TW200941136A - Photocurable resin composition, cured product pattern, and printed wiring board - Google Patents

Abstract

The invention provides an alkali developing type light-cured resin composition and a cured resin pattern and a printed board. The composition has high sensitivity for active energy ray, an exposure curability directly depicted by laser, and a developing ability, a finger touch dryness, a solder thermal endurance, a chemical gold plating resistance, an alkali tolerance, and a PCT and PCBT resistance are excellent, thus the composition can be used as a solder resist. The alkali developing type light-cured resin composition comprises: (A) a carboxylic acid-containing photosensitive resin shown as a general formula (I), (B) a photopolymerization initator, (C) a compound with more than two olefinic unsaturated groups in one molecule, in the general formula (I), R<1> is a hydrogen atom or a methyl, R<2> is a straight-chain, branched chain or cyclic alkyl with 2-6 carbon atoms, and R<3> is hydrogen atom or carboxylic acid ester residue.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali-developing photocurable resin composition which is excellent in sensitivity to an active energy ray and which can be used as a solder resist. [Prior Art] Recently, the exposure method of the solder resist for printed circuit boards has been popular for laser scanning in terms of excellent alignment Φ. Laser exposure is performed by scanning a solder resist on a circuit board on which a pattern is formed without using a photomask, but the solder resist has hitherto been exposed to an optimum exposure amount of 200 mJ/cm2 or more. The shortcomings of the long, corresponding to the laser exposure, the solder resist needs a very high sensitivity. In this context, a photosensitive composition capable of exhibiting high photopolymerization ability has been proposed (for example, refer to Patent Document 1 and Patent Document 2). However, in the photosensitive composition proposed so far, although it is possible to surely exhibit the ability of photopolymerization, the sensitivity required for direct laser exposure is not sufficient, and it is required for the photosensitive composition. The characteristics required outside of the sensitivity are also insufficient. Specifically, the composition disclosed in Patent Document 1 is exemplified by glycidyl methacrylate as a compound having a cyclic ether group and an ethylenically unsaturated group in one molecule for forming a photosensitive resin containing a carboxyl group. However, not only is the sensitivity insufficient, but if the amount of addition is large, the developing property tends to deteriorate. On the other hand, in the proposal of Patent Document 2, when an acrylate in which ε-caprolactone is subjected to a chain reaction of acrylate to modify a molecule-extended caprolactone is used, the sensitivity is improved, but the dryness of the touch is extremely deteriorated. And welding -5 - 200941136 tin heat resistance is insufficient. Further, the alkali-developing type photoresist has problems in durability. That is, compared with the conventional thermosetting type and solvent developing type, the alkali-developing type photoresist has poor chemical resistance, water resistance, heat resistance and the like. These are caused by the fact that the alkali-developing type solder resist can be subjected to alkali development and the hydrophilic group is used as a main component. Thereby, the chemical liquid, water, steam, and the like are easily impregnated, the chemical resistance is lowered, and the adhesion between the photoresist film and copper is lowered. As a result, the resistance to chemical resistance is weakened, and in particular, in semiconductor packages such as BGA and CSP, it is necessary to refer to PCT resistance (pressure cooker testability) which is particularly resistant to moist heat, but the current situation is such strict conditions. It only lasts for hours to tens of hours. Further, in many cases, the PCBT test in the state where the voltage is applied under the PCT condition is confirmed to be caused by the occurrence of the migration within a few hours. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2007-3590 (Patent Application). In view of the above problems, an object of the invention is to provide an alkali-developing photocurable resin composition which can be used as a solder resist, which is high in sensitivity to active energy rays and excellent in exposure hardenability of direct drawing. It is also excellent in developability, dryness to touch, solder heat resistance, electroless gold plating, scratch resistance, PCT and PCBT resistance. 200941136 [Means for Solving the Problems] As a result of intensive research to solve the above problems, the inventors of the present invention have found that a photocurable resin obtained by combining other components is used as a photosensitive resin containing a carboxylic acid-containing photosensitive resin having a specific structure. The composition can solve the above problems, and thus the present invention has been completed. That is, the present invention is an alkali-developable photocurable resin composition characterized by containing (A) a carboxylated phthalic acid-containing photosensitive resin having a structure represented by the general formula (I), and (B) photopolymerization. Starting agent, (C) a compound having two or more ethylenically unsaturated groups in one molecule: R1

In the formula (I), R1 represents a hydrogen atom or a methyl group, R2 represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, and R3 represents a hydrogen atom or an organic acid ester residue. Among them, the same state as R3 in the formula (I) is an acid anhydride residue or a (meth)acrylic acid residue. Further, the (B) photopolymerization initiator is an aminophenyl group selected from the group consisting of a pseudo ester photopolymerization initiator having a structure represented by the formula (π) and having a structure represented by the formula (in) 200941136. One or a mixture of two or more of a ketone-based photopolymerization initiator and a sulfhydrylphosphine-based photopolymerization initiator having a structure represented by the general formula (IV): (II) -C=N^ ~0-—C——r2

R5 R6

11 II R1 ο (III) ◎ (IV) In the general formulae (II) to (IV), R1 represents a hydrogen atom or a phenyl group (may also be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, a 2 to 20 carbon alkyl or benzylidene group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R 2 represents a phenyl group (alkyl group having 1 to 6 carbon atoms, phenyl group or a halogen-substituted one), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), and a carbon number of 5 to 8 a cycloalkyl group, a carbon number of 2 to 20 alkyl alkanoyl or a benzhydryl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R3 and R4 each independently represent a carbon number of 1 to 20; Chain, branched or cyclic alkyl or arylalkyl, -8- 200941136 R5 and R6 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R5 and R6 can be bonded to form a cyclic alkyl ether group, and R7 and R8 are each independently a linear, branched or cyclic alkyl group having 1 to 1 carbon atom, an alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (which may be substituted by a halogen atom, an alkyl group or an alkoxy group), or RC (=0)-Base (wherein R represents a hydrocarbon group having 1 to 2 carbon atoms), except when both R7 and R8 are RC (=0)-based 0. Further, the resin composition of the present invention may further contain (D) a thermosetting component. Further, the resin composition of the present invention is a solder resist further containing (E) a colorant. In another aspect of the invention, the photocurable resin composition of the present invention described above is applied onto a carrier film and the obtained photocurable dry film is dried. Further, in another aspect of the present invention, a cured image pattern formed of a resin layer composed of the photocurable resin composition is used, and the pattern is formed by irradiation of an active energy ray. Object pattern. Among them, the pattern formed by irradiation of the active energy ray is directly drawn using an active energy ray having a wavelength of 305 nm to 4 10 nm. Further, another aspect of the present invention is to provide a printed circuit board having the above-described cured pattern on a copper layer. Further, the (meth)acrylic acid in the present specification is used as a term indicating acrylic acid and/or methacrylic acid, and the other similar performances are also the same. [Embodiment] Hereinafter, each constituent component of the photocurable resin composition of the present invention will be described in detail. The photosensitive resin (A) containing a carboxylic acid contained in the photocurable resin composition of the present invention contains a structure represented by the formula (I), and further contains a carboxylic acid in the molecule.

(I) wherein R1 represents a hydrogen atom or a methyl group, R2 represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, and R3 represents a hydrogen atom or an organic acid ester residue, wherein R3 is The organic acid ester residue shown is an acid anhydride residue or a (meth)acrylic acid residue, and specific examples of the acid anhydride residue include (b) an unsaturated group-containing acid anhydride and (d) a polybasic acid anhydride. The carboxylic acid-containing photosensitive resin (A) of the present invention may have (a) a compound having at least two hydroxyl groups and one carboxyl group in one molecule, (b) an acid anhydride containing an unsaturated group, and (c) one molecule having The epoxy compound having at least two or more epoxy groups and (d) the polybasic acid anhydride are obtained in the following order) to (3), but are not limited thereto. That is, -10-200941136 (1) reacting a compound (a) having at least two hydroxyl groups and one carboxyl group in one molecule with an acid anhydride (b) containing an unsaturated group, and synthesizing two molecules in one molecule (methyl group) a compound of an acryloyl group and a carboxyl group. The obtained compound is characterized in that a system in which an epoxy compound (c) having at least two epoxy groups in one molecule is reacted and then reacted with a polybasic acid anhydride (d) to obtain cerium (1) is exemplified by Increasing the concentration φ of the photosensitive base can effectively increase the sensitivity. The details are not clear, but the visibility is also improved. It is considered that the emulsification effect is improved by the increase in the affinity with other components having no carboxyl group due to the increase in the concentration of the acrylonitrile group in the resins. Further, it was confirmed that the alkali resistance was improved with an increase in the crosslinking density, and the PCT and PCBT resistance were also improved with the increase in hydrophobicity. (2) reacting a compound (a) having at least two hydroxyl groups and one carboxyl group in one molecule with an acid anhydride (b) containing an unsaturated group, and synthesizing two (meth)acrylonyl groups and one molecule in one molecule. a compound of a carboxyl group. For the compound obtained from ruthenium, an epoxy compound (C) having at least two or more epoxy groups in one molecule is reacted. The obtained compound is further reacted with a compound (a) having at least two hydroxyl groups and one carboxyl group in one molecule, and then reacted with a polybasic acid anhydride (d). The characteristics of the system of (2) are the same as (1), and the sensitivity is high and the sensitivity is improved by increasing the photosensitive base concentration. Further, the system of (2) is characterized in that the photosensitive unit (acrylonitrile group) is completely separated from the development unit (carboxyl) alkane. It can be confirmed that the effect is still the same as (1) but the image life is longer than (1). In the same way, (1), it was confirmed that the development of the image was improved, and the improvement in PCT and PCBT tolerance was also confirmed. (3) An epoxy compound (c) having at least two or more epoxy groups in one molecule is reacted with a compound (a) having at least two hydroxyl groups and one carboxyl group in one molecule. The obtained compound is obtained by reacting an acid anhydride (b) containing an unsaturated group and further reacting it with a polybasic acid anhydride (d). The characteristics of the system of (3) are the same as (1) and (2)', and it is effective and highly sensitive by increasing the photosensitive base concentration. Also (3) is the same as (1) and (2), and the improvement in developability can also be confirmed. However, q which is different from (2) is a result of the randomness of the photosensitive unit (acryloyl group) and the developing unit (carboxyl group), and it has been found that it is difficult to completely control the resin structure. The systems of the above (1) to (3) each have their excellent characteristics, but it is considered that (2) or (1) is preferable in terms of the balance of photosensitivity and development properties and the properties of the obtained cured product. Specific examples of the compound (a) having at least two hydroxyl groups and one carboxyl group in one molecule of the (A) photosensitive resin containing a carboxylic acid described in the above (1) to (3) can be exemplified as For example, a monocarboxylic acid containing a polyhydroxy group such as dimethylolpropionic acid, bishydroxymethylacetic acid, dimethylolbutanoic acid, dimethylolvaleric acid or dihydroxymethylhexanoic acid. As a preferable one, for example, dimethylolpropionic acid or the like can be mentioned. Examples of the (b) acid anhydride containing an unsaturated group include acrylic anhydride and methacrylic anhydride, and these may be used alone or in combination of two or more.

