TW201207555A - Photocurable/thermosetting resin composition, dry film thereof and cured substance therefrom, and printed circuit board using the same - Google Patents

Abstract

The disclosed photocurable/thermosetting resin composition, which can be developed by an alkaline aqueous solution, can form a cured film that has properties important for a solder resist for semiconductor packages, namely PCT and HAST reliability and resistance to immersion gold plating and thermal shock. Said photocurable/thermosetting resin composition contains: (A) a carboxyl-containing resin (but not a carboxyl-containing resin made from an epoxy resin); (B) a photopolymerization initiator; and (C) a naphthalene-ring-containing epoxy resin. Preferably, the carboxyl-containing resin does not contain any hydroxyl groups and does contain a photosensitive group. Also disclosed is a printed circuit board on which the disclosed photocurable/thermosetting resin composition or a dry film thereof is used to form a cured film such as a solder resist.

Description

201207555 VI. Description of the Invention: [Technical Field] The present invention relates to a photocurable thermosetting resin composition which can be imaged by an aqueous alkaline solution, particularly a photo-curing agent which is photohardened by ultraviolet exposure or laser exposure. A composition, a dry film and a cured product thereof, and a printed wiring board having a hardened film formed using the same. [Prior Art] At present, some of the printed wiring boards for the people's livelihood and the solder resists of most industrial printed wiring boards are based on high-precision and high-density. Forming an image, and applying a heat-curable (or formally hardened) liquid-based development type solder resist by heat and/or light irradiation, based on environmental considerations, using an alkaline aqueous solution as an alkali-developing type of developing liquid Resistors have become mainstream, and are actually used in large quantities for the manufacture of printed wiring boards. In addition, in response to the recent increase in the density and thickness of electronic devices, the density of printed wiring boards has increased, and the workability and performance of solder resists have been required. However, the conventional alkali developing type photoresist is still problematic in terms of durability. That is, compared with the conventional thermosetting type and solvent developing type, the alkali resistance, water resistance, heat resistance and the like are inferior. The reason why it is considered that the alkali-developing type photoresist has a hydrophilic base as a main component and can easily penetrate a chemical liquid, water, water vapor, etc., so that chemical resistance is lowered or a photoresist film is used. The adhesion with copper is reduced. As a result, the alkali resistance as a chemical resistance is weakened, and in particular, a semiconductor package such as a BGA (ball grid array) or a CSP (grain ruler 201207555 inch package) particularly needs a pct resistance also known as heat and humidity resistance (pressure cooker test) (Pressure Cooker Test)), but the current situation can only reach hours to tens of hours under these strict conditions. Further, in the H A S T test (high acceleration life test) in a state where a voltage is applied under humidification conditions, in most cases, defects due to the occurrence of migration are confirmed within a few hours. In recent years, there has been a tendency to apply extremely high temperatures to packages due to the shift in surface mounting and the use of lead-free solders associated with environmental concerns. Along with this, the temperature of the inside and the outside of the package is remarkably high. In the past, the liquid photosensitive resist may cause deterioration of the coating film or change in characteristics due to thermal history, and peeling may occur, as the aforementioned PCT or HAST resistance is deteriorated. On the other hand, the carboxyl group-containing resin used in the past solder resists is generally an epoxy acrylate-modified resin derived from the modification of an epoxy resin. For example, a photosensitive resin and a photopolymerization initiator which are added to an acid anhydride of a reaction product of a novolac type epoxy compound and an unsaturated unit acid are reported in JP-A-61-243 869 (Patent Document 1). Solder resist composition of thinner and epoxy compound. Further, an epoxy resin-added (meth)acrylic acid obtained by reacting a reaction product of salicylaldehyde with a monovalent phenol with epichlorohydrin is disclosed in Japanese Laid-Open Patent Publication No. Hei-3-250012 (Patent No. 2). Next, a solder resist composition such as a photosensitive resin, a photopolymerizable initiator, or an organic solvent obtained by reacting with a polyvalent carboxylic acid or an anhydride thereof. The above-mentioned epoxy acrylate-modified resin has a large amount of residual hydroxyl groups derived from epoxy acrylate, and has a problem that the original water resistance is deteriorated. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. The object of the prior art is to provide a photocurable thermosetting resin composition which is required to have a high resistance to heat and a solder resist for semiconductor encapsulation, and which can form an important PCT resistance and HAST resistance. Hardened film with no electroplating resistance and thermal shock resistance. Further, an object of the present invention is to provide a dry film and a cured product which are excellent in the above properties obtained by using the photocurable thermosetting resin composition, and a hardened film in which a dry film or a cured product is formed into a solder resist or the like. Printed wiring board. [Means for Solving the Problem] In order to achieve the above object, according to the present invention, there is provided a photocurable thermosetting resin composition which can be developed by an aqueous alkaline solution, which comprises a carboxyl group-containing resin (but ' A resin containing a carboxyl group as a starting material, a photopolymerization initiator, and an epoxy resin having a naphthalene ring 201207555 The above carboxyl group-containing resin preferably has a photosensitive group. According to the present invention, there is provided a photocurable thermosetting dry film obtained by applying the photocurable thermosetting resin composition onto a carrier film and dried, and comprising the photocurable thermosetting resin. The material or the dry film is hardened, and the cured product obtained by photohardening into a pattern is preferably used with a light source having a wavelength of from 3 50 nm to 410 nm. Further, according to the present invention, there is provided a printed wiring board which is irradiated with an active energy ray, and is preferably directly drawn by ultraviolet rays, and the photocurable thermosetting resin composition or the dry film is photohardened into a pattern. (The effect of the invention) The photocurable thermosetting resin composition of the present invention contains a carboxyl group-containing resin which does not use an epoxy resin as a starting material, and contains a naphthalene ring in combination therewith. Since the epoxy resin is a component which can be imaged by an aqueous alkaline solution, not only the toughness and heat resistance of the cured coating film are improved, but also the physical properties of the coating film after heat treatment and under hardening are small. Further, it has been unexpectedly found that even if the heat hardening temperature is low, it has good hardenability, and even if heat is applied at a high temperature, the physical properties are not changed, and good characteristics are maintained. By using the photocurable thermosetting resin composition of the present invention, it is possible to form a cured film having excellent heat resistance such as PCT resistance, HAST resistance, and electroless plating resistance which are important as a solder resist for semiconductor encapsulation. 201207555 [Embodiment] As described above, the photocurable thermosetting resin composition of the present invention is characterized by containing a carboxyl group-containing resin, a photopolymerization initiator, and a naphthalene ring containing no epoxy resin as a starting material. Epoxy resin. As the carboxyl group-containing resin, a resin containing a carboxyl group which does not use an epoxy resin as a starting material can be used in various conventionally known residues-containing resins, but in terms of photocurability or development resistance. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in its molecule is preferred. Therefore, the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or such derivatives. Further, when only a carboxyl group-containing resin having no ethylenic unsaturated double bond is used, in order to make the composition photocurable, it is necessary to use a compound having one or more ethylenically unsaturated groups in a molecule to be described later (photosensitivity). monomer). Specific examples of the carboxyl group-containing resin which can be used in the present invention are preferably the following compounds (any of an oligomer and a polymer). (1) A condensate of bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, naphthol and aldehyde, condensate of dihydroxynaphthalene and aldehyde, etc. a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, and reacting a monocarboxylic acid having an unsaturated group such as (meth)acrylic acid, A carboxylic acid-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as maleic anhydride 'tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride or adipic acid into the obtained reaction product. (2) In a reaction product obtained by reacting a compound having 9 or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, a single unit containing an unsaturated group is used. The carboxylic acid is reacted to obtain a photosensitive resin containing a carboxyl group obtained by reacting a polybasic acid anhydride with the obtained reaction product. (3) A diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a polycarbonate polyol, a polyether polyol, or a polyester polyol Amino group obtained by polyaddition reaction of a diol compound such as a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group A urethane resin having a carboxyl group at the terminal obtained by reacting the terminal of the acid ester resin with an acid anhydride. (4) A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diisocyanate with a diol compound containing a carboxyl group such as dimethylolpropionic acid or dimethylolbutanoic acid, and a diol compound In the synthesis, a (meth)acrylated carboxyl group-containing urethane having a terminal having a hydroxyl group and one or more (meth)acrylinyl groups in a molecule such as a hydroxyalkyl (meth)acrylate is added. Resin. (5) In the synthesis of a carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diisocyanate with a diol compound containing a carboxyl group and a diol compound, isophorone diisocyanate and pentaerythritol are added. A (meth) acrylated carboxyl group-containing urethane resin having a terminal of a compound having one isocyanate group and one or more (meth) acrylonitrile groups in a molecule such as an acrylate. (6) A compound containing an unsaturated group such as (meth)acrylic acid and unsaturated carboxylic acid and styrene, -10- 201207555 α-methylstyrene, lower alkyl (meth)acrylate, isobutylene or the like The resulting carboxyl group-containing resin is copolymerized. (7) A polyfunctional oxetane resin as described later is reacted with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to form a phthalic anhydride on the primary hydroxyl group. Further, a polyester resin containing a carboxyl group formed by a dibasic acid anhydride such as tetrahydrophthalic anhydride or hexahydrophthalic anhydride is further added with glycidyl (meth)acrylate or α-methyl shrinkage (meth)acrylate. a photosensitive resin containing a carboxyl group and a compound having one epoxy group and one or more (meth)acryloyl group in one molecule, such as a glyceride, (8) a carboxyl group-containing resin according to the above (1) to (7) A photosensitive resin containing a carboxyl group formed by adding a compound having a cyclic ether group and a (meth)acryl fluorenyl group in one molecule. Further, in the present specification, the term "(meth)acrylate" is a term generally referred to as acrylate, methacrylate, and the like, and is similar to other similar expressions. The carboxyl group-containing resin used in the present invention is characterized in that since the epoxy resin is not used as a starting material, the halide content is extremely small. The carboxyl group-containing resin used in the present invention has a chloride ion impurity content of 0 to 100 ppm, preferably. It is 0 to 50 ppm, more preferably 0 to 30 ppm. Further, the resin containing a carboxyl group used in the present invention can easily obtain a resin containing no hydroxyl group. It is known that in general, the presence of a hydroxyl group also has an advantage of improving adhesion due to hydrogen bonding, but the moisture resistance is remarkably lowered. The advantages of the carboxyl