TW201102405A - Photocurable heat-curable resin composition - Google Patents

Abstract

Disclosed are: a photocurable heat-curable resin composition which enables the formation of a cured coating film having PCT resistance, HAST resistance, electroless gold plating resistance and thermal shock resistance which are important properties required for solder resists for semiconductor packages; a dried film produced from the composition and a cured product of the composition; and a printed wiring board having, formed thereon, a cured coating film (e.g., a solder resist) comprising the dried film or the cured product. Specifically disclosed is a photocurable heat-curable resin composition which can be developed with an aqueous alkaline solution, which comprises a resin containing a carboxyl group, a photopolymerization initiator, an elastomer containing a vinyl group, and a mercapto compound. Preferably, the resin containing a carboxyl group is not derived from an epoxy resin.

Description

201102405 VI. Description of the Invention: [Technical Field] The present invention relates to a photocurable thermosetting resin composition which can be developed by an aqueous alkaline solution, and more particularly to photohardening by ultraviolet exposure or laser exposure. A composition for solder resist, a dry film and a cured product using the composition, and a printed wiring board having a film formed by curing the film. [Prior Art] At present, some of the printed wiring boards for the people's livelihood and the solder resists of most industrial brush panels are made of high-precision and high-density. After ultraviolet irradiation, a screen is formed by development, and the final processing is performed by heat and/or light irradiation and hardened (this). In particular, due to concerns about environmental problems, an alkaline developing type photo solder resist using an aqueous solution as an aqueous solution is used in a large amount for use in the manufacture of an actual printed wiring board. . In recent years, the electronic equipment has become lighter and thinner, which corresponds to the high density of printed wiring boards, and also requires high workability for soldering photoresist. However, the current alkaline development type of light soldering prevention Resists have many problems in terms of durability. That is, the alkaline development type photo solder resist has poor alkali resistance, water resistance, heat resistance, and the like as compared with the conventional thermosetting type and solvent development type solder resist. In view of the fact that the alkaline development type photo solder resist is used for alkaline development, a substance having a hydrophilic group is used as a main component, and it is easy to permeate a chemical liquid, water, water vapor, etc., and is resistant to chemicals. The property is lowered or the adhesion between the photoresist film and copper is lowered. As a result, the testability as a chemical resistance is weak. In particular, in a semiconductor package such as a BGA (ball grid array) 戋 CSP (chip scale package), in particular, it is also called PCT resistance (pressure cooker) Test 3 201102405 (pressure cooker test) is a must. However, the current situation is that alkaline solder resists can only be held for several hours to ten times = under such strict conditions. Further, in the case of the hast test (highly accelerated life test) in the state where the alkaline development type photo solder resist is pressed under humidification conditions, in the case of a large $, it is confirmed that the migration occurs in a few hours (migrati〇n). Caused by bad. In recent years, with the shift in surface assembly and environmental concerns, the use of lead-free solder, etc., the temperature tending to be applied has become very high. Along with this, the inside and outside of the package are significantly higher, and in the case of the conventional liquid photosensitive photoresist, there is a thermal crack in the coating film, or a peeling problem from the substrate or the sealing material. Therefore, seek improvement. In the second aspect, the carboxyl group-containing resin used in the conventional solder resist is generally an epoxy acrylate-modified resin derived from the modification of an epoxy resin. For example, JP-A-61-243869 (Patent Document 1) discloses a report of a solder resist composition, which is composed of a photosensitive resin, a photopolymerization initiator, a diluent, and an epoxy compound. In the photosensitive resin, the acid is added to the reaction product of the varnish-type epoxy compound and the unsaturated monobasic acid (m〇n〇basie. Further, Japanese Laid-Open Patent Publication No. Hei-3-250012 (Patent Document 2) discloses A solder resist composition comprising a photosensitive resin, a photopolymerization initiator, an organic solvent, or the like, which is a reaction product of salicylic acid (Salicylic aldehyd) and monovalent phenol to make an epoxy chloride In the epoxy resin obtained by the addition of propane, (meth)acrylic acid is further added to obtain a polybasic carboxylic acid or an anhydride thereof. However, 'the carboxyl group-containing resin used in the conventional solder resist composition is used. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. ) 4 201102405 [Invention content] [ In order to solve the problems of the prior art, the present invention provides a photocurable thermosetting resin composition, a bean, and a cured film having a solder for use in a semiconductor package in view of the problems of the prior art. ^ Extremely important, PCT, HAST, eiectr〇iess gold plating, cold and thermal shock resistance. Further, it is an object of the present invention to provide a film and a cured product of the foregoing characteristics. The (four) storage area 帛 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In order to achieve the 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 (A), a photopolymerization initiator (B), and a vinyl group. The elastomer and the thiol compound (D). The carboxyl group-containing resin (A) is preferably a non-epoxy resin. In a suitable state, the photocurable thermosetting resin composition of the present invention is further The thermosetting component (E) is preferably a photocurable thermosetting resin composition for soldering photoresist further containing a coloring agent (H). Further, according to the present invention, a dry film characterized by drying The resin composition layer of the film is obtained by applying the photocurable thermosetting resin composition onto a film and drying the film. Further, according to the present invention, it is also possible to provide a cured product which is a photocurable thermosetting resin. The composition is applied onto a substrate and dried to form a coating film, and the photocurable thermosetting resin composition or coating film is photocured. The cured product of the present invention can also be obtained by using the resin of the dry film. The composition layer is bonded to the substrate and photohardened. It is preferably a cured product obtained by photohardening a light source having a wavelength of 35 〇 nm to 41 〇 nm into a pattern. Furthermore, according to the present invention, there is also provided a printed wiring board comprising a 201102405 hardened film which is obtained by applying the photocurable thermosetting resin composition onto a substrate and drying the film, or The dry film is irradiated with an active energy ray, preferably by direct drawing of ultraviolet light, and is photohardened into a pattern, and then heat-hardened. Further, the printed wiring board having the cured film of the present invention may be thermally cured by bonding the resin composition layer of the dry film to the substrate, photohardening by irradiation with an active energy ray, and then curing. be made of. The active energy ray is preferably ultraviolet light. [Effect of the Invention] The photocurable thermosetting resin composition of the present invention is combined with a carboxyl group-containing resin (A). The carboxyl group-containing resin (A) is a component which can be developed by an alkaline aqueous solution. Containing a vinyl-containing elastomer (c) and a thiol compound (D). The vinyl-containing elastomer (the yttrium not only improves the crack resistance of the obtained hardened coating film to the cold and heat cycle, but also has an effect of improving the adhesion of the solder resist, especially the pct resistance. On the one hand, the thiol compound The addition of (D) is based on the addition reaction of the photosensitive component to the vinyl-containing elastomer and the purpose of crosslinking, thereby preventing deterioration of coating film properties due to oxidation of the vinyl group. Since the addition of the compound (D) can achieve soft cross-linking, it contributes to the pCT resistance and HAST resistance of the photocurable thermosetting resin composition, and the hydrogen thiol compound (D) In order to function as a chain transfer agent and/or an emulsifier, the sensitivity of the composition can be improved and the adhesion f can be improved at the same time. As a result, the softness of the obtained hardened coating film can be improved, and the turtle resistant to the hot and cold cycle can be improved. Further, the cracking property can improve the adhesion of the solder resist, and in particular, the PCT resistance can be improved. According to the above, the hardenable thermosetting resin composition of the present invention can form a cured film having a cured film. In semiconductor package The PCT resistance, the HAST resistance, the electroless gold plating resistance, and the thermal shock resistance are extremely important in terms of the solder resist. [Embodiment] For example, the 'characteristics of the photocurable thermosetting resin composition of the present invention' It contains a base-containing resin (A), a photopolymerization initiator (B), a vinyl-containing elastomer 6 201102405 (C), and a hydrogenthio-based compound (〇). The above-mentioned carboxyl group-containing resin (A) can be used. It is preferred that we consider the use of carboxyl-containing resins in the case of ruthenium-based resins with poor insulation reliability (very low halide ion content), which does not use epoxy resin as a starting material. Among these, a carboxyl group-containing photosensitive resin having a ethylenically unsaturated double bond in the molecule is preferred in terms of photocurability or development resistance. Further, the unsaturated double bond is preferably acrylic or fluorenyl. In addition, 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 one or more of the molecules described later. Ethylene deficiency And a compound (photosensitive monomer) which can be used for the specific example of the carboxyl group-containing resin of the present invention, and the following compounds (which may be either an oligomer or a polymer). 