtained. When it exceeds the above range, the light absorption on the surface of the dry solder resist coating film is fast, and the deep portion tends to be hard. These photopolymerization initiators, photoinitiating aids, and sensitizers are used in combination of two or more. The photopolymerization initiator, the photoinitiator, and the sensitization are preferably in the range of less than 100 parts by weight based on 100 parts by mass of the carboxyl group-containing resin to be described later. When the amount is more than 35 parts by mass, the light hardenability tends to decrease. In the photocurable resin composition of the present invention, conventional N-phenylglycines, phenoxyacetic acids, acids, mercaptothiazoles and the like are used as the chain-linking agent. The chain has a fluorenylethanol, mercaptopropanol, mercaptobutanol, anthracene having a carboxyl group, such as mercapto succinic acid, mercaptoacetic acid, mercaptopropionic acid, azide acid, o-mercaptobenzoic acid, and derivatives thereof. a chain butyl thiol having a hydroxyl group, a butyl-3-mercaptopropionate, a methyl-3-mercapto group 1 (extended ethyldioxide), a propylene group, a hydroxybenzenethiol, a derivative thereof, or the like Alkyl mercaptan 'ethane thiol, 4, 11 yard thiol, propyl thiol, butyl thiol, pentane thiol, cyclopentane thiol, cyclohexane thiol, sulphide 2 When the carboxyl group-containing photosensitive resin is contained in an amount of 1 part by mass, the compounding property of the amine may not be lowered. The total amount of the agent alone may be 35 mass absorption and deep sensitivity, and a specific example of the sulfur phenoxy group B may be used. a cysteine chain shifting agent; a mercaptobutyryl mobile agent; a 1-valate ester, a 2,2-methylbenzenethiol mercaptan, a 1-octanol, a 4,4_sulfur-21 - 201124800 Phenyl mercaptan and the like. Further, as the heterocyclic compound having a mercapto group as a chain-linking agent, for example, mercapto-4-butyrolactone (alias: 2-indolyl-4-butyrolactone), 2-indolyl-4-methyl- 4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butylsulfona lactone, 2-mercapto-4-butylnamidamide 'N-A Oxy-2-mercapto-4-butylidene, N-ethoxy-2-mercapto-4-butylidene, N-methyl-2-indolyl-4-butaneamine, N -ethyl-2-mercapto-4-butylidene, N-(2-methoxy)ethyl-2-mercapto-4-butylidene, N-(2-ethoxy)B Base-2-mercapto-4-butylidene, 2-mercapto-5-valerolactone, 2-mercapto-5-pentalinamide, N-methyl-2-mercapto-5-pentyl Indoleamine, N-ethyl-2-mercapto-5-pentalinamide, N-(2-methoxy)ethyl-2-indolyl-5-pentalinamide, N-(2- Ethoxy)ethyl-2-mercapto-5-pentalinamide and 2-mercapto-6-caprolactam and the like. In particular, a heterocyclic compound having a mercapto group which does not affect the development of the photocurable resin composition, preferably mercaptobenzothiazole, 3-mercapto-4-methyl-4H- 1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole. These chain-linking agents may be used singly or in combination of two or more. In the photocurable resin composition of the present invention, a thermosetting component may be added in order to impart heat resistance. The thermosetting component used in the present invention may be an amine resin such as melamine resin or benzoguanamine, a blocked isocyanate compound, a cyclic carbonate compound, a polyfunctional epoxy compound, a polyfunctional oxirane compound or the like. A known thermosetting resin such as an ether resin or a melamine derivative. Particularly preferred is a thermosetting -22-201124800 component having a plurality of cyclic ether groups and/or cyclic thioether groups (hereinafter referred to as cyclic (thio)ether groups) in the molecule. The thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is any one of a cyclic ether group ' or a cyclic thioether group having a 3' 4 or a 5-membered ring in the molecule' or having a compound having two or more kinds of two groups, for example, a compound having a plurality of epoxy groups in a molecule, that is, a polyfunctional epoxide, a compound having a plurality of oxycyclobutane groups in the molecule, that is, a polyfunctional oxetane An alkane compound, a compound having a plurality of thioether groups in a molecule, that is, a surface sulfide resin. Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Nippon Epoxy Co., Ltd., Epiclon 840 manufactured by DIC Corporation, Epiclon 850, Epiclon 1 0 50, Epiclon 2 05 5, and Dongdu Chemical Co., Ltd. Epotot YD-011, YD-013, YD-127, YD-128, DER 317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Ltd., araldite 6071, araldite 6084, araldite GY250, araldite from Ciba Japan GY260, Sumi-epoxy ESA-011, ESA-014, ELA-115 'ELA-128, manufactured by Sumitomo Chemical Industries Co., Ltd., AER330, AER331, AER661, AER6 64, etc. by Asahi Kasei Kogyo Co., Ltd. Bisphenol A type epoxy resin; jERYL 903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152, Epiclon 165 manufactured by DIC Corporation, Epotot YDB-400 manufactured by Dongdu Chemical Co., Ltd., YDB-500, DER manufactured by Dow Chemical Co., Ltd. 542, araldite 801 of Ciba Japan, Sumi-epoxy ESB-400 manufactured by Sumitomo Chemical Industries Co., Ltd., ESB-700, VIII.11.711, VIII.11.714, etc. Name) brominated epoxy-23- 201124800 resin; jER 152, jER154 manufactured by Japan Epoxy Co., Ltd., DEN431, DEN43 manufactured by Dow Chemical Co., Ltd., Epiclon N-73 0 manufactured by DIC Corporation, Epiclon N- 770, Epiclon-8, Epotot YDCN-701, YDCN-704, manufactured by Dongdu Chemical Co., Ltd., araldite ECN 1 235 from Ciba Japan, araldite ECN 1 273, araldite ECN 1 299, araldite XPY3 07, manufactured by Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1 025 'EOCN-1020, EOCN-104S, RE-306, Sumi-Epoxy ESCN-195X manufactured by Sumitomo Chemical Industries, Ltd., ESCN-220, AER ECN-23 manufactured by Asahi Kasei Kogyo Co., Ltd. 5, ECN - phenolic epoxy resin of -299 (all are trade names); Epiclon 83 0 by DIC Corporation, jER807 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd. Ciba Japan's araldite XPY3 06 (all are trade names) bisphenol F-type epoxy resin; Dongdu Chemical Co., Ltd. Epotot ST-2004, ST-2007, ST-3000 (all trade names) hydrogenation double Phenolic A type epoxy resin; jER604 made by Japan Epoxy Resin Co., Ltd. Epotot YH-434 manufactured by Dongdu Chemical Co., Ltd., araldite MY720 from Ciba Japan, Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (both trade names), epoxy propylamine epoxy resin; araldite from Ciba Japan CY-3 50 (trade name), etc., uranyl-type epoxy resin epoxy resin; CELLOXID 2021 manufactured by Daicel Chemical Industry Co., Ltd., araldite CY175, CY 179, etc. of Ciba Japan Co., Ltd. (all are trade names) Alicyclic epoxy resin; YL-93 manufactured by Japan Epoxy Resin Co., Ltd., TEN, EPPN-501, EPPN-502, etc. (all are trade names) manufactured by Dow Chemical Co., Ltd., trihydroxyphenyl group 24-201124800 Epoxy resin: dimethyl hydroxy phthalate or bisphenol epoxy resin such as YL-6056, γ χ _ 4000, YL -6121 (both trade names) manufactured by Nippon Epoxy Co., Ltd. or a mixture thereof; EBS S-2 00 manufactured by PharmaTech, bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by EPX-30' DIC, manufactured by Asahi Kasei Co., Ltd.; jER 157S manufactured by Japan Epoxy Resin Co., Ltd. Bisphenol A phenolic epoxy resin; Japanese epoxy resin JERYL-931, manufactured by Ciba. Specialty Chemicals, araldite 163, etc. (all are trade names), tetraphenol ethane type epoxy resin; araldite PT810 from Ciba Japans, TEP 1C manufactured by Nissan Chemical Industries Co., Ltd., etc. Heterocyclic epoxy resin (all of which are trade names); diglycidyl acrylate resin such as Blenmer DGT manufactured by Sakamoto Oil Co., Ltd.: tetramethyl propyl acrylate of ZX-1063 manufactured by Dongdu Chemical Co., Ltd. Methyl phenol ethane resin; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-403 manufactured by DIC Corporation, EXA-475 