As for (c) an epoxy compound having at least two epoxy groups in one molecule, which is a conventionally used epoxy resin, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S can be used. Type epoxy resin, brominated bisphenol A -12- 200941136 type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol type bisphenol type epoxy resin, phenol novolac type epoxy resin varnish type ring a glycidyl ether compound such as an oxyresin or a brominated phenol novolac type epoxy resin novolac type epoxy resin; a glycidyl ester compound such as diglycidyl ester, diglycidyl hexahydrocarbonate or water glyceryl ester; a glycidyl group such as triglycidyl ester, N, N, N', N'-tetraglycidyl m-xylylenediamine, φ diglycidyl bisaminomethylcyclohexane, hydrazine, hydrazine-bi-dihydrate Amine compound. Among them, a phenol novolac and a cresol novolac type epoxy resin are preferable because they can provide a hardened coating film with high sensitivity. Further, the lacquer-type epoxy resin having a softening point of 60 ° C or higher is excellent in dryness to the touch, and the preferred epoxy compound may be used singly or in combination of two or more. Examples of the (d) polybasic acid anhydride include succinic anhydride, fumaric anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride φ phthalic anhydride, itaconic anhydride, and methyl 3-methyl endomethyl group. Trimellitic anhydride, pyromellitic anhydride, etc., may be used alone or in combination. Further, as the carboxylic acid-containing lipid (A) obtained in (1) to (3), a tree obtained by further reacting with a compound of the (e) 1 molecule and a compound having an ethylenically unsaturated group may be used as the tree. The compound of the above (e) 1 molecule having a cyclic ether group saturated group, which may be exemplified by (meth)acrylic acid 2-glycidyl ether, (meth)acrylic acid 2-hydroxypropyl ester glycidyl epoxy resin, Phenolic phenolic aldehyde, bisphenol A terephthalic acid dimer acid bis-isourea cyanide N, N, N, N'· glyceryl aniline type epoxy resin excellent cresol novolac. These photosensitive maleic anhydride, methyl hexahydrophthalic anhydride or a combination of two photosensitive trees have a cyclic ether resin. Ethylene non-hydroxyethyl condensate, (3--13- 200941136) 3-hydroxypropyl acrylate glycidyl ether, 2-hydroxybutyl methacrylate glycidyl ether, (meth) acrylate 4 - hydroxybutyl ester glycidyl ether, 2-hydroxypentyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl methacrylate (meth) acrylate or glycidyl (meth) acrylate, etc. Ethylene-unsaturated monomers, which may be used singly or in combination of two or more. Among the epoxy group-containing ethylenically unsaturated monomers, especially 4-hydroxybutyl (meth)acrylate glycidyl ether and glycidyl (meth)acrylate are moderately productive and photocurable. Preferably. The addition amount of the compound having a cyclic ether group and an ethylenically unsaturated group in the (e) molecule is preferably from 5% equivalent to 40% by weight, more preferably 10%, based on the acid anhydride residue. Equivalent to 30% equivalent. When the addition amount exceeds 5% by weight, it is preferable from the viewpoint of improvement in sensitivity or improvement in electroless gold plating resistance. On the other hand, when it exceeds 40% equivalent, the maximum development life is shortened, and dryness of the touch is deteriorated. The situation is less appropriate. By the modification of the compound (e), the crosslinking density is increased to confirm the synergistic effect of high sensitivity, alkali resistance, PCT and PCBT resistance. The acid value of the carboxyl group-containing photosensitive resin (A) is preferably in the range of 40 to 200 mgKOH/g, more preferably in the range of 80 to 1 20 m g Κ Ο H/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, alkali development becomes difficult. On the other hand, when it exceeds 200 mgKOH/g, the line is changed because the dissolution of the exposure portion of the developing liquid is too fast. In this case, the exposed portion and the unexposed portion are dissolved and peeled off by the developing solution without distinction, and thus the normal photoresist pattern drawing becomes difficult and is not appropriate. In addition, the weight average molecular weight of the carboxyl group-containing photosensitive resin (A) varies depending on the resin skeleton, but is usually from 2,000 to 50,000, and preferably from 5,000 to 20,000. When the weight average molecular weight is less than 200, the non-tack property is deteriorated, and the moisture resistance of the coating film after exposure is deteriorated, and the film is reduced at the time of development, and the resolution is greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 50,000, the development property is remarkably deteriorated, and the storage stability is deteriorated. The blending ratio of the carboxyl group-containing photosensitive resin (A) is preferably from 20 to 60% by mass, more preferably from 30 to 50% by mass, based on the total mass of the resin composition. When it is less than the above range, there is a case where the film strength is lowered and it is not preferable. On the other hand, when it is more than the above range, the viscosity is high, and the coating property of the photoresist is lowered, which is not preferable. In the present invention, in addition to the above-mentioned carboxylic acid-containing photosensitive resin (A), a conventionally used carboxylic acid resin may be further added, and a photosensitive carboxylic acid resin is preferable. 〇 Next, the photopolymerization initiator (B) will be explained. The photopolymerization initiator (B) is preferably selected from the group consisting of a lipoester-based photopolymerization initiator (B-1) having a structure of the following formula (Π): A-aminoacetophenone-based photopolymerization initiator (Β-2) having a structure, and a mercaptophosphorus-based photopolymerization initiator (Β-3) having a structure represented by the following formula (IV) One or more photopolymerization initiators of the group consisting of: -15- 200941136

In the formula (π) to (IV), R1 represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear or branched carbon number of 1 to 20 Or a cyclic alkyl group (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having a carbon number of 5 to 8, an alkanoyl group having a carbon number of 2 to 20 or a benzene group A fluorenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R2 represents a phenyl group (which may be substituted by an alkyl group having a carbon number, a phenyl group or a halogen atom), and a linear chain having a carbon number of 1 to 20 a branched or cyclic alkyl group (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having a carbon number of 5 to 8, and an alkane having a carbon number of 2 to 2 0 a benzyl or benzhydryl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R3 and R4 each independently represent a linear, branched or cyclic alkyl or arylalkyl group having 1 to 20 carbon atoms; The radicals R5 and R6 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R5 and R6 may be bonded to form a cyclic alkyl ether group, and R7 and R8 are independently independent. Indicates a linear or branched shape with a carbon number of 1 to 10. a cyclic alkyl group, an alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (which may be substituted by a halogen atom-16-200941136, an alkyl group or an alkoxy group), or an Rc(=o)- group (wherein r represents carbon The hydrocarbon group of 1 to 20 is excluded, except when both R7 and R8 are RC(=〇)- groups. The oxime ester-based photopolymerization initiator (B-1) represented by the above formula (II) is preferably exemplified by 2-(ethyloxyiminomethyl)thiophene represented by the following formula (V). Tons of-9-one:

(wherein R9 represents a hydrogen atom, a halogen atom, a linear one having a carbon number of 1 to 12, a branched or cyclic alkyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamyl group, or a carbon number; Alkoxycarbonyl group having 2 to 12 alkyl groups and alkoxycarbonyl group having 2 to 12 carbon atoms (when the carbon number of the alkyl group of the structure of -17-200941136 alkoxy group is 2 or more, the alkyl group may be substituted by one or more hydroxyl groups) , the alkyl chain may have more than one oxygen atom in the middle, or a phenoxycarbonyl group, and R1Q and R12 each independently represent a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and a carbon number. a linear, branched or cyclic alkyl group of 1 to 20 (which may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, a carbon number of 2 to 2 alkyl alkanoyl or benzhydryl (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R11 represents a hydrogen atom, a phenyl group (alkyl group having a carbon number of 1 to 6) a phenyl group or a halogen atom substituted), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), Carbon number 5 The 8 cycloalkyl group, having 2 to 20 carbon atoms of the acyl or benzoyl alkyl group (may be substituted by an alkyl group having 1 to 6 carbon atoms or the phenyl group)); and a compound represented by the following general formula (VII):

(wherein R13, R14 and R19 each independently represent a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and R15' R16, R17 and R18 each independently represent a hydrogen atom or a carbon number of 1 to 6 -18 - 200941136 A linear, branched or cyclic alkyl group, Μ represents 〇, S or NH, and m and η each independently represent an integer from 0 to 5). Among them, preferred is 2-(ethyloxyiminomethyl)thioxanthene-9-one represented by the formula (V) and a compound represented by the formula (VI). As for the commercial products, CGI-325, Irgacure ΟΧΕ01, Irgacure ΟΧΕ02, etc. manufactured by Steam Batt Chemical Company are listed. The photo-esterification photopolymerization initiators may be used singly or in combination of two or more. (X-Aminostyrene-based photopolymerization initiator (Β-2) having a structure represented by the formula (III) is exemplified as 2-methyl-1-[4-(methylthio)phenyl] -2-morpholinylacetone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-propan-1-one, 2-(dimethylamino)-2 -[(4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, anthracene, fluorene-dimethylaminoacetophenone, etc. The product is exemplified by Irgacure 907, Irgacure 369, Irgacure 3 79, etc., manufactured by Kabat Chemicals Co., Ltd. ° φ fluorenyl phosphorus oxide photopolymerization initiator (B-3) having a structure represented by the general formula (IV) Listed as 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphorus oxide, double (2, 6-Dimethoxybenzhydryl)-2,4,4-trimethyl-pentylphosphorus oxide, etc. Commercially available products are manufactured by LUCILIN TPO, manufactured by BASF Corporation, and by Steam Batt Chemical Company. Irgacure 819, etc. The blending ratio of the photopolymerization initiator (B) is preferably from 0.01 to 30 parts by mass, more preferably 100 parts by mass, based on 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). In the range of from 0.5 to 15 parts by mass, when it is less than 0.01 mass -19 to 200941136 parts, the photocurability on copper is insufficient, and coating film properties such as peeling of the coating film and chemical resistance are lowered, which is not preferable. On the other hand, when it exceeds 30 parts by mass, the light absorption on the surface of the solder resist coating film of the photopolymerization initiator (B) becomes strong, and the deep hardenability tends to be lowered, so that it is less appropriate. When the oxime ester photopolymerization initiator of the structure represented by the formula (III) is used, the amount thereof is preferably 100 parts by mass relative to the carboxylic acid-containing photosensitive resin (A), preferably from 1 to 20 by mass. The composition of the present invention may be selected from the range of 0.01 to 5 parts by mass. The composition of the present invention may be a photopolymerization initiator other than the above compound, or a photopolymerization initiator and a sensitizer, and may, for example, be a benzoin. a compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a xanthone compound, a tertiary amine compound, etc. Specific examples of the benzoin compound are exemplified by, for example, benzoin Benzoin methyl ether, Equivalent ethyl ether, benzoin isopropyl ether. Specific examples of the acetophenone compound are exemplified by, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-di Ethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone. Specific examples of the hydrazine compound are, for example, 2-methyl hydrazine, 2-ethyl hydrazine, and 2-third butyl. Base, 1-chloroindole. Specific examples of the thioxanthone compound are exemplified by, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2 Specific examples of the 4-diisopropylthioxanthone ketal compound are, for example, acetophenone dimethyl ketal, -20-200941136 benzyl dimethyl ketal. Specific examples of the benzophenone compound are, for example, benzophenone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'methylpredyl sulfide, 4-phenylene Mercapto-4-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide. Specific examples of the tertiary amine compound are exemplified by, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4'-dimethylaminobisφbenzophenone (NISSOKUA MABP manufactured by Nippon Soda Co., Ltd.), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), such as dialkylaminobenzophenone, 7-(diethylamino)-4-methyl-2H- a dialkylamino group-containing coumarin compound such as 1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin), 4-dimethylaminobenzoic acid B Ester (KAYAKUA-EPA manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylaminobenzoic acid ethyl ester (Quantacure DMB manufactured by International Biosynthesis Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) B Ester (Quantacure BEA manufactured by International Biosynthesis Co., Ltd.), isoamyl ethyl p-dimethylaminobenzoate (KAYAKUA-DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethyl 4-dimethylaminobenzoate Hexyl ester (Esolol 507, manufactured by Van Dyk Co., Ltd.), 4,4,-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.). Among the above, a thioxanthone compound and a tertiary amine compound are preferred. If it contains a thioxanthone compound, it is preferable in terms of deep hardenability, and among them, preferred is 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone. a thioxanthone compound such as 2,4-diisopropylthioxanthone. The blending ratio of the thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by weight or less, based on 100 parts by mass of the carboxylic acid-containing photosensitive resin (21). When the compounding ratio of the thioxanthone compound is too large, the film thickness hardenability is lowered, and it is less preferable because it is related to the increase in the cost of the product, and the tertiary amine compound is preferably a compound having a dialkylaminobenzene structure, wherein The most preferred is a dialkylaminobenzophenone compound, and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of from 3 to 50 nm. As for the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferred because of its low toxicity. A coumarin compound containing a dialkylamine group having a maximum absorption wavelength of 350 to 410 nm, which has a maximum absorption wavelength in the ultraviolet range, is less colored, and is provided as a raw material using a colorless and transparent photosensitive composition, and a coloring pigment is provided. A color solder mask film that reflects the color of the coloring pigment itself. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm. The compounding ratio of the tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0 to 1 to 10 parts by mass, per 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). When the compounding ratio of the tertiary amine compound is less than 0.1 part by mass, there is a tendency that a sufficient sensitizing effect cannot be obtained. When it exceeds 20 parts by mass, the light absorption on the surface of the dry solder resist coating film is enhanced by the tertiary amine compound, and the deep hardenability tends to be lowered. The photopolymerization initiator, photopolymerization initiation aid and sensitizer may be used singly or in combination of two or more. The total amount of the photopolymerization initiator (B), the photopolymerization initiation aid, and the sensitizer-22-200941136 is 35 masses based on 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). The following ranges are preferred. When it exceeds 35 parts by mass, the deep curing property tends to decrease due to such light absorption. Next, a compound (C) having two or more ethylenically unsaturated groups in the molecule will be described. The compound (C) having two or more ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation of an active energy φ line to cause the above-mentioned ethylenically unsaturated group. The carboxylic acid-containing photosensitive resin (A) is insoluble in an aqueous alkali solution or a compound which contributes to its insolubilization. These compounds are exemplified by diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and hydroxyl groups. a polyvalent alcohol such as an ethyl isocyanurate or a polyvalent acrylate such as an ethylene oxide adduct or a propylene oxide adduct; a phenoxy acrylate, a bisphenol A diacrylate, And polyvalent propylene Q acid esters such as ethylene oxide adducts or propylene oxide adducts of such phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl a polyvalent acrylate of a glycidyl ether such as ether or triglycidyl isocyanurate; and a melamine acrylate, and/or a methacrylate corresponding to the above acrylate. Further, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as a cresol novolac resin epoxy resin with acrylic acid, and a hydroxyl group of the epoxy acrylate resin and pentaerythritol triacrylate are listed. An epoxy group urethane propylene-23-200941136 acid ester compound obtained by reacting a hydroxy acrylate with a semi-carbamate compound of a diisocyanate such as isophorone diisocyanate. These epoxy propyl ester-based resins can improve the photocurability without deteriorating the dryness of the touch. The compounding ratio of the compound (C) having two or more ethylenically unsaturated groups in the molecule is preferably from 1 to 100 parts by mass based on 1 part by mass of the photosensitive resin (A) containing the carboxylic acid. More preferably in the proportion of 5 to 70 parts by mass. When the above compounding ratio is less than 1 part by mass, the photocurability is lowered, and it is difficult to form a pattern by alkali development after irradiation with an active energy ray, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the solubility in the alkaline aqueous solution is lowered, and the coating film tends to be brittle, which is not preferable. The thermosetting component (D) will be described below. The photocurable resin composition of the present invention may be provided with a heat curable component (D) in order to impart heat resistance. It is preferably a thermosetting component (D) having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter simply referred to as cyclic (thio)ether groups) in the molecule. Among the thermosetting components (D) having two or more cyclic (thio)ether groups in the molecule, there are two or more three, four or five membered cyclic ether groups or a ring in the molecule. Any one of the thioether groups or a compound of the two groups, for example, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1) having at least two or more in the molecule. a compound of an oxetanyl group, that is, a polyfunctional oxetane compound (D-2), a compound having two or more cyclic thioether groups in a molecule, that is, an episulfide compound (D-3) )Wait. Examples of the polyfunctional epoxy compound (D-1) include Epicoat 828, Epicoat 834, and -24-200941136 manufactured by Nippon Epoxy Co., Ltd.