1) In a difunctional or difunctional or higher polyfunctional (solid) epoxy resin described later, (mercapto)acrylic acid is reacted to form a hydrazine anhydride, tetrahydrophthalic anhydride, and hexahydrogen in the hydroxyl group present in the side chain. a slow-base salt-containing resin of a dibasic acid anhydride such as phthalic anhydride; (2) a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a difunctional (solid) epoxy resin described later with epichlorohydrin (meth)acrylic acid, a carboxyl group-containing photosensitive resin in which a hydroxyl group is added to a dibasic anhydride. (3) An epoxy compound having two or more epoxy groups in one molecule, having at least one molecule A compound having an alcoholic hydroxyl group and a phenolic hydroxyl group is reacted with an unsaturated group-containing monocarboxylic acid such as (mercapto)acrylic acid, and maleic anhydride or tetrahydrophthalic anhydride is obtained with respect to the alcoholic hydroxyl group of the obtained reaction product. 1,2, 4-benzenetricarboxylic anhydride, both Tetracarboxylic anhydride, adipic acid, etc. The resulting reaction polybasic acid anhydride group-containing photosensitive resin relief. (4) A condensate of bisphenol A, bisphenol F, bisphenol s, novolac type phenol resin, poly(p-hydroxystyrene), naphthol and aldehyde, dihydronaphthalene and a mixture, A compound having two or more phenolic hydroxyl groups in one sub-group; and an alkylene oxide such as ethylene oxide or propylene oxide are reacted to form a reaction of 7 201102405 to make (meth)acrylic acid or the like The unsaturated group is subjected to a mild acid reaction, and a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride in the obtained reaction product is obtained. (5) a reaction product obtained by reacting a compound having two or more desired trans groups in one molecule; and a cyclic carbonate compound such as ethyl carbonate or propyl carbonate; The reaction is carried out to obtain a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride with the obtained reaction product. (6) a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate; and a polycarbonate-based polyalcohol, a polyether-based polyalcohol, or a polyester polycondensation Addition polymerization of a diol compound such as an alcohol, a polyene-based polyalcohol, an acrylic polyalcohol, a bis-A-alkylene oxide adduct (diol), a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group ( Polyaddition reaction) The terminal carboxyl group-containing phthalate resin is formed by reacting an acid anhydride at the end of the urethane resin. (7) in the synthesis of a carboxyl group-containing urethane resin resulting from the addition polymerization reaction of a diisocyanate; a methyl group-containing diol compound such as methyl propionic acid or dimethylol butyric acid; A compound having a hydroxyl group and one or more (fluorenyl) acrylonitrile groups in a molecule such as a hydroxyalkyl (meth) acrylate, and a carboxyl group-containing phthalic acid ester acrylate which is acylated by a terminal (fluorenyl) group. (8) Addition of isophorone diisocyanate and triacrylate in the synthesis of a carboxyl group-containing phthalic acid ester resin resulting from the addition polymerization of a diisocyanate, a diol-containing compound, and a diol compound An equimolar reactant such as pentaerythritol ester, etc., a compound having one isocyanate group and one or more (meth)acryloyl group in the molecule, and a terminally (meth)-acrylated carboxyl group-containing ruthenium ruthenate Resin. (9) A copolymerization of an unsaturated carboxylic acid such as (fluorenyl)acrylic acid or an unsaturated group-containing compound such as styrene, α-mercaptostyrene, lower alkyl (meth) acrylate or isobutylene Carboxyl resin. (10) In the polyfunctional oxetane resin described later, a dicarboxylic acid such as adipic acid, citric acid or hexahydrofurfuric acid is reacted, and a primary hydroxyl group which has been produced is added, and a carboxyl group-containing polyaddition is added. Further, in the ester resin, a compound having one or more (meth) acrylonitrile groups in one molecule such as (meth)acrylic acid 201102405 cyclopropyl propyl ester or (meth)acrylic acid α-mercapto butyl propyl ester is added. The compound containing the carboxyl group (11) in the above (1) to (1〇) is added to a compound of a ring-shaped ring and a (meth) (tetra) silk containing a county-like green tree 'lipid. ^ In this specification (meth) acrylate refers to the collective term "mixture of acrylate, methyl" and other similar tables t Ϊ ί ί ί Α 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 Beauty? ί No, using epoxy resin as a starting material. This kind of soil and bismuth do not use epoxy resin as the starting material, so there is a chlorine ion amount of gluten II?) According to the above, it can be particularly suitable before use ίί Easy: obtained by providing hydrogen bond The excellent adhesion properties such as improved adhesion are significantly reduced. It is generally used in the case where the moisture resistance is excellent, and (4) is used as the starting resin to reduce the resin, and the introduction of the acid anhydride can be obtained. In the case of the synthesized epoxy, the acid having an equivalent amount of 400 to 500 in the double bond is not obtained after the base light is completely obtained, and the coating having the development resistance is not good in the water resistance of the exposure, and the subsequent brazing is further performed. The high acid value makes the ', the suffocation of the sputum, and the PCT resistance significantly reduced. That is, 201102405 It is extremely difficult to completely eliminate the hydroxyl group by using a similar phenolic novolac type epoxy resin. And the hydroxy acrylate resin can also easily synthesize a hydroxyl group-free resin by making the hydroxy oxime equivalent - "the system is not using phosgene as a starting material for isocyanate compounding. The carboxyl group-containing resin which is synthesized from the raw material of epiharohoy dHn is more preferably theoretically free of the base group. Using the previous specific party © with better, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Further, with respect to the mercaptoacrylic acid 3, 4_ having a compound having a cyclic ether group and an acrylonitrile group in one molecule by the slow-setting resin (9) obtained by agglomeration with an unsaturated group as previously shown The carboxyl group-containing photosensitive resin of the epoxycyclohexylmethyl group and the ester group can be suitably used because it has an alicyclic epoxy group and has a small amount of impurities.一方面 On the one hand, a reaction of a carboxyl group-containing resin (9) 'a glycidyl methacrylate having a cyclic ether group and a (meth) acryl fluorenyl group in one molecule, or an unsaturated group-containing compound The propylene glycol methacrylate co-g, will be concerned about the increased mass of chloride ions. Further, in the case of synthesizing an amine-based resin, an epoxy acrylate-modified raw material of a diol compound can also be used. Although it may cause infiltration of chaotic ions, it can be used from the viewpoint of controlling the mass of the gas ions and the like. Since the carboxyl group-containing resin (A) has a large number of free carboxyl groups in the side chain of the back bone polymer, it can be developed by an aqueous alkaline solution. Further, the carboxyl group-containing resin (A) The acid value is desirably in the range of 40 to 150 mgKOH/g, preferably in the range of 40 to 130 mgKOH/g. 201102405 When the acid value of the carboxyl group-containing resin (A) is less than 40 mgKOH/g, alkaline development becomes difficult. When it is more than 150 mgKOH/g, in order to dissolve the exposed portion of the developing solution, the wire is made thinner than necessary. Further, depending on the production condition, the coating film is dissolved by the developer without distinguishing between the exposed portion and the unexposed portion. Therefore, it is not suitable for the description of the normal photoresist pattern. Therefore, the weight average molecular weight of the above-mentioned carboxyl group-containing resin (A) varies depending on the resin, but generally it is preferably 2,000 to 15 〇. , 〇〇〇, and then ^ g 000 ~ 100, the range of 〇〇〇. The weight average molecular weight is less than 2, 〇〇〇, 合合, make taek free performance is poor. Therefore, exposure film The resistance of the second is deteriorated, and the film is thinned during development, and the resolution is greatly deteriorated. And changing the amount of the carboxyl group-containing resin (A) in the total composition by mass%, preferably 30 to 50% by mass. When f = 〇 in the mixture, the film strength is It is not appropriate to reduce it. _ When the range is small, the viscosity is high, or the coating property is lower than that of the photopolymerization agent (9). It is preferable to make the saki free and have the lower ten, t (II) The α-amino group of the group which is not in the group = (Β2); and the group of the base of the formula (m), 51 hair = 3) Photopolymerization L 11 201102405