group-containing resin of the present invention in comparison with the epoxy acrylate-based modified resin used in a general solder resist will be described below. -11 - 201207555 Phenolic novolak resins without chlorine are readily available. This can be obtained by acrylation of a portion of the phenol resin modified with an alkylene oxide, and introduction of an acid anhydride to obtain a double bond equivalent of 00 to 5,500, and a theoretically non-hydroxyl group in the range of an acid value of 40 to 120 mgKOH/g. Resin. On the other hand, the epoxy group of the epoxy resin synthesized from a similar phenol novolak resin is all acrylated, and when an acid anhydride is introduced to all of the hydroxyl groups, the acid value becomes extremely large at a double bond equivalent of 400 to 500, and exposure cannot be obtained. After that, it still has a coating film resistant to development. Further, since the acid value is high, the water resistance is poor, and the insulation reliability and PCT resistance are remarkably lowered. That is, since the epoxy acrylate-modified resin derived from a similar phenol novolak type epoxy resin is extremely difficult to be completely free of hydroxyl groups. Accordingly, the epoxy-modified acrylate-modified resin in the past has unavoidably possessed a hydroxyl group, but the presence of a hydroxyl group affects the reactivity of the epoxy resin with an acid not only from the viewpoint of water absorption. That is, it is known that a hydroxyl group promotes the reaction between an acid and an epoxy group, but the presence of a hydroxyl group can be predicted until the gelation of the hardened material, and the promotion effect is high, but the promoting effect of the reaction system after gelation is changed. weak. That is, the reaction of the acid with the epoxy group in the system in which a plurality of hydroxyl groups are present is considered to be slow to reach the end of the reaction, rather than starting prematurely. In terms of the start of the reaction too early, it is not preferable from the viewpoint of the usable time of the composition or the drying of the solvent until the development life before development, and further, since the gelation is formed at an early stage until the reaction is completed. High temperatures become necessary for a long time. Since the composition of the present invention reacts in the absence of a hydroxyl group, the reaction is a mild reaction. As a result, it is considered that the life before the development becomes longer, and the reaction is easy to complete. As a result, it is considered that an excellent reliability person can be obtained. The present -12-201207555 is more noticeable when using an epoxy resin containing a naphthalene ring as described later. This is considered to be because the naphthalene ring containing the epoxy resin of the naphthalene ring has a planar structure, so that the melt viscosity is low and the reactivity is increased. Further, the urethane resin can be easily synthesized into a resin containing no hydroxyl group by blending the equivalent of a hydroxyl group and an isocyanate group. The preferred resin is an isocyanate compound which does not use carbon ruthenium (Phosgene) as a starting material, and a carboxyl group-containing resin having a chloride ion mass of 0 to 30 ppm synthesized from a raw material which does not use epichlorohydrin is more preferably synthesized. A resin that theoretically does not contain a hydroxyl group. From these viewpoints, the resin (1) to (5) containing a carboxyl group as exemplified in the specific examples can be preferably used. Further, a resin having a carboxyl group-containing resin (6) obtained by copolymerization with a compound containing an unsaturated group as described above is used as a compound having a cyclic ether group and a (meth)acryl fluorenyl group in one molecule. The photosensitive resin containing a carboxyl group obtained by reacting a 3,4-epoxycyclohexylmethyl acrylate is preferably used because it has a small amount of chlorine ion impurities due to the use of an alicyclic epoxy group. On the other hand, in the resin (6) containing a carboxyl group, a glycidyl methacrylate which is a compound having a cyclic ether group and a (meth) acrylonitrile group in one molecule is reacted, or When a saturated group of compounds is copolymerized with glycidyl methacrylate, there is a concern that the amount of chlorine ions is increased. Further, when the urethane resin is synthesized, an epoxy acrylate-modified raw material may be used as the diol compound. Although chloride ion impurities may be mixed, it may be used because it can control the impurity quality of chloride ions.-13-201207555 The carboxyl group-containing resin as described above has a large number of free carboxyl groups in the side chain of the main chain polymer. It was developed by an aqueous alkaline solution. Further, the acid value of the carboxyl group-containing resin is preferably in the range of 40 to 150 mgKOH/g, more preferably 40 to 130 mgKOH/g. If the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, the alkali development becomes difficult. On the other hand, when it exceeds 150 mgKOH/g, the dissolution of the exposure portion of the developing solution is too fast, so that the line is formed. In this case, the exposed portion and the unexposed portion are dissolved and peeled off by the developing solution without distinction, and thus the normal photoresist pattern drawing becomes difficult and is less appropriate. Further, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is usually 2,000 to 150,000, and preferably 5,000 to 1,000,000. When the weight average molecular weight is less than 2,000, the non-tack property is deteriorated, and the moisture resistance of the coating film after exposure is deteriorated, and the film is reduced at the time of development, and the resolution is greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 1 50,000, the development property is remarkably deteriorated, and the storage stability is deteriorated. The compounding amount of the carboxyl group-containing resin is preferably from 20 to 60% by mass, more preferably from 30 to 50% by mass, based on the total amount of the composition. When it is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when it is more than the above range, the viscosity is high, and the coating property or the like is lowered, which is not preferable. When the resin composition of the present invention is composed of a photocurable resin composition or a photocurable thermosetting resin composition, a photopolymerization initiator can be added. A preferred initiator can be obtained by using an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and a fluorenyl phosphorus oxide photopolymer-14-201207555. One or more photopolymerization initiators selected from the group consisting of initiators. Commercially available products of the oxime ester photopolymerization initiator are CGI-325 manufactured by Ciba Corporation of Japan, Irgacure (registered trademark) OXEO1, Irgacure OXE02, N-1919 manufactured by Adeka Co., Ltd., NCI-831, and the like. Further, a photopolymerization initiator having two oxime ester groups in the molecule is also suitable. Specifically, it is an oxime ester compound having a carbazole structure represented by the following formula.

(wherein, X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having a carbon number, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms) , an amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, An amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, and Y and Z each independently represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and a carbon number of 1 to 8. Alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, an amine group, alkylamino group having an alkyl group having 1 to 8 carbon atoms) Or a dialkylamino group substituted), a naphthyl group (an alkyl group having a carbon number of 1 to 17, an alkoxy group having a carbon number of 1 to 8, an amine group, and a hospital base having a carbon number of 1 to 8) Or a hospital amine-substituted), fluorenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents a bond, or an alkyl group having a carbon number of 1 to 1, an alkyl group, a phenyl group , biphenyl, exopyridyl, anthranyl, thienyl, thiol, thiophene-15-201207555, furanyl, 2,5-pyridyl Ordole-diyl, 4,4,-stilbene diyl, 4,2'-styrenediyl, η is an integer of 0 or 1. In particular, in the above formula, X and oxime are respectively methyl or ethyl, hydrazine is methyl or phenyl, and η is O'Ar is preferably a bond, or a phenyl group, a naphthyl group, a thiophene group or a stretching group. Thienyl. The amount of the vinegar-based photopolymerization initiator to be added is preferably from 1 to 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When it is less than 1 part by mass, the photocurability is insufficient, and the film properties such as peeling of the coating film and chemical resistance are lowered. On the other hand, when it exceeds 5 parts by mass, the light absorption on the surface of the coating film becomes strong, and the deep hardenability tends to decrease. More preferably 0.5 to 3 parts by mass. The α-aminoacetophenone photopolymerization initiator is specifically exemplified as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1, 2-benzyl -2-dimethylamino-1-(4-morpholinylphenyl)-propan-1·one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]- 1·[4-(4-Morpholinyl)phenyl]-1-butanone, anthracene, fluorenyl-dimethylaminoacetophenone and the like. Commercially available products are Irgacure 907, Irgacure 3 69, Irgacure 3 79 manufactured by Ciba Corporation of Japan. The mercaptophosphorus oxide photopolymerization initiator is specifically exemplified as 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzamide) Phenylphosphine oxide, bis(2,6-dimethoxybenzhydryl)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products are LUCILIN TPO manufactured by BASF Corporation, Irgacure 819 manufactured by Ciba Corporation, etc., etc., such α-aminoacetophenone photopolymerization initiator, mercaptophosphorus oxide-16-201207555 photopolymerization The amount of the initiator to be added is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When it is less than 0.01 part by mass, the same photohardenability to copper is insufficient, and the coating film is peeled off, and the film properties such as chemical resistance are lowered. On the other hand, when it exceeds 15 parts by mass, the effect of reducing the gas release cannot be obtained, and the light absorption on the surface of the coating film is enhanced, and the deep hardenability tends to be lowered. More preferably, it is 0.5 to 10 parts by mass, and a photopolymerization initiator, or a photoinitiator and a sensitizer which can be used for the resin composition of the present invention are exemplified by a benzoin compound and a phenyl group. A ketone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, and a xanthone compound. The benzoin compound is specifically exemplified by, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like. The acetophenone compound is specifically exemplified by, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1, 1-Dichloroacetophenone and the like. The hydrazine compound is specifically exemplified by, for example, 2-methylhydrazine, 2-ethylhydrazine, 2-tert-butylphosphonium, 1-chloroindole or the like. The thioxanthone compound is specifically exemplified by, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone. Wait. Specific examples of the ketal compound include, for example, acetophenone dimethyl ketal, benzyl dimethyl ketal, and the like. The benzophenone compound is specifically exemplified by, for example, benzophenone, 4-phenyl-17-201207555 formazan diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzylidene-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenylsulfate, and the like. The tertiary amine compound is specifically exemplified by, for example, an ethanolamine compound or a compound having a dialkylaminobenzene structure. For example, a commercially available product is exemplified by 4,4 '-dimethylaminobenzophenone (manufactured by Nippon Soda Co., Ltd.). NISSOKUA MABP), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), etc. Dialkylaminobenzophenone, 7-(diethylamino)-4 Methyl-2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin) and other dialkylamine-containing coumarin compounds, 4-dimethyl Ethyl benzoate (KAYAKUA (registered trademark) EPA manufactured by Sakamoto Chemical Co., Ltd.), 2-dimethylaminobenzoic acid ethyl ester (Quantacure DMB manufactured by International Biosynthesis Co., Ltd.), 4-dimethylamino group Benzoic acid (n-butoxy)ethyl ester (Quantacure BEA manufactured by International Biosynthesis Co., Ltd.), p-dimethylaminobenzoic acid isoamyl ethyl ester (KAYAKUA-DMBI manufactured by Nippon Kayaku Co., Ltd.), 4-dimethyl 2-ethylhexyl benzoate (Esolol 507, manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), and the like. Among these, a thioxanthone compound and a tertiary amine compound are preferred. In particular, if it contains a thioxanthone compound, it is preferably in terms of deep hardenability, and preferably contains 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthene A thioxanthone compound such as a ketone or a 2,4-diisopropylthioxanthone. The compounding amount of the thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing resin. When the amount of the thioxanthone compound is adjusted to -18-201207555, the film thickness is more than 20 parts by mass. The hardenability is reduced and is associated with an increase in the cost of the product. More preferably, it is 10 parts by mass or less. As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferred, and a dialkylaminobenzophenone compound is preferred, and a dialkylamine group having a maximum absorption wavelength of 350 to 450 nm is contained. a coumarin compound and a keto coumarin. As for the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferred because of low toxicity. The coumarin compound containing a dialkylamine group has a maximum absorption wavelength of 3 50 to 410 nm and an ultraviolet range, so that the coloring is small, and the coloring pigment is used to reflect the coloring pigment itself. The color of the film. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one is preferred. The amount of the tertiary amine compound to be added is preferably 0.1 to 20 parts by mass based on 1 part by mass of the carboxyl group-containing resin. When the amount of the tertiary amine compound is less than 0.1 part by mass, there is a tendency that a sufficient sensitizing effect cannot be obtained. When it exceeds 20 parts by mass, the deep hardenability tends to decrease. More preferably, it is 0.1 to 10 parts by mass. 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 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep hardening property tends to decrease due to the light absorption. Further, since the photopolymerization initiator, the photoinitiator, and the sensitizer have a specific wavelength due to absorption of -19-201207555, the sensitivity is lowered in some cases, and it acts as an ultraviolet absorber. However, these are not intended to enhance the sensitivity of the composition to the user. The light of a specific wavelength can be absorbed as needed to increase the photoreactivity of the surface, and the line shape and opening of the coating film become vertical, pyramidal, and chamfered, and the processing precision of the line width and the opening diameter is improved. The photopolymerization initiator is preferably an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and a sulfhydryl phosphorus oxide photopolymerization initiator. One or more photopolymerization initiators selected from the group consisting of agents. Since the phthalic ester-based photopolymerization initiator has a good efficiency of the initiator, a small amount can effectively improve the sensitivity, so that after the formation of the photoresist film, it is known that the contamination or the volatilization due to the gas release during the heat treatment is small, and the film is effectively reduced. The warpage is preferred. Further, a tonoketone-based or coumarin-based sensitizer is preferable because it is effective in adjusting the cross-sectional shape of the resist. It is best to use both. The naphthalene ring-containing epoxy resin used in the photocurable thermosetting resin composition of the present invention can obtain a high heat-resistant coating film which is highly resistant to heat, in addition to the good overall reactivity of the prior art, and the resulting hardening. The coefficient of thermal expansion of the coating film (hereinafter referred to as CTE) does not decrease, and it is extremely effective for stress relaxation at the time of hardening of the solder resist. The naphthalene ring-containing epoxy resin is exemplified by, for example, HP-403 2 (manufactured by DIC), ΗΡ-4700 (manufactured by DIC), ESN-3 55 (manufactured by Tohto Kasei Co., Ltd.), and ESN-3. 75 (made by Toho Chemical Co., Ltd.), NC-73 00 (manufactured by Nippon Chemical Co., Ltd.). The most suitable ones are polyfunctional epoxy resins or derivatives thereof having a naphthalene ring skeleton and an aralkyl structure. The blending amount of the epoxy resin containing a naphthalene ring is preferably 5 parts by mass to 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the above-mentioned carboxyl group-containing -20-201207555 resin. When the amount of the epoxy resin containing a naphthalene ring is less than 5 parts by mass, the effect of the coating film is deteriorated, and the photoconductivity of the coating film is deteriorated, which may cause an image defect. Further, the photocurable thermosetting resin composition of the present invention may be added with a thermosetting component to impart heat resistance. The thermosetting component used in the present invention may be a protected isocyanate compound, an amine resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, or a polyfunctional ring. A thermosetting resin which is conventionally used, such as an oxygen compound, a polyfunctional oxetane compound, an episulfide resin, and a melamine derivative. The above-mentioned preferable thermosetting component is a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter simply referred to as cyclic (thio)ether groups) in one molecule. These thermosetting components having a cyclic (thio)ether group are commercially available in a wide variety of types, and various characteristics can be imparted depending on the structure. The thermosetting component having two or more cyclic (thio)ether groups in the molecule is any one of two or more three, four or five membered cyclic ether groups or cyclic thioether groups in the molecule. Or a compound of two kinds, for example, a compound having at least two or more epoxy groups in the molecule, that is, a compound having at least two or more oxetanyl groups in the molecule of the polyfunctional epoxy compound, that is, A functional oxetane compound, a compound having two or more thioether groups in its molecule, that is, an episulfide resin. As the polyfunctional epoxy compound, for example, jER (registered trademark) 828, jER834, jER1001 - 21 - 201207555, jER 1004 manufactured by Nippon Epoxy Co., Ltd., Epiclon (registered trademark) 840, Epiclon 850 manufactured by DIC Corporation are listed. Epiclon 1050, Epiclon 2055, EPOTOT (registered trademark) YD-011, YD-013, YD-127, YD-128 manufactured by Dongdu Chemical Co., Ltd., DER317, DER331, DER661, DER664 manufactured by Dao Chemical Co., Ltd. Japan's Ciba's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260' Sumitomo Chemical Industries, Inc. Sumi-epoxy ESA-011, ESA-014, E LA-115, ELA-128, AER330 manufactured by Asahi Kasei Industrial Co., Ltd. , AER331, AER661, AER664, etc. (both trade names) of bisphenol A epoxy resin; JERYL 903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152, Epiclon 165 manufactured by DIC Corporation, manufactured by Dongdu Chemical Co., Ltd. EPOTOT YDB-400, YDB-5 00 - DER542 manufactured by Dao Chemical Co., Ltd., Araldide 8011 from Ciba, Sumi-epoxy ESB-400, ESB-7 manufactured by Sumitomo Chemical Co., Ltd. 00, brominated epoxy resin manufactured by Asahi Kasei Industrial Co., Ltd. VIII.11.711, VIII.£.11.714 (both trade names); jER 152, jER 154 manufactured by Japan Epoxy Resin Co., Ltd., manufactured by Dao Chemical Co., Ltd. DEN431, DEN438, Epiclon N-730, Epiclon N-770, Epiclon N-865 manufactured by DIC, EPOTOT YDCN-701, YDCN-704 manufactured by Dongdu Chemical Co., Ltd., Araldide ECN 1 23 manufactured by Sakamoto Ciba 5. Araldide ECN 1 273, Araldide ECN1299, Araldide XPY307, EPPN (registered trademark) 011, EOCN (registered trademark) - 1 025, EOCN-1020, EOCN-104S > RE-306, manufactured by Nippon Kayaku Co., Ltd., Sumitomo Sumi-epoxy ESCN-195X, ESCN-220, manufactured by Chemical Industry Co., Ltd., AOC ECN-235, ECN-299, etc. JER807 manufactured by Epiclon 830' Japan Epoxy Resin Co., Ltd., EPOTO YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd., Araldide XPY306 manufactured by Japan Ciba (both are trade names) Phenol F epoxy Lithium; hydrogenated bisphenol A type epoxy resin manufactured by Dongdu Chemical Co., Ltd., EPOTOT ST-2004, ST-2007, ST-3 000 (trade name); jER604 manufactured by Japan Epoxy Resin Co., Ltd., EPOTOT manufactured by Dongdu Chemical Co., Ltd. YH-434, Araldide MY720 manufactured by Sakamoto Ciba, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (all trade names), glycidylamine epoxy resin; Araldide CY manufactured by Ciba Corporation of Japan -3 5 0 (trade name), etc., uranyl-type epoxy resin; Celloxide (registered trademark) 202 manufactured by Dicel Chemical Industry Co., Ltd. 1, Araldide CY 175 'CY 179 manufactured by Ciba Corporation, etc. Aliphatic epoxy resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd., TEN·, ΕΡΡΝ·501, ΕΡΡΝ-502, etc. (all trade names) manufactured by Dao Chemical Co., Ltd. Epoxy resin; bis-xylenol type or biphenol type epoxy resin such as YL-605 6 , ΥΧ-4000, YL-6121 (both trade names) manufactured by Japan Epoxy Resin Co., Ltd. or a mixture thereof; Japan EBPS-200, ADEK manufactured by Chemical Pharmaceutical Co., Ltd. A30 manufactured by Company A, bisphenol δ type epoxy resin such as ΕΧΑ-1514 (trade name) manufactured by DIC Corporation; bisphenol a phthalic acid varnish epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd. Resin; jERYL-931 manufactured by Japan Epoxy Resin Co., Ltd., Araldide 163 manufactured by Japan Automobile Enterprise Co., Ltd. (all trade names), tetraphenyl-23-201207555 mercaptoethane type epoxy resin; manufactured by Japan Ciba Araldide PT810 (trade name), a heterocyclic epoxy resin of TEPIC (registered trademark) manufactured by Nissan Chemical Industries Co., Ltd.; diglycidyl acrylate resin such as Blenmer (registered trademark) DGT manufactured by Nippon Oil & Fats Co., Ltd.: Dongdu Tetraglycidyl xylene decyl ethane resin such as ZX-1 063 manufactured by Kasei Co., Ltd.; ESN-190, ESN-3 60 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA manufactured by DIC Corporation -4700 epoxy resin containing naphthyl group; epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; glycidol such as CP-50S and CP-50M manufactured by Nippon Oil & Fats Co., Ltd. Methyl methacrylate copolymerization Epoxy resin; further, copolymerized epoxy resin of cyclohexylmalamine and glycidyl methacrylate; epoxy modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Dicel Chemical Industry Co., Ltd.) ), CTBN modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Dongdu Chemical Co., Ltd.), etc., but is not limited thereto. These epoxy resins may be used singly or in combination of two or more. In particular, the novolac type epoxy resin, the modified novolac type epoxy resin, the heterocyclic epoxy resin, the bisphenol type epoxy resin or a mixture thereof is preferably the aforementioned polyfunctional oxygen heterocycle. The butane compound is exemplified by bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether' 1 , 4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene , (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, methacrylic acid (3-methyl-3-oxo- 24 - 201207555 Heterocyclic butyl)methyl ester, (3-ethyl-3-oxetanyl)methyl methacrylate or polyfunctional oxetane such as oligomers or copolymers thereof And oxetane and novolak resins, poly(p-hydroxystyrene), CALDO type bisphenols, calixarene, resorcinol calixarenes (calixresorcinarene), or sesquiterpene oxide, etc. An etherified product of a resin having a hydroxyl group or the like. Further, it is exemplified by a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate. The episulfide compound having two or more cyclic (thio)ether groups in the above molecule is exemplified by, for example, YL7000 (bisphenol A type episulfide resin) manufactured by Nippon Epoxy Resin Co., Ltd., or YSLV manufactured by Toshiro Kasei Co., Ltd. -120TE and so on. Further, an episulfide resin such as an oxygen atom of an epoxy group of a novolac type epoxy resin may be replaced by a sulfur atom by the same synthesis method. The compounding ratio 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 2.5 equivalents, per mole of the carboxyl group of the carboxyl group-containing resin. A range of 2.0 equivalents. When the amount of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is less than 0.6, the heat resistance, alkali resistance, electrical insulation, and the like are lowered due to residual carboxyl groups in the solder resist film. Less good. On the other hand, when it exceeds 2.5 equivalents, it is less preferable because the low molecular weight cyclic (thio)ether group remains in the dried coating film to lower the strength of the coating film and the like. Further, the thermosetting component which can be preferably used is melamine derivative, benzoguanamine derivative or the like. For example, a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycol urea compound, and a methylol-25-201207555-based urea compound. In addition, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycol urea compound, and the alkoxymethylated urea compound are each It is obtained by converting a methylolamine compound, a methylol benzoguanamine compound, a methylol glycol urea compound, and a methylol group of a methylol urea compound into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and may, for example, be a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group or a butoxymethyl group. It is preferably a melamine derivative having a formalin concentration of 0.2% or less which is excellent for the human body or the environment. Such commercially available products can be exemplified by, for example, Cyrnel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 370, Cymel 325, Cymel 3 27, Cymel 701, Cymel 266, Cymel 267, Cymel 238, Cymel 114 1, Cymel. 