0, EXA-4700 and other epoxy resin containing naphthyl group; Epoxy resin having a dicyclopentadiene skeleton such as HP-7200 or HP-7200H; a glycidyl methacrylate copolymerized ring of CP-5〇S, CP-5〇M, etc. manufactured by Nippon Oil & Fats Co., Ltd. Oxygen resin; copolymerized epoxy resin of cyclohexylmaleimine and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivative (for example, D ai ce), manufactured by Chemical Industry Co., Ltd. B _ 3 6 0 0, etc., CTBN modified epoxy resin (for example, YR-102, YR-45 0, etc. manufactured by Dongdu Chemical Co., Ltd.) But these are not subject to restrictions. These epoxy resins may be used singly or in combination of two or more kinds. Among these, a smectic epoxy resin, a heterocyclic epoxy resin, a bisphenol A epoxy resin or a mixture thereof is particularly preferred. • 25- 201124800 The above polyfunctional oxetane compounds are, for example, bis[(3-methyl-3_oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxo) Heterocyclic butane methoxy)methyl]ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[( 3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxo) Heterocyclic butane) methacrylate, (3-methyl-3-hydroxybutanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl Polyfunctional oxetane such as acrylate or such oligomer or copolymer, and oxetane with novolak resin, poly(P-hydroxystyrene), cardo type bisphenol An etherified compound of a resin having a base such as a calixarene, a cup benzidine aromatic hydrocarbon or a sesquisulfate. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate. The compound having a plurality of cyclic (thio)ether groups in the molecule may be, for example, a bisphenol A-type thioether resin YL7000 manufactured by Nippon Epoxy Co., Ltd., or the same synthesis method, and the phenol type may be used. An episulfide resin in which an oxygen atom of an epoxy group of an epoxy resin is substituted with a sulfur atom. The amount of the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is preferably from 1 to 2.5 equivalents per 1 equivalent of the carboxyl group of the carboxyl group-containing resin described later. More preferably, it ranges from 8 to 2.0 equivalents. When the amount of the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is less than 6 equivalents, the carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, and the like are lowered. It is not good. In addition, when it is more than 2.5 equivalents, since a low molecular weight cyclic (thio)ether group remains in the dry coating film of -26-201124800, the strength of the coating film is lowered, which is not preferable. In the photocurable resin composition of the present invention, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule as a thermosetting component can be added. The compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in a molecule, that is, a polyisocyanate compound, or a blocky isocyanate having a plurality of molecules in one molecule. A compound such as a blocked isocyanate compound or the like. As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate are 4,4'-diphenylmethyl diisocyanate, 2,4-toluene diisocyanate 2,6-toluene diisocyanate, naphthalene-i,5-di Isocyanate, oxime-xylene diisocyanate, m-xylene diisocyanate, and 2,4-toluene dimer. Specific examples of the aliphatic polyisocyanate are tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis(cyclohexyl isocyanate). And isophorone diisocyanate. A specific example of the alicyclic polyisocyanate is dicycloheptane triisocyanate. Further, for example, an adduct of an isocyanate compound exemplified above, a biuret, and a trimer isocyanate. The blocked isocyanate group contained in the blocked isocyanate compound is a group which is temporarily inactivated by reaction of an isocyanate group with a block agent. When heated to a predetermined temperature, the block agent dissociates to form an isocyanate group. The block isocyanate compound is an addition reaction product of an isocyanate compound and an isocyanate block agent. Isocyanate which can be reacted with a block agent -27- 201124800, for example, a trimeric isocyanate type, a biuret type, an addition molding, or the like. The isocyanate compound is, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate are the compounds exemplified above. The isocyanate block agent is, for example, a phenolic blocker such as phenol, cresol, xylenol, chlorophenol or ethylphenol; ε-caprolactam, δ-valeroinamide, γ-butylide and hydrazine - an internal amide-based blocker such as propionamide; an active methylene blocker such as ethyl acetoacetate or acetonitrile; methanol, ethanol, propanol, butanol, pentanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, An alcohol-based block agent such as methyl lactate or ethyl lactate; a quinone blocker such as formaldehyde hydrazine, acetaldehyde oxime, acetamidine, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine or cyclohexane hydrazine; a thiol blocker such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophene, methyl thiophene or ethyl thiophene; acid amide amine such as decylamine or benzoguanamine a sulphate blocker such as succinimide succinimide or succinimide maleate; an amine blocker such as xylidine, aniline, butylamine or dibutylamine; imidazole, 2- Imidazole Blocking agent; methylene imine and propylene imine, etc. extending alkylene amine-based block or the like. The blocked isocyanate compound may be commercially available, for example, Sumijur BL3175, BL-4165, BL-1100, BL-1 265, Desmojur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmosamu 2170, desmosamu 2265 (The above is Sumitomo Bayer urethane company -28-201124800, trade name), Coronato 2512, Coronato 2513, Coronato 2520 (made by Japan Polyurethane Industrial Co., Ltd.), Mitsui Takeda Chemical Co., Ltd. B-83 0 'B-815, B- 846, B-870, B-874, B-882, TCA-B80E, 17B-60PX, E402-B80T (both trade names) manufactured by Asahi Kasei Chemicals. Further, 311111^1^81^-3 1 7 5 and B L - 4 2 6 5 are obtained by using methyl ethyl hydrazine as a block agent. The above-mentioned compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be used alone or in combination of two or more. The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is preferably from 1 to 100 parts by mass, more preferably from 2 to 10,000 parts by mass based on 1 part by mass of the carboxyl group-containing resin. The ratio of 70 parts by mass. When the amount of the above-mentioned compounding is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. Further, when it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable. Other thermosetting components include, for example, melamine derivatives, benzoguanamine derivatives, and the like. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, and a methylol urea compound. In addition, 'alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound are made by making each hydroxyl 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 examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group and the like. In particular, a melamine derivative having a formaldehyde water concentration of preferably 0.2% or less is preferred for human body or environment -29-201124800. Such commercial products include, for example, Cymel 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 Same as 1158, same as 1123, same as 1170, same as 1174, same as UFR65, same as 300 (above is Mitsui Cyan amide (share) system), Nikalac Mx-7 50, same as Mx-03 2, same as Mx-270, same Mx -280, the same Mx-290, the same Mx-706, the same Mx-708, the same Mx-40, the same Mx-31, the same Ms-11, the same Mw-30, the same Mw-30HM, the same Mw-3 90, the same Mw-100LM, same as Mw-750LM (above (three) and Chemical). These thermosetting components may be used alone or in combination of two or more. When the above-mentioned thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is used, it is preferred to contain a thermosetting catalyst. Such thermosetting catalysts are, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethylidene Imidazole derivatives such as phenyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide; benzyldimethylamine, 4-( Amines such as dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine a hydrazine compound such as a compound, adipic acid diamine or sebacic acid diamine; a phosphorus compound such as triphenylphosphine or the like. In addition, commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all are imidazole-based compounds) manufactured by Shikoku Chemical Industrial Co., Ltd., and U-CAT (registered trademark) manufactured by San-apro Co., Ltd. ) 3503N, U-CAT3502T (all trade names of block isocyanate compounds of dimethylamine), DBU, DBN, UC AT SA1 02, U-CAT 50 02 (all are bicyclic guanidine compounds and their salts), etc. - 30- 201124800. It is not particularly limited thereto, and the thermosetting catalyst of the epoxy resin or the oxetane compound or the epoxy group and/or the oxetane group may be reacted with the carboxyl group, and may be used alone or in combination of two or more. Mixed use. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-ethylene can be used. Benzyl-2,4-diamino-S-trisyl, 2-ethylidene- 4,6-diamino-S-triazine•trimeric isocyanate adduct, 2,4-diamine An S-triazine derivative such as a -6-methacryloxyethyloxy-S-triazine/trimeric isocyanate addition product, preferably used as an adhesion imparting agent Functional compound and the above thermosetting catalyst. The blending amount of the thermosetting catalyst may be a ratio of a general amount, for example, 100 parts by mass or more, preferably 0.1 to the carboxyl group-containing resin or a thermosetting component having a plurality of cyclic (thio)ether groups in the molecule. 20 parts by mass, more preferably 0.5 to 15 parts by mass. As the carboxyl group-containing resin, conventionally known various residue-containing resins having a carboxyl group in the molecule can be used. In particular, from the viewpoint of photocurability or development resistance, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable. The unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof. Specific examples of the carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule or a carboxyl group-containing photosensitive resin having no ethylenically unsaturated double bond in the molecule can be used as the oligomer (or oligomer or Any of the polymers). (1) By including an unsaturated carboxylic acid such as (meth)acrylic acid with styrene, α-methylstyrene, a lower-grade (meth)acrylic acid vinegar, and an isobutylene-31 - 201124800 The carboxyl group-containing resin obtained by copolymerization of an unsaturated group compound. (2) A diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a carboxyl group such as dimethylolpropionic acid or dimethylolbutanoic acid a diol compound, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based epoxide adduct diol, and a phenol A carboxyl group-containing urethane resin obtained by a polymerization addition reaction of a diol compound such as a hydroxyl group or an alcoholic hydroxyl group. (3) A diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a polycarbonate polyol, a polyether polyol, or a polyester system Amine obtained by a polymerization addition reaction of a diol compound such as a polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based epoxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group a terminal carboxyl group-containing urethane resin ruthenium (4) obtained by reacting a terminal of an ethyl urethane resin with an acid anhydride, by using a diisocyanate, a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, (Meth) acrylate of a bifunctional epoxy resin such as a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol type epoxy resin, or a bisphenol type epoxy resin, or a partial acid anhydride thereof A carboxyl group-containing photosensitive urethane resin obtained by a polymerization addition reaction of a property, a carboxyl group-containing diol compound, and a diol compound. (5) In the synthesis of the resin of the above (2) or (4), a molecule having a hydroxy-32-201124800 alkyl (meth) acrylate or the like is added to have a hydroxyl group and one or more (meth) groups. A compound of acryl group (A cry 1 ), a carboxyl group-containing photosensitive urethane resin thiolated with a terminal (meth) propylene. (6) In the synthesis of the resin of the above (2) or (4), a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added, and one isocyanate group and one or more molecules are contained in the molecule ( A methyl group-containing acryl-based compound 'a carboxyl group-containing photosensitive urethane resin thiolated with a terminal (meth) propylene group. (7) reacting a bifunctional or bifunctional or higher polyfunctional (solid) epoxy resin with (meth)propionic acid such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrobenzene A two-membered acid anhydride such as formic anhydride is added to a carboxyl group-containing photosensitive resin which is formed by a hydroxyl group of a side chain. (8) A polyfunctional epoxy resin obtained by epoxidizing a bifunctional (solid) epoxy resin as described below is reacted with (meth)acrylic acid, and a hydroxyl anhydride is added to the resulting hydroxyl group. A carboxyl group-containing photosensitive resin. (9) A cyclic ether such as ethylene oxide, a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as phenolic, and the obtained hydroxyl group is partially esterified with (meth)acrylic acid, and the remaining hydroxyl group A carboxyl group-containing photosensitive resin that reacts with a polybasic acid anhydride. (10) A molecule such as glycidyl (meth) acrylate or α-methyl glycidyl (meth) acrylate has one epoxy group and one or more (meth) acrylonitrile groups. The carboxyl group-containing photosensitive resin formed by the addition of the compound to the above (1) to (9) is not limited to the ones described above, and may be used alone or in combination of plural kinds. In the present specification, (meth) acrylate means a term of a general term for acrylate, methacrylate and the like, and the other similar descriptions are also the same. Since the carboxyl group-containing resin has a large number of carboxyl groups on the side chain of the backbone/polymer, it can be developed by a dilute aqueous alkali solution. Further, the above-mentioned carboxyl group-containing resin is preferably in the range of 40 to 200 mgKOH/g, preferably 45 to 120 mgKOH/g. When the acid enthalpy of the carboxyl group-containing resin exceeds 200 mg KOH/g, the exposed portion is dissolved by the developing solution, and the line is made thinner than necessary, and the exposed portion and the unexposed portion are both dissolved and peeled off by the developing solution. Depicting a normal photoresist pattern is not good. Further, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, and is generally in the range of 2,000 to 1,500, preferably 5,000 to 1 Torr. When the weight average molecular weight is less than 2,000, the dryness of the touch is sometimes poor, and the moisture resistance of the coating film after the exposure is not good, and the film is reduced at the time of development, and the resolution is largely deteriorated. Further, when the weight average molecular weight exceeds 1,500,000, the development property is remarkably deteriorated, and the storage stability is not good. The compounding amount of the carboxyl group-containing resin is in the range of 20 to 60% by mass, preferably 30 to 50% by mass, based on the total composition. When the amount of the carboxyl group-containing resin is less than the above range, the film strength is lowered, which is not preferable. Further, when it is more than the above range, the viscosity of the composition becomes high, and the coatability and the like are lowered, which is not preferable. -34- 201124800 These carboxyl group-containing resins are not limited to those listed above, and may be used in combination of one kind or plural kinds. The photocurable resin composition of the present invention can be formulated with a coloring agent L. The coloring agent can be used in the conventional coloring of red, blue, green, yellow, etc. i, or any of pigments, dyes, and pigments. However, it is better to use halogens instead of reducing the environmental burden and the impact on the human body. Red coloring agent; red coloring agent is, for example, monoazo system, bis-1 nitrogen system, azo lake system, benzimidazolone system, lanthanide, diketopyrrolopyrene peak; system (Dike topyrrolopyi: r 〇1 e), condensed azo, lanthanide, quinophthalone, etc., specifically as follows, attached to the Colour Index (CI.; The S 〇ci ety of Dyers and Colourists) No. 