TW201032003A - Photosetting resin composition, dry film and cured product of the same, and printed wiring board using them - Google Patents

Abstract

Disclosed is a photocurable resin composition that can form a dried coating film, which is highly dry to the touch, has high sensitivity, and can form a cured film which is soft and particularly has a high insulating resistance under high temperature and humidified conditions. Also disclosed are a dry film and a cured product of the photocurable resin composition, and a printed wiring board comprising a cured film such as a solder resist formed using the photocurable resin composition, the dry film and the cured product. The photocurable resin composition is alkaline-developable and comprises a photosensitive resin having a structure represented by general formula (I), a carboxyl group-containing resin, and a photopolymerization initiator. Preferably, the photocurale resin composition further comprises a heat curable component and more preferably further comprises a colorant. In general formula (I), R1s, which may be the same or different, represent a hydrogen atom and an organic group having 1 to 20 carbon atoms; R2 represents at least one functional group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, alkylene groups having 1 to 10 carbon atoms, and phenylene groups; R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R5 represents a hydrogen atom or a methyl group; p is an integer of 1 to 5; q is an integer of 3 or more; m is an integer of 1 to 4; and n is an integer of 1 to 10.

Description

201032003 VI. Description of the Invention: [Technical Field] The present invention relates to a photocurable resin composition which can be developed by a dilute aqueous alkali solution, in particular, a solder resist which is photohardened by ultraviolet exposure or laser exposure. A composition, a dry film and a cured product thereof, and a printed circuit board having a hardened film formed using the same. φ [Prior Art] Conventionally, an alkali-developing photosensitive resin composition has been widely used as a solder resist for printed circuit boards. The solder resist is mainly composed of a carboxyl group-containing resin, a polyfunctional acrylate compound, a photopolymerization initiator, a thermosetting resin, or the like in order to protect the circuit of the printed circuit board. The above polyfunctional acrylate-based compound is mainly used in the form of liquid polyfunctional polyester acrylate from the viewpoint of high sensitivity and development resistance. However, when exposed, when the negative film is directly attached to the dry exposure film, the dry film is required to be touched. • Dry (non-stickiness). In order to improve the photocurability, a photosensitive resin composition of a liquid polyfunctional polyester acrylate is used in a large amount, and there is a problem that the dryness of the dry coating film is poor. Therefore, the amount of the liquid polyfunctional polyester acrylate used is limited. In response to this, it is proposed to use a semi-solid polyester (meth) acrylate to improve the dryness of the touch (refer to Patent Document 1). However, at this time, since the polyester (meth) acrylate is bifunctional and has a semi-solid shape, the sensitivity is lowered, and in order to improve the softening point of the dried coating film, the developing property is lowered. Further, the solder resist is as described above for protecting the surface of the printed circuit board -5 - 201032003, and requires high solder heat resistance and electrical insulation. However, since the photosensitive resin is an acrylate-based compound, it is inferior in hydrophobicity and alkali resistance, and needs to be improved in terms of electrical insulation properties in which the insulation resistance 値 is lowered under high-temperature humidification conditions, and ion migration occurs to cause an inter-circuit short circuit. The problem. In this regard, Patent Document 2 discloses a carboxyl group-containing photosensitive product obtained by reacting a reaction product of an epoxy compound having two or more epoxy groups and a monocarboxylic acid containing an unsaturated group in a molecule with a polybasic acid anhydride. The resin-containing resin, the reaction product of the phenolic phenol resin and the epoxide, and the carboxyl group-containing photosensitive resin obtained by reacting the reaction product obtained by reacting the monocarboxylic acid containing the unsaturated group with the polybasic acid anhydride, have good dryness to the touch. An example of a photosensitive composition excellent in adhesion. However, the carboxyl group-containing photosensitive resin obtained by reacting a reaction product of a phenolic phenol resin and an epoxide with a reaction product obtained by reacting a monocarboxylic acid containing an unsaturated group with a polybasic acid anhydride is added to a hydroxyl group produced by ring opening of an epoxide Since the unsaturated group contains a carboxylic acid and a polybasic acid anhydride, the content of the unsaturated group is reduced in order to obtain a necessary acid value, and in order to contain a large amount of unsaturated groups, the necessary acid value cannot be obtained, and the sensitivity and the display are apparent. Like the choice of ©. Patent Document 1: International Publication No. WO 03/075095 A1 (Application No.) Patent Document 2: JP-A-2003-2801 No. 89 (Application No.) [Summary of Invention] Problem to be Solved by the Invention -6 - 201032003 The present invention is related to In view of the above conventional problems, the object of the present invention is to provide a dry coating film which is excellent in finger-drying property, high in sensitivity, soft solder heat resistance, electroless gold resistance, moisture resistance, electrical insulation, and the like, particularly A photocurable resin composition of a hardened film such as a solder resist having a high insulation resistance at high temperature and humidification can be formed. Further, an object of the present invention is to provide a dry film and a cured product which are excellent in the above-described properties obtained by using such a photocurable resin composition, and a cured film formed by forming a solder resist such as a dry film and a cured product. In order to achieve the above object, in accordance with the present invention, a photocurable resin composition capable of providing an alkali developability, characterized in that it contains a photosensitive material having a structure represented by the following general formula (I) A resin (hereinafter referred to as "photosensitive resin"), a ruthenium-based resin, and a photopolymerization initiator. ❷ 【化1】