Epicoat 1001, Epicoat 1004, Epiclon 840, Epiclon 8 50, Epiclon 1 050, Epiclon 2055 manufactured by Dainippon Ink Chemical Co., Ltd., EPOTOT YD-011, YD-013, YD-127, YD-128 manufactured by Dongdu Chemical Co., Ltd. DER317, DER331, DER661, DER664 manufactured by Chemical Company, Araldide 6071 from Arbatide Chemical Company, Araldide 6084 'Araldide GY250 ' Araldide GY260, Sumi-epoxy ESA-011, ESA-014 manufactured by Sumitomo Chemical Co., Ltd. , |^ELA-115, ELA-128, AER330, AER331, AER661, AER6 64, etc. (all trade names) manufactured by Asahi Kasei Industrial Co., Ltd. (bis-type A epoxy resin); manufactured by Japan Epoxy Resin Co., Ltd. EPICOAT YL 903, Epiclon 152, Epiclon 165 manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPOTOT YDB-400, YDB-500 manufactured by Dongdu Chemical Co., Ltd., DER542 manufactured by Dao Chemical Co., Ltd., Araldide 801 from Kabat Chemical Company 1, 8111111-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., bromine ring of φ A_E.R.71 1 and AER714 (all trade names) manufactured by Asahi Kasei Industrial Co., Ltd. Resin: EPICOAT 152, EPICOAT 154 manufactured by Japan Epoxy Resin Co., Ltd., DER431, DER438 manufactured by Dao Chemical Co., Ltd., Epiclon N-730, Epiclon N-770, Epiclon N-8 65 manufactured by Dainippon Ink Chemical Industry Co., Ltd. EPOTOT YDCN-701 and YDCN-704 manufactured by Dongdu Chemical Co., Ltd., Araldide ECN1235, Araldide ECN 1 273 ' Araldide ECN1 299, Araldide XPY307, manufactured by Nippon Kayaku Co., Ltd., and EPPN-201, EOCN-1025, manufactured by Nippon Kayaku Co., Ltd. EOCN-1020, EOCN-104S, RE-3 06, manufactured by Sumitomo Chemical Co., Ltd. -25-200941136