RR! >-c· (m) (wherein R1 represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a stupid group or a halogen atom), and an alkyl group having 1 to 20 carbon atoms; a group (which may be substituted by more than one hydroxyl group, may have more than one oxygen atom in the middle of the alkyl chain), a cyclodextrin having a carbon number of 5 to 8, and an alkanoyl group or a benzoquinone having a carbon number of 2 to 20. Stuffed base (can be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R2 represents a phenyl group (which can be substituted by a 1-6 group or a phenyl group or a halogen atom), and has a carbon number of 1~ a burnt group of 20 (may be substituted by more than one meridional group, may have more than one oxygen atom in the middle of the burnt chain), a cycloalkyl group having a carbon number of 5 to 8, a fluorenyl group having a carbon number of 2 to 20 or a benzoquinone A mercapto group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group); R 3 and R each independently an alkyl group or an aralkyl group having 1 to 2 carbon atoms; and R 5 and R each independently represent a hydrogen atom; An alkyl group having a carbon number of i to 6 or a cyclic alkyl ether group bonded with a diyl group; R 7 and R 8 each independently a linear or branched bond group of a carbon number 1 (); Cyclopentyl, aryl, or self-atomic, alkyl or alkane A aryl group substituted by an oxy group, wherein one of R7&R8 may represent a R_c(=0)_ group (wherein R is a ketone of 1 to 2 oxime)). In the case of the oxime ester-based photopolymerization initiator (B1) of the group, the following formula (IV) is preferably exemplified by xanthene-9-ketone, the following general formula ~, and Ting Ding 2 - (Ethoxyimin ▼ Swallows a compound of the formula (V), a compound represented by the following general formula (VI) 12 201102405. More preferably, it is 2-(B) represented by the following formula (IV) a compound represented by the formula (V), and a compound represented by the formula (V). [Chemical 2] /0\ /CH3

II L I (N) [Chemical 3]

、, (wherein R9 represents a hydrogen atom, a halogen atom, a carbon number of 1 to 12, a cyclodecyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoinyl group, and a carbon number of 2 to 12 An alkoxycarbonyl group having a number of 2 to 12 alkyl groups (when the alkyl group number of the alkoxy group is = or more, the alkyl group may be substituted by one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain. 】, or phenoxycarbonyl; # R , Rl2 represents a separate phenyl (can be substituted by a carbon number of 1 to 6, alkyl or halogen atom), a carbon number of 1 to 20 (can be a Substituted by the above hydroxyl group, may have more than one oxygen atom in the middle of the alkyl chain), a cycloalkyl group having a carbon number of 5 to 8, an alkanoyl group having a carbon number of 2 to 2, or a benzoyl group (a carbon number of 1) ～Alkyl or phenyl substituted); R11 represents a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl 13 201102405 or a halogen atom), and a number 1 to 20 a group (which may be substituted by more than one radical, or may have more than one oxygen atom in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzene group Acyl (which may be substituted with an alkyl group of 1~6 carbon atoms or a phenyl group [Formula 4]

(wherein R13 and R14 represent independently an alkyl group having 1 to 12 carbon atoms; and R15, R16, R17 and R18 represent an independently hydrogen atom or a carbon number of 1 to 6; η represents an integer of 0 to 5; CGI-325, Irgacure OXE01, Irgacure OXE02, etc. by Ciba Japan Co., Ltd. can be mentioned as a commercial item of the oxime ester type photoinitiator (Β1) which has the group of the general formula (1). These ester-based photopolymerization initiators (B1) may be used singly or in combination of two or more. The α-aminoethyl fluorene-based photopolymerization initiator (Β2) having a group represented by the general formula (II) can be exemplified by 2-methyl-1-[4-(methylthio)phenyl ]_2_ morpholino acetone-1, 2-pyryl-2-dimethylamino_ι_(4-mercaptophenyl)-butan-1-one, 2-(diamine -2-[(4-methylphenyl)indenyl]-H4_(4_morpholinyl)phenyl]-1-butanone, N,N-diguanidinoethyl benzene _ and the like. For the commercial product, irgacure 9〇7, Irgacure 369, Irgacure 379, etc., manufactured by Ciba Japan K.K., may be mentioned. The bismuth oxide phosphine-based photopolymerization initiator (B-3) having a group represented by the general formula (III) may, for example, be oxidized 2,4,6-trimethylsulfonylbiphenyl, oxidized double (2,4,6-xylene ketone) Benzene, oxidized bis(2 6-diindole 201102405 oxyphenyl fluorenyl)-2,4,4-trimethyl-pentanephosphine. For the commercial product, Lucinin ΤΡ〇 and Ciba Japan K.K., manufactured by BASF Corporation, can be exemplified.