(wherein R1 is a hydrogen atom or an organic group having 1 to 20 carbon atoms, which may be the same or different. R2 represents an alkyl group selected from carbon number 10, an alkyl group having 1 to 10 carbon atoms, and 201032003 a functional group of at least one of the groups, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R5 represents a hydrogen atom or a methyl group, P system An integer of 1 to 5 is represented, q is an integer of 3 or more, m is an integer of 1 to 4, and η is an integer of 1 to 1 )). A preferred embodiment is the photocurable resin composition of claim 1, wherein the photosensitive resin does not contain an acid and has a double bond equivalent of 200 or more than 400. Further, the photosensitive resin is a photosensitive resin obtained by reacting a compound having three or more phenolic hydroxyl groups in one molecule with a cyclic ether compound or a cyclic carbonate compound, and reacting the generated hydroxyl group with a compound having an ethylenically unsaturated group. Resin. In this case, a compound having three or more phenolic hydroxyl groups in one molecule is preferably a compound having a phenolic hydroxyl group having a softening point of room temperature or higher, and the compound having an ethylenically unsaturated group is preferably Methyl propylene D acid. Preferably, the oxime contains a thermosetting component, preferably 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. According to the present invention, it is possible to provide a photocurable dry film obtained by applying the photocurable resin composition onto a carrier film and dried, or curing the photocurable resin composition or the dry film. A cured product or a cured product obtained by photohardening, in particular, on copper, or a cured product obtained by photohardening into a pattern of -8 - 201032003. According to the present invention, it is possible to provide a printed wiring board having a cured film obtained by thermally curing the photocurable resin composition or a photocured film of a dry film. Advantageous Effects of Invention The photocurable resin composition of the present invention is a photosensitive resin containing a structure represented by the general formula (I), and particularly contains no acid, and has a double bond equivalent of 200 or more and 400 or less. . The photosensitive resin is obtained by reacting a compound having three or more phenolic hydroxyl groups in one molecule with a cyclic ether compound or a cyclic carbonate compound, and reacting the resulting hydroxyl group with a compound having an ethylenically unsaturated group, and drying and coating The film is excellent in dryness to the touch, high in sensitivity, soft solder heat resistance, electroless gold resistance, moisture resistance, electrical insulation, and the like, and particularly, a hardened film having high insulation resistance at high temperature and humidification can be formed. Further, the photosensitive resin and the carboxyl group-containing resin are contained, and the resulting photocurable resin composition can be developed by an aqueous alkali solution. Therefore, the photocurable resin composition of the present invention can be suitably used for a hardened film of a printed circuit board or a solder resist which forms a flexible printed circuit board. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described. As described above, the photocurable resin composition of the present invention is characterized in that the photosensitive resin is a photosensitive resin containing the structure represented by the above general formula (I). According to the inventors of the present invention, it has been found that the dry coating film of the photocurable resin composition obtained by the photosensitive resin having the structure represented by the above formula (I) is excellent in finger-drying property and hardened. The insulation resistance of the film under high-temperature humidification conditions is high, and there is no ion migration in the case where the photosensitive resin is not contained, and there is no problem for a long time. In particular, a compound containing no such acid and having a double bond equivalent of 200 or more and 400 or less, and a compound having three or more phenolic hydroxyl groups in one molecule is reacted with a cyclic ether compound 或 or a cyclic carbonate compound to form a reaction product. When the photosensitive resin obtained by reacting a hydroxyl group with a compound having an ethylenically unsaturated group, the sensitivity was found to be improved. More surprisingly, as the amount of the photosensitive resin used is increased, the elongation of the cured film can be improved. Therefore, the cracking resistance, the flexibility, and the impact resistance of the hardened film are excellent, which is an unexpected effect that is unexpected. The photosensitive resin contains three or more structures (q23) represented by the above general formula (I) in one molecule. When the structure 〇 represented by the above general formula (I) is two or less in one molecule, high sensitivity cannot be achieved by one of the objects of the present invention, and particularly in the case of a solder resist, the surface has poor hardenability, and as a result, high temperature humidification The electrical insulation is low and ion migration occurs. Similarly, a double bond equivalent of 200 or less is structurally impossible, and when it is 400 or more, high sensitivity cannot be achieved, and electrical insulation and ion mobility are poor. Therefore, the double bond equivalent is preferably 200 or more and 400 or less. The photosensitive resin containing the structure represented by the above general formula (I) can be synthesized by a conventionally known method, and it is preferred to use a compound having a phenolic hydroxyl group of three - 10 2010 3 2003 or more and a cyclic ether compound in one molecule. Or a photosensitive resin obtained by reacting a cyclic carbonate compound with a compound having an ethylenically unsaturated group. Further, when the photosensitive resin obtained by reacting the alcoholic hydroxyl group with the compound having an ethylenically unsaturated group has three or more structures represented by the above general formula (1), the alcoholic hydroxyl group may remain. The compound having three or more phenolic hydroxyl groups in the above-mentioned one molecule is, for example, a novolac type phenol resin. The novolac type phenol resin is obtained by the condensation of phenol with formaldehyde, and usually these reactions are carried out in the presence of an acidic catalyst. The phenols used for the synthesis of the phenolic phenol resin include, for example, phenol, cresol, ethyl phenol, propanol, butanol, hexanol, octylphenol, indophenol, phenol, cumene, bisphenol A, bisphenol F, These may be used alone or in large quantities, such as dimethicone. Further, a condensate of a phenol and an aromatic aldehyde having a phenolic hydroxyl group, a condensate of poly-P-hydroxystyrene, 1-naphthol or 2-naphthol and an aldehyde (that is, a naphthol type phenol resin), Condensate of 1,2-, 1,3-, 1,4-, 1,5-, 1,6-' 2,3-, 2,6-, 2,7-dihydroxynaphthalene and aldehydes, single a condensate of naphthol with the above dihydroxynaphthalene and an aldehyde, a condensate of a mono- or dihydroxynaphthalene with a xylene glycol, an adduct of a mono- or dihydroxynaphthalene with a diene compound, a phenol and a bis (methoxy A condensate of a methyl group)biphenyl, etc., but is not limited thereto. In particular, the phenol resin is preferably one having an average number of phenol cores of 3 or more. In the above-mentioned cyclic ether compound or cyclic carbonate compound, the cyclic ether compound may, for example, be ethylene oxide, propylene oxide, 1,2-butylene oxide, trimethylmethane, tetrahydrofuran or tetrahydropyran. Further, the cyclic carbonate compound is, for example, ethylene carbonate and/or propylene carbonate. Particularly preferred are ethylene oxide and propylene oxide. -11-201032003 The compound having an ethylenically unsaturated group is, for example, a acrylic acid or a methacrylic acid, and is particularly preferably methacrylic acid from the viewpoint of alkali resistance or electrical insulating properties. The photosensitive resin using methacrylic acid is highly sensitive, in particular, excellent in alkali resistance and electrical properties, and can provide a high insulating resistance at high temperature and humidification, which is an unexpected result that has not been seen in the past. The amount of the photosensitive resin to be added is, for example, 1 to 100 parts by mass, preferably 5 to 60 parts by mass, more preferably 10 to 40 parts by mass, per 1 part by mass of the carboxyl group-containing resin. When the amount of the photosensitive resin is more than @ in the above range, the alkali developability is lowered, and the solution produces a development residue. When the amount is 1 or less, the image forming ability is affected, which is not preferable. The carboxyl group-containing resin is a conventionally known various carboxyl group-containing resin having a carboxyl group in its molecule in order to impart alkali developability. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in its molecule is more preferable in terms of photocurability or development resistance. The unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof. Specific examples of the carboxyl group-containing resin are preferably, for example, an anthracene compound (oligomer or polymer) exemplified below. (1) A copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with a compound containing styrene or an unsaturated group containing (X-methylstyrene, lower alkyl (meth) acrylate or isobutylene) a carboxyl group-containing resin. (2) A diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a dimethylol group A carboxyl group-containing diol compound such as an acid or dimethylolbutanoic acid, a polycarbonate polyol, a polyether polyol, a polyester polyol-12-201032003 alcohol, a polyolefin polyol, or an acrylic polyol A carboxyl group-containing urethane resin obtained by a polymerization addition reaction of a diol compound such as a bisphenol A-based alkylene oxide adduct diol or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group. (3) Diisocyanate and bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, dimethicone epoxy resin, bisphenol type (meth)acrylic acid of 2-functional epoxy φ resin such as epoxy resin a photosensitive carboxyl group-containing urethane resin obtained by a polymerization addition reaction of an ester or a partial acid anhydride modified product thereof, a carboxyl group-containing diol compound, and a diol compound. (4) In the above (2) or (3) In the synthesis of the resin, a compound having one hydroxyl group and one or more (meth)acrylic groups in a molecule such as a hydroxyalkyl (meth) acrylate is added, and the terminal (meth) acrylated photosensitive content is added. a carboxyl group of a urethane resin. (5) In the synthesis of the resin of the above (2) or (3), a molar reaction product such as iso-p-bulcone diisocyanate and pentaerythritol triacrylate is added in the molecule. A carboxyl group-containing urethane resin having a terminal (meth) acrylated compound having one isocyanate group and one or more (meth)acrylic groups. (6) The following bifunctional or bifunctional or higher functional group The polyfunctional (solid) epoxy resin reacts with (meth)acrylic acid to attach a dibasic acid anhydride to the photosensitive carboxyl group-containing resin of the hydroxyl group of the side chain. (7) The following bifunctional (solid) epoxy resin is used. The hydroxyl group is further treated with epichlorohydrin An epoxidized polyfunctional epoxy resin, which reacts with (meth)acryl-13-201032003 acid to attach a dibasic acid anhydride to a photosensitive carboxyl group-containing resin which is formed into a hydroxyl group. (8) The following bifunctional oxygen is used. The heterocyclic butane resin is reacted with a dicarboxylic acid, and a dibasic acid anhydride is added to the carboxyl group-containing polyester resin in which the first-order hydroxyl group is formed. (9) In the above (1) to (8) resin, one molecule is added in one molecule. A photosensitive carboxyl group-containing resin formed of a compound having an epoxy group and one or more (meth)acrylic groups. Further, in the present specification, the (meth)acrylate is an acrylate or a methacrylate. The general term for these mixtures is also the same for other similar functions. The above-mentioned carboxyl group-containing resin can be expressed by a dilute aqueous alkali solution because it has a plurality of free carboxyl groups in the side chain of the backbone polymer. image. Further, the acid value of the carboxyl group-containing resin is in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, alkali imaging is difficult, and when it is more than 200 mgKOH/g, the film is dissolved in the exposed portion by the developing solution, so that the line becomes too fine, or sometimes the exposed portion is The unexposed portions are all dissolved and peeled off by the developing solution, and it is difficult to draw a normal photoresist pattern, which is not preferable. Further, the weight average molecular weight of the above carboxyl group-containing resin varies depending on the resin skeleton, and is usually in the range of 2,000 to 150,000, preferably in the range of 5,000 to 10,000,000. When the weight average molecular weight is less than 2,000, there is a case where the coating film has poor tackiness (dryness of touch), and the moisture resistance of the coating film after exposure is poor, and film formation is reduced during development, and sometimes The resolution is very poor -14-201032003. Further, when the weight average molecular weight is more than 150,000, 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. On the other hand, when the amount 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.

The use of the carboxyl group-containing resin is not limited to the above-mentioned ones, and it may be used alone or in combination of two or more.

The photopolymerization initiator is preferably selected from the group consisting of the following general formula (II)

An oxime ester photopolymerization initiator represented by the group, an α-aminoacetophenone photopolymerization initiator having the group represented by the following general formula (III), and/or having the following formula (IV) One or more kinds of photopolymerization initiators in a group of a mercaptophosphine-based photopolymerization initiator represented by the group. [Chemical 2]

—C=N—Ο—C—R7

(Π)

(HI)

(1V> -15-201032003 (wherein R6 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), and an alkyl group having 1 to 2 carbon atoms ( 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 a benzhydryl group (may be An alkyl group having 1 to 6 carbon atoms or a phenyl group); R7 represents 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 an alkyl group having 1 to 2 carbon atoms ( It may be substituted by one or more hydroxyl groups, may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkylidene group having a carbon number of 5 to 8, an alkanoyl group having a carbon number of 2 to 20 or a benzhydryl group ( It may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group; R8 and R9 each independently represent an alkyl group or an aralkyl group having 1 to 12 carbon atoms; R1Q and R11 each independently represent a hydrogen atom and a carbon number. 1 to 6 alkyl groups, or 2 bonded cyclic alkyl ether groups; R12 and R13 each independently represent a linear or branched alkyl group having a carbon number, a cyclohexyl group, a cyclopentyl group , aryl, or by halogen atom, alkyl or alkoxy a substituted aryl group, but one of R12 and R13 may represent R-@C(=0)- group (wherein R is a hydrocarbon group having 1 to 20 carbon atoms). The group having the above general formula (Π) The oxime ester photopolymerization initiator is preferably, for example, 2-(ethylhydrazinylmethyl)thioxanthene-9-one represented by the following formula (V), which is represented by the following general formula (VI). a compound and a compound represented by the following general formula (VII): -16- 201032003 [Chemical 3]

[化4] (V)

(VI) (wherein r14 represents a hydrogen atom, a halogen atom, an alkyl group of a carbon number, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamyl group, a carbon number of 2 to 12 a mercapto group or an alkoxycarbonyl group having 2 to 12 carbon atoms (when the carbon number of the alkyl group constituting the alkoxy group is 2 or more, the alkyl group may be substituted by one or more hydroxyl groups, and the alkyl chain may have one or more in the middle. An oxygen atom), or a phenoxycarbonyl group; R15 and R17 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 an alkyl group having 1 to 20 carbon atoms (may be One or more hydroxy groups may be substituted, 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 alkyl fluorenyl group having 2 to 20 carbon atoms or a benzhydryl group (carbon Number 1 to 6 alkyl or phenyl substituted); R16 is 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-17-201032003 atom), and a carbon number of 20 a hospital base (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, an alkylene group having a carbon number of 2 to 2 or benzamidine Base (alkane which can be 1 to 6 carbon atoms) Substituted or substituted by phenyl)). 【化5】