〇 偶 azo : P igment Red 1,2,3 ,4,5 ,6, 8,9 > 12, 14, 15, 16 ,17 , 21 , 22 , 23 , 3 1,32, 112, 114 146 ,147,15 1, 170,184, 187, 188,193, 2 10, 245 2 5 3 : ,258 , 266 , 267 ,268 , 269 ° Diazo nitrogen system : Pi! jment Red 37,38 ,41 ° azo color System: 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 ° Benzimidazolone series : Pigment Red 171 , Pigment Red 175 , Pigment Red 176 , Pigmen t Red 185' P i g m e n t R e d 2 0 8. Philippine: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149 ' Pigment Red 166 ' Pigment -35- 201124800

Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194' Pigment Red 224 o Diketopyrrolopyrrole: Pigment Red 254, Pigment Red 25 5, Pigment Red 264, Pigment Red 270, Pigment Red 272 « Condensed Azo Line: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 ' Pigment Red 242. Awake system: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, S ο 1 vent R ed 2 0 7 o Quinone: Pigment Red 122, Pigment Red 202, Pigment Red 206 ' Pigment Red 207 ' P i gm en t R ed 2 0 9. Blue coloring agent: Blue coloring agent is a halogen-based, lanthanide-based, pigment-based compound classified as a pigment (Pigment), specifically, for example, 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' P i gm ent B lu e 6 0. For dyes, 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, an alizarin compound substituted with a metal or substituted with $36-201124800 can also be used. Green colorants: Green colorants are also available in alizarin, lanthanide, and lanthanide. For specific purposes, Pigment Green 7, Pigment Green 36, Solvent

Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. In addition to the above, a metal-substituted or unsubstituted anthraquinone compound can also be used. Yellow coloring agent: The yellow coloring agent may be a monoazo system, a disazo system, a condensed azo system, a benzimidazolone system, an isoindolinone system, an anthraquinone system or the like, and specifically, for example, the following. Onion system: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202 o Different D noise extraction system: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139 Pigment Yellow 179 ' Pigment Y e 11 ow 1 8 5 〇 Condensation azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155 ' Pigment Yellow 166, Pigment Yellow 180. Benzopyridinone P ketone series: pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154 ' Pigment Yellow 156 ' Pigment Y e 11 ow 1 7 5, P igment Y e 11 ow 1 8 1 〇 monoazo system: Pigment Yellow 1,2,3,4,5' 6' 9' -37- 201124800 10, 12 , 61 , 62 - 62 :1, 65 , 73 , 74 , 75 · 97 * 1 00 1 104, 105, 11 1 , 116, 167, 168, 169, 182, 183° Diazo: Pigment Yellow 12,13, 14 , 16 , 17, 5 5 , 63, 81 , 83, 87, 126, 127, 152, 170, 172, 174 176, 188, 198° Others For the purpose of adjusting the color tone, a coloring agent such as purple, orange, brown or black may be added. For example, Pigment Violet 1 9, 23, 29, 32, 36, 38, 4 2, Solvent Violet 13, 36, CIPigment Orange 1 , CIPigment Orange 5 ' C · I. Pi gment Orange 13 C . I. P i gm ent Orange 14 , CIPigment Orange 16 , C · I · P i gm ent Orange 17 , CIPigment Orange 24 , CIPigment Orange 34 , CIPigment Orange 36 , C · I · P i gm en t Orange 38 ' CI Pigment Orange 40, CIPigment Orange 43, CIPigment Orange 49, CIPigment Orange 5 1 , CIPigment Orange 61 , CIPigment Orange 63 , CIPigment Orange 64 , CIPigment Orange 7 1 , CIPigment Orange 73 > CIPigment Brown 23, CIPigment Brown 25, CIPigment Black 1, CIPigment Black7, etc. The proportion of the above-mentioned coloring agent is not particularly limited, and the solid content of the composition is 〇 to 5% by mass, preferably 0.01 to 3% by mass, and is used with respect to the carboxyl group-containing resin when used in the case of the carboxyl group-containing resin described later. And/or a carboxyl group-containing photosensitive-38-201124800 resin, 100 parts by mass, preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass. In order to improve the physical strength and the like of the coating film, the photocurable resin composition of the present invention may be formulated with an enamel agent as needed. The chelating agent may be at least one selected from the group consisting of conventional inorganic hydrazines or organic hydrazines, preferably inorganic hydrazines, particularly barium sulphate, spheroidal cerium oxide and talc. Further, a white photoresist can be formed by adding titanium oxide as a white chelating agent. Further, in order to impart flame retardancy, fine particles of a metal hydroxide may be added, and specific examples thereof include aluminum hydroxide, magnesium hydroxide or boehmite. These chelating agents may be used alone or in combination of two or more. The blending amount of the above-mentioned chelating agent is 1 to 70% by mass of the solid content of the composition, preferably 0.1 to 50% by mass, and when the carboxyl group-containing resin described later is used, it is relative to the carboxyl group-containing resin and/or The carboxyl group-containing photosensitive resin is preferably used in an amount of from 300 parts by mass or less, more preferably from 0.1 to 300 parts by mass, even more preferably from 0.1 to 150 parts by mass. When the blending amount of the lubricant exceeds the above range, the viscosity of the solder resist composition increases, and the printability is lowered, or the cured product becomes brittle, which is not preferable. The resin composition of the present invention can be used in order to improve the dryness of the touch, the like, and the like, and a binder polymer can be used. For example, a polyester-based polymer, a polyurethane-based polymer, a polyester urethane-based polymer, a polyamide-based polymer, or a polyester amide-based polymer can be used. A cellulose polymer, a polylactic acid polymer, or a phenoxy polymer #. These binder polymers may be used singly or in combination of two or more kinds. The solder resist composition of the present invention can be used in order to impart flexibility, to improve the brittleness of the hardened material -39 to 201124800, and the like. For example, a polyester-based elastomer, a polyurethane-based elastomer, a polyester urethane-based elastomer, a polyamide-based elastomer, a polyester amide-based elastomer, or an acryl-based elastomer can be used. Body, olefin elastomer. Further, a resin modified with a carboxylic acid-modified butadiene-acrylonitrile rubber having a part or all of an epoxy group having various skeletons may be used. Further, an epoxy group-containing polybutadiene-based elastomer, an acryl-containing fluorenyl-based polybutadiene-based elastomer, a hydroxyl group-containing polybutadiene-based elastomer, a hydroxyl group-containing isoprene-based elastomer, or the like can also be used. These elastomers may be used singly or in combination of two or more kinds. In the photocurable resin composition of the present invention, an organic solvent can be used in order to synthesize the carboxylic acid resin, the carboxyl group-containing resin or the carboxyl group-containing photosensitive resin or the preparation composition, or to adjust the viscosity applied to the substrate or the carrier film. Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. Specifically, for example, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellos 〇lve, methyl sirosu, and butyl Glycerose, carbitol, carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Esters of methyl ester, ethyl lactate, butyl lactate, ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol butyl ether acetate, etc. Alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent petroleum brain. These organic solvents may be used singly or in combination of two on -40 to 201124800. In general, the majority of the polymer materials are oxidatively degraded continuously when the oxidation starts, and the function of the polymer material is lowered. Therefore, in order to prevent oxidation, the resin composition of the present invention can be added to invalidate the radical generated by (1). The radical scavenger or/and the antioxidant which decomposes the peroxide produced in (2) into a harmless substance and avoids a new radical generating peroxide decomposing agent. An antioxidant which acts as a radical scavenger, and specific compounds such as hydroquinone, 4-t-butylcatechol, 2-t-butyl hydroquinone, hydroquinone monomethyl ether, 2, 6-di-t-butyl-P-cresol, 2,2-methylene-bis(4-methyl-6-t-butylphenol), 1, 1 ,3-paran (2-methyl 4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4-hydroxybenzyl) Benzo, 1,3,5-paraxion (3',5'-di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-( 1H,3H,5H ) Alkene compounds such as ketones such as triketone, oxime compounds such as m-benzoquinone and benzoquinone, and bis-(2,2,6,6-tetramethyl-4-piperidyl)sebacate or phenothiazine Wait. The radical scavenger may be a commercially available product such as ADEKA STAB AO-30, ADEKA STAB AO- 3 30, ADEKA STAB AO-20, ADEKA STAB LA-77, ADEKA STAB LA-57, ADEKA STAB LA-67, ADEKA STAB LA-68 ' ADEKA STAB LA-87 (above is manufactured by Asahi Kasei Co., Ltd.), IRGANOX 1010, IRGANOX 1035, IRGANOX 1 076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 2 92 , TINUVIN 5100 (above is Ciba Japan, trade name -41 - 201124800). An antioxidant which acts as a peroxide decomposing agent, and specific compounds are, for example, a phosphorus compound such as triphenylphosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate or distearyl sulfonate. A sulfur-based compound such as a 3,3,-thiodipropionate or the like. The peroxide-decomposing agent can be a commercially available product, for example, ADEKA STAB TPP (made by Asahi Kasei Co., Ltd., trade name), Mark AO-412S (made by AADEKA ARGUS CHEMICAL Co., Ltd., trade name), SU ΜILIZ ERTPS (made by Sumitomo Chemical Co., Ltd., product) Name) and so on. The above antioxidants may be used alone or in combination of two or more. In general, since the polymer material absorbs light and is decomposed and deteriorated, the resin composition of the present invention can be used for the stabilization of ultraviolet rays. In addition to the above-mentioned antioxidant, an ultraviolet absorber can be used. The ultraviolet absorber is, for example, a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, an amine anisate derivative, Benzomethane methane derivatives and the like. Specific examples of the benzophenone derivative include 2-hydroxy-4 methoxy-benzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-dihydroxy-4-. Methoxybenzophenone and 2,4-dihydroxybenzophenone. Specific examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, and 2,4-di-t-butylphenyl. -3,5-di-t-butyl-4-hydroxybenzoate and cetyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative are, for example, 2-( 2'-hydroxy-5,-t-butylphenyl)benzotriazole, 2-(2,-hydroxy-5'-methylphenyl)benzene. And triazole, 2-(-42- 201124800 2,-hydroxy-3,-t-butyl-5,-methylphenyl)-5-chlorinated benzotriazole, 2·( 2,-hydroxy- 3,5,-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5,-methylphenyl)benzotriazole and 2-(2 , -hydroxy-3',5'-di-t-pentylphenyl)benzotriazole, and the like. Specific examples of the triazine derivative include a phenyl phenyl triazine, a bisethylhexyl oxy methoxy methoxy triazine, and the like. The ultraviolet absorber may be a commercially available product such as TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 3 84-2 'TINUVIN 900 'TINUVIN 928, TINUVIN 1130, TINUVIN 400 ' TINUVIN 405 > TINUVIN 460, TINUVIN 479 (above) It is a company, product name, etc. of Ciba Japan. The above-mentioned ultraviolet absorbers can be used singly or in combination of two or more kinds, and the molded article obtained from the resin composition of the present invention can be stabilized by using the above-mentioned antioxidant. The photocurable resin composition of the present invention can be blended with conventionally known thermal polymerization inhibitors, fine powdered cerium oxide, organic bentonite, montmorillonite, hydrotalcite, and the like. An antifoaming agent and/or a flat agent such as an oxygen-based, fluorine-based or fluoro-system, a conventionally used additive such as a decane coupling agent such as an imidazole-based compound, a thiazole-based or a triterpenoid, or a rust preventive agent. The above thermal polymerization inhibitor can be used to prevent thermal polymerization or time-lapse polymerization of the aforementioned polymerizable compound. The thermal polymerization inhibitor is, for example, a 1-methoxy fluorene-based or a thiol-substituted hydrogen, a t-butyl catechin, a pyroic acid, a 2-carbyl-based ketone, a 4-methoxy-2 _ A ketone-methyl ketone 'copper chloride, phenothiazine, naphthylamine, β-naphthoquinone, 2,6-di-t-butyl-4-methylhydrazine, 2,2,·methylene Bis(4-methyl-6 small butyl phenol), pyridine, nitrobenzene, dinitrobenzene, 5 -43- 201124800 picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactants A methyl ester, a phenothiazine, a nitroso compound, a chelating agent of a nitroso compound and A1, and the like. The solder resist composition of the present invention is adjusted to a viscosity suitable for a coating method by, for example, the above-mentioned organic solvent, and is subjected to a dip coating method, a flow coating method, a roll coating method, a bar coating method, a screen printing method, A method such as a curtain coating method is applied to a substrate, and the organic solvent contained in the composition is volatilized and dried (pre-dried) at a temperature of about 60 to 100 ° C to form a non-stick property. Coating film. Further, the composition is applied onto a carrier film, dried, and attached to a substrate in the form of a film to form a resin insulating layer. Then, by contact (or non-contact), by forming a pattern of the mask, by selective exposure of the active energy line, or by direct exposure of the laser exposure machine, the unexposed portion is thinned An aqueous alkali solution (for example, 0.3 to 3% aqueous sodium carbonate solution) is developed to form a photoresist pattern. Further, when the thermosetting component is contained, for example, by heat-heating to a temperature of about 140 to 180 ° C, the carboxyl group of the carboxylic acid resin or the carboxyl group-containing resin and a plurality of cyclic ether groups in the molecule are The thermosetting component of the cyclic thioether group is reacted to form a cured coating film having various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. When the thermosetting component is not contained, it is subjected to thermal radical polymerization by heat treatment, and