Irgacure 819 and so on. The amount of the photopolymerization initiator (B) to be added is preferably from 0.01 to 30 parts by mass, more preferably from 5 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). When the amount is less than 0.01 part by mass, the photocurable coating film on the copper is insufficient in light hardenability, and the coating film is peeled off, or the coating property such as chemical resistance is lowered. On the other hand, when the amount is more than 3 parts by mass, the light absorption of the photopolymerization initiator (B) is extremely high, and the light absorption on the surface of the fcf photoresist film is violent, which tends to lower the deep hardenability. Further, in the case of using the ester-based photopolymerization initiator (B1) having the group represented by the formula (I), it is selected from the desired mixture of the terpene-containing resin (A). It is preferably in the range of 0.01 to 20 parts by mass, more preferably in the range of 〇.〇1 to $ parts by mass. Other examples of the photopolymerization initiator (B), the photoinitiation aid, and the sensitizer which can be suitably used in the photocurable thermosetting resin composition of the present invention include benzoin compounds, acetophenone compounds, and ruthenium compounds. , 9_oxysulfur ^ Yamaguchi 1 compound, ketal compound, benzophenone compound, π-ketone compound, and secondary amine compound. — Specific examples of the benzoin compound may, for example, be benzoin, benzoin ether, benzoin ethyl ether or benzoin isopropyl ether. ^ Specific examples of the benzene compound can be exemplified by, for example, acetophenone, 2 2 -dimethoxy-2-benzyl, and 2,2-ethoxy-2-phenyl b. 1 1 chloroethyl benzene. Specific examples of the monomethane compound include, for example, 2-mercapto onion, 2-acetone, 2-tributylphosphonium, and 1-carbene. " Specific examples of the soil 9-oxosulfurium sulphate nj bevelate, for example, 2,4_dioxime 9-oxosulfuric nJjD, 2,4-ethylidene 9-oxosulfurium sigma π , 2-gas 9-oxo 0 mountain scorpion house, 2, 4-diisopropyl 9-oxo sulfur π mountain comet. Specific examples of the ketal compound include, for example, acetal ketal and 15 201102405 benzyl diketal. Specific examples of the benzophenone compound include, for example, benzophenone, 4-phenylmercaptodiphenyl sulfide, 4-benzylidene-4'-mercaptodiphenyl sulfide, 4-benzoquinone. Mercapto-4'-ethyldiphenyl sulfide, 4-phenylmercapto-4'-propyldiphenyl sulfide. Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylamine benzene structure, for example, 4,4'-dimethylamine benzophenone (Nissocure MABP manufactured by Nippon Soda Co., Ltd.), 4, 4'- Dialkylamine benzophenone, 7-(diethylamino)-4-mercapto-2H-1-benzopyran-2, such as diethylamine benzophenone (EAB by HODOGAYA CHEMICAL CO., LTD.) a dialkylamine coumarin compound such as ketone (7-(diethylamino)-4-methylcoumarin) or ethyl 4-dimethylamine benzoate (Kayacure EPA manufactured by Nippon Kayaku Co. Ltd.) , 2-diguanamine phthalic acid ethyl ester (Quantacure DMB manufactured by International Bio-Synthes, Inc.), 4-diamine benzoic acid (n-butoxy) ethyl ester (Quantacure BEA, manufactured by International Bio-synthetics), Isoamyl dimethylamine benzoate (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylamine benzoate (manufactured by Van Dyk Co., Ltd.)

Escalol 507), 4, 4'-diethylamine benzophenone (EAB manufactured by HODOGAYA CHEMICAL CO., LTD.). Among the foregoing, it is preferably a 9-oxosulfurium π-d compound and a tertiary amine compound. In the aspect of the composition of the present invention, from the aspect of deep hardenability, it is preferred to contain a 9-oxosulfonate compound, which is preferably 2,4-dimethylnonane 9-oxosulfanyl Yamaguchi, 2, 4-diethyl 9-oxosulfur π mountain d star, 2-chlorothio D ketone (xanth〇ne), 2, 4 diisopropyl 9-oxosulfur π mountain p star, etc. 9-oxo sulfur p Mountain π star compound. The amount of the 9-oxosulfur compound is preferably 2 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). When the mixture of 9_oxysulfide-star compound = thick film hardenability is reduced, it is closely related to the cost increase of the product, so it is not suitable. In the case of the tertiary amine compound, a compound 201102405 having a dialkylamine benzene structure is preferable, and among them, a dialkylamine benzophenone compound and a diamine coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferred. The toxicity of 4,4'-diethylamine diphenyl hydrazine is also low in the bis-amine benzophenone compound. The dialkylamine coumarin compound having a maximum absorption wavelength of 350 to 410 nm has less coloration because the maximum absorption wavelength is in the ultraviolet region, and the colorless and transparent photosensitive composition uses a coloring pigment from the beginning to provide a soldering light. A resist film that reflects the color of the color of the coloring pigment itself. In particular, 7-(diethylamino)-4-mercapto-2H-1-benzophenanthroline (pyran)-2-one exhibits excellent sensitization effect with respect to laser light having a wavelength of 400 to 410 nm. . The amount of the tertiary amine compound to be mixed is preferably from 0.1 to 20 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the above-mentioned retardation-containing resin (A). When the compounding amount of the tertiary amine compound is less than or less than 0.1 part by mass, a sufficient sensitizing effect is not obtained. When the amount of the mixture exceeds 20 parts by mass, the light absorption on the surface of the dried solder resist film caused by the tertiary amine compound becomes intense, and the deep hardenability tends to decrease. These photopolymerization initiators (B), photoinitiation aids, and sensitizers may be used singly or as a mixture of two or more. The total amount of such a photopolymerization initiator (B), a photoinitiator, and a sensitizer is preferably in the range of 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (A). When it exceeds 35 parts by mass, the deep hardenability tends to decrease by such light absorption. The vinyl-containing elastomer (C)' used in the photocurable thermosetting resin composition of the present invention can not only improve the crack resistance of the obtained cured coating film to the thermal cycle, but also improve the adhesion of the solder resist. In particular, it improves the effect of resistance to pcT. The above-mentioned compound is not particularly limited as long as it is an elastomer having a vinyl group in the skeleton, and it can be suitably used in order to impart the above properties to the butyl dibasic derivative. Specific examples of the 3 ethylene-based elastomer (C) include Ep〇lead PB3600, Epofriend CT310, and ep0friend AT501 (the above are trade names of Daicd Chemical Industry Co., Ltd.), Ric〇nl3〇, Ric. 〇nl31, 17 201102405

Riconl34, Riconl42, Riconl50, Riconl52, Riconl53, Riconl54, Riconl56, Riconl57, RiconP30D, Ricon657, RiconlOO, Riconl81, Riconl84, Riconl30MA8, Riconl30MA13, Riconl30MA20, Riconl31MA5,