2 7 2. Cymel 2 0 2. Cymel 1156, Cymel 1158, Cymel 1123, Cymel 1170, Cymel 1174, Cymel UFR65, Cymel 3 00 (all manufactured by Mitsui Cyanamide Co., Ltd.), NIKALAC (registered trademark) Mx-750 , NIKALAC Mx-032, NIKALAC Mx-270, NIKALAC Mx-280, NIKALAC Mx-290, NIKALAC Mx-706, NIKALAC Mx-708 'NIKALAC Mx-40, NIKALAC Mx-3 1, NIKALAC Ms-1 1 , NIKALAC Mw -30, NIKALAC Mw-30HM, NIKALAC Mw-390, NIKALAC Mw-IOOLM, NIKALAC Mw-7 50LM (above is manufactured by Sanwa Chemical Co., Ltd.). The above-mentioned thermosetting component may be used singly or in combination of two or more. Further, the photocurable thermosetting resin composition of the present invention may be added with a compound having two or more isocyanate groups or blocked isocyanate groups in the molecule of -26 to 201207555 to improve the hardenability of the composition and the resulting hardening. The toughness of the film. The compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is exemplified as a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or two or more in one molecule. A compound which blocks an isocyanate group, that is, a blocked isocyanate compound or the like. As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate are 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene Diisocyanate, m-xylene diisocyanate and 2,4-toluene dimer. Specific examples of the aliphatic polyisocyanate are tetramethylammonium diisocyanate, hexamethylene diisocyanate, methyl diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methyl bis(cyclohexyl). Isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate are biscycloheptane triisocyanate. And the previously listed isocyanate compound adduct, biuret and isocyanurate body. The blocked isocyanate group contained in the blocked isocyanate compound is protected by reacting the isocyanate group with the blocking agent. The basis for temporary inertization. Upon heating to a specific temperature, the blocking agent dissociates to form an isocyanate group. The blocked isocyanate compound is an addition reaction product of an isocyanate compound and an isocyanate blocking agent. The isocyanate compound obtained by the reaction with a blocking agent is exemplified by an isocyanurate type, a biuret type, an addition type, and the like. -27- 201207555 The isocyanate compound can be, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate are exemplified as the compounds exemplified above. The isocyanate blocking agent is exemplified by a phenolic terminal blocking agent such as phenol, cresol, xylenol, chlorophenol or ethylphenol; ε-caprolactam, δ-valeroinamide, γ-butyrolactone and An internal amide-based blocking agent such as Ρ-propionalamine; an inert methyl-terminated blocking agent such as acetamidine acetate and acetonitrile; methanol, ethanol, propanol, butanol, pentanol, and ethylene Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate , alcohol-based terminal blocking agents such as diacetone alcohol, methyl lactate and ethyl lactate; oxime systems such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine, cyclohexane hydrazine Blocking agent; thiol-based capping agent such as butyl mercaptan, hexyl mercaptan, tert-butyl mercaptan, thiophenol, methyl thiophenol, ethyl thiophenol; acetamidine, benzamidine Amidoxime-based blocking agent such as amine: a quinone imine blocking agent such as amber quinone and maleimine; an amine blocking agent such as xylidine, aniline, butylamine or dibutylamine; , imidazole seals such as 2-ethylimidazole The terminal agent; an imide-based blocking agent such as methylimine and propylimine. The blocked isocyanate compound is commercially available, and is exemplified by, for example, Sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062, TPLS. -2078, TPLS-2117, Desmotherm 2170 'Desmotherm 2265 (above is Sumitomo Bayer Urethane, trade name), -28- 201207555

Coronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (above is manufactured by Japan p〇1yurethane Industrial Co., Ltd.), B- 8 3 0 'B-815, B-846, B-870, B-874, B -882 (manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA_B80E, 17B-60PX, E402-B80T (product name manufactured by Asahi Kasei Chemicals Co., Ltd.). Further, 'Sumiduf BL_3175 and BL-4265 are those obtained using methyl ethyl hydrazine as a terminal blocking agent. The compound having two or more isocyanate groups or blocked isocyanate groups in the above molecule may be used alone or in combination of two or more. The compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably from 1 to 1 part by mass based on 100 parts by mass of the carboxyl group-containing resin. It is a ratio of 2 to 70 parts by mass. When the amount of the above formulation is less than 1 part by mass, sufficient coating film toughness cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable. In the photocurable thermosetting resin composition of the present invention, a urethanization catalyst may be added to promote a hardening reaction of a hydroxyl group or a carboxyl group with an isocyanate group. As the urethane-based catalyst, one or more selected from the group consisting of a tin-based catalyst, a metal chloride, a metal acetylacetonate, a metal sulfate, an amine compound, or an amine salt is preferably used. The urethane-based catalyst The tin-based catalyst is exemplified by an organic tin compound such as stannous octoate or dibutyltin dilaurate, or an inorganic tin compound. -29- 201207555 The metal chloride is a chloride of a metal composed of Cr, Μη, Co, Ni, Fe, Cu or A1, and is exemplified by cobalt chloride, nickel chloride, iron chloride and the like. The aforementioned metal ethyl pyruvate is an ethyl phthalate pyruvate of a metal composed of Cr, Mn, Co, Ni, Fe, Cu or A1, and is exemplified by, for example, cobalt acetylacetonate and acetylpyruvate. Nickel, iron acetylacetonate and the like. The metal sulfate is a sulfate of a metal composed of Cr, Mn, Co, Ni, Fe, Cu or A1, and is exemplified by, for example, copper sulfate. The aforementioned amine compound is exemplified by, for example, conventionally used triethylenediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, bis(2-dimethylaminoethyl)ether, N ,N,N',N'',N"-pentamethyldiethylideneamine, N-methyloxime, N-ethylmorpholine, N,N-dimethylethanolamine, dimorpholinyl Diethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N'-(2-hydroxyethyl)-N,N,N'-trimethyl-bis(2-aminoethyl Ether, N,N-dimethylhexanolamine, >1,>1-dimethylaminoethoxyethanol, ;^,:^,:^'-trimethyl->^' -(2-hydroxyethyl) ethylenediamine, N-(2-hydroxyethyl)-N,N',N",N"-tetramethyldiethylenetriamine, N-(2-hydroxypropane ))-N,N',N",N"-tetramethyldiethylenetriamine, hydrazine, hydrazine, Ν'-trimethyl-Ν'-(2-hydroxyethyl)propanediamine, N- Methyl-Ν'-(2-hydroxyethyl)piperidine, bis(indole, Ν-dimethylaminopropyl)amine, bis(indole, Ν-dimethylaminopropyl)isopropanolamine , 2-aminoquinine ring (quinuclidine), 3-aminoquinine ring, 4-aminoquinine ring 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1-(2'-hydroxypropyl)imidazole, 1-(2'-hydroxypropyl)-2-methyl Imidazole, 1-(2'-hydroxyethyl)imidazole, 1-(2'-hydroxyethyl)-2-methylimidazole, 1-(2'-hydroxy-30- 201207555-propyl)-2 Methylimidazole, 1-(3aminopropyl)imidazole, 1-(3,-aminopropyl)-2-methylimidazole, 1-(3,-hydroxypropyl)imidazole, 1-(3hydroxyl) Propyl)-2-methylimidazole, N,N-dimethylaminopropyl-Ν'-(2-hydroxyethyl)amine 'Ν, Ν-dimethylaminopropyl-Ν', Ν '-Bis(2-hydroxyethyl)amine, hydrazine, hydrazine-dimethylaminopropyl-hydrazine, Ν'-bis(2-hydroxypropyl)amine, hydrazine, hydrazine-dimethylamino Ethyl-hydrazone, Ν'-bis(2-hydroxyethyl)amine, hydrazine, hydrazine-dimethylaminoethyl-hydrazine, Ν'-bis(2-hydroxypropyl)amine, melamine and/or Or benzoguanamine or the like. The amine salt is exemplified by an amine salt of an organic acid salt such as DBU (1,8-diaza-bicyclo[5,4,0]undecene-7). It is sufficient that the amount of the urethane catalyst is adjusted in a usual amount. For example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10.0 parts by mass, per 100 parts by mass of the resin (A) containing a carboxyl group. The above molecule has two or more cyclic (thio)ether groups. In the case of a thermosetting component, it is preferred to contain a thermosetting catalyst. Examples of such thermosetting catalysts are, for example, imidazole, 2-methylimidazole '2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- An azole derivative such as phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Dicyanodiamine, benzyldimethylamine, 4-(dimethylamino) hydrazine, hydrazine-dimethylbenzylamine, 4-methoxy-hydrazine, hydrazine-dimethylbenzylamine, An amine compound such as 4-methyl-hydrazine or hydrazine-dimethylbenzylamine; an anthracene compound such as diammonium adipate or diterpene sebacate; or a phosphorus compound such as triphenylphosphine. In addition, the market name is, for example, 2ΜΖ-Α, 2ΜΖ-ΟΚ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ (all trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., Ltd.' -31 - 201207555 U-Manufactured by SAN-APRO CAT (registered trademark) 3503N, U-CAT 3502T (both trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic guanidine compounds and their salts) )Wait. In particular, it is not limited to these, and if it is a thermosetting catalyst of an epoxy resin and an oxetane compound, or a reaction promoting an epoxy group and/or an oxetane group and a carboxyl group, it is used alone or Mixing two or more uses is fine. Further, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2- Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine • isophthalic acid adduct, 2,4-diamino-6 - an S-triazine derivative such as a methacryloxyethyl-S-triazine or an isocyanuric acid adduct, and a compound which functions as an adhesion imparting agent and the above-mentioned thermosetting property Catalyst use" The amount of these thermosetting catalysts is sufficient in the proportion of the usual amount, for example, relative to the heat of the carboxylic acid-containing resin or the molecule having two or more cyclic (thio)ether groups. The curable component is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass. The photocurable resin composition of the present invention can be formulated with a colorant. As the coloring agent, any of the conventional coloring agents 'pigment' dyes and pigments such as red, blue, green, and yellow may be used. Specifically, the number of the color coefficient (C.I., issued by The Society of Dyers and Colourists) is attached. However, in terms of reducing environmental load and affecting human body, it is preferred that halogen is not contained. -32- 201207555 Red coloring agent: Red coloring agent is monoazo, diazo, soluble azo dye, benzimidazolone, lanthanide, diketopyrrolopyrrole, condensed azo, hydrazine Anthraquinone, quinacridone, etc., specifically, may be exemplified by a color coefficient (CI·, Dyes and Color Association (The Society of

Dyers and Colourists) issued) number. 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 system: Pigment red 37, 38, 41. Soluble monoazo dye series: Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53 :2, 57:1, 58:4, 63:1 ' 63:2, 64:1, 68. Benzimidazolone type: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208. Lanthanide: Solvent Red 135, Solvent Red 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. Diketopyrrolopyrrole: Pigment Red 254, Pigment Red 25 5, Pigment Red 2 64, Pigment Red 270, Pigment Red 272. Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 2 1 4, Pigment Red 2 2 0, Pigment Red 2 2 1 , Pigment Red 2 4 2 . Lanthanum: Pigment Red 168, Pigment Red 177, Pigment Red 216, Pigment -33- 201207555 Red 1 4 9 , Pigment Red 1 50, Solvent Red 5 2, Solvent Red 2 0 7. Quinacridone type: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209. Blue coloring agent: The blue coloring agent is a phthalocyanine system or an anthraquinone system, and the pigment system is classified into a pigment (Pigment). Specifically, it can be exemplified as follows: Pigment Blue 15, Pigment Blue 15:1 , Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60. For the dye system, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 122, solvent blue 136, solvent blue 67, solvent blue can be used. 70 and so on. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used. Green colorants: Green colorants also have phthalocyanine, lanthanide, and lanthanide. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. In addition to the above, a ruthenium compound which is substituted with or without a metal may also be used. Yellow coloring agent: The yellow coloring agent is a monoazo-type diazo-based, a condensed azo-based, a benzimidazolone-based, an isoindolinone-based, an anthraquinone-based or the like, and specifically, the following are listed. -34- 201207555 惠醒系: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 1〇8, Pigment Yellow M3, Pigment Yellow 147, Pigment Yellow 199, _Huang 2〇^ / Isodecanone·Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185. Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180. Benzimidazolone: Pigment Yellow 12〇, Pigment Yellow 151, Pigment Yellow I54, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181. Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 1 (), 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 1〇4 , 105, 111, 116, 167, 168, 169, 182, 183. - azo system: pigment yellow 12, 13, 14, 16, 17, 55, 63, 81 '83, 87, 126, 127, 152' 170, 172, 174, 176, 188, 198 ° In addition, in order to adjust the color tone Colorants such as purple, orange, brown, and black can also be added. Specific examples are pigment purple 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, CI pigment orange 1, CI pigment orange 5, CI pigment orange 13, CI pigment orange 14, CI · pigment orange 16' CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51. C_I. Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black 7, and the like. -35-201207555 The blending ratio of the coloring agent is not particularly limited, but is preferably from 0 to 10 parts by mass, and most preferably from 0.1 to 5 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin. The compound having two or more ethylenically unsaturated groups in the photocurable thermosetting resin composition of the present invention is photohardened by irradiation of an energy ray to cause the carboxyl group-containing resin to be in an aqueous solution. Insoluble, or help insoluble. These compounds are conventionally used in the conventional polyester (meth) acrylate, polyether (methyl) propyl ester, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (A Base) acrylate and the like. Specifically, it is exemplified by alkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl methacrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Acrylates: N,N-dimethyl decylamine, N-hydroxymethyl decylamine, N,N-dimethylaminopropyl acrylamide, etc. Acrylamide N,N-dimethylamino Aminoalkyl acrylates such as ethyl acrylate and N,N-dimethylaminopropyl acrylate: hexanediol, trimethylolpropane, tetraol, dipentaerythritol, tris-hydroxyethyl isocyanuric acid a polyvalent acrylate such as an ester of ethylene oxide such as an acid ester, a propylene oxide adduct or an ε-hexane adduct; a phenoxy acrylate, a bisphenol sebacate, and Ethylene oxide adducts of such phenols or polyvalent acrylates such as propylene oxide; glycerol diglycidyl ether, glycerol trigest ether, trimethylolpropane triglycidyl ether, triglycidyl a polyvalent acrylate of a glycidyl ether such as a cyanoester; not limited to the above, but a polyether polyol, a polycarbonate diol, and a hydroxyl group It is preferred that the molecularly active basicity be a propyl acrylate such as acrylic acid propylene glycol; propylene pentaerythritol or lactone propylene glycerol uric acid may be a poly acrylate direct acrylate such as diene-36-201207555 or polyester polyol. Or acrylates and trimerates which are esterified with urethane by acid esters, and/or various methyl acrylates corresponding to the above acrylates. Further, an epoxy acrylate resin obtained by reacting a cresol novolak resin type epoxy resin epoxy resin with acrylic acid to exemplify a hydroxyl group of an epoxy acrylate resin and a hydroxy acrylate such as pentaerythritol tripropylene An epoxy group amino acid formate compound obtained by reacting a diisomeric carbamate compound such as isophorone diisocyanate. These epoxy propyl ester-based resins can improve photocurability without lowering the drying property. The compounding amount of the two or more ethylenically unsaturated groups in the molecule is from 5 to 100 parts by mass, more preferably from 1 to 70 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the amount is less than 5 parts by mass, the photocurability is lowered, and the active energy ray is difficult to form a pattern by alkali development, which is not preferable. On the other hand, when the amount is more than 1 part by mass, the solubility in the alkaline aqueous solution tends to become brittle, which is not preferable. The photocurable thermosetting resin composition of the present invention is a physical strength of the film, and may be formulated as needed. These may be filled with conventional inorganic or organic chelating agents, but particularly preferably used, spherical cerium oxide and talc. Further, metal hydroxides such as oxidized oxides and aluminum hydroxide may be used. Body pigments for white appearance or flame retardancy. The dosage of the stimulating agent is di-isocyanurate acrylate or the like, and the olefinic acid ester cyanate ester propylene finger-contact dry compound is preferably prepared at a blending rate, and when it is super, the coating film is high. The coating agent may be a barium sulphate titanium or a ruthenium sulphate, and 100 parts by mass of the resin containing a residue, preferably from 200 to 15 parts by mass, more preferably from 0.1 to 150 parts by mass, most preferably from -37 to 201207555. 1 to 1 part by mass. When the blending ratio of the ruthenium filler is more than 200 parts by mass, the viscosity of the composition becomes high, the printability is lowered, and the cured product becomes brittle, which is not preferable. Further, the photocurable thermosetting resin composition of the present invention may also use a binder polymer to improve dryness, dryness, and the like. For example, a polyester polymer 'polyurethane type polymer, a polyester urethane type polymer, a polyurethane polymer, a polyester urethane type polymer, a poly A amide-based polymer, a polyester amide-based polymer, an acrylic polymer, a cellulose-based polymer, a polylactic acid-based polymer, or a phenoxy-based polymer. These binder polymers may be used singly or in combination of two or more. Further, the photocurable thermosetting resin composition of the present invention may be an elastomer or other elastomer containing a hydroxyl group to impart flexibility, to improve the brittleness of the cured product, and the like. For example, a polyester-based elastomer, a polyurethane-based elastomer, a polyester urethane-based elastomer, a polyamide-based elastomer, a polyester amide-based elastomer, an acrylic elastomer, or the like can be used. Olefin-based elastomer. Further, a resin obtained by modifying some or all of the epoxy groups having one or more kinds of epoxy resins to be a two-terminal carboxylic acid-modified butadiene-acrylonitrile rubber may be used. Further, a polybutadiene-based elastomer containing an epoxy group, a polybutadiene-based elastomer containing acrylic acid, or the like can be used. These elastomers may be used singly or in combination of two or more. Further, the photocurable thermosetting resin composition of the present invention may be used for the above-mentioned resin synthesis or composition of a carboxyl group-containing compound-38-201207555, or for coating on a substrate or a carrier film. Viscosity. Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, it is a ketone such as methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; a cellosolve, a methyl cellosolve, or a butyl cellosolve; Glycol ethers such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc.; ethanol, propanol Alcohols such as ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent petroleum brain. These organic solvents may be used singly or in combination of two or more. In general, when most of the polymer material starts to oxidize, subsequent oxidative degradation of the chain is caused, and the function of the polymer material is lowered, so that the photocurable thermosetting resin composition of the present invention can be added for use. (1) a radical scavenger that invalidates the generated radicals and/or (2) a peroxide decomposing agent that decomposes the generated peroxide into a harmless substance without generating new radicals. Oxidizer. Specific examples of the antioxidant which acts as a radical scavenger are hydroquinone, 4-tert-butylcatechol, 2-tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di -T-butyl-p-cresol, 2,2-methyl-bis(4-methyl-6-tert-butylphenol), 1,1,3-gin (2-methyl-4-) Hydroxy-5-third-39-201207555 butylphenyl)butane, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4-hydroxyl) Benzyl)benzene, 1,3,5-gin (3',5'-di-t-butyl-4-hydroxybenzyl)-3-trisole-2,4,6-(11^,311,51 A quinone compound such as quinone or a phenolic compound such as pyrogallol or benzoquinone, bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate or phenothiazine (Phenothiazin) An amine-based compound, etc. The radical scavenger can be commercially available, and is exemplified by, for example, ADEKASTAB (registered trademark) AO-30, ADEKASTAB AO-3 3 0 , ADEKASTAB AO-20, ADEKASTAB LA-7 7, and ADEKASTAB LA-57. , ADEKASTAB LA-67, ADEKASTAB LA-68, ADEKASTAB LA · 8 7 (all manufactured by ADEKA, trade name), IRGANOX (registered trademark) 1010, IRGANOX 1 03 5 'IRGANOX 1 076 , IRGANOX 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (all of which are manufactured by Ciba Corporation, trade name), etc. As the oxidizing agent, specific compounds are exemplified by phosphorus compounds such as triphenyl ester, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3'-thiodipropionic acid. A sulfur-based compound such as an ester, etc. The peroxide-decomposing agent is commercially available, and is exemplified by, for example, ADEKASTAB TPP (manufactured by ADEKA Corporation, trade name), MARK AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), and SUMILIZER (registered). Trademark) TPS (manufactured by Sumitomo Chemical Co., Ltd., trade name), etc. -40- 201207555 The above antioxidants may be used singly or in combination of two or more. In general, polymer materials absorb light and cause decomposition. • Deterioration, the photocurable thermosetting resin composition of the present invention is prepared in addition to the above antioxidants in order to stabilize the ultraviolet rays. A UV absorber can be used. The ultraviolet absorber is exemplified by a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, an ortho-aminobenzene. a formate derivative, a benzhydrylmethane derivative or the like. Specific examples of the benzophenone derivative are exemplified by 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-dihydroxy-4- Methoxybenzophenone and 2,4-dihydroxybenzophenone. Specific examples of the benzoate derivative are exemplified by 2-ethylhexyl salicylate, phenyl salicylate, p-t-butylphenyl salicylate, and 2,4-di-t-butyl group. Phenyl-3,5-di-t-butyl-4-hydroxybenzoate and cetyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative are exemplified by, for example, 2-( 2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-( 2'-hydroxy-5'-methylphenyl group. Benzotriazole, 2-( 2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2,-hydroxy-3,, 5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2,-hydroxy-5'-methylphenyl)benzotriazole and 2-(2,-hydroxy- 3,5'-di-t-butylphenyl) benzotriazole and the like. Specific examples of the triazine derivative are hydroxyphenyltriazine, bisethylhexyloxyphenylmethoxyphenyltriazine and the like.

The ultraviolet absorbers are commercially available, and are listed, for example, as TINUVIN PS-41 - 201207555, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (all of which are manufactured by Japan Ciba, trade name). The above-mentioned ultraviolet absorbers may be used singly or in combination of two or more kinds, and the stability of the molded article obtained from the photocurable thermosetting resin composition of the present invention can be achieved by using the above-mentioned antioxidant. As the photocurable thermosetting resin composition of the invention, a conventionally used N-phenylglycine, phenoxyacetic acid, thiophenoxyacetic acid, mercaptothiazole or the like can be used as a chain transfer agent to improve sensitivity. Specific examples of the chain transfer agent include a chain transfer agent having a carboxyl group such as mercapto succinic acid, thioglycolic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof. a hydroxyl group-containing chain transfer agent such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and its derivatives; 1-butanethiol, butyl- 3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethyl mercaptan, 4-methylbenzenethiol, dodecane Mercaptan, propanethiol, butanol, pentyl mercaptan, 1-octyl mercaptan, cyclopentanethiol, cyclohexane alcohol, thioglycerol, 4,4-thiobisbenzenethiol, etc. A polyfunctional thiol compound can be used without particular limitation, but for example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether can be used. An aliphatic thiol such as dimercaptodiethyl thioether, an aromatic thiol such as xylene dithiol, 4,4'-dimercaptodiphenyl sulfide or 1,4-benzenedithiol ; ethylene glycol bis(mercaptoacetate), polyethylene glycol double (毓-42- 201207555 amide), propylene glycol bis(mercaptoacetate), glycerol ginseng (mercaptoacetate), trimethylolethane thiol (mercaptoacetate), trimethylolpropane ginseng Poly(mercaptoacetate) of polyvalent alcohols such as pentaerythritol), pentaerythritol (mercaptoacetate), dipentaerythritol (mercaptoacetate); ethylene glycol bis(3-indenyl) Propionate), polyethylene glycol bis(3-mercaptopropionate), propylene glycol bis(3-mercaptopropionate), glycerol (3-mercaptopropionate), trimethylolethane (mercaptopropionate), trimethylolpropane ginseng (3-mercaptopropionate), pentaerythritol bismuth (3-mercaptopropionate), dipentaerythritol (3-mercaptopropionate), etc. Poly(3-mercaptopropionate) of the valency alcohol; 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-gin(3-mercaptobutoxyethyl)- Poly(indenyl