the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state during the exposure to improve the coating film properties, and heat treatment can be performed for the purpose and use. (thermal hardening). In addition to using a printed circuit board or a flexible printed circuit board in which a circuit is formed in advance, the above-mentioned substrate may be made of paper-phenol resin, paper-epoxy resin, glass-44-201124800 glass cloth-epoxy resin, glass-polyphthalene. All grades of composite materials such as imine, glass cloth/non-woven fabric-epoxy resin, glass cloth/paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, etc. (FR-4, etc.) ) Copper-clad laminates, polyimide films, PET films, glass substrates, ceramic substrates, wafer boards, and the like. The volatilization drying after applying the photocurable or thermosetting resin composition of the present invention can be performed by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a conveyor belt oven, or the like (using a method of heating air by steam) The heat source 'does the method of contacting the hot air in the dryer countercurrently or by blowing the nozzle on the support). The coating film obtained by applying the photocurable resin composition of the present invention to the present invention is exposed to light (after irradiation with an active energy ray). The coating film exposure portion (the portion irradiated by the active energy ray) is hardened. The exposure machine used for the above active energy ray irradiation can use an ultraviolet exposure machine equipped with a (super) pressure mercury lamp or a metal halide lamp or a direct drawing device (for example, directly depicting an image by laser using CAD data of a computer) Laser direct imaging device). The active energy ray may be any of a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gas laser, a solid laser, or a semiconductor laser as long as it uses light having a maximum wavelength of 3 5 0 to 4 1 Onm. Further, the exposure amount varies depending on the thickness of the film, and is generally 5 to 800 mJ/cm 2 ', preferably 1 〇 to 5 〇〇 mJ/cm 2 , more preferably 1 〇 to 3 〇〇 mJ/cm 2 . . The above development method may be, for example, a dipping method, a rinsing method, a spraying method, a brushing method of -45 to 201124800, etc., and a potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate or ammonia may be used as the developing solution. An aqueous alkali solution of an amine or the like. The photocurable resin composition of the present invention may be coated with a polyethylene terephthalate or the like in advance, in addition to a method of directly applying a liquid to a substrate. The film is used in the form of a dry film of a solder resist layer formed by drying. When the photocurable resin composition of the present invention is used as a dry film, it is as follows. The dry film has a structure in which a carrier film, a solder resist layer, and a peelable protective film which are used as necessary are laminated. The solder resist layer is a layer obtained by applying a solder resist composition to a carrier film or a protective film and drying the layer. After the solder resist layer is formed on the carrier film, a protective film is laminated thereon or a resist layer is formed on the protective film, and when the laminate is laminated to the carrier film, a dry film can be obtained. As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm can be used. In the solder resist layer, the photocurable resin composition is uniformly applied to the carrier film at a thickness of 10 to 150 μm using a knife coater, a lip coater, a twin roll coater, a film coater or the like. Or a protective film that is formed by drying. As the protective film, a polyethylene film, a polypropylene film or the like can be used, but it is preferable that the adhesion to the solder resist layer is smaller than that of the carrier film. When a protective film (permanent protective film) is formed on a printed circuit board using a dry film, after the protective film is peeled off, the solder resist layer and the substrate on which the circuit is formed are laminated, and laminated using a laminator or the like on the substrate on which the circuit is formed. Form a solder resist -46- 201124800 layer. When the solder resist layer after the formation is subjected to exposure, development, and heat curing in the same manner as described above, a cured coating film can be formed. The carrier film may be peeled off before or after exposure. EXAMPLES The present invention will be more specifically described by the following examples and comparative examples, but the present invention is not limited to the following examples, and the modifications of the present invention include the technology of the present invention without departing from the spirit of the invention. Within the scope. In the following, when there is no special statement, "parts" means "parts by mass" and "%" means "mass%". Synthesis Example 1 192 parts of a PET sheet (manufactured by Mitsubishi Chemical Corporation: Nov apex (trade name)) was placed in a 500-neck round bottom separable flask equipped with a stirrer, a nitrogen introduction tube, and a cooling tube. After forming a nitrogen atmosphere in the flask, it was immersed in a salt bath heated to 300 °C. When the PET was dissolved, stirring was started, and 0.65 parts of dibutyltin oxide was added. Next, 134 parts of dissolved trimethylolpropane was previously added to the temperature of 1 30 ° C in a state where the curing of the PET was avoided. At this time, in the stage where the viscosity is lowered, the stirring speed is increased to 150 rpm. Next, the salt bath was changed to an oil bath which was previously heated to 240 ° C, and the inner temperature of the flask was maintained at 220 ° C ± 1 (TC, after reacting for 5 hours, and then cooled to room temperature. Secondly, tetrahydrophthalic anhydride was added (hereinafter Referred to as ΤΗ PA ) 9 1 _ 2 parts, 22 parts of carbitol acetate, a nitrogen atmosphere is formed in the flask, and then immersed in an oil bath heated to -47-201124800 1 2 5 ± 5 °c. The stirring was started, and the reaction was carried out for 3 hours to obtain a residual acid resin varnish a having a nonvolatile content of 65% and a solid content of 83 mg KOH/g. Synthesis Example 2 A four-hole round of 500 mL equipped with a stirrer, a nitrogen introduction tube, and a cooling tube. In a bottom separable flask, 192 parts of a PET sheet (manufactured by Mitsubishi Chemical Corporation: Novapex (trade name)) was placed, and a nitrogen atmosphere was formed in the flask, followed by immersion in a salt bath heated to 300 ° C. When the PET was dissolved, Stirring was started, and 0.65 parts of dibutyltin oxide was added at the same time. Then, in the state where the PET was cured, a little 134 parts of the dissolved trimethylpropane was preheated to 130 ° C each time. At this time, the viscosity was lowered. In the stage, increase the stirring speed to 150 rpm. Secondly, change from salt bath to pre-liter In an oil bath of 24 ° C, the internal temperature of the flask was maintained at 22 (TC ± 10 ° C, after 5 hours of reaction, cooled to room temperature. Secondly, 121.6 parts of tetrahydrophthalic anhydride (THPA), carbitol B was added. 240 parts of the acid ester, a nitrogen atmosphere was formed in the flask, and then immersed in an oil bath heated to 125 ± 5 ° C. The stirring was started slowly, and the reaction was carried out for 3 hours to obtain a nonvolatile matter of 65%, and the solid content of the acid was obtained. 