Sumi-epoxy ESCN-195X, ESCN-220, AER ECN-235, ECN-299, etc. (all trade names) manufactured by Asahi Kasei Kogyo Co., Ltd. (all are brand name) novolak type epoxy resin; Epiclon 830 manufactured by Dainippon Ink Chemical Industry Co., Ltd. EPICOAT 807 manufactured by Japan Epoxy Resin Co., Ltd., EPOTO YDF-170, YDF-175, YDF-2 004 manufactured by Dongdu Chemical Co., Ltd., Araldide XPY306 from Steam Batt Chemical Company (both trade names), bisphenol F type Epoxy resin; hydrogenated bisphenol A type epoxy resin such as EPOTOT ST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd.; EPICOAT 604 manufactured by Japan Epoxy Resin Co., Ltd., manufactured by Dongdu Chemical Co., Ltd. EPOTOT YH-434, Araldide MY720 from Steam Batt Chemical Company, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (both trade names), glycidylamine-based epoxy resin; Araldide CY-350 (trade name), etc., such as uranyl urethane epoxy resin; Celloxide 2021 manufactured by Dicel Chemical Co., Ltd., Araldide CY175, CY179, etc. of Steam Batt Chemical Company (all trade names) Alicyclic epoxy resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd., TEN·, EPPN-501, EPPN-502, etc. (all trade names) manufactured by Dow Chemical Co., Ltd. : a bis-xylene oxime type or a biphenol type epoxy resin such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Nippon Epoxy Co., Ltd. or a mixture thereof; manufactured by Nippon Kayaku Co., Ltd. EBPS-200, EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink Chemical Industry Co., Ltd., etc. EPIC0 AT 15 manufactured by Japan Epoxy Resin Co., Ltd. 7S (commercial 200941136 product name) and other bisphenol A novolac type epoxy resin; EPICOAT YL-931 manufactured by Japan Epoxy Resin Co., Ltd., Araldide 163 (all trade name) of gasoline company Batt Chemical Company, etc. Mercaptoethane type epoxy resin; Araldide PT810 from Steam Batt Chemical Company, heterogeneous epoxy resin of TEPIC (all trade name) manufactured by Nissan Chemical Industries Co., Ltd.; Blenmer DGT and other shrinkage water manufactured by Nippon Oil & Fats Co., Ltd. Glyceryl phthalic acid Ester resin; tetrahydroglycidyl fluorene xylene decyl ethane resin such as ZX-1 063 manufactured by Dongdu Chemical Co., Ltd.; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP manufactured by Dainippon Ink Chemical Industry Co., Ltd. -4032, EXA-475 0, epoxy resin containing naphthyl group such as EXA-4700; epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink Chemical Industry Co., Ltd.; The company's CP-50S, CP-50M and other glycidyl methacrylate copolymer epoxy resin; further, a copolymerized epoxy resin of cyclohexylmalamine and glycidyl methacrylate; epoxy modification Polybutadiene rubber derivatives (for example, PB-3600 manufactured by Dicel Chemical Industry Co., Ltd.), CTBN modified epoxy resins (for example, YR-102, YR-450, etc. manufactured by Dongdu Chemical Co., Ltd.), etc. Not limited to these. These epoxy resins may be used singly or in combination of two or more. Among these, a novolak type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is preferable. The above polyfunctional oxetane compound (D-2) is exemplified by bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3_ethyl_3_oxygen) Heterocyclic butyl methoxy) methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3) -oxetanylmethoxy-27- 200941136 yl)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, acrylic acid (3-ethyl-3: oxetanyl) Methyl ester, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or such oligomers or Polyfunctional oxetane such as copolymer, and oxetane with novolak resin, poly(p-hydroxystyrene), CALDO type bisphenol, calixarene, resorcinol calixarene An etherified product of a resin having a hydroxyl group such as (calix resorcin are ne) or a sesquioxane. Further, it is exemplified by a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate. The above episulfide compound (D-3) is exemplified by bisphenol A type episulfide resin YL7000 manufactured by Nippon Epoxy Co., Ltd., and the like. Further, an episulfide resin or the like which replaces the oxygen atom of the epoxy group of the novolac type epoxy resin with a sulfur atom by the same synthesis method can also be used. The compounding ratio of the thermosetting component (D) having two or more cyclic (thio)ether groups in the above molecule is preferably 〇.6 based on 1 equivalent of the carboxyl group of the carboxylic acid-containing photosensitive resin (A). ~2.5 equivalents, more preferably in the range of 0.8 to 2.0 equivalents. When the amount of the thermosetting component (D) having two or more cyclic (thio)ether groups in the molecule is less than 0.6 equivalent, it is a cause of residual carboxyl groups in the solder resist film, in which case heat resistance and alkali resistance are caused. Sexuality, electrical insulation, etc. are declining, which is less favorable. On the other hand, when it exceeds 2.5 equivalents, since the low molecular weight cyclic (thio)ether group remains in the dried film, the film strength and the like are lowered, which is not preferable. When the thermosetting component (D) is used in the photocurable resin composition of the present invention, it is preferred to use a thermosetting catalyst in combination. These thermosetting catalysts-28-200941136 are exemplified by, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, An azole derivative such as 1-cyanoethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamine, benzyldi Methylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-indole, hydrazine-dimethylbenzylamine, 4-methyl-hydrazine, hydrazine- An amine compound such as dimethylbenzylamine, an anthracene compound such as diammonium adipate or diterpene sebacate; a phosphorus compound such as triphenylphosphine; and the commercially available φ are listed as, for example, Shikoku Chemical Industry Co., Ltd. Manufactured 2ΜΖ-Α, 2ΜΖ-ΟΚ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ (all trade names of imidazole compounds), U-CAT3503N, U-CAT3502T manufactured by SAN-APRO Co., Ltd. (all block isocyanates of dimethylamine) The trade name of the compound), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic hydrazine compounds and salts thereof). In particular, it is not limited to these, if it is a thermosetting catalyst of an epoxy resin and an oxetane compound, or a reaction that promotes the reaction of an epoxy group and/or an oxetane group with a carboxyl group, it is used alone or Mixing two or more types makes it easy to use. Further, guanamine, acetammine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl- can be used. 2,4-Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Isocyanuric acid adduct, 2,4-diamino-6-methyl The S-triazine derivative such as a propylene oxyethyl-S-triazine-isocyanuric acid addition product is preferably used in combination with the above-mentioned thermosetting catalyst as a compound having a function as a tackifier. The blending ratio of the thermosetting catalyst is sufficient in a usual amount, and for example, it is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the photosensitive resin (A) or the thermosetting component (D) containing a carboxylic acid. The mass fraction is more preferably -29-200941136 〇·5~15·0 parts by mass. Next, a coloring agent (Ε) which can be used in the photocurable resin composition of the present invention will be described. The photocurable resin composition of the present invention can be formulated with a colorant. As the coloring agent, any of the conventional coloring agents, pigments, dyes, and pigments conventionally used such as red, blue, green, yellow, and black may be used. However, in terms of reducing environmental load and affecting human body, it is preferred that halogen and azo compounds are not contained. Blue coloring agent: Blue coloring agent is phthalocyanine, lanthanide, and pigment system is classified as a pigment. Specifically, it is accompanied by a color coefficient (CI; Dye and Color Association ( Issued by The Society of Dyers and Colourists): Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60. As the dye, 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 can be used. 70 and so on. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used. Green coloring agent: Green coloring agents are also available in the form of phthalocyanine or lanthanide. Specifically, pigment green 7, pigment green 36, solvent green 3, solvent green 5, solvent green 20, and solvent green 28 can be used. In addition to the above, a phthalocyanine compound substituted with or without a metal may also be used. Yellow coloring agent: -30- 200941136, condensed azo type, benzene, specifically, the lower yellow coloring agent is a monoazo type, a diazo-type imidazolidinone type, an isoindolinone type, a hydrazine type, etc. Lister. Lanthanum: Solvent Yellow 163, Pigment Yellow, Yanhuanghuang 108, Pigment Yellow 193, Pigment Yellow Pigment Yellow, &quot;, Pigment Yellow 2〇2. Different 嗣 :: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, _ Yellow 179, Pigment Yellow 185. Ο condensed azo system: Pigment Yellow 93' Pigment Yellow 94, Pigment Yellow 95 Material Yellow 128, Pigment Yellow 155, Pigment Yellow I66, Pigment Yellow 180. Benzimidazolone series: Pigment Yellow 12〇, Pigment Head Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181. Single gas system: Pigment Yellow 1, 2, 3, 4, s Λ 6' ΐ〇. 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 1 〇〇, 1 〇 4 1 〇 5 111, 116, 167, 168, 169, 1 82, 1 83. Diazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 8, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 ° Red Colorant: Red Examples of the coloring agent include a monoazo type, a diazo type, a soluble azo dye type, a benzimidazolone type, an anthraquinone type, a diketopyrrolopyrrole type, a condensed azo type, an anthraquinone type, a quinacridone type, etc. 'Specifically listed as the following. Single gas system: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, U7, 151, 170, 184, 187, 188, 193, 210, 245, 253, -31 - 200941136 258 '266, 267, 268, 269. Diazo system: Pigment red 37, 38, 41. Soluble monoazo dye series: Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53 :2, 57:1, 58:4, 63:1, 63:2, 64:1, 68. Benzimidazolone type: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208. Lanthanide: solvent red 135, solvent red 197, pigment red 133, pigment red 149, pigment red 166, pigment red 178, pigment red 179, pigment red 190, pigment red 194, pigment red 224. Diketopyrrolopyrrole: Pigment Red 254, Pigment Red 25 5, Pigment Red 264, Pigment Red 270, Pigment Red 272. Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166' Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242. Lanthanide: Pigment Red 168, Pigment Red I77, Pigment Red 216, Solvent Red 149, Solvent Red 1 50, Solvent Red 5 2. Solvent Red 2 0 7. Quinacridone type: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209. In addition, a coloring agent such as purple, orange, brown, or black for adjusting the color tone may be added. Specific examples are Pigment Violet 19, 23, 29, 32, 36, 38, 42 Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, (: 1. Pigment Orange 14 (:.1. Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, C_I. Pigment Orange 36, CI Pigment-32-200941136 Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, Cl Pigment Orange 51, C_I. Pigment Orange 61, Cl Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25 , CI Pigment Black 1, CI Pigment Black 7, etc. The specific blending ratio of the colorant is not affected by the type of the colorant used and other additives, but it is inconsistent with respect to the photosensitive resin composition of the present invention. 100 parts by mass of the carboxylic acid-containing photosensitive resin, preferably blended with 〇 parts by mass to 5 parts by mass. More preferably from 0.05 parts by mass to 3 parts by mass of the preferred colorant, and blue and green are phthalocyanine , lanthanide, in yellow is lanthanide, in red is diketopyrrolopyrrole, lanthanide, and Further, the blue and green color of the pigment are preferable from the viewpoint of heat resistance, and the blue, green and red colorants of the dye are preferable from the viewpoint of sensitivity and resolution. The photocurable resin composition may be blended with a chelating agent in order to increase the physical strength of the coating film. The chelating agent may be a conventionally used inorganic or organic chelating agent, but is particularly preferably used. Barium sulfate, spheroidal cerium oxide, and talc. Further, it may be used in a compound having one or more ethylenically unsaturated groups or Hanse- in which a nano cerium oxide is dispersed in the above polyfunctional epoxy resin (D-1). NANOCRYL (trade name) manufactured by Chemie Inc. XP 03 96, XP 0596, XP 073 3, XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names) or manufactured by Hanse-Chemie NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (all product grade names), etc. These may be used alone or in combination of two or more. The blending ratio of the sputum is for the above Photosensitive resin of carboxylic acid (A) 100 parts by mass It is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, and most preferably 〇.1 to 15 parts by mass. When the blending ratio of the enamel agent exceeds 300 parts by mass, the viscosity of the photosensitive composition is The high printability is lowered, and the hardened material becomes brittle, so it is not preferable. Further, the photocurable resin composition of the present invention can be used for synthesizing the above-mentioned carboxylic acid-containing photosensitive resin (A) or a modulating composition or for adjusting the viscosity applied to a substrate or a carrier film. Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, it is a ketone such as methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; a cellosolve, a methyl cellosolve, or a butyl cellosolve; Glycol ethers such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc.; ethanol, propanol Alcohols such as 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 or more. The photocurable resin composition of the present invention may further contain a known conventional use of hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothi-34-200941136azine, etc., if necessary. Thermal polymerization inhibitor; known conventional tackifiers such as fine powder of cerium oxide, organic bentonite, montmorillonite; antifoaming agents and/or admixtures of antimony, fluorine, and polymer, imidazole, and thiazole A conventionally used additive such as a decane coupling agent such as a triazole system, an antioxidant, or a rust preventive agent. The photocurable resin composition of the present invention is adjusted to a viscosity suitable for a coating method by, for example, the aforementioned organic solvent, and is applied to a substrate by dip coating, flow coating, roll coating, bar coating, screen printing. After coating by a printing method or a curtain coating method, the organic solvent contained in the composition is volatilized (temporarily dried) at a temperature of about 60 to 100 ° C to form a non-sticky coating film. Further, the resin composition of the present invention is applied onto a carrier film, dried to form a dry film, and the dry film winder is bonded to a substrate to form a resin insulating layer. The coating film obtained as described above or the resin layer on the carrier film (referred to as "resin layer" together with the above-mentioned "coating film") is exposed by irradiation with an active energy ray, and the exposed portion is irradiated with active energy rays. Partially) hardened. © Specifically, by contact (or non-contact), by using a pattern-shaped reticle to selectively expose by active energy lines or using a laser direct exposure machine, etc., by direct depiction of active energy lines The pattern is exposed, and the unexposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% aqueous sodium carbonate solution) to form a photoresist pattern. Further, it is heated and cured at a temperature of, for example, about 140 to 180 ° C, whereby the carboxyl group of the carboxylic acid-containing photosensitive resin (A) and the molecule have two or more cyclic ether groups and/or a ring. The thermosetting component of the thioether group reacts to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. -35- 200941136 As the above substrate, paper phenol 'paper epoxy, glass cloth epoxy, glassy polyimide, glass cloth / non-woven epoxy, glass cloth / paper epoxy, synthetic fiber ring can be exemplified. All grades (FR-4) of copper-clad laminates, other polyimide films, PET films, etc., which are made of copper-clad laminates, such as oxygen, fluorine, polyethylene, PPO, cyanate, etc. Glass substrate, ceramic substrate, wafer board, etc. The photocurable resin composition of the present invention is subjected to volatilization and drying after application, and a hot air circulating type drying furnace, an IR furnace, a heating plate, a ventilating oven, or the like (a dryer using a heat source having an air heating method by steam) can be used. The method of convective contact between the hot air and the method of blowing the support by the nozzle). As the exposure machine for the active energy ray irradiation, an ultraviolet ray irradiation device and a direct drawing device (for example, a laser direct imaging device that directly draws an image by laser data from a computer) can be used. As the active energy line, any laser beam or solid laser can be used as long as the laser light having a maximum wavelength of 3 5 0 to 4 1 Onm is used. Further, the exposure amount varies depending on the film thickness, etc., but it is usually 5 to 200 mJ/cm2, preferably 5 to 100 mJ/cm2, and more preferably 5 to 50 mJ/cm2. As the above-described direct drawing device, for example, a product manufactured by ORBETECH Co., Ltd., PENTAX Corporation, or the like can be used, and any device can be used as long as it is oscillated by laser light having a maximum wavelength of 550 to 410 nm. As the above development method, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, an amine or the like can be used by a dipping method, a rinsing method, a spraying method, a brushing method, or the like. The aqueous alkali solution is used as a developing solution. -36-200941136 Row 0 [Examples] The present invention will be specifically described below, but the present invention is not limited to the following examples. &lt;Synthesis of carboxylic acid-containing photosensitive resin (A)&gt; Φ Resin Synthesis Example 1 (A-1) 44 2.2 parts (3.3 m) was added to 600 g of diethylene glycol monoethyl ether acetate. Dimethylolpropionic acid, 1031.8 parts (6.7 moles) of methacrylic anhydride, 3.0 parts of methylhydroquinone, 8-5 parts of triphenylphosphine, and the reaction was carried out at 95 ° C for 8 hours. Then, 800 g of diethylene glycol monoethyl ether acetate and 2140 g of o-cresol novolac type epoxy resin were produced (manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPICLON N-695, softening point 95 ° C, Epoxy equivalent 214, average functional group number 7.6] (glycidyl number (total aromatic ring): 10.0 mol), 3.0 parts of methylhydroquinone, 1 000 carbitol acetate, heated to 90 °C with stirring The reaction mixture was dissolved. Then, the reaction solution was cooled to 60 ° C', and 10.0 parts of triphenylphosphine was fed and heated to 100 ° C to carry out a reaction for about 30 hours. Then, '912 parts (6.0 mol) of tetrahydrophthalic anhydride was fed, and the mixture was heated to 95 ° C, and the reaction was carried out for about 6 hours, and then cooled to obtain a solid content of 74 mg KOH / g of solid content of 65%. A carboxylic acid-containing photosensitive resin (varnish A-1). Resin Synthesis Example 2 (A-2) -37- 200941136 442.2 parts (3.3 mol) of dimethylolpropionic acid and 1031.8 parts (6.7 m) were added to 800 g of diethylene glycol monoethyl ether acetate. Methacrylic anhydride, 3.0 parts of methylhydroquinone, 8.5 parts of triphenylphosphine, and the reaction was carried out at 95 ° C for 8 hours. Then, 1 gram of diethylene glycol monoethyl ether acetate and 2846.2 g of o-cresol novolac type epoxy resin were produced. [Manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPICLON N-695, softening point 95 °C, epoxy equivalent 214, average functional group number 7.6] (glycidyl number (total aromatic ring): 13.3 moles), 442.2 parts (3.3 moles) of dimethylolpropane, 3.0 parts of methylhydroquinone, 13 00 The carbitol acetate was heated to 90 ° C with stirring to dissolve the reaction mixture. Then, the reaction solution was cooled to 6 Torr:, 12.0 parts of triphenylphosphine was fed, and the mixture was heated to 100 ° C to carry out a reaction for about 25 hours. Next, 1064 parts (7.0 mol) of tetrahydrophthalic anhydride was fed thereto, and the mixture was heated to 95 ° C to carry out a reaction for about 6 hours, followed by cooling to obtain a solid content concentration of a solid content of 67 mg KOH / g. 65% of a carboxylic acid-containing photosensitive resin (varnish A-2). Resin Synthesis Example 3 (A-3) 670 parts (5.0 mol) of dimethylolpropionic acid, 1.5 parts of methylhydroquinone, and 7.5 parts were added to 600 g of diethylene glycol monoethyl ether acetate. Phenylphosphine is heated to dissolve to dissolve. 770 parts (5.0 mol) of methacrylic anhydride dissolved in 75 g of diethylene glycol monoethyl ether acetate was slowly added dropwise thereto over 2 hours, followed by a reaction for 5 hours. Then, 2140 g of o-cresol novolac type epoxy resin was fed [manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPICLON N-695, softening point 95 ° C, 200941136 epoxy equivalent 214, average functional group number 7.6] (glycidol) Base (total number of aromatic rings): 10.0 mol), 3 to 5 parts of methylhydroquinone, 1100 parts of carbitol acetate, and heated to 90 ° C with stirring to dissolve the reaction mixture. Then, the reaction solution was cooled to 60 ° C, and 12.0 parts of triphenylphosphine was fed, and the mixture was heated to 100 ° C to carry out a reaction for about 25 hours. Next, 10 64 parts (7.0 mol) of tetrahydrophthalic anhydride was fed thereto, and the mixture was heated to 95 ° C, and the reaction was carried out for about 6 hours, followed by cooling to obtain an acid value of a solid content of 85 mg KOH/g Q. A carboxylic acid-containing photosensitive resin (varnish A-3) having a solid concentration of 65%. Resin Synthesis Example 4 (A-4) 400 parts of bisphenol F-type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C, and 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide were dissolved and stirred. 81.2 parts of 98.5% NaOH was added at 70 ° C in 1 minute, and the reaction was further carried out at 70 ° C for 3 hours. Then, a large part of the excess unreacted epichlorohydrin and dimethyl hydrazine is distilled off under reduced pressure, and the reaction product containing the by-product salt and Q dimethyl hydrazine is dissolved in 750 parts of methyl isobutyl ketone, and further Add 10 parts of 30% NaOH and react at 70 °c for 1 hour. After the reaction was completed, water was washed twice with 200 parts of water. After the oil-water separation, methyl isobutyl ketone was distilled from the oil layer to obtain 370 parts of epoxy resin (a-Ι) having an epoxy equivalent of 290 and a softening point of 62 °C. Next, 642.2 parts (3.3 moles) of dimethylolpropionic acid, 1031.8 parts (6.7 moles) of methacrylic anhydride, and 3.0 parts of methylhydroquinone were added to 600 g of diethylene glycol monoethyl ether acetate. 8.5 parts of triphenylphosphine, and the reaction was carried out at 95 ° C for 8 hours. Then feed 700 g of diethylene glycol monoethyl ether B-39-200941136 acid ester, 2900 parts (10 moles) epoxy resin (ai), 3.0 parts of methylhydroquinone, 1 part of carbitol The acetate was heated to 90 ° C with stirring to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C, and 16.7 parts of triphenylphosphine was fed and heated to 1 ° C for about 32 hours. Next, 786 parts (7.86 mol) of succinic anhydride and 450 parts of carbitol were fed thereto, and the mixture was heated to 95 ° C to carry out a reaction for about 6 hours, and after cooling, the acid value of the solid component was 85 mgKOH/g. A carboxylic acid-containing photosensitive resin (varnish A-4) having a solid content of 65%. Resin Synthetic Example 5 (A-5) 44 2.2 parts (3.3 mol) of dimethylolpropionic acid and 1031.8 parts (6.7 mol) of methacrylic acid were added to 700 g of diethylene glycol monoethyl ether acetate. Anhydride, 3.0 parts of methylhydroquinone, 8.5 parts of triphenylphosphine, and the reaction was carried out at 951 for 8 hours. Then, 95 g of diethylene glycol monoethyl ether acetate and 2140 g of o-cresol novolac type epoxy resin were produced ([Japan Japan Ink Chemical Industry Co., Ltd. manufactured] EPICLON N-695' softening point 95 ° C 'Epoxy equivalent 214, average functional group number 7.6' (glycidyl number (total aromatic ring): 1 〇. 〇 Moel), 3 〇 part of methylhydroquinone, 1 00 parts of carbitol acetate, The mixture was heated and stirred at 90 ° C to dissolve the reaction mixture. Then, the reaction solution was cooled to 60, and 10.0 parts of triphenylphosphine was fed to 100 ° C to carry out a reaction for about 30 hours. Next, 1140·0 parts (7.5 mol) of tetrahydrophthalic anhydride was fed therein, and the mixture was heated to 95 ° C for about 6 hours. Further, 21.3 g (1.5 mol) of glycidyl methacrylate was fed into the obtained reaction solution, and the reaction was carried out at 115 ° C for 4 hours ' 65% 200941136 The acid value of the solid component was 68 mgKOH. a carboxylic acid-containing photosensitive resin (varnish A-5) having a solid concentration of /g. Comparative Synthesis Example 1 (R-1) 1070 cresol novolak-type epoxy resin was added to 600 g of diethylene glycol monoethyl ether acetate [manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPICLON N-695, softened Point 95 ° C, epoxy equivalent 0, average functional group number 7.6] (glycidyl number (total aromatic ring 5.0 moles), 360 grams (5.0 moles) of acrylic acid and 1_5 grams of hydroquinone l ° ° C heating and stirring, obtained Then, 4.3 g of triphosphine was fed, and after heating to 1 l〇t for 2 hours, the temperature was raised to 120 ° C, and further reacted for 2 hours. 415 g of aromatic SOLVESSO 150) was added to the obtained reaction solution, 4 5 6 · 0 g (3.0 mol) of tetrahydrobenzene was reacted at 110 ° C for 4 hours, and after cooling, a resin solution having a solid acid value of 89 mg KOH / g and a solid content of 65% was obtained. This ❿ varnish R-1. Comparative Synthesis Example 2 (R-2) Addition of 1070 cresol novolac type epoxy resin to 650 g of diethylene glycol monoethyl ether acetate [Manufactured by Dainippon Ink Chemical Industry Co., Ltd., EPICLON N-695, softened Point 95 ° C, epoxy equivalent, average functional group number 7.6] (glycidyl number (total aromatic ring 5.0 moles), 360 grams (5.0 moles) of acrylic acid and 1.5 grams of hydroquinone 100 ° C heating and stirring, to obtain a uniform solution Next, feed 4.3 g of three gram of finite 214):, a hydrocarbon in the phenyl group (an acid anhydride component called ketone limited 214):, phenyl-41 - 200941136 phosphine, heated to 1 1 (Tc reaction for 2 hours) Thereafter, an additional 1.6 g of triphenyl scale was added, and the temperature was raised to 120 ° C to carry out a reaction for 12 hours. 525 g of an aromatic hydrocarbon (SOLVES SO 150) and 608 g (4.0 mol) of tetrahydrogen were added to the obtained reaction solution. Phthalic anhydride, and the reaction was carried out for 4 hours at 110 ° C. Further, 142.0 g (1.0 mol) of glycidyl methacrylate was fed into the obtained reaction solution, and the reaction was carried out at 1 15 t for 4 hours. , obtaining a resin having a solid content of 77 mg KOH/g and a solid content of 65% This is called varnish R-2. Comparative Synthesis Example 3 (R-3) 400 parts of bisphenol F-type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C as 925 parts of epichlorohydrin and 462.5 After the dimethyl amide was dissolved, 81.2 parts of 98.5% Na〇H was added in 1 hour at 37 ° C with stirring, and the reaction was further carried out at 70 ° C for 3 hours, followed by distillation under reduced pressure. Excessive amount of unreacted epichlorohydrin and dimethyl argon, the reaction product containing by-product salt and dimethyl hydrazine is dissolved in 750 parts of methyl isobutyl ketone, and further added 30 parts % NaOH and reacted at 70 ° C for 1 hour. After the reaction was completed, it was washed twice with 200 parts of water. After separation of oil and water, methyl isobutyl ketone was distilled from the oil layer to obtain 3 70 parts of epoxy equivalent. 290, epoxy resin (a-Ι) with a softening point of 62 ° C. Feed 2900 parts (10 equivalents) of epoxy resin (a-1), 72 0 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone, 1 95 0 parts of carbitol acetate, and the mixture was heated and stirred at 90 ° C to dissolve the reaction mixture. Then, the reaction solution was cooled to 60 ° C to feed 16.7 parts of triphenylphosphine and heated to l 〇〇 ° C, the reaction was carried out for about 32 hours to obtain a reactant of acid-42-200941136 at a price of 1.0 mg/g. Then, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol were fed therein. The acetate 'heated to 95 ° C and the reaction was carried out for about 6 hours to obtain a resin solution having a solid content of acid 〇〇 mg KOH / g and a solid content of 65%. This is called varnish R-3 °. Example 1 Using the resin solution of the above synthesis example, each component (parts by mass) was adjusted to f) the various components shown in Table 1 were mixed, and after premixing with a stirrer, three rolls were used. The mill is kneaded to prepare a photocurable resin composition. Among them, the particle size measurement was carried out by a honing tester manufactured by ERIKSEN Co., Ltd., and the degree of dispersion of the obtained photocurable resin composition was 15 μm or less. ❹ -43- 200941136 [Table i] Table 1 (Composition Example J) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Case 7 Case 8 Case 9 Example 10 Varnish (A-1) 155 155 - _ Varnish (A -2) - 155 faces • Varnish (A-3) - - 155 - - Varnish (A-4) - - Stomach 155 Varnish (A-5) - - - _ 155 - - . - Varnish (R-1) - - • • • 155 155 - Varnish (R-2) - - - • • • 155 - Varnish (R-3) - - 155 Photopolymerization_Out-1)" 1 - 1 1 1 1 1 1 Photopolymerization Starting agent (B-1)*2 - - 0.6 photopolymerization initiator (B-2)·3 5 5 5 5 5 5 5 5 5 5 photopolymerization initiator (B-3)*4 - 10 - _ _ _ - 10 - Chemical fiber C-1), 20 20 20 20 20 20 20 20 20 20 Faceting composition (D-1)*6 15 15 15 15 15 15 15 15 15 15 Faceting composition (D- 1)*7 25 25 25 25 25 25 25 25 25 25 Thermal curing catalyst melamine 5 5 5 5 5 5 5 5 5 5 Colorant (E-1)*8 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Colorant (E-2)*9 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Barium sulfate*10 100 100 100 100 100 100 100 100 100 100 Antimony defoamer 3 3 3 3 3 3 3 3 3 3 Organic solvent DPM ·11 5 5 5 5 5 5 5 5 5 5