(VII) (wherein R18, R19 and R24 each independently represent an alkyl group having 1 to 12 carbon atoms, and R2Q, R21, R22 and R23 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; The lanthanide system represents 0, S or NH, and the X and y groups each independently represent an integer of 〇~5. The oxime ester photopolymerization initiator is more preferably 2-(T) represented by the above general formula (V). Ethyl mercaptomethyl)thioxan-9-one and compounds not of formula (VI). Commercially available products are CGI-3 25 manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE OXEO1, IRGACURE OXE02, N-1919 manufactured by ADEKA Co., Ltd., and the like. These oxime ester-based photopolymerization initiators can be used singly or in combination of two or more. The α-amino acetophenone-based photopolymerization initiator having the group represented by the general formula (III) is, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine. Acetone-1,2-benzyl-2-dimethylamino-1(4-morpholinophenyl)-butane-1- -18- 201032003 ketone, 2-(dimethylamino)-2 -[(4-Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, and the like. Commercially available products include IRGACURE 907, IRGACURE 369, and IRGACURE 3 79 manufactured by Ciba Specialty Chemicals. The mercaptophosphine oxide-based photopolymerization initiator having the group represented by the general formula (IV) is, for example, 2,4,6-trimethylbenzimidyl diphenyl scaly oxide, bis (2, 4) ,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-φdimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide Wait. Commercially available products include Lucirin TPO manufactured by BASF Corporation and IRGACURE 819 manufactured by Ciba Specialty Chemicals. The blending amount of the photopolymerization initiator is preferably in the range of 1 to 30 parts by mass, preferably 0.5 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the amount is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating properties such as peeling of the coating film or 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 becomes severe, and the deep hardenability tends to decrease, so that it has the above general formula ( In the case of the above-mentioned base ester-based photopolymerization initiator, it is preferably 〇_〇1 to 20 parts by mass, more preferably 0.01 to 100 parts by mass of the carboxyl group-containing resin. A range of 5 parts by mass. The combination of ethylene-dimerized benzene, light and substance hydrates into a ketone group due to the fat-reducing couple, the benzene-like property of the compound, such as the hard ketone light agent, the sensitization of thiophene, the hair and the substance The initial use of the auxiliary is 蒽, and the light, the external and the physical agent are combined to form the ketone-19- 201032003 benzophenone compound, xanthone compound and tertiary amine compound. Specific examples of the benzoin compound are benzoin, benzoin methyl ether, benzoin acetic acid, and benzoin isopropyl ugly. Specific examples of the acetophenone compound are acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1- Specific examples of the dichloroacetophenone oxime compound are 2-methyl hydrazine, 2-ethyl hydrazine, 2 - t-butyl hydrazine, and chloropurine. Specific examples of the thioxanthone are 2,4-dimethylthioxanthone, 2,4-diethylthioketone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone. Specific examples of the ketal compound are acetophenone dimethyl ketal and benzyl dimethyl ketal. Specific examples of the benzophenone compound are benzophenone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzylidene group. -4,-Ethyl diphenyl sulfide 4-benzylidene-4'-propyldiphenyl sulfide. Specific examples of the 3-polar amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4'-dimethylaminobenzophenone (made by Nippon Soda Co., Ltd. 33; (1^6) Diethylaminobenzophenone, 7-(diethylamino)-4, etc., such as 6?), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) a dialkylamino group-containing coumarin compound such as methyl-2H-bromopyran-2-one (7-(diethylamino)-4-methylcoumarin), 4-di Methylaminobenzoic acid ethyl ketone (Kayacure EPA, manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylaminobenzoic acid vinegar (Quantacure DMB, manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) B) 201032003 vinegar (Quantacure BEA, manufactured by International Bio-Synthetics Co., Ltd.), isoamyl ethyl p-dimethylaminobenzoate (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-diethylaminobenzoic acid 2-B Hexyl ester (Van

ESOOO1 507), 4,4'-diethylaminobenzophenone (EAB made by Hodogaya Chemical Co., Ltd.) manufactured by Dyk Co., Ltd. Among the above compounds, a thioxanthone compound and a tertiary amine compound are preferred. In the composition of the present invention, a φ thioxanthone compound is preferred from the viewpoint of deep hardenability, and among them, 2,4-dimethylthioxanthone and 2,4·diethyl thioxanthone are preferred. A thioxanthone compound such as 2-chlorothioxanthone or 2,4-diisopropylthioxanthone. The amount of the thioxanthone compound to be added is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 1 part by mass of the carboxyl group-containing resin. When the amount of the thioxanthone compound is too large, the thick film hardenability is lowered, and the cost of the product is increased, which is not preferable. The tertiary amine compound is preferably a compound having a dialkylaminobenzene structure, wherein a dialkylaminobenzophenone compound and a dialkylamine group having a maximum absorption wavelength of from 3 to 50 nm are preferably used. Coumarin compound. The dialkylaminobenzophenone compound is preferred because it has a low toxicity due to its 4,4'-diethylaminobenzophenone. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 41 Onm is a coloring pigment because the maximum absorption wavelength is in the ultraviolet range, and the colorless and transparent photosensitive resin composition is initially used as a coloring pigment. A colored solder resist film reflecting the color of the coloring pigment itself is provided. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm. In the case of 100 parts by mass of the carboxyl group-containing resin, the amount of the above-mentioned tertiary amine compound is preferably from 1 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass. When the amount of the tertiary amine compound is not more than 1 part by mass, there is a tendency that a sufficient sensitizing effect is obtained. In addition, when it exceeds 20 parts by mass, the light absorption on the surface of the dry solder resist coating film of the tertiary amine compound becomes severe, and thus the deep hardenability tends to be lowered. These photopolymerization initiators, photoinitiating aids, and sensitizers may be used singly or in combination of two or more. The total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is preferably in the range of 35 parts by mass or less based on 1 part by mass of the carboxyl group-containing resin. When the amount is more than 35 parts by mass, the light is absorbed and the deep hardening property tends to be lowered. In the photocurable resin composition of the present invention, in order to improve the sensitivity, conventional N-phenylglycines, phenoxyacetic acids, sulfurized phenoxyacetic acids, mercaptothiazoles, and the like can be used as the chain-linking agent. . Specific examples of the chain-linking agent include a chain-linking agent having a carboxyl group such as mercapto succinic acid, mercaptoacetic acid, mercaptopropionic acid, azlaconic acid, cysteine, ortho-benzoic acid, and derivatives thereof: mercapto group a chain-shifting agent having a hydroxyl group such as ethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3- Mercaptopropionate, methyl-3-mercaptopropionate, 2,2-(extended ethylene dioxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecane Thiol, propane thiol, butane thiol, pentane thiol, 1-octane thiol, cyclopentane thiol, cyclohexane thiol, glycerol sulfide, 4,4-sulfurized benzene sulfide Alcohol, etc. -22- 201032003 In addition, as a chain-shifting agent, a heterocyclic compound having a mercapto group, for example, a mercapto-4-butyrolactone (alias: 2-mercapto-4-butyrolactone), 2-mercapto-4 -methyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butylsulfide lactone, 2-mercapto-4-butylidene, N _Methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butylidene, N-methyl-2-mercapto-4-butylidene, N-ethyl-2-mercapto-4_butylide, N-(2-methoxy)-ethyl-2-mercapto-4-butylidene, N-(2-ethoxyl Ethyl-2-mercapto-4-pyridylamine, 2-mercapto-5-valerolactone, 2-mercapto-5-pentalinamide, N-methyl-2-indenyl- 5-pentalinamide, N-ethyl-2-mercapto-5-pentalinamide, N-(2-methoxy)ethyl-2-mercapto-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 a 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 can be used alone or in combination of two or more. In the photocurable resin composition of the present invention, a thermosetting resin 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 a sulfur. A known thermosetting resin such as an ether resin or a melamine derivative. Particularly preferred is a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule. -23- 201032003 The thermosetting component having two or more cyclic (thio)ether groups in the molecule is a cyclic ether group having 3, 4, or 5 rings in the molecule, or a cyclic thioether group. Any one or a compound having two or more kinds of two groups, for example, a compound having at least two or more epoxy groups in a molecule, that is, a polyfunctional epoxide having at least two or more oxygen ring groups in the molecule A compound of an alkyl group, that is, a polyfunctional oxycyclobutane compound, or a compound having two or more thioether groups in a molecule, that is, a surface sulfuric acid resin. The polyfunctional epoxy compound is, for example, Q JER82 8 manufactured by Nippon Epoxy Co., Ltd., JER834, JER1 00 1, JER 1 004, Epiclon 840, Epiclon 850, Epiclon 1 050' manufactured by Dainippon Ink and Chemicals.

Epiclon 2055, Epotot YD-011, YD-013, YD-127, YD-128, manufactured by Dongdu Chemical Co., Ltd., DER 317, DER331, DER661, DER664, manufactured by Dow Chemical Co., Ltd., araldite607 from Ciba · Specialty Chemicals 1 , araldite60 84, ara 1 dite GY250, araldite GY260, Sumitomo Chemical Co., Ltd., Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Industrial Co., Ltd. AER330, AER331, AER661, AER664, etc. (both trade names) of bisphenol A epoxy resin; JERYL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152 manufactured by Dainippon Ink Chemical Industry Co., Ltd., Epiclon 165, Epotot manufactured by Dongdu Chemical Co., Ltd. D. E · R · 5 4 by YDB-400, YDB-500, Dow C h em ic al 2

Ciba · Specialty · Chemicals company's araldite 8011, Sumitomo Chemical Industries Co., Ltd. Sumi-epoxy ESB-400, ESB-700, Asahi Kasei Industrial Co., Ltd. AER 711, AER714, etc. (all are business -24 - 201032003 product name) Brominated epoxy resin; JER 1 52 manufactured by Japan Epoxy Resin Co., Ltd., JER154, DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., Epiclon N-730, Epiclon N-770 manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epiclon N-865, Epotot YDCN-701, YDCN-704, manufactured by Dongdu Chemical Co., Ltd., araldite ECN 1 235, araldite ECN1273, araldite ECN1299 'araldite XPY3 07, manufactured by Ciba Specialty Chemicals, EPPN-201, manufactured by Nippon Kayaku Co., Ltd. EOCN-1 025, EOCN-1020, EOCN-104S, RE-3 06, Sumi-Epoxy ESCN-195X manufactured by Sumitomo Chemical Industries, Inc., ESCN-220, AER ECN-235, ECN-299, etc., manufactured by Asahi Kasei Industrial Co., Ltd. (all are trade names) phenolic epoxy resin; Epiclon 830 manufactured by Dainippon Ink Chemical Industry Co., Ltd., JER807 manufactured by Japan Epoxy Resin Co., Ltd., manufactured by Dongdu Chemical Co., Ltd.