3 mg KOH/g of carboxylic acid resin varnish B. Examples 1 to 1 and Comparative Examples 1 to 4 Using the resin solutions of the above respective synthesis examples, the various components shown in Table 1 and the ratios shown in Table 1 (parts by mass) After the preliminary mixing was carried out using a stirrer, the photosensitive resin composition for the solder resist was prepared by kneading in a three-roller. Here, the dispersion of the obtained photosensitive resin composition was evaluated by measuring the particle size by a particle size analyzer manufactured by Erichsen Co., Ltd. 1 5μπι以下。 -48- 201124800 Table 1 Composition Examples Comparative Example (parts by mass) 1 2 3 4 5 6 7 8 9 10 1 2 3 4 Varnish A 1 100 100 50 50 50 50 50 50 Carb Resin Varnish B 100 50 *1 50 50 *2 10 light hardening Compound*3 60 60 60 30 30 30 30 30 30 30 30 30 30 30 *4 155 155 155 155 155 155 *5 155 155 Carboxyl group-containing resin*6 155 *7 155 *8 222 Photopolymerization initiator*9 2 2 2 2 2 2 2 2 2 2 2 2 2 2 *10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Thermosetting component *11 15 15 15 15 15 15 15 15 15 15 15 15 15 *12 10 i Catalyst*13 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Antioxidant*14 2 2 2 2 2 2 2 2 2 2 2 Chain-linking agent*15 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Shake imparting agent *16 5 5 5 5 5 5 5 5 5 5 5 Each coloring agent *17 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 Coloring agent *18 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*19 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 ii? Antimony defoamer*20 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Organic solvent DPM *21 3 3 3 3 3 3 3 3 3 3 3 3 3 3 *1 JONCRYL68 (manufactured by Johnson Polymer) *2 trimellitic acid *3 dipentaerythritol hexaacrylate ( DPHA: Nippon Chemical Co., Ltd.) *4 R-2000 manufactured by DIC Corporation (solid content: 65%); description corresponding to the above-mentioned carboxyl-containing resin (6) *5 ZFR-1401H manufactured by Nippon Kayaku Co., Ltd. (solid form) 65%); equivalent to the above-mentioned description of the carboxyl group-containing resin (7) *6 UXE-3000 (solid content: 65%) manufactured by Nippon Kayaku Co., Ltd.; equivalent to the description of the above-mentioned carboxyl group-containing resin (3) *7 DIC ( UE-9210 (solid content: 65%); an acid-modified alkoxy acrylate which reacts a carboxyl group of a resin of the above-mentioned carboxyl group-containing resin (6) with glycidyl methacrylate to increase a photoreactive group *8 Cyclomer P (ACA) Z250 (solid content: 45%) manufactured by DAICEL Chemical Industry Co., Ltd. (corresponding to the above-mentioned carboxy-containing resin) (1) *9 Irgacure OXE02 (manufactured by Ciba Japan) *10 NIKALAC MW-100LM ((3) phenolic epoxy resin (DEN438: manufactured by Dowchemical Co., Ltd.) *12 Block isocyanate (TPA-B80E; manufactured by Asahi Kasei Chemicals Co., Ltd.) *13 Melamine*14 IrganoxlOl 0 (Ciba Japan) Company-made) *15 2-Mercaptobenzothiazole (ACEL Μ: manufactured by Kawaguchi Chemical Industry Co., Ltd.) *16 DHT-4A (Concord Chemical Industry ( ))) 17 CIPigment Blue 15 '· 3 *18 CIPigment Yellow 147 *19 Barium Sulfate (B-30: 堺Chemical Co., Ltd.) *20 Dipropylene Glycol Monogram _ -49 - 201124800 <Best Exposure amount> The circuit pattern substrate with a copper thickness of 35 μm is subjected to 彳·7 polishing light (buff γ〇η), honed, washed with water, dried, and then fully coated with the foregoing examples and compared by screen printing. The photocurable thermosetting resin composition of the example was dried in a hot air circulating drying oven at 80 ° C for 60 minutes. After drying, exposure was carried out using a staged exposure meter (Kodak No. 2) using an exposure apparatus equipped with a partial pressure mercury lamp (short arc lamp), and developed in 60 seconds (30 ° C, 0.2 MPa, lwt% Na2C〇) In the case of 3 aqueous solutions, the remaining exposure amount of the staged exposure meter is 7 segments as the optimum exposure amount. <Developing property> The photocurable thermosetting resin composition of the above examples and comparative examples was applied onto a copper Bet a substrate by a screen printing method to have a film thickness after drying of about 25 μm. 8 (The hot air circulating drying oven of TC was dried for 30 minutes. After drying, the development was carried out by a 1 wt% Na2CO3 aqueous solution by a timer until the time when the dried coating film was removed. <Diacle imaging of the through hole>

A hole was punched in a Φ200 μm boring machine on a copper laminate of l.Ommt, and through-hole plating was performed by a predetermined method to form a substrate having 400 holes of a through hole of about Φ150 μm. The photocurable thermosetting resin composition of the above-described examples and comparative examples was printed on the substrate twice by screen printing, and the photohardenable thermosetting resin composition was subjected to a buried hole at 80°. The hot air circulating drying oven of C was dried for 30 minutes and cooled to room temperature. Then, a 1 wt% Na2C03 aqueous solution of 3 〇 ° C - 50 - 201124800 was developed under the conditions of a spray pressure of .2 MPa for 120 seconds, and evaluated according to the following criteria. ◎: 1 time to 2 times of development, 1 〇 〇 % through hole can be imaged. 〇: Perform 3 times to 5 times of development, and 1 0 0 °/〇 through hole can be imaged. △: 3 times to 5 times of development, and 5 0 to 9 % of through holes can be visualized. X: The through-hole can be imaged at 50% or less even if the development is performed 5 times. <Resolvability, and resolution when the through hole can be developed> The circuit pattern substrate having a line/pitch of 300/3 00 111 and a copper thickness of 35 卩 111 is subjected to polishing roller honing, and then washed with water. After drying, the photocurable thermosetting resin composition of the above examples and comparative examples was applied by a screen printing method, and dried in a hot air circulating drying oven at 8 ° C for 30 minutes. After drying, exposure was carried out using an exposure apparatus equipped with a high pressure mercury lamp. The exposure pattern is used for the negative (negative) line on the line of 20/30/40/50/60/70/80/90/100μιη. The exposure amount is a state in which the active energy ray is irradiated in a state in which the photosensitive resin composition is optimally exposed. After the exposure, a 1 wt% Na2CO3 aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 0.2 MPa for 60 seconds, and a hardened coating film was obtained by thermal curing at 150 ° C for 60 minutes. The minimum residual line of the hardened coating film of the obtained photosensitive resin composition for a solder resist was determined by an optical microscope adjusted to 200 times, which was taken as the resolution. Further, the photohardenable thermosetting resin composition of each of the examples and the comparative examples was subjected to the same test as described above at a time when the through holes were developable. Similarly, the minimum residual line -51 - 201124800 of the cured coating film of the photosensitive resin composition for the solder resist obtained was obtained by using an optical microscope adjusted to 200 times, which is a resolution at the time of development of the through hole. In addition, all the lines disappeared after being developed and recorded as -. <Surface state of coating film> The composition of each of the above Examples and Comparative Examples was completely applied onto a copper foil substrate on which a pattern was formed by screen printing, and dried at 80 ° C for 30 minutes. Cool to room temperature. An exposure device equipped with a high-pressure mercury lamp (short-arc lamp) was used for the substrate, and the solder resist pattern was exposed at an optimum exposure amount, and an aqueous solution of 1 wt% Na2C03 at 30 ° C was sprayed at a pressure of 2 kg/cm 2 for image development. After 60 seconds, the state of the surface of the coating film after the development was observed, and it was evaluated based on the criteria shown below. 