* 1 2-(Ethyloxyiminomethyl)thioxanthene-9-one*2, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indole Zyrid-3-yl]-1-(0-ethenylhydrazine) (Irgacure OXE 02; manufactured by Steam Batt Chemical Company) *3 2-Methyl-1-(4-methylthienyl)·2· Morpholinyl ketone ketone (Irgacufe 9〇7; manufactured by Steam Batt Chemicals) *4 *5 *6 *7 *8 *9 2^6-trimethylbenzyl-diphenyl-pity Oxide dipentaerythritol hexaacrylate (DPHA/Nippon Chemical Manufacturing &gt; Phenolfurfural varnish type epoxy resin (DEN-431; manufactured by Dao Chemical Co., Ltd.) Dixylene alcohol type epoxy resin (YX-4000, Japan Epoxy Resin company advises CI Co., Ltd. 15:3 er曰A mouth"-) CI Gu Huang 147 »10 堺Chemical company made sulphuric acid lock B3〇*11 dipropylene glycol monomethyl 酴-44- 200941136 Performance evaluation: &lt; Optimum exposure amount> The above-mentioned photocurable resin composition prepared by the screen printing method is entirely coated on a circuit pattern substrate having a copper thickness of 35 μm, and the substrate is honed by a non-woven roll (Buff roll). , washed with water, dried, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. Then, using a direct drawing device (Paragon 8000 manufactured by ORBOTECH φ) equipped with a semiconductor laser with a maximum wavelength of 355 nm, a direct drawing exposure machine equipped with a high-pressure mercury lamp (a direct-drawing exposure machine equipped with an ultra-high pressure mercury lamp) Makulex manufactured by Nippon Screen Co., Ltd. or an exposure device equipped with a high-pressure mercury lamp (an exposure machine manufactured by ORC Corporation equipped with a mercury short arc lamp), and exposed by a Step Tablet (Kodak 2) for imaging (30°) C, 0.2 MPa, 1% by mass aqueous sodium carbonate solution) When the pattern of the residual step change pattern is 7 segments, the optimum exposure amount is 60 seconds. 〇 <finger dryness> Each of the above-mentioned prepared by screen printing The photocurable resin composition is entirely coated on the copper foil substrate on which the pattern is formed, dried at 80 ° C for 20 minutes, and allowed to cool to room temperature. The substrate is contacted with a negative film made of PET, and The ORC company (HMW680-GW20) was pressed under reduced pressure for one minute, and then the negative film was peeled off, and the stretched state of the film at this time was evaluated. 〇: The film was peeled off without resistance Δ: the film was peeled off However, there is still a small amount of trace on the film. -45- 200941136 X: Resistance is removed when the film is peeled off, and clear traces are left on the film. <Maximum development life> The above-mentioned photohardenability is modulated by screen printing. The resin composition was completely coated on a copper foil substrate on which a pattern was formed, and dried at 80 °C. The substrate was taken out every 10 minutes from 20 minutes to 80 minutes after the start of the drying and left to cool at room temperature. The substrate was developed with a 1% Na2CO3 aqueous solution at 30 ° C for 60 seconds under a spray pressure of 2 kg/cm 2 , and the maximum allowable drying time of the residue without residue was referred to as the maximum development lifetime. Characteristic test: (Production of coating film evaluation substrate) Each of the prepared photocurable resin compositions prepared by screen printing was applied onto a copper foil substrate on which a pattern was formed by screen printing, and dried at 80 ° C for 20 minutes. 'And let cool to room temperature. A direct drawing device equipped with a semiconductor laser having a maximum wavelength of 355 nm was used on the substrate, and the solder resist pattern was exposed at an optimum exposure amount, and 3 (TC of 1% Na2C03 aqueous solution was sprayed at a pressure of 2 kg/cm 2 ). The development was carried out for 6 sec., and a photoresist pattern was obtained. The substrate was subjected to ultraviolet irradiation at a cumulative exposure of 1 000 mJ/cm 2 in a UV conveyor belt furnace, and then cured by heating at 150 ° C for 60 minutes. The obtained printed circuit board (evaluation substrate) was evaluated for its characteristics as follows. <Solder heat resistance> The evaluation substrate coated with the rosin-based flux was immersed in a solder bath set at -46-200941136 260 °C in advance. After the flux was washed with the modified alcohol, the expansion and peeling of the photoresist layer were visually evaluated. The criteria for the determination were as follows. 〇*: The immersion was repeated 6 times or more for 10 seconds, and no peeling 〇 was observed: repeated 3 times No peeling was observed for the above immersion for 10 seconds. Δ: Repeating for 3 times or more, immersing for 10 seconds, slightly peeling off X: immersion within 3 times, lapse of 1 〇 second, expansion of the photoresist layer, peeling &lt; electroless gold plating resistance gt ; Use of electroless nickel plating bath and electroless plating for commercial products The gold bath was electroplated under conditions of nickel 0.5 μm and gold 0·03 μm, and the photoresist layer was visually evaluated for peeling and the presence or absence of plating penetration, and the photoresist layer was peeled off by tape peeling. The judgment criteria were as follows. 〇* : No soaking or peeling was found: After plating, it was confirmed that there was a little soaking, but there was no peeling after peeling off the tape. △: Only a little soaking was observed after plating, and G peeling was also observed after peeling of the tape: peeling occurred after plating. Evaluation of the alkalinity> The evaluation substrate was immersed in a 10 volume% NaOH solution for 30 minutes at room temperature, and the penetration or coating film dissolution was visually confirmed, and peeling was confirmed by tape peeling. 〇: no penetration or dissolution, and After the tape was peeled off, no peeling was observed. Δ: no penetration or dissolution, and it was confirmed that only a little peeling was observed after peeling off the tape -47- 200941136 X: there was penetration or dissolution, and peeling after tape peeling &lt;PCT resistance&gt; Using PCT device (ESPEC shares) The HAST SYSTEM TPC-4 12MD manufactured by the Co., Ltd. was treated under the conditions of 1 2 1 ° C, saturation, and 0 · 2 MP a for 50 hours to visually confirm the state of the coating film. The peeling was confirmed by tape peeling. The judgment criteria were as follows. 〇: no penetration or dissolution, and peeling was not confirmed after peeling of the tape. △: no penetration or dissolution, and peeling off after tape removal confirmed only a little peeling X: soaked or dissolved, and tape Peeling after peeling &lt;PCBT resistance&gt; The copper foil substrate was replaced by IPC, and the evaluation electrode substrate was fabricated under the above conditions using a comb-shaped electrode B test piece of B-25, and a bias current of DC 30 V was applied to the comb-shaped electrode. The PCT device (HAST SYSTEM TPC-412MD manufactured by ESPEC Co., Ltd.) was treated under a condition of 12 It and a humidity of 97% for 96 hours to evaluate whether or not discoloration or migration occurred. The judgment criteria are as follows. 〇*: No discoloration or migration occurred. 〇: Only a slight discoloration or migrating person occurs. △: Discoloration or migration occurred. X: The color change is remarkable, and the electrode that moves from one side to the other side of the electrode. -48- 200941136 &lt;Electrical characteristics&gt; The copper foil substrate was replaced by IPC, and the evaluation electrode substrate was fabricated under the above conditions using a comb-shaped electrode B test piece of B-2 5, and DC 1 10 V was applied to the comb-shaped electrode. The voltage is biased, and it is confirmed that there is a migration after 1,100 hours under the constant temperature and humidity conditions of 85 ° C and a humidity of 85%. The judgment criteria are as follows. 〇: The change is not confirmed at all. △: There are only a few changes. φ X : The mover occurred. &lt;Coating film color&gt; The color of the cured product was visually judged. The results are not in Table 2. [Table 2] Table 2 (composition examples) Example 1 Example 2 ---1 Example 3 Case 4 Case 5 Case 6 Case 7 Case 8 Case 9 Case 10 Tone green green green green green green green high pressure mercury lamp exposure sensitivity (mJ/cm2) 60 110 60 80 250 19Π /|y|v ΊΠΓ\ 70 4ΠΠ High-pressure mercury lamp Direct exposure sensitivity • y (mJ/cm) 60 110 60 80 250 50 120 jUU 300 70 400 355 nm laser exposure sensitivity (mJ/cm2) 70 130 60 100 300 60 150 80 4^π Finger touch drying 〇〇〇〇Λ jA j Λ 〇V Maximum development life (minutes) 60 60 70 60 50 60 ΙΛ Ζ_Λ AC\ Af\ Solder heat resistance 〇* 〇 , 〇Δ 〇* J\J 〇〇〇*tU Electroless gold plating resistance 〇* X 〇* 〇〇〇* Λ Λ 耐 Testability 〇〇〇〇〇〇ΔΛ Λ /Λ Λ 〇/Λ Λ PCT resistance 〇〇〇〇Λ 〇Λ χ \y Λ ΖΛ χ PCBT resistance 〇* 〇〇* 〇〇* Δ /.Λ Λ 〇Characteristics 〇* 〇— — X 〇* 〇Δ 〇* Δ Δ 〇Δ -49- 200941136 Example 2 &lt;Dry film evaluation&gt; Example 1 of the composition used in Example 1 was diluted with methyl ethyl ketone, coated on a PET film and dried at 80 ° C After 30 minutes, a photosensitive resin composition layer having a thickness of 20 μm was formed. Further, a cover film was attached thereto to obtain a dry film. Subsequently, the cover film was peeled off, and the film was thermally laminated on the copper foil substrate on which the pattern was formed, and then exposed under the same conditions as those used in the evaluation of the film properties of Example 1. After the exposure, the carrier film was peeled off, and heat-hardened in a hot air dryer at 150 ° C for 60 minutes to prepare a test substrate. The test substrate having the obtained hardened film was subjected to various characteristics evaluation tests by the above test methods and evaluation methods. The results are shown in Table 3. [Table 3] Table 3 (composition examples) Example 1 High-pressure mercury lamp exposure sensitivity (mJ/cm2) 60 High-pressure mercury lamp direct exposure sensitivity (mJ/cm2) 60 3 5 5 nm laser exposure sensitivity (mJ/cm2) 70 Touch Dryness 〇 Maximum development lifetime (minutes) 60 Solder heat resistance 〇* Electroless gold plating resistance 〇* Alkali resistance 〇 PCT resistance 〇 PCBT resistance 〇 * Electrical characteristics 〇 * Displayed in Table 2 in Examples 1 and 2 As a result shown in Table 3, the photocurable tree composition containing the carboxylic acid-containing photosensitive resin (A) of the present invention contained in the range of -50 to 200941136 has higher sensitivity and developability than the conventional resin. Finger touch drying, solder heat resistance, electroless gold plating resistance, alkali resistance, and PCT resistance are excellent in PCBT resistance, and can be used as a photoresist ink. Further, it is determined that the photocurable resin composition of the present invention can correspond to monochromatic light or ray light such as i-line or h-line or ultraviolet light source such as a high-pressure mercury lamp. ❹