Epotot YDF-170, YDF-175, YDF-2004, Ciba · Specialty • Chemicals company araldite XPY306 (all are trade names) bisphenol F-type epoxy resin; Dongdu Chemical Co., Ltd. Epotot ST-2004, φ Hydrogenated bisphenol A epoxy resin such as ST-2 007 and ST-3000 (both trade names); JER604 manufactured by Nippon Epoxy Co., Ltd., Epotot Y Η - 4 3 4 manufactured by Dongdu Chemical Co., Ltd., Ciba · Specialty · agardite MY720 from Chemicals, Sumi-Epoxy ELM-120 from Sumitomo Chemical Industries, Inc. (both trade names), epoxy propylamine epoxy resin, and araldite CY-3 5 0 from Ciba Specialty Chemicals Product name) Ethyl urea-based epoxy resin type epoxy resin; CELLOXID 202 manufactured by Daicel Chemical Industry Co., Ltd., aralditeCY175, CY179, etc. (all are trade names) manufactured by Ciba Specialty Chemicals Co., Ltd.环-25- 201032003 Oxygen resin; YL-93 made by Nippon Epoxy Co., Ltd. 3, TEN 'EPPN-501, EPPN-502, etc. (all trade names) made by Dow Chemical Co., Ltd. Resin; Japan Oxygen resin company 联1_ 6056, YX-4000, YL-6121 (both trade names) and other bi-xylenol type or bisphenol type epoxy resin or a mixture of these; EBPS-200 made by Nippon Kayaku Co., Ltd. Epoxy resin company EPX-30, Dainippon Ink Chemical Industry Co., Ltd. EXA-1514 (all trade name) and other bisphenol S type epoxy resin; Japan Epoxy resin company JER 15 7S (trade name) Bisphenol A phenolic epoxy resin; JERYL-931 manufactured by Nippon Epoxy Co., Ltd., araldite 163 manufactured by Ciba ♦ Specialty Chemicals Co., Ltd. (all are trade names), tetraphenol ethane type epoxy resin Ciba · araldite PT810 manufactured by Specialty Chemicals Co., Ltd., TEP 1C manufactured by Nissan Chemical Industries Co., Ltd. (all of which are trade names), heterocyclic epoxy resin, and diethylene propyl benzoate such as Blenmer DGT manufactured by Nippon Oil & Fats Co., Ltd. Acid ester resin; tetra-glycidyl dimethyl phenol 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-4750, EXA-4 700, etc. containing naphthyl Epoxy resin; epoxy resin having a dicyclopentadiene skeleton such as HP-72 00 and HP-7200H manufactured by Dainippon Ink Chemicals Co., Ltd.; epoxy propyl group of CP-50S, CP-50M, etc. manufactured by Nippon Oil & Fats Co., Ltd. a methacrylate copolymerized epoxy resin; a copolymerized epoxy resin of cyclohexylmaleimide and a glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative (for example, 〇3)丨〇61 Chemical Industry Company? 8-3600, etc., CTBN modified epoxy tree (for example, YR_i〇2, YR-201032003450, etc. manufactured by Tosho Kasei Co., Ltd.), etc., but are not limited thereto. These epoxy resins may be used alone or in combination of two or more. Among these, a phenolic epoxy resin, a heterocyclic epoxy resin, a bisphenol A epoxy resin or a mixture thereof is particularly preferred. The above polyfunctional oxetane compound is, for example, bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetan) Alkyl methoxy)methyl]ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl) 3--3-oxetanemethoxy φ)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxocycle) Butyryl)methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methylmethyl An acrylate or a polyfunctional oxetane such as an oligomer or a copolymer thereof, an oxetane with a novolak resin, a poly(P-hydroxystyrene), a cardo type bisphenol, An etherified product of a resin having a hydroxyl group such as calixarene, cup-containing resorcinol aromatic hydrocarbon or sesquiterpene oxide. Other examples include unsaturated oxirane rings and copolymers of monomers and alkyl (meth) acrylates. Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A-type thioether resin YL7000 manufactured by Nippon Epoxy Co., Ltd., and the like. Further, the same synthesis method may be employed, in which an oxygen atom of an epoxy group of a novolac epoxy resin is substituted with a sulfur atom-containing episulfide resin. The amount of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is preferably from 0.6 to 2.5 equivalents, more preferably from 0.8 to 2.0, per equivalent of the carboxyl group of the carboxyl group-containing resin. The range of equivalents. When the amount of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is less than 0.6 equivalent, the carboxyl group remains in the solder resist and has heat resistance and alkali resistance. Electrical insulation and the like are lowered, which is not preferable. In addition, when the amount of the cyclic (thio)ether group having a low molecular weight remains in the dried coating film, the strength of the coating film or the like is lowered, which is not preferable. In the photocurable resin composition of the present invention, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule as a thermosetting component can be added. The compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more different isocyanate groups in one molecule, that is, a polyisocyanate compound, or in one molecule. A compound having two or more blocked isocyanate groups, that is, a blocked isocyanate compound or the like. As the aforementioned polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisofluoride or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate are 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, oxime-xylene Isocyanate, m-xylene diisocyanate and 2,4-toluene dimer oxime. 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 protected by the reaction of the isocyanate group with the block agent, and is temporarily deactivated by heating the base to an inert temperature at a predetermined temperature of -28-201032003. The isocyanate group block isocyanate compound is an addition reaction product of an isocyanate compound and an isoester block agent. The isocyanate which can be reacted with the block agent, for example, a trimeric isocyanate type, a biuret type, or an addition type isocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyacrylate or an alicyclic polyisocyanate. Specific 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, φ toluene diisocyanate, naphthalene-1,5-diisocyanate, oxime-xylene diisoester, m- aromatic polyisocyanate Xylene diisocyanate and 2,4-toluene dimer. Specific examples of the aliphatic cyanate ester are tetramethylene diisocyanate, hexamethylene dicarboxylate, methylene diisocyanate, and trimethylhexamethylene diisocyanate 4,4-methylene double ( Cyclohexyl isocyanate) and isophorone diisocyanide. A specific example of the alicyclic polyisocyanate is dicycloheptane triisocyanate. The isocyanate block agent is, for example, a phenolic blocker such as phenol, cresol, xylenol or chlorophenol or the like: ε·caprolactam, δ-valeroinamide, γ-butanamine and β-propene. An internal amide-based block agent such as guanamine; an active methylene-based block agent such as ethyl acetoacetate; methanol, ethanol, butanol, pentanol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene dibutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, ethanol ester, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate Agent; anthraquinone blocker such as formaldehyde hydrazine, acetald oxime, acetamidine, methyl ethyl ketone oxime, fluorenyl hydrazine, cyclohexane hydrazine, etc.; butyl thiol, hexanol, t-butyl thiol a sulfur block agent such as thiophene, methylthiophene or ethylthiophene; an acid amide group block such as decylamine or benzoguanamine; cyanate esterification. Examples of the isocyanide are 2,6-cyanocyanine polyisocyanate, acid ester and ethyl decyl ester, and propanol mono-acid methyl alcohol thiol amber -29-201032003 bismuth imide and horse An imide blocker such as bismuthimide; an amine blocker such as xylidine, aniline, butylamine or dibutylamine: an imidazole blocker such as imidazole or 2-ethylimidazole An imine blocker such as methyleneimine or propylimine. The blocked isocyanate compound may be a commercially available product, for example, Sumijur BL3175, BL-4165, BL-1100, BL-1 265, Desmojur TPLS-2957 > TPLS-2062, TPLS-2078, manufactured by Sumitomo B aer urethane Co., Ltd. TPLS-2117 ' Desmosamu 2170, desmosamu 2265, Coronato 2512, Coronato 2513, Coronato 2520, manufactured by Mitsui Takeda Chemical Co., Ltd., B-830, B-815, B-846, B-870, B-874, manufactured by Polyurethane Industries, Japan , B-882, TCA-B80E, 17B-60PX, E402-B80T (both trade names) manufactured by Asahi Kasei Chemicals. Further, Sumijur BL-3175 and BL-4265 were obtained by using methyl ethyl hydrazine as a block agent.

The compound having two or more isocyanate groups or blocked isocyanate groups in one molecule may be used alone or in combination of two or more. G such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 1 part by mass based on 1 part by mass of the carboxyl group-containing resin. Good for a ratio of 2 to 70 parts by mass. When the amount of the above-mentioned compounding amount is less than 1 part by mass, the sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the preservation stability is lowered, which is not preferable. The thermosetting component is, for example, a melamine derivative or a benzoguanamine derivative. For example, there are a methylol melamine compound, a methylol benzoguanamine -30-201032003 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 the human body or the environment. Such commercially available products are, for example, Cymel 3 00, 301, 3 03, 370, 3 25, 327, 701, 266, 267, 238, and 1141, manufactured by Mitsui Cyanamide Co., Ltd. , the same 272, the same 202, the same 1156, the same 1158, the same 1123, the same 1170, the same 1174, the same UFR65, the same 300, three and the chemical system of the Nikalac Μx-75 0, the same x038 2, with Mx -270, the same as Mx-28 0, the same Mx-290, the same Mx-706, the same Mx-708, the same Mx-40, the same Mx-31, the same Ms-11' with Mw-30, the same Mw-30HM, the same Mw-390, the same Mw-100LM, the same Mw-750LM (above is the trade name). The above-mentioned thermosetting component may be used alone or in combination of two or more. When the above-mentioned thermosetting component having two or more cyclic (thio)ether groups in the molecule is used, it is preferred to contain a thermosetting catalyst. The thermosetting catalyst is, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl Imidazole derivatives such as -2-phenylimidazole, ll-CS-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide; benzyldimethylamine, 4-(dimethyl Amino group)-Ν, Ν-dimethyl-31 - 201032003 Benzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-indole, hydrazine-dimethylbenzylamine, etc. A hydrazine compound such as an amine compound, adipic acid diamine or sebacic acid diamine; a phosphorus compound such as triphenylphosphine or the like. In addition, commercially available products include, for example, 2ΜΖ-Α, 2ΜΖ-ΟΚ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ (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 blocked isocyanate compounds of dimethylamine), 0811, 081^, 1; -CAT SA102, U-CAT 5 002 (all are bicyclic guanidine compounds and their salts) Wait. 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. Base-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine•trimeric isocyanate adduct, 2,4-diamino group- An S-triazine derivative such as a 6-methacryloxyethyloxy-S-triazine/trimeric isocyanate addition product, preferably used as a Q 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 of the thermosetting component having a carboxyl group-containing resin or a cyclic (thio)ether group having two or more molecules in the molecule, preferably 20 parts by mass, more preferably 0.5 to 15.0 parts by mass. In the photocurable resin composition of the present invention, a "adhesion promoting agent" can be used in order to improve the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate. Specific examples include benzimidazole, benzoxazole, benzothiazole, 2-indole-32-201032003, benzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinyl Methyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinylmethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole , triazole, tetraterpene, benzotriazine, carboxybenzotriazole, amine-containing benzotriazole, decane coupling agent, and the like. The compound having two or more 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 to form a carboxyl group containing the ethylenically unsaturated group. The resin φ is insoluble in an aqueous alkali solution or contributes to insolubilization. Such a compound is, for example, a diacrylate of a glycol of ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol or the like; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, trihydroxyethyl a polyhydric alcohol such as a polytrimethylene isocyanate or a polyacrylate such as an ethylene oxide adduct or a propylene oxide adduct; a phenoxy acrylate, a bisphenol A diacrylate, and the like a polyacrylate such as an ethylene oxide adduct or a propylene oxide adduct; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane tri-condensed glycerol ether, triglycidyl a polyacrylate of a glycidyl ether such as a trimeric isocyanate; 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 acrylate resin and pentaerythritol triacrylate, etc. An epoxy group-ethyl urethane compound obtained by reacting a hydroxy acrylate with an ethyl melamine compound of a diisocyanate such as isophorone diisocyanate. These epoxy acrylate-based resins do not reduce the dryness of the fingertips and can improve the photocurability of -33-201032003. The compounding amount of the compound having two or more ethylenically unsaturated groups in the molecule is preferably 5 to 1 part by mass, more preferably 70 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin. proportion. When the amount of the above-mentioned compounding is less than 5 parts by mass, since the photocurability is lowered, the alkali image after irradiation by the active energy ray is difficult to form a pattern, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the coating film becomes brittle due to a decrease in solubility in an aqueous alkali solution, which is not preferable. The photocurable resin composition of the present invention can be formulated with a colorant. As the coloring agent, a conventional coloring agent such as red, blue, green or yellow may be used, or any of a pigment, a dye and a coloring matter may be used. However, in terms of reducing the environmental burden and affecting the human body, it is preferable to have no halogen. Red coloring agent: Red coloring agents are, for example, monoazo, diazo, azo color, benzimidazolone, oxime, dioxopyrazole, condensed azo, hydrazine For example, a quinacridone system or the like, specifically, for example, the following. Monoazo system: Pigment Red 1,2,3,4,5,6,8,9,12,14, 15, 16, 17, 21, 22, 23, 31,32, 112, 114, 146 ,147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269 ° Diazo nitrogen system: Pigment Red 37, 38, 41. Azo color killing line: Pigment Red 48: 1,48: 2,48: 3,48 :4 , 49 : 1 , 49 : 2 , 50 : 1 , 52 : 1 , 52 : 2 , 53 : 1 , 53 - 34- 201032003 : 2 , 57 : 1 , 58 : 4 , 63 : 1 , 63 : 2 , 64 : 1 , 68 ° benzopyridone : Pigment Red 171 , Pigment Red 175 , Pigment Red 176 , Pigment Red 185 , Pigment Red 208. Line: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224. Lu dioxo oxime is slightly more than ± J ± slightly: 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. Wake up: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207. Quino Rehabilitation: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209 ° Blue Colorant: Blue colorants are alizarin, lanthanide, and pigments are classified as pigments ( Pigment compounds, in particular, for example, the following color index (CI; The Society of Dyers and Colourists) number; Pigment Blue 15 ' Pigment Blue 15 : 1, Pigment Blue -35- 201032003 15:2 Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 6〇