butyrate) such as 1,3,5-triazine-2,4,6 (1H,3H,5H)-trione or pentaerythritol bismuth (3-mercaptobutyrate). Such commercially available products can be exemplified by, for example, BMPA, MPM, EHMP, NOMP 'MBMP, STMP, TMMP 'PEMP, DPMP, and TEMPIC (all of which are manufactured by 堺Chemical Industries Co., Ltd.), KARENZ (registered trademark) MT-PE1 , KARENZ MT-BD1, and KARENZ NR1 (above are manufactured by Showa Denko). Further, the heterocyclic compound having a mercapto group functioning as a chain transfer agent is exemplified by, for example, mercapto-4-butyrolactone (alias: 2-mercapto-4-butyrolactone), 2-weiyl-4-methyl group -4-butyrol vinegar '2-sulfo-4-ethyl-4-butyrolactone, 2-mercapto-4-butane lactone (Butyrothiolactone), 2-mercapto-4-butylidene, N -Methoxy-2-carbyl--4-butyrolactam, N-ethoxy-2-sulfo-4-butylidene, Ν-methyl-2-mercapto-4-butene Amine, Ν-ethyl-2-mercapto-4-butylidene, Ν-(2-methoxy)ethyl-2-mercapto-4-butylidene, Ν·( -43- 201207555 2 -ethoxy)ethyl-2-carbo-4-butylidene, 2-thio-5-valerolactone, 2-mercapto-5-pentalinamide, N-methyl-2- Mercapto-5-valeroinamide, N-ethyl-2-mercapto-5-pentalinamide, N-(2-methoxy)ethyl-2-indolyl-5-pentane , N-(2-ethoxy)ethyl-2-sulfo-5-pentalactam, 2-phenylbenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2- Mercapto-6-caprolactam, 2,4,6-tridecyl+triazine (manufactured by Sankyo Chemical Co., Ltd.: trade name DISUNETE F), 2-dibutylamino-4,6-di ki-S-triazine Sankyo Chemical Co., Ltd. manufactures: trade name DISUNETE DB), and 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Co., Ltd.: trade name DISUNETE AF). In particular, the heterocyclic compound having a mercapto group of a chain transfer agent which does not impair the developability of the photocurable thermosetting resin composition is preferably mercaptobenzothiazole or 3-mercapto-4-methyl-4H- 1,2,4-triazole, 5-methyl-1,3,4-septadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole. These chain transfer agents may be used singly or in combination of two or more. In the photocurable thermosetting resin composition of the present invention, an adhesion promoter can be used 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-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi) AXEL(R) manufactured by Chemical Industry Co., Ltd., 3-morpholinylmethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinylmethyl-thiazole-2-sulfur Ketone, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, benzotriazole containing an amine group, decane coupling agent and the like. • 44 - 201207555 The photocurable thermosetting resin composition of the present invention may further contain a powder shaker such as fine powder of ceria, organic bentonite, montmorillonite or hydrotalcite as needed. The stability over time as a shake change agent is preferably excellent for organic bentonite, aluminum magnesium carbonate, and especially aluminum magnesium carbonate. In addition, a thermal polymerization inhibitor, an antifoaming agent such as an anthrone, a fluorine or a polymer, and/or a leveling agent, a decane coupling agent such as an imidazole type, a thiazole type or a triazole type, a rust preventive agent, and a double can be used. A conventionally used additive such as a phenol-based or triazine thiol-based copper-preventing agent. The aforementioned thermal polymerization inhibitor can be used to prevent thermal polymerization or time-lapse polymerization of the aforementioned polymerizable compound. The thermal polymerization inhibitor is exemplified by, for example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, tert-butylcatechol, biphenyltriol, 2-hydroxybenzophenone, 4- Methoxy-2-hydroxybenzophenone, chlorinated ketone, phenothiazine, Chloranil, naphthylamine, p-naphthol, 2,6-di-t-butyl-4- Cresol, 2,2'-extended methyl bis(4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, Methyl blue, organic chelating agent reactant with copper, methyl salicylate, and phenothiazine, nitroso compound, chelating compound of nitroso compound and A1, and the like. The photocurable thermosetting resin composition of the present invention is adjusted to a viscosity suitable for a coating method by, for example, the organic solvent, and is applied to a substrate by a dip coating method, a flow coating method, a roll coating method, a rod coating method, or the like. After coating by a screen printing method or a curtain coating method, the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of about 60 to 100 ° C, thereby forming a finger-free tack. Coating film. Subsequently, by means of contact (or non-contact), by forming a -45-201207555 patterned mask, the active energy line is selectively exposed or directly exposed by a laser direct exposure machine, etc., without exposure The portion is developed with an alkaline aqueous solution (for example, 0.3 to 3% aqueous sodium carbonate solution) to form a photoresist pattern. Further, in the case of a composition containing a thermosetting component, it is heated and cured at a temperature of, for example, about 130 to 180 ° C, whereby the carboxyl group of the carboxyl group-containing resin and the molecule have two or more cyclic ethers. The thermosetting component of the group and/or the cyclic thioether group reacts to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. In addition, in order to improve the coating film characteristics, the ethylenically unsaturated bond of the remaining residual photocurable component in the unreacted state at the time of exposure can be thermally radically polymerized by heat treatment even when the thermosetting component is not contained. Therefore, it can be heat treated (thermosetting) according to the purpose and use. As the above substrate, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimine, glass can be used. Cloth/non-woven fabric-epoxy resin, glass cloth/paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, etc. All grades (FR-4, etc.) Copper laminate, polyimide film, PET film, glass substrate, ceramic substrate, wafer board, and the like. The photocurable thermosetting resin composition of the present invention is subjected to volatilization and drying after application, and a hot air circulation type drying furnace, an IR furnace, a heating plate, a ventilating oven, or the like (using a heat source having a heating method by air caused by steam) can be used. The hot air convection contact method in the dryer and the manner in which the support is blown by the nozzle are performed. -46-201207555 The photocurable thermosetting resin composition of the present invention is applied as follows, and after evaporation and drying, the obtained coating film is exposed (irradiation of active energy rays). The coating film is hardened at the exposed portion (the portion irradiated with the active energy ray). As an exposure machine for the above-described active energy ray irradiation, a direct drawing device (for example, a laser direct image forming device that directly draws an image from a CAD data of a computer) can be used, and an exposure machine equipped with a metal halide lamp can be mounted. (Ultra) high-pressure mercury enamel exposure machine, exposure machine equipped with mercury short-arc xenon lamp, or direct drawing device using ultraviolet light such as (ultra) high-pressure mercury lamp. As for the active energy ray, any one of a gas laser and a solid laser can be used as long as the laser light having a maximum wavelength of 350 to 410 nm is used. Further, the amount of exposure varies depending on the film thickness, etc., but it is usually in the range of 5 to 500 mJ/cm2, preferably 10 to 300 mJ/cm2. As the direct drawing device, for example, a device manufactured by ORBETECH Co., Ltd., PENTAX Corporation, or the like can be used, and any device can be used as long as the device can oscillate laser light having a maximum wavelength of 550 to 41 Onm. As for the above-mentioned developing method, a dipping method, a rinsing method, a spraying method, a brushing method, or the like may be used, and potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, an amine or the like may be used. The aqueous alkali solution is carried out as a developing solution. The photocurable thermosetting resin composition of the present invention may be applied to a film such as polyethylene terephthalate or the like in advance, in addition to the method of directly applying the liquid to the substrate. It is dried and formed into a form of a dry film having a solder resist layer. The case where the photocurable thermosetting resin composition of the present invention is used as a dry film is shown below. -47- 201207555 The dry film is a structure having a carrier film, a solder resist layer, and a peelable cover layer as needed. The solder resist layer is a layer obtained by applying an alkali developable photocurable thermosetting resin composition onto a carrier film or a cover film and dried, and after forming a solder resist layer on the carrier film, the cover film is laminated. A solder resist layer is formed on the cover film, and the laminate is laminated on the carrier film to obtain a dry film. As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used. In the solder resist layer, the alkali-developing photocurable thermosetting resin composition is uniform in thickness of 10 to 150 μm by a blade coater, a lip coater, a Koma coater, a film coater or the like. It is formed by coating on a carrier film or a cover film and drying it. However, the film laminate is added with one, the weight-protecting agent, and the film of the welding material of the same material, and the film is formed by a long-lasting resistance. {Look-shaped light exposure of the film is exposed to the film or the core of the protective material before the line, the Μ / conformal base into the light film and the thin film of the IIV layer is the same as the agent on the agent Welding into the front load-carrying line resistance and. With the use of the film, the film can be brushed, and the layer can be coated with the release agent film layer. The thin film film and the like can be formed into a shape of a solderable dry thin machine, that is, the cover can be separated from the cover layer and peeled off, so that it can be used for the purpose of the lower case. EMBODIMENT The following examples and comparative examples are specifically described to illustrate the present invention, but the present invention is not limited by the following examples. In addition, the following "parts" and "%" are all based on -48- 201207555 unless otherwise stated. Synthesis Example 1 A novolac type cresol resin (produced by Showa Polymer Co., Ltd., trade name "SHONOL CRG951", OH equivalent) was fed into an autoclave equipped with a thermometer, a nitrogen gas introduction device, and an alkylene oxide introduction device and a stirring device. : 1 1 9 _ 4 ) 1 1 9 · 4 parts, potassium hydroxide 1 · 19 parts and toluene 1 19 · 4 parts, the system was replaced with nitrogen after stirring, and heated to heat. Subsequently, 63·8 parts of the epoxy propylene compound was slowly added dropwise, and the reaction was carried out at 125 to 132 ° C for 0 to 4.8 kg/cm 2 for 16 hours. Subsequently, it was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain an epoxy of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. Propane reaction solution. It is an average of 1.08 moles of alkoxylated gas per phenol equivalent of a phenolic hydroxyl group. Next, 293.0 parts of the alkylene oxide reaction solution of the obtained novolac type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were fed with a stirrer, a thermometer, and an air blowing tube. In the reactor, air was blown at a rate of 10 ml/min, and reacted at 1 1 ° C for 12 hours while stirring. The water produced by the reaction distilled 1 2.6 parts of water in an azeotropic mixture with toluene. Subsequently, it was cooled to room temperature, and the resulting reaction solution was neutralized with 3 5.3 5 parts of a 15 % aqueous sodium hydroxide solution, followed by washing with water. Subsequently, the toluene was distilled off with 118 parts of diethylene glycol monoethyl ether acetate as an evaporator to obtain a novolac type acrylate resin solution. Then, '332 parts of the obtained novolac type acrylate resin solution and i.22 parts of triphenylphosphine were fed into a reactor equipped with a stirrer, a thermometer and an air blowing tube at a rate of -49-201207555 10 ml/min. Air was blown in, and 60.8 parts of tetrahydrophthalic anhydride was gradually added thereto while stirring, and the mixture was reacted at 95 to 101 ° C for 6 hours. A resin solution of a photosensitive resin containing a carboxyl group having a solid content of 8811^1 &lt;:011/8 and a nonvolatile content of 71% was obtained. Hereinafter, this is called paint A-1. Synthesis Example 2 A polycaprolactone diol as a polymer polyol (PLACCEL 208 manufactured by Daicel Chemical Industry Co., Ltd., molecular weight 830) 1,245 was fed into a 5 liter separable flask equipped with a thermometer, a stirrer, and a reflux condenser. Parts: 201 parts of dimethylolpropionic acid as a dihydroxy compound having a carboxyl group, 777 parts of isophorone diisocyanate as a polyisocyanate, and 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group. Then, 0.5 part of p-methoxyphenol and di-tert-butylhydroxytoluene were separately