Riconl31MA10, Riconl31MA17, Riconl31MA20, Riconl84MA6, Riconl56MA17, CN301, CN307 (the above are sold under the trade name of Sartomer), Denalex R_45EPT (trade name by Nagase Chemte X Co., Ltd.), BAC-45 (Osaka Organic Chemical Industry Co., Ltd.) The product name of the stock system), Poly bd, Poly ip, Epol (the above is the trade name of the company, and the name of the product of Mitsubishi Chemical Corporation). The amount of the vinyl-containing elastomer (C) to be mixed is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more, and 50 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A). The following. When the amount of the mixture was less than 5 parts by mass, the effect of the vinyl-containing elastomer (C) could not be confirmed. On the other hand, when the compounding amount exceeds 60 parts by mass, the coating film may be caused to be sticky or poorly developed, which may be undesirable. α The photocurable thermosetting resin composition of the present invention may contain a hydrogenthio group compound (D) for the purpose of addition reaction and crosslinking of the vinyl group-containing elastomer (C). By the addition of the thiol compound (D), it is possible to prevent deterioration of coating film properties due to vinylation. Further, in order to obtain a soft crosslinked product by the addition of the hydrogenthio group-based compound, the composition is improved in pCT resistance, HAST property, etc. Further, the hydrogenthio compound (D) is intended to function. The transfer agent, /* imparts an adhesive agent, so that the composition sensitivity and the appearance of the child can be obtained at the same time. For the mercapto compound (D), for example, hydrogen (mercapt^) can be exemplified. Ethyl alcohol, hydrogen thiopropanol, hydrothiobutanol, hydrogen thiodithiobutanol, hydroxybenzene thiol and its derivatives; butyl thiol, dipropionic acid vinegar, methyl-3-hydrothiopropionic acid Vinegar, 2, 2_(extended ethyldioxy)diethylthiofuranol, 4-mercaptothiol'dodecylmercaptan, propanethiol, butanethiol, cucurone 18 201102405 alcohol, 1- An octyl mercaptan, a cyclopentyl mercaptan, a cyclohexyl mercaptan, a thioglycerol, a 4, 4-thiobisbenzenethiol, etc. Examples of such commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, and STMP. , TMMP, PEMP, DPMP, and TEMPIC (manufactured by Seiko Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, Karenz-NR1 (above, Showa Denko Co., Ltd.), etc. Further, In the miscellaneous As the sulfonium compound (D) of the ring, for example, thiothio-4-butyrolactone (other names: 2-hydrothio-4 γ·butanolide), 2-hydrogen sulfide can be exemplified. 4-mercapto-4-butyrolactone, 2-hydrothio-4-ethyl-4-butyrolactone, 2-hydrothio-4-butane lactone, 2-hydrothio-4 -butyroamine, N-methoxy-2-hydrothio-4-butylidene, N-ethoxy-2-hydrothio-4-butylidene, N-methyl-2 -Hexylthio-4-butylidene, N-ethyl-2-hydrothio-4-butylidene, N-(2-methoxy)ethyl-2-hydrothio-4- Butane amide, N_(2-ethoxy)ethyl-2-hydrothio-4-butylidene, 2-hydrothio-5-valerolactone, 2· thiothio-5-pentyl Indoleamine, N-mercapto-2-hydrothio-5-pentalinamide, N-ethyl-2-hydrothio-5-pentalamine, N-(2-methoxy)B Alkyl-2-hydrothio-5-pentanoic acid amine, Ν-(2·ethoxy)ethyl 2·hydroxythio-5-pentalinamide, 2-hydrothiazolidine, 2 -Hexylthio-5-indole thioxadiazole, 2-hydrosulfanyl-6-caprolactam, 2, 4, 6 · trihydrothio-s-three tillage (Sankyo Chemical Co., Ltd. system: Trade name zisnet F), 2-dibutylamino-4,6-dihydrothio-s_three tillage (product name: Zisnet DB), 2-anilino _4,6-dihydrothio-s-three ploughing (manufactured by Sankyo Chemical Co., Ltd.: trade name ZisnetAF), etc. Hydrogen thiobenzimidazole, 2-hydrogenthiobenzoxazole, 2-hydrothiobenzothiazole (manufactured by Kawaguchi Chemical Industry Co., Ltd.: trade name Accel M), 3-hydrothio- 4-mercapto-4H- 1,2,4-triazole, 5-mercapto-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-hydrothio-1H-tetrazole, and the like. These hydrogenthio compounds (D) may be used singly or in combination of two or more. The amount of the hydrosulfide-based compound (D) to be added is appropriately 1 part by mass or more, 1 part by mass or less, more preferably 0.05 part by mass or more, and 5 parts by mass, based on the mass of the carboxyl group-containing resin. When the amount is less than 0.01 parts by mass, the addition effect of the hydrogenthio compound (D) cannot be confirmed. 19 201102405 'The fear of causing light drying to manage the stretchability. On the one hand, the amount of the mixture exceeds 10· When the amount of the curable thermosetting resin composition is less than 0 parts by mass, it is not suitable for development, and the like, and the heat-curable component can be added to the heat-resistant layer of the present light-curing thermosetting resin. (6) For use in the thermosetting component (Ε) of the present invention, a blocked isocyanate compound, an amine ester, a maleimide compound, a benzoxazine resin, or a carbodiimide resin can be used. A thermosetting tree, such as a cyclic carbonate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, or an episulfide resin, which is well-received. Hardening component (E) a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter referred to as cyclic (thio)ether groups) in one molecule. The heat having such cyclic (thio)ether groups The curable component (E) is commercially available in a wide variety of properties, and various properties can be imparted by this structure. The thermosetting component (E) having two or more cyclic (thio)ether groups in the molecule has a molecule Any one of a cyclic ether group or a cyclic thioether group of 3, 4 or 5 membered rings, or a compound having two or more kinds of two groups. For example, there may be at least two or more epoxy groups in the molecule. a compound, that is, a polyfunctional epoxy compound (E-1); a compound having at least two or more oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound (E_2); More than one thioether-based compound, that is, an episulfide resin (E_3) or the like.

Examples of the polyfunctional epoxy compound (E-1) include jER828, jER834, jER1001, and jER1004 manufactured by Nippon Epoxy Co., Ltd.; Epiclon 840, Epiclon 850, Epiclon 1050, and Epiclon 2055 manufactured by DIC Corporation; Epotohto YD-011, YD-013, YD-127, YD-128 manufactured by Dongdu Chemical Co., Ltd.; DER317, DER331, DER661, DER664 manufactured by Dow Chemical Company; araldite 6071, araldite of HUNTSMAN ADVANCED MATERIALS KK 6084, araldite GY250, araldite GY260; Sumi-epoxy 20 201102405 ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd.; AER330, AER331, AER manufactured by Asahi Kasei Co., Ltd. 661, AER664, etc. (both trade names) of bisphenol A epoxy resin; JERYL903 manufactured by Epoxy Epoxy Co., Ltd.; Epiclon 152, Epiclon 165 manufactured by DIC Co., Ltd.; Epotohto YDB-made by Dongdu Chemical Co., Ltd. 400, YDB-500; DER542 manufactured by Dow Chemical Co., Ltd.; Araldite 8011 manufactured by HUNTSMAN ADVANCED MATERIALS KK; Sumi-epoxy ESB-400, ESB_7〇0 manufactured by Sumitomo Chemical Industries Co., Ltd.; AER7 manufactured by Asahi Kasei Co., Ltd. 11. AER714 and other brominated epoxy resins (both trade names); jER152 and jER154 manufactured by Epoxy Epoxy Co., Ltd.; DEN431 and DEN438 manufactured by Dow Chemical Co., Ltd.; Epiclon N-made by DIC Co., Ltd. 730, Epiclon N-770, Epiclon N-865; Epotot YDCN-701, YDCN-704 manufactured by Dongdu Chemical Co., Ltd.; araldite ECN1235 manufactured by HUNTSMAN ADVANCED MATERIALS KK· araldite ECN1273, araldite ECN1299, araldite XPY307; Nippon Kayaku EPPN-2CH, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 manufactured by Co., Ltd.; Sumi-epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries Co., Ltd.; Asahi Kasei AERECN-235, ECN-299, etc. (all are trade names) made of acid and varnish type epoxy resin; Epiclon 830 manufactured by DIC Corporation; jER807 manufactured by Japan Epoxy Resin Co., Ltd.; Epotohto YDF-170, YDF-175, YDF-2004, manufactured by HUNTSMAN ADVANCED MATERIALS KK, araldite XPY306 (all are trade names), bisphenol F-type epoxy resin; Epotohto ST, manufactured by Tohto Kasei Co., Ltd. -2004, ST-2007, ST-3000 (trade name), etc. Bisphenol A type epoxy resin; jER604 manufactured by Epoxy Epoxy Co., Ltd.; Epotohto YH-434 manufactured by Tohto Kasei Co., Ltd.; araldite MY720 manufactured by HUNTSMAN ADVANCED MATERIALS KK; Sumi-made by Sumitomo Chemical Industries Co., Ltd. Epoxypropylamine type epoxy resin such as epoxy ELM-120 (all trade names); allantoin 21 such as araldite CY-350 (trade name) manufactured by HUNTSMAN ADVANCED MATERIALS 2011·Κ. 201102405 (hydantoin) type Epoxy resin; Celloside 2021 manufactured by Daicel Chemical Industry Co., Ltd.; HUNTSMAN ADVANCED MATERIALS 脂·Κ. araldite CY175, CY179, etc. (all trade names) alicyclic epoxy resin; YL manufactured by Epoxy Epoxy Co., Ltd. -933; DT, EPPN-501, EPPN-502, etc. (all trade names) manufactured by Dow Chemical Co., Ltd.; YL-6056, YX-4000, manufactured by Japan Epoxy Resin Co., Ltd. ED-6121 (all trade names), etc., bis xylenol type or biphenol type epoxy resin or the like; EBPS-200 manufactured by Nippon Kayaku Co., Ltd.; EPX-30 manufactured by ADEKA Co., Ltd.; DIC Co., Ltd.