O dye system can use Solvent Blue 35, Solvent Blue 63,

Solvent Blue 68, Solvent Blue 70, Solvent Blue 83,

Solvent Blue 87, Solvent Blue 94, Solvent Blue 97,

Solvent Blue 122, Solvent Blue 136, Solvent Blue 67,

Solvent Blue 70 and more. In addition to the above, a halogen-substituted or unsubstituted alizarin compound can also be used. Green colorants: Green colorants are also available in alizarin, lanthanide, and lanthanide, specifically such as 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.蒽Cool: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 1 93, Pigment

Yellow 147, Pigment Yellow 199, Pigment Yellow 202. 201032003 Isoindolone: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139 ' Pigment Yellow 179 ' Pigment Y e Π o w 1 8 5. Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181 o Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 6, 5, 7 3, 74, 7 5, 9 7, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183° Nitrogen system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81 '83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 ° 〇 Others for the purpose of adjusting the color tone A coloring agent such as purple, orange, brown, or black may be added. Specifically, for example, Pigment Violet 19, 23, 29, 32, 36, 38, 4 2 , Solvent Violet 13, 36, CIPigment Orange 1 'C. I. Pi gment Orange 5, C.I. Pigment Orange 13, CIPigment Orange 14 , C. I. P i gm en t Orange 16 , CIPigment Orange 17 , CIPigment Orange 2 4 , CIPigment Orange 34 , CIPigment Orange 36 , CIPigment Orange 3 8 , CIPigment Orange 40 , -37- 201032003 C. I.Pigment Orange 43, C. I. P i gm ent Orange 46 , CIPigment Orange 49 , C · I · P i gm ent Orange 5 1 , CIPigment Orange 6 1 , CIPigment Orange 63 , CIPigment Orange 64, C. I. P i gm ent Orange 7 1 , C. I. Pigment Orange 73 , CIPigment Brown 23 ' CIPigment Brown 25 ' CIPigment Black 1 > CIPigment Black 7 and so on. The proportion of the above-mentioned coloring agent is not particularly limited, and it is preferably from 0 to 10 parts by mass, more preferably from 0.1 to 5 parts by mass, per part by mass of the carboxyl group-containing resin.