injected. After heating to 60 ° C with stirring, the heating was stopped, and 0.8 parts of dibutyltin dilaurate was added. When the temperature in the reaction vessel begins to decrease, it is heated again, and stirring is continued at 80 ° C. The infrared absorption spectrum confirms that the absorption spectrum of the isocyanate group (2280 CHT1 ) disappears, and the reaction is terminated to obtain a viscous liquid urethane acrylate compound. . The carbitol acetate was adjusted to a nonvolatile content = 50% by mass. A resin solution of a solid component having an acid value of 47 mgKOH/g and a nonvolatile content of 50% of a carboxyl group-containing urethane (meth) acrylate compound was obtained. Hereinafter, this is called paint A-2. Synthesis Example 3 900 parts of diethylene glycol dimethyl ether as a solvent was added to a two-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen-50-201207555 gas introduction tube, and as a polymerization. The third butylperoxy 2-ethylhexanoate of the initiator (manufactured by Nippon Oil & Fats Co., Ltd., trade name: PERBUTYL®) 21.4 parts was heated to 90 °C. After heating, 309.9 parts of methacrylic acid, 116.4 parts of methyl methacrylate, and 2-hydroxyethyl methacrylate (PLACCELFM1: manufactured by Daicel Chemical Industry Co., Ltd.) modified with lactone and 109.8 parts of a polymerization initiator Bis(4-tert-butylcyclohexyl)peroxydicarbonate (manufactured by Nippon Oil & Fats Co., Ltd., trade name; PEROYL TCP) 21.4 parts were added dropwise thereto within 3 hours, followed by ripening for 6 hours. This gave a copolymerized resin containing a carboxyl group. Further, the reaction was carried out under a nitrogen atmosphere. Next, 363.9 parts of 3,4-epoxycyclohexyl methacrylate (manufactured by Daicel Chemical Industry Co., Ltd., trade name; CYCLOMER A200), and 3.6 parts of dimethylbenzylamine as a ring-opening catalyst were used. Further, 1.80 parts of hydroquinone monomethyl ether as a polymerization inhibitor was added to a polymer resin containing a carboxyl group, and the mixture was heated to 100 ° C to carry out a ring-opening addition reaction of an epoxy group by stirring. After 16 hours, a resin solution having a solid content of 108.9 mgKOH/g, a weight average molecular weight of 25,000 and a solid content of 54% was obtained. Hereinafter, it is referred to as Paint A-3 Synthesis Example 4, and 650 parts of diethylene glycol monoethyl ether acetate is fed into o-cresol novolac-type epoxy resin (DIC (manufactured by DIC)' EPICLON N- 695 'softening point 95. (:, epoxy equivalent 214, average functional group number 7.6) 1070 parts (reduced 201207555 water glyceryl number (total aromatic ring): 5.0 moles), 360 parts of acrylic acid ( 5. 〇 Mo ear), and 1.5 parts of hydroquinone, heated and stirred until l ° ° C 'dissolved uniformly. Next, fed 3 3 parts of triphenylphosphine 'heated to 1 1 〇 ° C and reacted for 2 hours, then added triphenylphosphine 1.6 The temperature was raised to 120 ° C and the reaction was carried out for 12 hours. 525 parts of aromatic hydrocarbon (SOLVESSO 1 50 ) and 608 parts of tetrahydrophthalic anhydride (4.0 moles) were fed into the obtained reaction liquid. The reaction was carried out for 4 hours at ° C. Next, 142.0 parts (1.0 mol) of glycidyl methacrylate was fed to the obtained reaction liquid, and the reaction was carried out at 115 ° C for 4 hours to obtain a solid content acid value of 77 mgKOH/g, solid. 65% of the resin solution of the composition. Hereinafter referred to as paint R-1. Synthesis Example 5 in 200 parts of diethylene glycol monoethyl ether acetate O-cresol novolac-type epoxy resin (manufactured by DIC, EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average functional group number 7.6) 1 070 parts (glycidyl number (total number of aromatic rings) : 5.0 moles, 360 parts of acrylic acid (5.0 moles), and 1.5 parts of hydroquinone, heated and stirred to 100 ° C, and uniformly dissolved. Next, 4.3 parts of triphenylphosphine was fed, heated to 1 10 t and reacted for 2 hours. Thereafter, the temperature was raised to 120 ° C and the reaction was carried out for another 12 hours. In the obtained reaction liquid, 415 parts of aromatic hydrocarbons (SOLVESSO 150) and 45 6.0 parts of tetrahydrophthalic anhydride (3.0 moles) were fed, at 1 l〇. The reaction was carried out for 4 hours at ° C. After cooling, a resin solution having a solid content of 89 mg KOH/g and a solid content of 65% was obtained. Hereinafter, it was referred to as a paint R-2. • 52-201207555 Synthesis Example 6 Feeding A Phenolic novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent 220) 2200 parts, 134 parts of dimethylolpropionic acid, 648.5 parts of acrylic acid, methyl hydrogen醌 4.6 parts, 1131 parts of carbitol acetate and 484.9 parts of Solvent naphtha, heated to 9.0 ° C and Mixing the reaction mixture was dissolved. Then, the reaction was cooled to 60 ° C, fed 13.8 parts of triphenylphosphine was heated to 100 ° C, about 32 hours reaction, an acid value of 0.5 mgKOH / g of reactants. Then, 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate, and 58.8 parts of solvent oil were fed thereto, heated to 95 ° C, and reacted for about 6 hours, and cooled to obtain a solid content acid value of 40 mgKOH. / g, a resin solution of a photosensitive resin containing 65% of a carboxyl group. Hereinafter, it is referred to as paint R-3. Synthesis Example 7 400 parts of a bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C was dissolved in 925 parts of epichlorohydrin and 462.5 parts of dimethyl argon, and then stirred at 70 ° C under stirring. 98.5% of NaOH 8 1.2 parts were added over 100 minutes. After the addition, the reaction was carried out at 70 ° C for 3 hours. Next, the excess of the unreacted epichlorohydrin and the majority of the dimethyl hydrazine are distilled off under reduced pressure, and the reaction product containing the by-product salt and the dimethyl sulfite is dissolved in 750 parts of methyl isobutyl ketone, followed by addition. 10 parts of 30% NaOH, and reacted at 70 ° C for 1 hour. After the reaction was completed, the mixture was washed twice with 200 parts of water. After the oil-water separation, methyl isobutyl ketone was distilled from the oil layer to obtain 370 parts of epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 °C. Feeding the obtained epoxy resin (a-1) 2900 parts (10 equivalents), -53-201207555 acrylic acid 720 parts (l〇 equivalent), methylhydroquinone 2.8 parts, carbitol acetate 195 parts, The reaction mixture was dissolved by heating to 90 ° C 'with stirring'. Next, the reaction liquid was cooled to 60 ° C to feed 16.7 parts of triphenylphosphine, and heated to 1 Torr. (:, the reaction was carried out for about 32 hours, and an acid value of 1.〇11^1 (: 01^8 reactant) was obtained. Next, 786 parts of succinic anhydride (7·86 mol) and carbitol acetic acid were fed thereto. 423 parts of the ester was heated to 95 ° C, and the reaction was carried out for about 6 hours to obtain a resin solution having a solid content of 1 〇〇 mg KOH / g and a solid content of 65%. Hereinafter, it is referred to as lacquer R-4. ～13 and Comparative Examples 1 to 3 Using the resin solution of the above Synthesis Example, the ratios (mass parts) shown in Table 1 were prepared together with the various components shown in Table 1 below, and premixed with a stirrer to obtain three rolls. The mill was kneaded to prepare a photosensitive resin composition for a solder resist. Here, the particle size of the obtained photosensitive resin composition was measured by a particle size analyzer manufactured by ERIKSEN Co., Ltd. and evaluated to be 15 μm or less. - 201207555 [Table 1] Composition (parts by mass) . Degree of application ± m 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 A-1 141 141 141 141 141 141 141 \Ai dd 71 141 of δδ 141 A-2 6ΰ A-3 $6 Paint R-1 11 R-2 1b4 R-3 46 r-4 154 Also take (Β-1Γ1 IS ship 1 (B-3)·4 1.5 1.5 1.5 1.5 1.5 ii 1.5 1.S 1.S 1.5 1.5 1.6 \.b 1.5 1.5 HP-4032 *4 20 20 20 20 10 10 id iO 2ΰ ίύ Ο) 20 2Q VI^4700CA90,,:, 2ί 13 iSN355CA9(T. zi 13 T04PCA75,, ib - tortoise*β 0.3 0.3 ΰ.3 ΰ.3 0.3 0.3 0.3 0.3 ύ.3 0.5 0.3 0.3 0.3 oa ΰΛ 0.3 u 0.8 ύ.6 0.6 0.8 Od 0·δ ΰ.ό 0.8 ύ.6 0.6 0.8 ύ.8 0.6 ύ.ύ ύ.ύ U.tt phenothiazine Ot 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 2 2 2 2 2 2 2 2 2 B-33 *12 260 2όύ 200 ύόύό 2. 0 200 ίύύ 佥όο 2όύ 200 206 ίύό ίόό ίύο 200 ACTINYLAM*, J 25ΰ DHT-4A*m 5 5 S 5 5 5 S 5 S 5 SS 5 S b 5 Defoamer 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 A-dcp* , a 5 5 5 SS 5 S 5 δ 5 ί 5 5 5 S 5 DPHA • _ o 1S IS 15 a 15 15 1古IS 15 15 15 15 15 15 u&gt; ii 1 PA-B80E*&quot; 17.5 Mw-100LM&quot;ie 12.5 ♦1 : 2-methyl-1-(4-methylthiophenyl)-2- Morpholinylpropan-1-one (IRGACURE 907: manufactured by Nippon Ciba) *2 : 2,4* diethylthioxanthone (1〇1^人01; 11£0孤-3: 曰本化薬Nor: 〉Company system) *3: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-yttrium-3-yl]-1,1-(0- IR 醯 ( (IRGACURE OXE 02: manufactured by Nippon Ciba) *4 : Naphthalene epoxy resin (made by DIC) »5: Naphthalene ring grease (made by DIC), HP-4700, carbitol Acid ester interception product 90%) »6: Naphthalene epoxy resin (made by Dongdu Chemical Co., Ltd.) ESN355 carbitol acetate extract 90% of individual components *7: Cresol novolac varnish epoxy resin化化成(股)) 704P card mustard acetic acid vinegar interception (solid content 75%) *8 : CI Pigment Blue 15:3 *9 : CI Pigment Yellow 147 *10 ·· 2-Silylbenzothiazole *11: Antioxidant (manufactured by Nippon Ciba Company) Note *12: Barium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.) *13: Amine group of SILLITIN which is a compound composed of spherical silica sand and platy kiln Decane coupling Material processing product (manufactured by HOFFMANN MINERAL Co., Ltd.) *14 ··Hydrate talc (Kyowa Chemical Industry Co., Ltd.) *15: Diethylene sulphur monoethyl acetate vinegar *16: Dipentaerythritol hexaacrylate vinegar *17: lion isophthalic acid Ester (made by Asahi Kasei Chemicals Co., Ltd.) *18: Methylated trimeric amine resin (manufactured by Sanwa Chemical Co., Ltd.) Performance evaluation: &lt;Optimum exposure amount&gt; A circuit pattern substrate having a copper thickness of 18 μm is passed through a copper surface After roughening treatment (MEC ETCH BOND CZ-8100 manufactured by MEC), after washing with water and drying, the above-mentioned examples and comparative examples were fully coated by screen printing method -55-201207555 Photocuring thermosetting The resin composition is 80. (: The hot air circulating drying oven was dried for 60 minutes. After drying, exposure was carried out by using an exposure apparatus equipped with a high-pressure mercury lamp through a Step Tablet (Kodak No. 2) to perform development (30 ° C, 0.2 MPa, Lwt% sodium carbonate aqueous solution) The pattern of the step change pattern remaining at 60 seconds is the optimum exposure amount in the case of 7 stages. &lt;Developability&gt; The screen printing method is used to make the film thickness after drying to about 25 μm. The method of applying the photocurable thermosetting resin composition of the above examples and comparative examples to a bare copper substrate, and drying in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, it was 1 wt%. The sodium carbonate aqueous solution was subjected to development, and the time until the drying of the coating film was removed was measured by a stopwatch. <Maximum development lifetime> The composition of the above examples and comparative examples was completely coated on the screen to form a pattern by screen printing. On a copper foil substrate, it was dried at 80 ° C for 20 minutes to 80 minutes, and the substrate was taken out every 10 minutes, and allowed to cool to room temperature. The substrate was subjected to a pressure of 0.2 MP a at a pressure of 30 ° C of 1 wt% carbonic acid. The sodium aqueous solution was imaged for 60 seconds, with the most residue remaining. Allowable drying time as the maximum development life &lt;contacting property&gt; The composition of the foregoing examples and comparative examples was completely applied to the patterned copper foil substrate by screen printing, and the hot air circulation type at 80 ° C was used. Drying oven-56-201207555 Drying for 30 minutes' Let cool to room temperature. The negative film made of PET is brought into contact with the substrate, and HMW_GW2〇 manufactured by 〇RC company is pressed under reduced pressure for 1 minute 'subsequent' The column was evaluated for the state of film bonding when the negative film was peeled off. 〇: When the film was peeled off, there was no resistance at all, and no trace of the film remained. Δ: When the film was peeled off, it was only slightly blocked, and the film marks were small. X·· When peeling the film, Obstructed and clear film characteristics test: The composition of the foregoing examples and comparative examples were completely coated on the copper foil substrate of the pattern by screen printing, dried at 80 ° C for 30 minutes, and allowed to cool to the chamber. For the substrate, an exposure apparatus equipped with a high-pressure mercury lamp was used to expose the solder resist pattern with an optimum exposure amount, and a 1 wt% sodium carbonate aqueous solution at 30 ° C was used for development under the conditions of a spray pressure of 2 2 MPa. 90 seconds, get the photoresist pattern The substrate was irradiated with ultraviolet rays under the conditions of a cumulative exposure amount of 1000 mj/cm 2 by a UV transfer furnace, and then cured by heating at 150 ° C for 60 minutes. The obtained printed circuit board (evaluation substrate) was evaluated as follows. &lt;Acid resistance &gt; At room temperature, the evaluation substrate was immersed in a 10 v 〇l% H 2 SO 4 aqueous solution for 30 minutes, and the infiltration or coating film was visually confirmed to be eluted, and peeling was confirmed by tape peeling. 