-51 -

Claims (1)

200941136 X. Patent Application No. 1 · A photocurable resin composition for alkali-developing, which is characterized in that it contains (A) a carboxylic acid-containing photosensitive resin having a structure represented by the general formula (I), and (B) a photopolymerization initiator; (C) a compound having two or more ethylenically unsaturated groups in one molecule: In the formula (I), R1 represents a hydrogen atom or a methyl group, R2 represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, and R3 represents a hydrogen atom or an organic acid ester residue. 2. The photohardenable tree of the alkali-developable image according to the first aspect of the patent application, wherein the R3 in the formula (I) is an acid anhydride residue. 3. The photocurable resin composition for alkali-developable image according to the first aspect of the patent application, wherein r3 in the formula (1) is a (meth)acrylic acid residue 〇4. The alkali-developable photocurable resin composition, wherein the (B) photopolymerization initiator is one or a mixture of two or more selected from the group consisting of: The oxime ester photopolymerization of the structure - 52-200941136, an amine acetophenone-based photopolymerization initiator containing a structure represented by the following formula (III); and a compound represented by the following formula (IV) Constructed fluorenyl phosphorus oxide photopolymerization initiator; ——C=N—0 C~—R〗 ζην L II (,,) In the general formulae (II) to (IV), R1 represents a hydrogen atom, a phenyl group (may also be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), and has a linear chain of 1 to 20 carbon atoms. Branched or cyclic alkyl group (may also 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, and an alkyl group having 2 to 20 carbon atoms Anthracenyl or benzhydryl group (may also be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R2 represents a phenyl group (which may also be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (may be substituted by one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), and a cycloalkane having 5 to 8 carbon atoms. Base, carbon number 2~2 0 alkyl alkalyl group or benzamidine group (can also be substituted by alkyl group with 1 to 6 carbon atoms or phenyl group); -53- 200941136 R3 and R4 are independent of each other Table 7: carbon number 1 ～20 linear, branched or cyclic alkyl or arylalkyl groups, R5 and R6 independently represent a hydrogen atom, a linear chain of 1 to 6 carbon atoms, a branched or cyclical matrix, or R5 And R6 can also be combined to form a cyclic alkyl ether group, R7 and R8 Independently, a linear, branched or cyclical group having a carbon number of 1 to 10, a decyloxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (which may also be substituted by a tooth atom, an alkyl group or an alkoxy group), Or RC(= 〇)-yl (wherein R represents a hydrocarbon group having 1 to 20 carbon atoms) 'except when both R7 and R8 are R_C(= 〇)-based. 5. The photocurable resin composition which can be imaged by the alkali of claim 1 and further contains (D) a thermosetting component. 6. The photocurable resin composition which can be imaged by the alkali of claim 1 of the patent application, which further comprises (E) a colorant. A photocurable dry film obtained by applying a photocurable resin composition according to any one of claims 1 to 6 to a carrier film and drying it. A cured image pattern formed by using a resin layer composed of the photocurable resin composition according to any one of claims 1 to 6 which is characterized by the pattern The formation is carried out by irradiating the active energy ray. 9. The sclerosing pattern of claim 8 of the patent application, wherein the pattern is formed by irradiation of an active energy ray, is directly depicted using an active energy ray having a wavelength of from 3 50 nm to 410 nm. -54- 200941136 i. A printed circuit board characterized by having a hardened pattern of the eighth item of the patent application on the copper layer. -55- 200941136 VII. Designated representative map: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the best display invention. Chemical formula of the feature: none