Double-anti-S type epoxy resin such as EXA-1514 (trade name); bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Epoxy Epoxy Co., Ltd.; jERYL_93i manufactured by Japan Epoxy Resin Co., Ltd. ; HUNTSMAN ADVANCED MATERIALS KK araldite 163 (all trade names) of tetraphenyl (phenylol) ethane type epoxy resin; HUNTSMAN ADVANCED MATERIALS KK araldite PT810; Nissan Chemical Industry Co., Ltd. TEI> IC, etc. Heterocyclic epoxy resin of the product name), epoxide ester of phthalic acid, such as Bremmer DGT, manufactured by Toei Oil Co., Ltd.; tetramethyl propyl dioxime, ZX_1063, etc., manufactured by Tohto Kasei Co., Ltd. Xylenolyl ethane resin; esn_19〇 manufactured by Nippon Steel Chemical Co., Ltd., ESJ^36^, DIC ΗΡ4〇32, ΕχΑ_475〇, ΕχΑ47〇〇, etc. Epoxy resin of _ ΪΪΐ Ϊ HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP HP Further, it is an epoxy resin of cyclohexyl (tetra) acid propylene acrylate; oxime (example) YR_102 manufactured by Tohto Kasei Co., Ltd., and two or more of them are not limited to these. These epoxy resins can be used alone or in an epoxy resin. Anthraquinone-type epoxy resin or such a mixture. Comparing with 3% of the ΐΐ ΐΐ 环 环 环 化合物 化合物 compound (Ε·2), can be exemplified by bis [(3-methyl-3-milk% butyl methoxy)曱), 双 [(3_乙乙氧氧丁丁丁丁22 201102405 曱 曱 曱 曱 曱 ] 2011 2011 2011 2011 2011 2011 2011 2011 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 醚 2011 2011 Methyl]benzene, 1,4-bis[(3_ethyl_3_oxetanylmethoxy)indolyl], &acrylic acid (3-indolyl-3-oxetane) Anthracene ester, acrylic acid (3-ethyl_3_oxebutane) decyl ester, methacrylic acid (3-fluorenyl-3-oxetane) methyl ester, methacrylic acid (3-ethyl- 3-oxobutane) oxime ester or such oligomers or copolymerized second-order polyfunctional oxetane, other than 'exemplified with oxetane and novolac resin, poly (p-hydroxystyrene), cardinal type, acid-testing, cyclic acid (calixarene), brewing An ether compound of a resin having a hydroxyl group such as a calidresorcinarene or a silsesqui〇zane, etc. Other unsaturated monomers having an oxetane ring and a (fluorenyl group) may also be exemplified. A copolymer of an alkyl acrylate or the like. In the case of the episulfide resin (E-3) having two or more cyclic thioether groups in the molecule, for example, YL7® (double-type A-type episulfide resin) manufactured by Nippon Epoxy Co., Ltd., Or yslv_12〇te, etc., manufactured by Toho Chemical Co., Ltd. Further, in the same synthesis method, an episulfide resin or the like which replaces an oxygen atom in the epoxy group of the varnish-type epoxy resin with a sulfur atom can also be used. The amount of the thermosetting component (E) having one or more cyclic ether (ethyl sulfide) groups in the molecule is preferably from 0.6 to 2.5 equivalents per 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A). More preferably, it is a range of 8 to 2 equivalents. When the mixture of the thermosetting component (E) having two or more cyclic ether (ethyl sulfide) groups in the molecule is less than 0.6 equivalents, 'the carboxyl group remains in the solder resist film, and the heat resistance and alkali resistance are lowered. It is not suitable for electrical insulation. On the other hand, when the amount of the mixture exceeds 2.5 equivalents, the low-molecular weight cyclic ether (ethyl sulfide) group remains in the dried coating film, which is unfavorable because the strength of the coating film is lowered. In the case of the thermosetting component (E) to be used, an amine resin such as a trimeric organism or a benzoguanamine derivative can be exemplified. There are, for example, a hydroxymethyl polyamine compound, a hydroxymethyl benzoguanamine compound, a methylol group, a methyl urea compound, and the like. Further, the oxygenated methylated trimer compound, the oxygenated methylated benzoguanamine compound, the burned oxygen methylation 23 201102405 acetylene urea compound and the oxygenated methylated urea compound are each passed through The melamine compound, the hydroxytoluene and the guanine amine compound, the oxindole acetylene urea compound, and the hydroxy thiol group of the oxycarbendazole compound are converted into an alkoxy group. The type of the alkoxy group is not particularly limited, and may, for example, be a methoxymethyl group, an ethoxylated group, a propoxymethyl group or a butoxy group. It is particularly preferred as a melamine derivative having a milder concentration of 0.2% or less on the human body or the environment. For such commercial products, for example, Saimel 300, same as 301, same as 303, same as 370, same as 325, same as 327, same as 701, the same as 266, the same as 267, the same as 238, the same 1141, the same as 272, the same 202, Same as 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above Nihon Cytec Industries Inc.), Nikalac Mx-750, Mx-032, Mx-270, and Mx-280 Same as Mx-290, Μχ·706, same Mx-708, same Mx-40, same Mx-31, same Ms-1 Bu Mw-30, same Mw-30HM, same Mw-390, same Mw-100LM And the same Mw-750LM (above the three and chemical companies (shares) system). The thermosetting component (E) may be used singly or in combination of two or more. Further, in the photocurable thermosetting resin composition of the present invention, in order to improve the curability of the composition and the toughness of the obtained cured film, it is possible to add two or more isocyanate groups or blocked isocyanate groups in one molecule. Compound (F). The compound (F) having two or more isocyanate groups or blocked isocyanate groups in one molecule may, for example, be a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound (F4); Or a compound having two or more blocked isocyanate groups in one molecule, that is, a blocked isocyanate compound (F-2). As the polyisocyanate compound (F4), for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate include 4,4,-diphenyl sulfonium diisocyanate, 2,4-methyl phenylene diisocyanate, and diisocyanate 2 , 6-methyl-f-ester, n-isocyanate naphthalene 丨, 5_ester, o-xylylene diisocyanate, diisosorbent I, sub-unit, and 2,4-methyl benzene ( Tolylene) dimer. Fat 24 201102405 Specific examples of the dioxic acid brewing can be exemplified by diisocyanate, Ding, Zi, 4, 4, methyl ester, decyl diisocyanate, tridecyl hexaisophthalate ester.具体r俨; 曱 双 bis (cyclohexyl isocyanate) and isophorone diisocyanate t, a specific example of the polyisocyanate may be exemplified by a triisocyanate bicyclic ring - and the aforementioned isocyanuric acid vinegar An adduct of a compound, a uret-urea (=et) body, and a hetero-cyanide-body. The blocked isocyanate group contained in the ester compound (F-2), which is inert when it is protected by the reaction with a blocking agent. Foundation. When heated to the set temperature, the capping agent", isocyanate group. ^ People ^^^ segment of the acid ester compound (F-2), the use of isocyanate ruthenium ruthenium, Ϊ丨, seal The addition reaction product of the terminal agent (d) may be, for example, an isocyanurate compound, a condensed form, an adduct type or the like in terms of the isocyanate compound (c) to be blocked. The isocyanate compound (C) can be used, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or a waxy cyanine vinegar. In terms of specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate For example, the compound 0 Μ isocyanate capping agent (d) as exemplified above may be, for example, a phenolic terminal blocking agent such as a sulfonate, a methyl phthalate, a dimethyl phthalate, a chlorine test, and an acetol; _Caprolactam, Valerolactam, γ·butyrolactam and β-propionalactam (propi〇lactam), etc. Active methylene-based blocking agent for acetone, etc.; methanol, ethanol, propanol, butanol, pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Alcohol-based blocking agent such as monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, decyl lactate and ethyl lactate; Aldehyde, acetoxime, acetoxime, hydrazine, diethyl hydrazine, cyclohexane hydrazine, etc.; butyl mercaptan, hexyl mercaptan, tertiary butyl a mercaptan blocking agent such as mercaptan, thiophenol, methyl mercaptan or ethyl thiophenol; an acid amide amine blocking agent such as decylamine benzoguanamine; quinone succinate and 25 201102405 An imide end-capping agent such as bismuth methylene iodide; an amine-based blocking agent such as xylidine, aniline, butylamine or dibutylamine; imidazole, 2-ethylimidazole, etc. The imidazole-based blocking agent; an imide-based blocking agent such as methyleneimine or propyleneimide, etc. The blocked isocyanate compound (F-2) may be a commercially available one, and may, for example, be exemplified by

Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmosam 2170, Desmosam 2265 (above) Sumika Bayer Urethane Co" Ltd. 'Product name', Coronet 2512, Coronet 2513, Coronet 2520 (above Nippon Polyurethane Industry Co" Ltd. 'product name', B-830, B_815, B-846, B-870, B-874, B-882 (The above is manufactured by Mitsui Chemicals Co., Ltd., trade name), TPA-B80E, 17B-60PX, and E402-B80T (the above is manufactured by Asahi Kasei Chemicals Co., Ltd., trade name). Further, Sumidur BL-3175 and BL-4265 were obtained by using ruthenium acetonide as a terminal blocking agent. The compound (F) having two or more isocyanate groups or blocked isocyanate groups in the above-mentioned one molecule may be used alone or in combination of two or more. The compounding amount of the compound (F) having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass, more preferably 100 parts by mass based on 100 parts by mass of the fluorenyl group-containing resin (A). A ratio of 2 to 70 parts by mass is appropriate. When the amount is less than one part by mass, sufficient coating film toughness cannot be obtained, which is not preferable. On the other hand, when the amount of the mixture exceeds 100 parts by mass, it is not preferable because the storage stability is lowered. In the photocurable thermosetting resin composition of the present invention, in order to promote the curing reaction of a hydroxyl group or a carboxyl group with an isocyanate group, an amine bismuth ruthenate (G) can be added. The amino phthalic acid g is preferably a catalyst (G) selected from the group consisting of tin-based catalyst (G-1), metal chloride (G-2), and metal acetophenone-acid salt (G-3). And one or more amino phthalate catalysts of the group consisting of metal sulfate (G-4), amine compound (G-5), and/or amine salt (G-6). The tin-based catalyst (G-1) may, for example, be an organotin compound such as stannous octoate (tannous 26 201102405 ate) monolaurate monolaurate or an inorganic tin compound. The metal vapor (G-2) aspect can be exemplified by a vapor of a metal composed of chromium, a bell, a ruthenium, a ruthenium, a copper, or a copper, such as a vaporized cobalt (m) (c〇baltic = 1〇nde) ), nickel chloride, ferric chi〇ride, the metal acetate pyruvate (G-3), which may be exemplified by chromium, fission, knot, nickel, iron, copper or aluminum The acetic acid pyruvate of the composition metal may, for example, be a cobalt acetonate pyruvate salt, a nickel acetonate pyruvate salt or an iron acetylacetonate iron salt. The metal sulfate (G-4) may be a sulfate of a metal composed of chromium, manganese, cobalt, nickel, iron, copper or aluminum, and examples thereof include copper sulfate. The amine compound (G-5) may, for example, be a conventionally known triethylenediamine, N,N,N',N,-tetradecyl-1,6-hexanediamine or bis(2-di). Indole ethyl) ether, N, N, N', N", N"-pentaethylenediethylenetriamine, N-mercaptopurine, N-ethyl eucalyptus, N,N-dimethylethanolamine , 二昧林基二乙谜,N-曱 "rice bran, diamine 0 bite, triazine, N'-(2-ethyl)-N,N,N,-trimethyl-bis ( 2-Aminoethyl) bond, N,N-dioxanolamine, N,N-dimethylamine ethoxyethanol, N,N,Ν'-trimethyl-N'-(2-hydroxyethyl Ethylenediamine, N-(2-hydroxyethyl)-N, N,N", N''-tetramethyldiethylenediamine, N-(2-propyl)_ν,Ν', N",N"_tetradecyl diethylenetriamine, hydrazine, hydrazine, Ν'-trimethyl-N'-(2-hydroxyethyl)propanediamine, N-methyl-N'-(2 -ethyl)hexahydro-11-homo, bis(N,N-diguanamine)amine, bis(N,N-dimethylaminopropyl)isopropanolamine, 2-amine quinucidine ), 3-amine quinuclidine ring, 4-amine quinuclidine ring, 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, ι·(2,_hydroxypropyl) Imidazole 1-(2'-hydroxypropyl)-2-methylimidazole, 1-(2'-hydroxyethyl)imidazole, iota-(2,-hydroxyethyl)-2-methylimidazole, 1-(2'- Hydroxypropyl)-2-methimazole, 1-(3,-aminopropyl)imidazole, 1-(3'-aminopropyl)-2-methylimidazole, 1-(3'-hydroxypropyl)imidazole, 1_ (3,-hydroxypropyl)-2-indolizole, N,N-diguanamine propyl-N'-(2-hydroxyethyl)amine, n,N-diguanamine propyl-N', hydrazine '-bis(2-hydroxyethyl)amine, N,N-dimethylaminopropyl-N,, Ν'·bis(2-hydroxypropyl)amine, hydrazine, hydrazine-dimethylamine ethyl-hydrazine ,Ν,-bis(2-hydroxyethyl) 27 201102405 Amine, N,N dimethylamine ethyl_N,,N,-bis(2-hydroxypropyl)amine, melamine and / or benzoguanamine The amine salt (G-6) can be exemplified by an amine salt of an organic acid salt such as DBU (1,8-difluorene-bicyclo[5,4, fluorene] _7). The compounding amount of the urelate-forming catalyst (G) is preferably '% by mass, for example, relative to 100 parts by mass of the carboxyl group-containing resin (A), preferably from 1 to 20 parts by mass, preferably 0. 5~1〇.〇质量份。 When using the thermosetting component (Ε) having two or more cyclic ether (ethyl sulfide) groups in the above molecule It is preferable to contain a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-benzimidazole, and 4-benzene. Imidazole derivatives such as imidazole, 1-cyanoethyl-2-benzimidazole, 1-(2-yl)-2-ethylimidazole, etc.; diguanamine dicyanide, dimethyl phthalocyanine, 4 mercaptoamine An amine compound such as dimethylbenzylamine, 4-methoxy-N,N-:-benzylamine, 4-mercapto-n,N-dimethylbenzylamine, etc. An anthracene compound such as diterpene acid; a phosphorus compound such as triphenylphosphine or the like. In the case of the commercially available product, for example, 4MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all are the trade names of the azole compound) manufactured by Shikoku Chemical Industrial Co., Ltd.; U CAT (registered trademark) 35f3N, U-CAT3502T (all of the block isocyanate compounds of diamine), DBU, DBN, U-CATSA102, U-CAT5002 (all of which are ruthenium compounds and salts thereof). In particular, it is not limited to these, as long as it is a thermosetting catalyst of an oxygen resin or an oxetane compound, or a substance which promotes the reaction of an epoxy group and/or an oxetane group with a carboxyl group. These substances may be used singly or in combination of two or more. Also, guanamine, guanosine, guanine, melamine, 2,4-diamino-6-nonylaminopropenyloxyethyl ss-triazine, 2_ethylene _ can also be used. 2, 4-diamino-s-triazine, 2-ethylene-4,6-diamino-8-triazine, iso-cyanate adduct, 2,4-diamino-methylpropane The s_diindole derivative of the dilute oxyethyl_S_triterpene/isocyano cyanate adduct or the like is preferably used as a compound for imparting the adhesion agent together with the thermosetting catalyst. . 28 201102405 These thermosetting catalysts are combined in a normal amount ratio, for example, with respect to the carboxyl group-containing resin (A) or two thermosetting groups with a 2-ring ether (ethyl sulfide) group. The sexual component (E) is 100 parts by mass, preferably 〇 parts by mass, more preferably 0.5 to 15.0 parts by mass. The photocurable resin composition of the present invention may be mixed with a coloring agent (H). As the coloring agent, a conventionally known coloring agent such as red (H-1), blue (H-2), green (H-3) or yellow (H_4) may be used, and any of a pigment, a dye, and a pigment may be used. In the absence of a reduction in environmental load and impact on the human body, it is desirable to have no halogen. Red colorant (H-1): For red colorants, there are monoazo, diazo, azolake, benzimidazolone, anthracene, diketopyrrolopyrrole , condensed arsenazo, enthalpy, 喧*» fluorenone (qUinacrjd〇ne), etc., specifically, the following color index (CI; The Society of Dyers and The Society of Dyers and Colourists) issued) number. Early azoquinone. 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 : pigment red 37 , 38 , 41 . Single azolake (azolake): Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: Bu 52: 1, 52: 2, 53 : 1 , 53 : 2, 57 : 1, 58 : 4, 63 : 1, 63 : 2, 64 : 1, 68. Benzimidazolone type: Pigment Red 17 Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208. Lanthanum: 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 255, Pigment 29 201102405 Red 264, Pigment Red 270, Pigment Red 272. Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242. En 1 series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207. Quinacridone is a pigment red 122, a pigment red 202, a pigment red 206, a pigment red 207, and a pigment red 209. Blue coloring agent (H-2): A blue coloring agent is a compound in which a phthalocyanine system or a quinone-based pigment system is classified as a pigment, and specifically, it can be exemplified by the following: 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 70 and the like. In addition to the foregoing, a metal-substituted or unsubstituted phthalocyanine compound can also be used. Green coloring agent (H-3): In the case of green coloring agents, 'the same kind of phthalocyanine, lanthanide, and lanthanide. Specifically, pigment green 7, pigment green 36, solvent green 3, solvent green 5, solvent can be used. Green 20, solvent green 28, etc. In addition to the foregoing, a metal-substituted or unsubstituted phthalocyanine compound can also be used. Yellow coloring agent (H-4): ^ Yellow coloring agent is monoazo, diazo, condensed azo, benzopyrazole, isoindolinone , brewing, etc. 'Specific words can be cited as the following. Lanthanide: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202. 201102405 Isoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185. Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180. Benzophenone ketones: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 18 Bu Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6 9, 9, 10, 12, 62, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183. Diazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198. Others, in order to adjust the color tone, it is also possible to add a coloring agent such as purple, orange, brown or black. 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, C 丄 pigment orange 40, CI pigment orange 43, CI pigment orange 46, CI pigment orange 49, CI pigment Orange 51, CI 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. The mixing ratio of the coloring agent (H) is not particularly limited, and is preferably 〇 to mass parts, particularly preferably 0.1 to 5 parts by mass, based on the mass of the ruthenium-containing resin (A). full. The compound (I) having one or more ethylenically unsaturated groups in the molecule used in the photocurable thermosetting resin composition of the present invention is photocured by irradiation with an active energy ray to form the carboxyl group-containing resin. (A) Insoluble in an aqueous alkaline solution or contributing to insolubilization. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, amide decyl acrylate, carbonate (mercapto) acrylate can be used. , (A 31 201102405 base) acrylate epoxy ester, etc., specifically, 2-hydroxypropyl acrylate such as hydroxyalkane 2; olefinic di 2-hydroxyethyl ester, ethylene glycol, polyethylene glycol, Ethylene glycol such as propylene glycol, decyloxytetramethyl, decylamine, N-hydroxymethacrylamide; N, N: acrylamides such as decylamine; N-aminopropyl acrylate N, N- a polyvalent alcohol such as acetaminophen, such as acetaminophen, acrylic acid, neodymidine, dipentaerythritol, diol or triterpene, or such oxidized Base soil ^; polychao acid 酉曰) L,, i ε _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