〇: No change was confirmed Δ: only a slight change -57-201207555 X: Swelling and peeling caused by coating film expansion &lt;Alkaline resistance&gt; The evaluation substrate was immersed in a 10 vol% aqueous NaOH solution for 30 minutes at room temperature to visually confirm the dissolution of the infiltration or coating film, and then Peeling was confirmed by tape peeling. 〇: It is confirmed that there is no change Δ: only a slight change X: swelling of the film caused by swelling of the film &lt; solder heat resistance&gt; The evaluation substrate coated with the rosin-based flux is immersed in a solder bath set at 260 ° C in advance After the flux was washed with the modified alcohol, the expansion/peeling of the photoresist layer was visually evaluated. The judgment criteria are as follows. 〇: 3 or more times of immersion for 10 seconds, no peeling was observed. Δ: 3 times of immersion for 10 seconds, a little peeling, X: immersion within 3 times, 10 seconds after the photoresist layer was expanded, peeled &lt; Electrolytic gold plating&gt; Electroless nickel plating bath and electroless gold plating bath using a commercially available product were electroplated under the conditions of nickel 5 μm, gold ruthenium 〇 5 μm, and the resist layer was peeled off by tape peeling, and After the plating was infiltrated, the resist layer was peeled off by tape peeling. The judgment criteria are as follows. 〇: After electroplating, it was confirmed that there was only a little infiltration' but no peeling after peeling off the tape-58-201207555 △: It was confirmed that only a little infiltration was observed after plating, and peeling X was also found after peeling of the tape: peeling after plating &lt; pc τ resistance&gt; The evaluation substrate on which the solder resist hardening coating film was formed was treated at 121 ° C, saturated, and 0.2 MPa for 168 hours using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Co., Ltd.), and the state of the coating film was evaluated. The judgment criteria are as follows. 〇: no swelling, peeling, discoloration, dissolution △: only a little swelling, peeling, discoloration, dissolution X: multiple expansion, peeling, discoloration, dissolution & cold heat shock resistance > The evaluation substrate of the solder resist hardening film of the 〇 pattern. The obtained evaluation substrate was subjected to a thermal shock tester (manufactured by ETAC) at -55 ° C / 30 minutes to 150 ° C / 30 minutes as a cycle, and subjected to a resistance test of 1,000 cycles. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged based on the following criteria. 〇: The cracking rate is less than 30% △: The cracking rate is 30 to 50% X: The cracking rate is over 50% &lt;HAST characteristics&gt; -59- 201207555 The comb-shaped electrode is formed (line/space=50 A solder resist hardening coating film was formed on the BT substrate of μm/50 μm to prepare an evaluation substrate. The evaluation substrate was placed in a high-temperature and high-humidity bath at 130 ° C and a humidity of 85%, charged at a voltage of 12 V, and subjected to a HAST test in the tank for 168 hours. The insulation resistance 槽 in the tank after 1 68 hours was evaluated according to the following judgment criteria. 〇: more than 108 Ω Δ : 106 to 108 Ω X : less than 1 〇 6 Ω The results of the above evaluation tests are shown in Table 2 below. 【Table 2】

Characteristic Goods Comparative Example 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 Optimum exposure (mJ/cm2) 400 150 150 150 150 150 150 150 130 150 150 150 150 ISO 150 130 Imaging ( Seconds) 35 36 33 34 29 28 30 26 34 33 34 36 36 31 35 47 Maximum mirror life (minutes) 70 60 60 60 60 60 60 60 60 60 60 60 60 60 60 40 Cracking Δ △ Δ Δ Δ Δ △ Δ △ △ △ 〇〇 Δ 〇 △ acid resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 alkali resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 solder heat resistance Sex resistance to electroless gold plating 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 △ 〇 PCT resistance 0 〇〇〇 △ 〇〇〇〇〇厶〇〇〇XX Thermal shock resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇△ △ A HAST characteristic 〇〇〇〇〇〇〇〇〇〇Δ 〇〇〇 XX characteristic test The above implementation is carried out by screen printing The composition of Example 1 3 and Comparative Example 1 was completely coated on On the copper foil substrate on which the pattern was formed, it was allowed to 'dry at 8 ° C for 30 minutes' and allowed to cool to room temperature. On the substrate, an exposure apparatus equipped with a high-pressure mercury lamp was used to expose the solder resist pattern with an optimum exposure amount, and the image was developed at a spray pressure of 0.2 MPa with a 1 wt% sodium carbonate-60-201207555 aqueous solution at 3 °C. At 90 seconds, a resist pattern was obtained, which was Example I4 and Comparative Example 4, respectively. The substrate was irradiated with ultraviolet rays under conditions of an accumulated exposure amount of 1 000 mJ/cm 2 in a UV conveyor belt furnace at 130 ° C, 140 ° C, 150 ° C, 160 ° C, 17 ° C, and 180 °. (: or 19 (the TC was heated for 60 minutes and hardened) The obtained printed circuit board (evaluation substrate) was evaluated for its characteristics as follows. The results are shown in Tables 3 and 4. [Tg measurement> TMA6100 manufactured by Seiko Instrument Co., Ltd., Apply a load of 10g to a hardened film of 3mm x 10mm size, and perform a tensile test at a temperature rise rate of 0 °C ~ 26 (TC) at a certain temperature rise rate, calculate the extrapolation point to calculate the glass transition temperature Tg » &lt CTE measurement&gt; A TMA 6100 manufactured by Seiko Instrument Co., Ltd. was subjected to a tensile test at a temperature rise of 0 ° C to 26 (TC) while applying a load of 10 g to a hardened film of 3 mm x 10 mm size. The linear thermal expansion coefficient CTE was calculated from the elongation of the hardened film for temperature. [Table 3] Characteristic Example 1 &lt; Hard" g 130 ° C 140 ° C 150 ° C 160 ° C 170 ° C 180 ° C 190 ° C Solder Heat resistance 〇〇〇Ο 〇〇 无 resistance to electroless gold plating PCT PCT resistance Ο 〇〇〇〇〇ο Thermal shock resistance 〇〇Ο 〇〇 AST HAST characteristics 〇〇Ο 〇〇〇ο Tg (°C) 125 126 124 125 125 124 127 CTE (ppm) 36 35 36 36 34 34 35 201207555 [Table 4] Characteristic comparison example 4 Hardening temperature 130 ° C 140 ° C 150 ° C 160 ° C 170 ° C 180 ° C 190 ° C Solder heat resistance Δ Ο 〇0 Ο 〇〇 resistance to electroless gold plating X 〇0 0 Δ Δ X PCT resistance XX ο 〇 Δ Δ. Δ Thermal shock resistance Δ Δ Δ Δ Δ XX HAST characteristic X Δ ο ο ο Δ Δ Tg (°C 90 95 100 115 120 125 130 CTE (ppm) 65 57 55 55 50 45 40 Examples 15 to 22 and Comparative Examples 5 to 7 were prepared by diluting with methyl ethyl ketone in the proportions shown in Table 1. Each of the compositions of Examples 1, 3, 4, 6, 7, 8, 9, 11 and Comparative Examples 1, 2, and 3 was coated on a PET film and dried at 80 ° C for 30 minutes to form a thickness of 20 μm The photosensitive resin composition layer was further bonded to the cover film to form a dry film, which were Examples 15 to 22 and Comparative Examples 5 to 7, respectively. <Dry Film Evaluation> The dry film release coating film obtained as described above was used. The film was thermally laminated on the copper foil substrate on which the pattern was formed, and then exposed under the same conditions as those used in the evaluation of the film properties of the foregoing examples. After the exposure, the carrier film was peeled off, and development was carried out for 90 seconds at a spray pressure of 0.2 MPa at a temperature of 0.2 MPa at a spray temperature of 30 ° C to obtain a resist pattern. The substrate was cured by UV irradiation at a cumulative exposure of 1 000 mJ/cm 2 and then heated at 15 ° C for 60 minutes in a UV conveyor belt furnace. The evaluation test of each characteristic was carried out for the test substrate having the obtained hardened film by the above test method and evaluation method. The results are not shown in Table 5. -62- 201207555

[Table 5] Characteristic square m Comparative example 15 16 17 18 19 20 21 22 5 6 7 Optimum exposure amount (m J/cm 2 ) 400 150 150 150 150 150 130 150 150 150 130 Development 渺) 37 36 36 31 33 29 37 36 33 37 50 Acid resistance, alkali resistance, solder heat resistance, resistance Electrolytic age 〇〇〇〇〇〇〇〇〇Δ 0 PCT resistance 〇〇〇〇〇〇〇△ 〇XX Thermal shock resistance 〇〇〇〇〇〇〇〇Δ Δ Δ HAST characteristic 〇〇〇〇〇〇〇△ 〇XX &lt;dry film evaluation&gt; The dry film peeling cover film obtained as described above using the composition of the above-mentioned Example 1 and Comparative Example 1 was thermally laminated on the copper foil substrate on which the pattern was formed, and then, The conditions were the same as those of the substrate used in the evaluation of the coating film characteristics of the foregoing examples. After the exposure, the carrier film was peeled off, and development was carried out for 90 seconds under a condition of a spray pressure of 0.2 MPa at 30 ° C of a 1 wt% aqueous sodium carbonate solution, and the resist pattern was obtained as Example 23 and Comparative Example 8, respectively. The substrate is in a UV conveyor belt furnace, and after irradiation with ultraviolet rays under the condition of an accumulated exposure amount of 1 000 mJ/cm 2 'at 130 ° C, 140 ° C, 15 (TC, 1601, 17 〇. (:, 180 ° C or The test was performed by heating at 190 ° C for 60 minutes. The test of each of the properties of the test substrate having the obtained hardened film was carried out by the above test method and evaluation method. The results are shown in Tables 6 and 7. -63 - 201207555 [Table 6] Features 2 2 Hardening mystery 130°C 140°C 150°C 160°C 170°C 180°C 190°C Solder heat resistance 无Resistant to electroless gold plating oo PCT resistance, thermal shock resistance, 〇0 〇〇〇〇o HAST characteristics 〇〇〇〇〇〇o Tg(°C) 125 126 124 125 125 124 127 CTE (ppm) 21 21 22 21 22 22 22 [Table 7] Characteristic comparison example 8 Hardening stress 130 ° C 140 ° C 1 50 ° C 160 ° C 170 ° C 180 ° C 190 ° C solder heat resistance Δ 〇〇〇〇〇 〇〇〇〇〇 resistance to electroless gold plating X 〇 〇〇Δ Δ X PCT resistance XX 〇〇Δ Δ Δ Thermal shock resistance Δ Δ Δ Δ Δ XX HAST characteristics X Δ 〇〇 Δ Δ Δ Tg (°C) 91 95 107 118 128 129 135 CTE (ppm) 65 60 57 55 49 41 39 From the results shown in Tables 6 and 7 above, the light curability of the present invention is clearly understood. In the thermosetting resin composition, it is confirmed that a photocurable thermosetting resin composition which has both PCT resistance, thermal shock resistance, and HAST characteristics (electrical characteristics) necessary for a solder resist for semiconductor encapsulation can be used. Possible use] By using the photocurable thermosetting resin composition of the present invention, a cured film excellent in PCT resistance, HAST resistance, electroless gold plating resistance, heat resistance, and the like can be formed, so that it can be preferably used for forming printing. Solder resists such as wiring boards or flexible wiring boards, especially solder resists for semiconductor packages. -64-

Claims (1)

201207555 VII. Patent application scope: 1. A photocurable thermosetting resin composition which can be imaged by an aqueous alkaline solution, which comprises: a resin containing a carboxyl group (however, an epoxy resin is used as a starting material) Except for the carboxyl group-containing resin), a photopolymerization initiator, and an epoxy resin having a naphthalene ring. 2. The photocurable thermosetting resin composition according to claim 1, wherein the carboxyl group-containing resin is a phenol resin as a starting material 〇3. The photocuring thermosetting method according to claim 1 A resin composition in which the carboxyl group-containing resin has a photosensitive group. A photocurable thermosetting dry film which is coated on a carrier film and dried by the photocurable thermosetting resin composition according to any one of claims 1 to 3 above. Got it. A hardened material obtained by photohardening a photocurable thermosetting resin composition according to any one of claims 1 to 3, or a photocurable thermosetting resin. The product is coated on a carrier film and dried to obtain a dry film which is photohardened. 6. A printed wiring board having a hardened film which is irradiated with an active energy ray by the photocurable thermosetting resin composition according to any one of claims 1 to 3 After curing in a shape, it is obtained by thermosetting, or the photocurable thermosetting resin composition is applied onto a carrier film and dried to obtain a dry film, which is photohardened by irradiation with an active energy ray. After the shape, it is obtained by heat hardening. -65- 201207555 Four designated representatives: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201207555 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention: no