〇: There is no change in surface gloss and film thickness. △: There was no change in the film thickness, but the surface was slightly developed and the surface was foggy. X: The film thickness is reduced by the development, and the surface gloss disappears. Characteristic test: The compositions of the respective Examples and Comparative Examples were applied by a screen printing method to a copper foil substrate on which a pattern was formed, dried at 80 ° C for 30 minutes, and allowed to cool to room temperature. For this substrate, an exposure device equipped with a high-pressure mercury lamp (short arc lamp) was used to expose the barrier pattern at an optimum exposure amount, and a 1 wt% Na2CO3 aqueous solution at 30 ° C was imaged under the conditions of a pressure of 0.2 MPa. In 60 seconds, a photoresist pattern is obtained. The substrate was irradiated with ultraviolet rays under the conditions of a cumulative exposure of 1 000 m J / c m2 using a UV transfer furnace, and then cured by heating at 60 ° C for 60 minutes - 52 - 201124800 hours. The obtained printed circuit board (evaluation substrate) was evaluated for characteristics as described below. <Welding heat resistance> The evaluation substrate on which the rosin-based auxiliary solvent was applied was immersed in a solder bath set at 260 ° C in advance, and the auxiliary solvent was washed with a modified alcohol, and then the expansion and peeling of the photoresist layer were visually evaluated. . The judgment criteria are as follows. ◎: No peeling was observed even if the immersion was repeated for 10 times or more for 10 seconds. 〇: No peeling was observed even if the immersion was repeated 10 times or more for 10 seconds. △: When immersed for 1 or more times of 3 times or more, it was slightly peeled off. X: When immersed for 1 sec. within 3 times, the resist layer is expanded and peeled off <electroless gold plating resistance> Commercially available electroless nickel plating bath and electroless gold plating bath, nickel 0·5μηι Plating was carried out under the conditions of gold 0.03 μηι, and the presence or absence of peeling of the photoresist layer or the presence or absence of plating of the photoresist layer was evaluated by tape peeling, and the peeling of the photoresist layer was evaluated by tape peeling. The judgment criteria are as follows 〇 ◎: No penetration or peeling. 〇: After the mineral deposit, 'slightly infiltrated' but the knee strip was not peeled off. △: After plating, only a slight infiltration occurred, and after the tape was peeled off, peeling occurred. X: Peeling after plating. -53- 201124800 <Alkaline resistance> The evaluation price plate was immersed in a 10 wt% aqueous solution of N a Ο 3 for 30 minutes at room temperature, and the solution was infiltrated or coated, and confirmed by tape peeling. Stripped. The criteria for determination are as follows. 〇: no penetration or dissolution, no peeling. △: Slightly infiltrated, dissolved or peeled off. X: Obviously infiltrated, dissolved or peeled off. <Dry film production> The photosensitive resin compositions for the solder resists of Example 4 and Comparative Example 1 were each appropriately diluted with methyl ethyl ketone, and then coated on a PET film using a coater (Toray FB-made by Toray Industries, Inc.) 50:16 pm), the film thickness after drying was changed to 30 μm, and dried at 40 to 100 ° C to obtain a dry film. <Substrate preparation> After the substrate on which the circuit was formed was polished and honed, the dry film produced by the above method was vacuum laminate machine (MVLP-500 manufactured by Nihon Seiki Co., Ltd.) at a pressurization degree: 〇8 MPa, 70 Heating lamination was carried out under the conditions of ° C, 1 minute, and vacuum degree: 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer. The obtained substrate was evaluated for characteristics in the same manner as described above. The evaluation results are shown in Table 2. -54- 201124800 Table 2 Characteristic Example Comparative Example 2 3 4 5 6 7 8 9 10 1 2 3 4 Solder resist form (D: dry film 'L·. liquid) LLLLDLLLLLLLDLLL Optimum exposure (mJ/cm2) 300 310 300 250 250 250 230 260 190 230 250 250 240 260 240 230 Development (seconds) 15 17 11 15 15 14 45 20 16 21 8 35 36 18 20 57 Visualization of through holes ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ XX 〇Δ X Resolving Um) 60 60 60 50 50 50 50 50 50 50 50 60 60 60 60 60 Resolution of the through hole for imaging (β m) 70 70 70 60 60 60 70 60 60 60 30 — — 80 80 — Surface morphology of the coating film △ A Δ 〇〇〇0 〇〇〇〇〇〇XXX Welding heat resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 electroless gold plating Resistance to alkali resistance 〇〇〇〇〇〇0 As shown in Table 2 above, Examples 1 to 1 0 phase Compared with Comparative Examples 1 to 4, the developability, particularly the development of the via holes, is good, and the solder heat resistance and power are not obtained. Since the gold plating resistance, the moisture resistance, and the electrical insulating properties are also excellent, it can be used as a photosensitive resin composition of an alkali developing type. [Industrial Applicability] The photocurable resin composition of the present invention or a dry film thereof is suitably used for forming a cured film of a solder resist or the like on a printed circuit board or a flexible printed circuit board. -55-

Claims (1)

201124800 VII. Patent application scope: 1 . An alkali-developing photocurable resin composition characterized by containing a carboxylic acid resin derived from a compound having a structure represented by the following general formula (1), and 1 molecule a compound having a plurality of ethylenically unsaturated groups and a photopolymerization initiator, R1 〇4-R3-l 0-R2 (I) (wherein R1 represents a (m + 1)-valent polyol derivative, m and η are 1 or more, an integer of less than 10, 1 is 0 or 1 or more, and R2 represents CH2, C. Any of iH4, C3H6, C4H8, a substituted or unsubstituted aromatic ring, and R3 means a substituted or unsubstituted aromatic ring). 2. The alkali-developing photocurable resin composition of the first aspect of the invention, wherein the carboxylic acid resin is a polyol having (a) a polyester having a plurality of hydroxyl groups in (b) 1 molecule; At the same time as or after the depolymerization, (c) a saturated or unsaturated polybasic acid or an anhydride thereof is obtained. 3. The alkali-developing photocurable resin composition according to claim 2, wherein the polyester (a) is a recycled polyester. 4. The alkali-developable photocurable resin composition according to the first aspect of the invention, which further comprises a photocurable thermosetting resin composition containing a thermosetting component. A photocurable dry film obtained by applying a photocurable resin composition according to any one of items 1 to 4 of the above-mentioned patent application to a film and drying it. -56-201124800 A cured product of the photocurable resin composition or the photocurable resin composition according to any one of the above claims 1 to 4, which is coated on a film. The dry photohardenable dry film is obtained by photohardening into a pattern. A printed circuit board having the photocurable resin composition or the photocurable resin composition according to any one of the above claims 1 to 4, which is applied to a film and dried The photocurable dry film obtained by photohardening is patterned into a hardened film obtained by thermal curing. -57- 201124800 IV. Designated representative map: (1) The representative representative of the case is: None. (II) Simple description of the symbol of the representative figure: None 201124800 V If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none