When most of the polymer materials are oxidized, the chain oxidation is deteriorated, and the function of the polymer material is lowered. Therefore, in the photocurable resin composition of the present invention, in order to prevent oxidation, it is possible to add (1) The radical scavenger which is deactivated by the radical is generated and/or the peroxide produced by (2) is decomposed into a harmless substance, and an antioxidant such as a peroxide decomposing agent of a new radical is not produced. As the antioxidant of the radical scavenger, specific compounds are, for example, hydroquinone, 4-tert-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t -butyl-P-cresol, 2,2-methylene-bis-(4-methyl-6-t-butanol), 1,1,3-parade (2-methyl-4-hydroxy- 54-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-gin (3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3 a phenolic system such as 5-paraxyl (3',5'-di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, Anthraquinone compounds such as m-benzoquinone and benzopyrene, bis(2,2,6,6-tetramethyl-4-piperidyl)-phthalate, phenothiazine, etc. -38-201032003 Amine compounds Wait. The free radical supplement can be a commercially available product, for example, ADK STAB AO-30, ADK STAB A Ο-3 3 Ο, AD KS TAB ΑΟ-20, ADK STAB LA-77, ADK STAB LA-made by Asahi Kasei Co., Ltd. 57, ADK STAB LA-67 > ADK STAB LA-68, ADK STAB LA-87 (all of the above), Ciba · Specialty . Chemicals company IRGANOX 10 10 , IRGANOX 1 035 IRGANOX 1 076, ❷ IRGANOX 113 5. TINUVIN 1 1 1FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5 1 00 (all of which are trade names), etc. As the antioxidant of the peroxidizing agent decomposing agent, specific compounds include, for example, a phosphorus compound such as triphenylphosphite, pentaerythritol tetralauryl sulfide propionate, dilauryl sulfide dipropionate, and distearyl 3,3. a sulfur-based compound such as '-thiodipropionate. The peroxide decomposing agent may be a commercially available product, for example, φ ADK STAB TPP manufactured by Asahi Kasei Co., Ltd., M ac A Ο-412S manufactured by Adeka·A g ar s Chemical Co., Ltd., Sumilizer TPS manufactured by Sumitomo Chemical Co., Ltd. (both trade names) )Wait. The above-mentioned antioxidants may be used alone or in combination of two or more. Since the polymer material absorbs light and is decomposed and deteriorated, the photocurable resin composition of the present invention can be used for the stabilization of ultraviolet rays, and an ultraviolet absorber can be used in addition to the above-mentioned antioxidant. 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, Benzobenzamide derivatives, etc. -39- 201032003. Specific benzophenone derivatives are, for example, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxy Benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, etc.; specific benzoate derivatives, such as 2-ethylhexyl water Salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzene Formate and cetyl·3,5-di-1 -butyl-4-hydroxybenzoate; etc.; specific benzotriazole derivatives such as 2-(2'-hydroxy-5'-t -butylphenyl)benzotriazole, 2-(2,-hydroxy-5,-methylphenyl)benzotriazole, 2-(2,-hydroxy-3,-t-butyl-5' -methylphenyl)-5-chlorinated benzotriazole, 2-(2'-hydroxy-3',5'-di-4-butylphenyl)-5-chlorobenzotriazole, 2- (2'-Hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di-t-butyl-aminophenyl)benzotriazole: Specific examples of the three-exposed derivative include hydroxyphenyltriazine, bisethylhexyloxyphenol methoxyphenyltriazine 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, manufactured by Ciba Specialty Chemical Co., Ltd. TINUVIN 460, TINUVIN 479 (all of which are trade names), etc. The above-mentioned ultraviolet absorbing agent can be used alone or in combination of two or more kinds thereof, and the molded article obtained from the photocurable resin composition of the present invention can be stabilized by using the above-mentioned antioxidant. 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. As the chelating agent, a conventional inorganic hydrazine or an organic hydrazine conventionally used may be used. In particular, barium sulfate, spheroidal cerium oxide and talc are preferably used. Further, in order to obtain a white appearance or flame retardancy, a metal hydroxide such as an oxide or a metal oxide or aluminum hydroxide can be used as the extender of the extender pigment. The blending amount of the chelating agent is preferably 75% by mass or less, more preferably 0.1% to 60% by mass or less based on the total amount of the composition. When the blending amount of the lubricant exceeds 75% by mass of the total amount of the composition, the viscosity of the insulating composition becomes high, coating and moldability are lowered, and the cured product becomes brittle, so φ is not preferable. Further, in the photocurable resin composition of the present invention, an organic solvent can be used in order to synthesize the carboxyl group-containing resin or to prepare a composition, or to adjust the viscosity when applied to a substrate or a carrier film. Such organic solvents are, for example, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve Φ, butyl cellosolve, and carbene Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl hydrazine, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, acetic acid Esters such as butyl ester, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; An aliphatic hydrocarbon such as octane or decane; a petroleum solvent such as petroleum ether 'naphtha, hydrogenated naphtha or solvent oil. This organic solvent may be used singly or in combination of two or more. The photocurable resin composition of the present invention can be adjusted as needed. The known tackifiers, polybenzazoles such as thermal polymerization inhibitors, fine powdered cerium oxide, organic bentonite, montmorillonite, etc. An antifoaming agent and/or a flat agent such as an oxygen-based, fluorine-based or polymer-based polymer, or a conventional additive such as a decane coupling agent such as an imidazole-based compound, a thiazole-based or a triazole-based compound, an antioxidant, or a rust preventive agent. The above thermal polymerization inhibitor is used to prevent thermal polymerization or polymerization over time of the polymerizable compound. The thermal polymerization inhibitor is, for example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrophenol, 2-hydroxybenzophenone, 4-methoxyl -2-hydroxybenzophenone, copper chloride, phenothiazine, chlorin, naphthylamine, P-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'- Methylene bis(4-methyl-6-t-butyl fluorene), ruthenium, nitrobenzene, dinitrobenzene 'picric acid' 4-toluidine' methylene blue, copper and organic chelating agent reactant, water Methyl salicylate, phenothiazine, nitroso compound, chelating agent of nitroso compound and A1, and the like. The photocurable resin composition of the present invention is adjusted to a viscosity suitable for the coating method by the above organic solvent, for example, by a dip coating method, a flow coating method, a roll coating method, a bar coating method, or screen printing. A method such as a curtain coating method or the like is applied to a substrate, and the organic solvent contained in the composition is volatilized and dried (pre-dried) by a temperature of about 60 to 1 Torr (TC). Forming a non-stick coating film, and 'coating the above composition on the carrier film, drying' will be attached to the substrate in the form of a film, and a resin insulating layer can be formed, and then by contact (or Non-contact method), by forming a pattern of the mask "selective exposure by active energy rays, or direct pattern exposure by a laser exposure machine" to make the unexposed portion by a dilute aqueous alkali solution (for example, -42-201032003 0.3~3 wt% sodium carbonate aqueous solution) is developed to form a photoresist pattern. Further, it is thermally hardened by heating to a temperature of about 140 to 180 ° C, for example, to have a carboxyl group and a molecule in the above carboxyl group-containing resin. More than 2 cyclic ether groups and/or rings The thermosetting component of the ether group reacts to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. The substrate is used in addition to a printed circuit board or a circuit in which a circuit is formed in advance. Outside the flexible φ printed circuit board, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimine, glass cloth/non-woven fabric-epoxy resin, glass cloth/paper- All kinds of composite materials such as epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, etc. (FR-4, etc.) copper-clad laminate, polyimide film, PET film, glass A substrate, a ceramic substrate, a wafer plate, etc. The volatile drying after the application of the photocurable resin composition of the present invention can be carried out using a hot air circulating drying oven, an IR furnace, a hot plate, a conveyor belt oven, etc. The heat source of the air by the vapor is heated in a countercurrent contact with the hot air in the dryer or by blowing the nozzle onto the support. The photocurable resin composition of the present invention is applied as follows. get on After drying, the obtained coating film is exposed (irradiation of active energy rays), and the exposed portion of the coating film (portion irradiated by the active energy ray) is cured. The exposure machine used for the active energy ray irradiation can be used. Direct drawing device (for example, -43-201032003 laser direct imaging device with direct laser image drawing by computer CAD data), exposure machine equipped with metal halide lamp, and exposure machine equipped with (ultra) high pressure mercury lamp An exposure device equipped with a mercury short arc lamp or a direct drawing device using an ultraviolet lamp such as a (ultra) high pressure mercury lamp. The active energy line may be a gas laser as long as it uses a laser beam having a maximum wavelength of 3 50 to 41 Οηχη. Or any one of the solid lasers. Further, the exposure amount varies depending on the film thickness and the like, and is generally 5 to 200 mJ/cm 2 , preferably 5 to 100 mJ/cm 2 , more preferably 5 to 50 mJ/cm 2 . . For the above-described direct drawing device, for example, a device manufactured by Orbotech Co., Ltd., and a @Pentax company can be used, and any device can be used as long as it can oscillate laser light having a maximum wavelength of 3 50 to 41 〇 nm. Examples of the development method include a dipping method, a rinsing method, a spraying method, a brushing method, and the like. The developing solution may be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia or an amine. An aqueous alkali solution. The photocurable resin composition of the present invention may have a solder resist layer formed by applying a solder resist to a film such as polyparaphenylate or a film formed by drying, in addition to a method of directly applying a liquid to a substrate. The form of the dry film is used. 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 photo-curable resin composition having a bismuth-developing property to a carrier film or a protective film and drying the composition. After the solder resist layer is formed on the carrier film, a protective film is laminated thereon or a solder resist layer is formed on the protective film, and when the laminate is laminated to the carrier film, a dry film can be obtained. -44 - 201032003 A thermoplastic film such as a polyester film having a thickness of 2 to 150 μm can be used as the carrier film. In the solder resist layer, the alkali-developable photocurable resin composition is uniformly applied to a thickness of 10 to 150 μm using a knife coater, a lip coater, a twin roll coater, a film coater, or the like. A carrier film or a protective film 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 force of φ and 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 by using a dry film, the protective film is peeled off, and then overlapped with the solder resist layer and the substrate on which the circuit is formed, and laminated using a laminator or the like to form a substrate on the circuit. A solder resist layer is formed thereon. When the solder resist layer after the formation is exposed, developed, and heat-cured 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. [Embodiment] EXAMPLES Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. In the following, "parts" and "%" are quality benchmarks when there is no special statement. Photosensitive Resin Synthesis Example 1 : A phenolic phenol resin (a product of Showa Polymer (-45-201032003), hydroxyl equivalent 106) was placed in a pressure cooker equipped with a thermometer, a nitrogen gas introduction device, an epoxide introduction device, and a stirring device. 106 parts, 2.6 parts of 50% aqueous sodium hydroxide solution and 100 parts of toluene/methyl isobutyl ketone (mass ratio = 2/1), and nitrogen substitution in the system while stirring, followed by heating and heating, at 150 ° C, 8 kg / Under cm2, 60 parts of propylene oxide was slowly introduced to carry out the reaction. The reaction was continued for about 4 hours until the gauge pressure was 0.5 kg/cm 2 and then cooled to room temperature. To the reaction solution, a mixture of 3.3 parts of a 3 % aqueous hydrochloric acid solution was added to neutralize sodium hydroxide. This neutralization reaction product was diluted with toluene, washed with water three times, and the solvent was removed by an evaporator to obtain an epoxide adduct of a phenolic phenol resin having a hydroxyl equivalent of 164 g/eq. This is a hydroxyl group of 1 equivalent average addition epoxide 1 mole. 1 64 parts of the epoxide adduct of the obtained novolac type phenol resin, 86 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 5 parts of hydroquinone monomethyl ether hydrazine, and 100 parts of toluene were charged. The reactor equipped with a stirrer, a thermometer, and an air blowing tube was stirred while being blown in air, and reacted at 110 ° C for 6 hours. The water formed by the reaction was in the form of an azeotropic mixture with toluene, and after the distillation was started, the mixture was further reacted for 5 hours and cooled to room temperature. The obtained reaction solution was washed with a 5 % aqueous solution of sodium chloride, and the toluene was distilled off using an evaporator, and carbitol acetate was added to obtain a phenolic type PO addition methacrylate resin solution having a nonvolatile content of 70% ( Double bond equivalent 250g/eq · Acid price 〇). This is called A-1 varnish. Photosensitive Resin Synthesis Example 2: 64 parts of an epoxide adduct of a novolac type phenol resin obtained in Synthesis Example 1, 72 parts of acrylic acid, and 3.0 parts of p-toluenesulfonic acid 'hydroquinone monomethyl ether 〇. 100 parts of toluene was placed in a counter-201032003 equipped with a stirrer, a thermometer, and an air blowing tube, and while stirring, air was blown and reacted at 90 ° C for 12 hours. The water formed by the reaction was in the form of an azeotropic mixture with toluene, and after the distillation was started, the reaction was further carried out for 5 hours and cooled to room temperature. The obtained reaction solution was washed with a 5 % aqueous solution of sodium chloride, and the toluene was distilled off using an evaporator, and carbitol acetate was added to obtain a phenolic type PO addition acrylate resin solution having a nonvolatile content of 70% (double bond) Equivalent 236g/eq · Acid value 0). This is called A-2 lacquer.感光 Photosensitive Resin Synthesis Example 3: In a pressure cooker equipped with a thermometer, a nitrogen gas introduction device, an epoxide introduction device, and a stirring device, 106 parts of a novolac type phenol resin (manufactured by Showa Polymer Co., Ltd., hydroxyl equivalent 106) was placed. 2.6 parts of a 50% aqueous sodium hydroxide solution and 100 parts of toluene/methyl isobutyl ketone (mass ratio = 2/1), and nitrogen substitution in the system while stirring, followed by heating and heating, at 150 ° C, 8 kg / cm 2 , 50 parts of ethylene oxide was slowly introduced to carry out the reaction. The reaction lasted for about 4 hours # until the surface pressure 〇.〇kg/cm2, and then cooled to room temperature. To the reaction solution, 3.3 parts of a 3 % hydrochloric acid aqueous solution was added and neutralized with sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and the solvent was removed by an evaporator to obtain an epoxide adduct of a phenolic phenol resin having a hydroxyl equivalent of 150 g/eq. This is a hydroxyl group of 1 equivalent average addition epoxide 1 mole. 150 parts of the epoxide adduct of the obtained novolac type phenol resin, 86 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 5 parts of hydroquinone monomethyl ether hydrazine, and 100 parts of toluene were charged. In a reactor equipped with a stirrer, a thermometer, and an air blow-in tube, the mixture was stirred while blowing air, and reacted at 1 l ° C for 6 hours. -47- 201032003 The water formed by the reaction was in the form of an azeotropic mixture with toluene. After the distillation began, the reaction was further carried out for 5 hours and cooled to room temperature. The obtained reaction solution was washed with a 5% aqueous sodium chloride solution, and the toluene was distilled off using an evaporator, and carbitol acetate was added to obtain a phenolic EO addition methacrylate resin solution having a nonvolatile content of 70% ( Double bond equivalent 236g/eq · Acid value 0). This is called A-3 varnish. Comparative Synthesis Example 1: @ In a pressure cooker equipped with a thermometer, a nitrogen gas introduction device, an epoxide introduction device, and a stirring device, a monofunctional phenol compound (hydroxyl equivalent 94) 94 parts of a '50% sodium hydroxide aqueous solution 2.6 parts and toluene were charged. /Methyl isobutyl ketone (mass ratio = 2 / 1) 1 〇〇 part, while stirring, the system is replaced with nitrogen, then heated to heat, and slowly introduced into the epoxy B at 150 ° C, 8 kg / cm 2 50 parts of the alkane was reacted. The reaction was continued for about 4 hours until the gauge pressure was 0.0 kg/cm2, and then cooled to room temperature. To the reaction solution, 3.3 parts of a 36% aqueous hydrochloric acid solution was added to neutralize sodium hydroxide. This neutralized reaction product was diluted with toluene and washed three times with water to remove the solvent by an evaporator to obtain an epoxide adduct of a phenol compound having a hydroxyl equivalent of 138 g/eq. This is the equivalent of hydroxy oxime equivalent to epoxide 1 mole. 1 3 8 parts of the epoxide adduct of the obtained phenol compound, 86 parts of methacrylic acid, 3.0 parts of p-toluenesulfonic acid, 5 parts of hydroquinone monomethyl ether, 5 parts of toluene, and 1 part of toluene were charged. Into a reactor equipped with a stirrer, a thermometer, and an air blow-in tube, the mixture was stirred while blowing air, and the reaction was carried out for 1 hour (TC reaction for 6 hours. The water formed by the reaction was in the form of an azeotrope with toluene, after the start of distillation. , -48- 201032003, further reacted for 5 hours, and cooled to room temperature. The obtained reaction solution was washed with a 5% aqueous solution of sodium chloride, and the toluene was distilled off using an evaporator to obtain a nonvolatile matter by adding carbitol acetate. 70% EO addition methacrylate resin solution (double bond equivalent 224g / eq · acid value 0). This is called A-4 varnish. Carboxylated resin (B-1) synthesis example: with a mixer, thermometer ' A cresol novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent) was introduced into a 2-liter separable flask of a reflux cooling tube, a dropping funnel, and a nitrogen/introduction tube. 220) 660g, carbitol acetate 421.3g and solvent naphtha 180.6g, heated to 90 The solution was stirred and dissolved at ° C. Then, it was temporarily cooled to 60 ° C, and 216 g of acrylic acid, 4.0 g of triphenylphosphine, and 1.3 g of methylhydroquinone were added, and the reaction was carried out at 100 ° for 12 hours to obtain an acid value of 0.2 mg KOH / g. The product was added with 241.7 g of tetrahydrophthalic anhydride, and heated to 90 ° C for 6 hours, thereby obtaining an acid value of 50 mgKOH/g and a double bond equivalent (unsaturated group per 1 mole of # resin) 400), a carboxylic acid-containing resin having a weight average molecular weight of 7,000. Hereinafter, the carboxylic acid-containing resin solution is a B-1 varnish. The carboxyl group-containing resin (B-3) is synthesized by a thermometer and a nitrogen gas introduction device. In the epoxide introduction device and the pressure cooker of the i-stirring device, a phenolic cresol resin (manufactured by Showa Polymer Co., Ltd., trade name "Shonol CRG951", OH equivalent: 119.4), 119.4 g, and potassium hydroxide 1.19 g and Toluene li 9.4 g, while stirring, the system was subjected to nitrogen substitution, followed by heating and heating. Then, 63.8 g of propylene oxide-49-201032003 was added dropwise, and the reaction was carried out at 125-132 ° C, 〇~4.8 kg/cm 2 for 16 hours. Then, cool to room temperature and add to the reaction solution. By mixing 89% phosphoric acid with 1.56 g and neutralizing potassium hydroxide, a propylene oxide reaction solution of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl group value of 182.2 g/eq was obtained. This is a phenolic hydroxyl group per 1 equivalent. An average of 1.08 moles of epoxide. The epoxide reaction solution of the obtained novolac type cresol resin was 293. Og, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and toluene. 252.9 g was placed in a reaction reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min, and the reaction was carried out at 1 l ° C for 12 hours while stirring. 12.6 g of water was distilled off by means of an azeotropic mixture of water and toluene formed by the reaction. Then, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.3 g of a 15% aqueous sodium hydroxide solution, followed by washing with water. Then, toluene was replaced with diethylene glycol monoethyl ether acetate 118.lg by an evaporator while distilling off to obtain a novolac type acrylate resin solution. Next, 332.5 g of the obtained novolac type acrylate resin solution and 1.22 g of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer and an air blowing tube, and the air was made l〇ml/ The mixture was blown in at a minute speed, and 60.8 g of tetrahydrophthalic anhydride was slowly added thereto while stirring, and the reaction was carried out at 9 5 to 10 ° C for 6 hours. The acid value of the solid matter was 8811^艮0114, and the carboxyl group-containing photosensitive resin having a nonvolatile content of 71% was obtained. Hereinafter, the reaction solution is referred to as varnish B-3. Examples 1 to 15 and Comparative Examples 1 to 5 Using the resin solutions of the following Synthesis Examples, various types shown in Table 1 were prepared in the range of -50 to 201032003 and the ratios shown in Table 1 (parts by mass), and premixed using a blender. Thereafter, the mixture was kneaded by a three-roll mill to prepare a photosensitive resin composition for a solder resist. Here, the degree of dispersion of the obtained photosensitive resin composition was measured by a pelletizer manufactured by Erichsen Co., Ltd., and when evaluated, it was found to be 15 μm or less. [Table 1]

(Quality lion 寅 application ratio _ 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 1 2 3 4 5 A-1 20 60 10 20 20 20 20 20 60 20 20 20 20 A-2 20 10 A -3 20 A-4 20 A-5*' 20 60 60 Α-β*2 20 Α-7*3 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Β-1 155 155 155 155 155 108 155 155 155 155 155 155 155 155 155 155 Β-2*4 75 Β—3 140 Β-4*5 160 Β-5*6 151 Β-6*7 167 C-1*8 5 5 5 5 5 5 5 5 5 S 5 5 5 5 5 5 5 C-2*» 1 1 1 1 1 1 1 1 3 3 1 1 1 1 1 1 1 1 3 D-1*10 15 15 15 15 15 15 10 10 15 10 15 15 15 15 15 15 15 15 D-2*” 25 25 25 25 25 25 20 20 25 15 25 25 25 25 25 25 25 25 mimm Triple shed 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Coloring ΛΓ* 0.3 0.3 0.3 0.3 0*3 〇·3 (U 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 03 0.3 0.3 0.3 ) ^ί·13 0.8 0.8 0.8 0.8 0.8 0.8 0·8 ο.β 0.8 0.8 0.8 0.8 0.8 0Λ 0· 8 0.8 0.8 0.8 0Λ Fine 钡 w 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Poly sand gas defoamer 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 DPM·1* 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 TPA-B80E *ιβ 20 Mw-10 0LM*'7 10 10 phenothiazine〇· 2 02 0·2 02 0.2 0.2 02 IRGANO X101CT1® 2 2 2 2 2 2 2 -51 - 201032003 Remarks : NKester BPE-9 00 (made by Shin-Nakamura Chemical Industry Co., Ltd.) contains epoxy B of bisphenol A skeleton Alkyl-modified bifunctional acrylate (double bond equivalent · · · 5 56 ) *2 : KAYARAD DPCA-60 (manufactured by Sakamoto Chemical Co., Ltd.) (double bond equivalent · · · 210) • 3: dipentaerythritol hexaacrylate Ester (DPHA: Nippon Chemical Co., Ltd.) (double bond equivalent · · · 108) φ *4 : Syclomer P ( ACA) 320 ( Daicel Chemical Industry Co., Ltd.) : ZFR-1 124 (Nippon Chemicals (股6) Φ6: ZCR-1601H (made by Nippon Kayaku Co., Ltd.) SPV-1000L (made by Showa Polymer Co., Ltd.) 2_Methyl-indole-(4-methylphenylthio)-2-? Olinone propane-1- (IRGACURE 90 Ciba · Specialty Chemicals, Inc.): 2-(ethoxycarbonylmethyl) thioxanthene-9-one ©: phenol novolac type epoxy resin (DEN 43 8: manufactured by Dow Chemical) M1: Lianji Methyl phenol type epoxy resin (YX-4000; made by Japan Epoxy Resin Co., Ltd.) *12 : CIPigment Blue 15 : 3 *13 : CIPigment Yellow 147 M4: Barium sulfate (B-30: 堺Chemical Co., Ltd.) M 5 : Dipropylene glycol monomethyl ether - 52 - 201032003 : Block isocyanate (made by Asahi Kasei Chemicals Co., Ltd.) : Methyl methacrylate resin (manufactured by Chemicals Co., Ltd.): Antioxidant (Ciba· Specialty. Chemicals Company performance evaluation = <Optimum exposure amount> φ The circuit pattern substrate with a copper thickness of 35 μm is subjected to a buff roll honing, washed with water, dried, and then fully coated by screen printing. The photocurable thermosetting resin composition of the above examples and comparative examples was dried in a hot air circulating drying oven at 80 ° C for 60 minutes. After drying, exposure was carried out using a staged (optical density) exposure meter (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and development was performed in 60 seconds (30 ° C, 〇 2 MPa). In the case of the lwt% Na2C03 aqueous solution, the pattern of the remaining staged exposure meter is 7 segments as the optimum exposure amount. <Touch Drying> The photocurable thermosetting resin composition described in Table 1 was applied to the copper foil substrate on which the pattern was formed by screen printing, and was dried by hot air circulation of 8 (TC). The oven was dried for 30 minutes, and allowed to cool to room temperature. The pet film was pressed against the substrate, and then the state of bonding of the film when the negative film was peeled off was evaluated. ◎: When the film was peeled off, there was no resistance at all, on the coating film. -53- 201032003 〇: When peeling off the film, there is no resistance at all, but there is a slight trace on the film. △: When the film is peeled off, there is only a slight resistance, and there is a slight trace on the film. When the film is peeled off, there is resistance, and there is a clear trace on the coating film. <Resolving property> The circuit pattern substrate having a line/pitch of 300/300 μm and a copper thickness of 35 μm is subjected to polishing roller honing, washed with water, and dried. The photocurable thermosetting resin composition of the examples and the 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, a high-pressure mercury lamp was used (short). Arc lamp) exposure device The exposure pattern is used for the glass dry plate of the line of 20/30/40/50/60/70/80/90/100μηη at the pitch portion. The exposure amount is the optimum exposure amount of the photosensitive resin composition. The active energy ray was irradiated in the state. After exposure, the image was imaged by a 1 wt% Na2CO3 aqueous solution at 30 ° C, and the pattern was drawn, and the hardened coating film was obtained by thermal hardening at 150 ° C for 60 minutes. The minimum residual line (resolution) of the cured coating film of the photosensitive resin composition for the solder resist obtained by optical microscopy was obtained. < Tensile modulus, tensile strength (tensile strength), elongation (tensile failure) Extension)> The composition of each of the above composition examples and comparative composition was applied by screen printing on a water-washed and dried PTFE (polytetrafluoroethylene) plate, and a heat-54-201032003 air circulation type drying oven was used. It was dried at 80 ° C for 30 minutes. After cooling to room temperature, it was exposed to an appropriate exposure amount, and a 1 wt% Na 2 CO 3 aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 2 kg/cm 2 for 60 seconds. The substrate was used in a UV transfer furnace. In the condition of cumulative exposure l〇〇〇mJ/Cm2 After the ultraviolet rays were irradiated, they were dried at 150 ° C for 60 minutes using a hot air circulating drying oven. After cooling to room temperature, the cured coating film was peeled off from the PTFE sheet to obtain an evaluation sample. By a tensile-compression tester (( )) manufactured by Shimadzu Corporation) Measure the tensile modulus, tensile strength (tensile failure strength), and elongation (tensile failure elongation) of the above-mentioned evaluation sample. <Softness> The composition of each of the above Examples and Comparative Examples was applied by screen printing on an amine material (thickness 25 μm), and dried by a hot air circulation type drying oven at 8 (TC for 30 minutes). After cooling to room temperature, 'exposure device using a high-pressure mercury lamp (short arc lamp) is exposed to the appropriate exposure amount 〇 30 . (: 1 wt% Na2C03 aqueous solution was developed under the conditions of a spray pressure of 2 kg/cm 2 for 60 seconds. The substrate was irradiated with ultraviolet rays under the conditions of a cumulative exposure amount of 1 〇〇〇 mJ/cm 2 in a UV transfer furnace, and 150 The mixture was heated for 60 minutes at ° C for hardening to obtain a sample for the folding resistance test and the soft test. The side portion of the film-like test piece produced by processing the obtained cured film into a width of 90 mm was placed on the electronic scale. 'The other side edge bending method is 3 mm between the films, and the maximum load applied to the electrons is used as the rebounding force, and is evaluated on the basis of the following criteria. 〇: Less than 1 〇g -55- 201032003 △ : 1 0~Unsupplied 30g X: 30g or more characteristic test: The composition of each of the above examples and comparative examples was completely applied by screen printing on the copper foil substrate on which the pattern was formed, and the film thickness after drying was 20 μm. Dry at 80 ° C for 30 minutes, and let it cool to room temperature. For this substrate, use an exposure device equipped with a high-pressure mercury lamp (short arc lamp) to expose the solder resist pattern with an appropriate exposure amount, and lwt% Na2C03 at 30 °C. The aqueous solution is sprayed at 2kg/cm2 The film was developed for 60 seconds to obtain a photoresist pattern. The substrate was irradiated with ultraviolet light under conditions of a cumulative exposure amount of 1000 mJ/cm 2 in a UV transfer furnace, and then cured by heating at 150 ° C for 60 minutes. Evaluation of the substrate) Evaluation of characteristics as follows. <Welding heat resistance> The evaluation substrate coated with the rosin-based auxiliary solvent was immersed in a solder bath previously set at 2 60 ° C to wash the solvent after the modified alcohol was washed. 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 6 times or more for 1 sec. 〇: Even if 1 〇 dipping was repeated 3 times or more, No flaking was observed. △: When immersed for 3 or more times in 1 sec., it was slightly peeled off. X: When immersed for 1 sec. within 3 times, the photoresist layer was swollen and peeled off -56-201032003 < Electroless gold plating> Electroless ore plating was carried out using a commercially available electroless nickel plating bath and electroless gold plating. The electric ore was subjected to n 0.5 μηιη, gold 0·〇3 μιη, and the photoresist was evaluated by tape peeling. Whether the layer is peeled or electroplated or not The peeling of the photoresist layer was evaluated by tape peeling. The judgment criteria were as follows: 〇 ◎: no penetration or peeling. φ 〇: slightly infiltrated after plating, but not peeled off after peeling off the tape. △: After plating, only Slightly infiltrated, peeled off after peeling off the tape. X: Peeling after plating. <Electrical characteristics> Instead of the copper foil substrate, a comb-shaped electrode pattern having a line and a pitch of 50/50 μm was used, and an evaluation substrate was produced under the above conditions. For this comb-shaped electrode, a bias voltage of DC 10 V was applied, and the absolute φ edge resistance 100 after 100 hours was measured in a bath at 130 ° C and 85% RH. The measurement voltage was carried out at DC 10V. <Alkali resistance> The evaluation substrate was immersed in a 10 wt% aqueous NaOH solution at 50 ° C for 30 minutes to perform infiltration or dissolution of the coating film, and peeling was confirmed by tape peeling. The criteria for determination are as follows. 〇: no penetration or dissolution, no peeling. △: Slightly infiltrated, dissolved or peeled off. X: Infiltration, dissolution or significant peeling. -57-201032003 <Dry film production> The photosensitive resin compositions for the solder resists of Example 1 and Comparative Example 1 were each appropriately diluted with methyl ethyl ketone, and then coated on a PET film using a coater (East). LB-50: 16 μm), the film thickness after drying was 20 μηχ, and dried at 8 ° C for 30 minutes 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 Machine Co., Ltd.), and the degree of pressurization was 〇8 MPa, 7 〇. t:, i minute, degree of vacuum: 1333 ρ & conditions were heated and laminated to obtain a substrate (unexposed substrate) having an unexposed solder resist layer. The evaluation results are shown in Table 2. 201032003 [Table 2]

Characteristic Examples Comparative Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 1 2 3 4 5 Solder Mask Form D: Dry Film B: Liquid DLLLLLLLLLLL 1 LLLDLLLLL Female Exposure Setting {m}/cm^ 90 100 150 80 100 90 80 100 150 120 150 80 140 120 120 140 180 200 150 180 100 100 Finger touch drying / 〇〇Ο Ο 〇〇〇〇〇〇〇Ο 〇〇〇 / X Δ X Δ X resolution (minimum residual) Line width: μ m) 50 50 60 50 50 55 50 55 S5 SQ 5S 55 5& 5S & 5 60 70 60 £0 50 Tensile modulus (GPa) 3.2 3.0 2.8 3.0 3.0 3.0 2.9 3.0 3.0 3.0 3.0 2- 7 3.0 2.8 3.2 2.6 3.0 2.9 2.8 2.S 3.2 2.3 Leg contact (MPa) 80 75 70 75 75 75 70 70 70 7S 75 65 75 70 75 65 3S 30 60 40 70 50 Elongation W 5.0 4.5 5.0 4.5 4.3 4.4 4.3 4.0 4.0 4.5 4.5 4-2 4.5 S.0 4.2 4.7 3.0 2.S 3.5 5.5 4.0 3.0 Softness Ο 〇〇〇〇〇〇 〇〇〇〇〇〇 〇Ο 〇Ο 〇〇Ο Δ Δ .〇X Δ Solder heat resistance 0 XXX XXX XXX Ο XXX XXX Δ Ο X mmnm gold plating Ο 〇 Ο Ο ο ο ο ο Δ ο 〇 Ο Δ Δ Δ Δ Ο X Electrical characteristics (Ω) 2 χ10· 1 xlO* 5 xlO7 3 χ10· 2 xlO7 2 χΙΟ7 5 χ10τ 8 χΙΟ1 6 χΙΟ1 1 χΙΟ» 2 χΙΟ7 1 χ1〇7 3 χ10β 1 χΙΟ7 2 χΙΟ, 4 χ10? 2 χΙΟ1 3 χ10β 7 xl〇s 4 χΙΟ* 1 χΙΟ* 3 zl0s 耐 〇Ο Ο Δ Δ Ο 〇Ο 〇Ο Ο Δ Δ Ο 〇Ο XX XX Δ Δ Δ X mmn 〇ο ο 〇ο ο 〇ο 〇〇 ο Ο 〇Ο Ο 〇 Δ Δ 〇〇〇Ο As shown in the above Table 2, the cases of the first to fifteenth embodiments of the present invention 'the touch dryness is not lowered as compared with the comparative examples 1 to 5' The sensitized 'hardened film obtained has excellent flexibility. In particular, an example of using a photosensitive resin A·1 in which propylene oxide and methacrylic acid are added to a novolac type phenol resin is excellent in solder heat resistance, electroless gold plating resistance, and electrical characteristics, and can be used as an alkali-developing photohardenability. The resin composition is used. On the other hand, in Comparative Examples 1 and 2 in which A-4 and A-5 having a nucleus number of 3 or less were used, the dryness of the touch, the heat resistance of soldering, and the electrical characteristics were inferior. -59- 201032003 Industrial Applicability As described above, the present invention can provide a dry coating film which is excellent in dryness to the touch, high in sensitivity and softness, and particularly can form a hardening film of a hardened film having a high insulation resistance at high temperature and humidification. A resin substrate, a dry film and a cured product thereof, and a printed circuit board formed by forming a hardened film such as a solder resist.

-60-

Claims (1)

201032003 VII. Patent application scope: 1. A photo-developing photocurable resin composition characterized by containing a photosensitive resin having a structure represented by the following general formula (I), a carboxyl group-containing resin, and photopolymerization. Starting agent, 【化1】 (wherein R1 is a hydrogen atom and an organic group having 1 to 20 carbon atoms, and the same or different R2 represents an alkyl group selected from the group consisting of a C 1 to 10 carbon group, a C 1 alkyl group, and a phenyl group. At least one functional group, Φ R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R5 represents a hydrogen atom or a methyl group, and P represents An integer of 1 to 5, q represents an integer of 3 or more, m represents an integer of 1 to 4, and η represents an integer of 1 to 10). 2. The photocurable resin composition according to claim 1, wherein the photosensitive resin does not contain an acid and has a double bond equivalent of 200 or more and 400 or less. 3. The photocurable resin composition according to the first aspect of the invention, wherein the photosensitive resin is a compound having a phenolic hydroxyl group of 1 or more and a cyclic ether compound or ring The photo-curable resin composition obtained by reacting the generated hydroxyl group with a compound having an ethylenically unsaturated group. The photocurable resin composition of the second aspect of the invention, wherein the one molecule has three The above phenolic hydroxyl group compound has a softening point above room temperature. 5. The photocurable resin composition of claim 1 which contains a thermosetting component. @6. A photocurable dry film which is obtained by applying a photocurable resin composition according to any one of claims 1 to 5 to a film and drying it. 7. A cured product comprising the photocurable resin composition according to any one of claims 1 to 5, which is applied to a substrate, dried or coated with the photocurable resin composition. On the film, the dried dry film is laminated on a substrate, and the formed dried coating film is photohardened on copper. A hardened resin composition according to any one of claims 1 to 5, which is coated on a substrate, dried or coated with the photocurable resin composition. On the film, the dried dry film is laminated on the substrate, and the formed dried coating film is photohardened into a pattern. 9. A printed circuit board having the following features: The photocurable resin composition according to any one of the above 5 is applied to a substrate, dried, or coated with the photocurable resin composition on a film, and the dried film obtained by drying-62-201032003 is laminated on the substrate. On the material, the formed dried coating film is photohardened into a pattern, and then the hardened film obtained by thermal curing is performed. -63- 201032003 IV. Designated representative map: (1) The designated representative circle of this case is: None (2) The symbol of the representative circle is simple: No -3- 201032003 V If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -4-