Multi-valent acrylic vinegar, glycerol triglyceride, trishydroxyl glycerol, glycerol mono-glycidyl triglycidyl ester, etc. ::: = ether, iso-in: said, can be exemplified by polymyol, polycarbonate, =, j-end = diene, polyester, polyalcohol, etc. Butyl diisocyanate is acrylated with urethane: or '竺 from = oleic acid vinegar, and/or bismuth oxime epoxy 2 corresponding to the aforementioned acrylic vinegar in the base of the epoxy acrylate resin, making three Two: = four = acrylic surface and different Buddha _ diisocyanate vinegar and other two sulphuric acid vinegar = J-based formic acid S, the reaction of the reaction of epoxy amine A (four) (10) (four) compound two #. Such an oxime acrylate-based resin can improve photocurability without lowering the dry-to-touch. The compounding amount of the compound (1) having two or more ethylenically unsaturated groups in the molecule is 5 to 1 part by mass, preferably 1 to 70 parts by mass based on 1 part by mass of the carboxyl group-containing resin (A). The ratio of shares. When the amount is less than 5 parts by mass, the photocurability is lowered, and the alkali development after irradiation with the active energy ray is difficult to form a pattern, which is not preferable. On the one hand, the amount of the mixture exceeds 1 〇〇 32 201102405. When the product is damaged, the solubility with respect to the alkaline aqueous solution is lowered, and the coating film becomes brittle and unfavorable. In the photocurable thermosetting resin composition of the present invention, in order to improve the physical strength and the like, the filler (J) may be mixed as needed. In the case of such a charge (= J), although it is possible to use a conventional inorganic or organic filler, it is not preferable to use barium sulfate, spherical cerium oxide and talc. Further, in order to obtain a color appearance or flame retardancy, titanium oxide, a metal oxide or a metal hydroxide of a hydroxide can be used as a primer filler. The amount of the filler (7) to be added is preferably 100 parts by mass or less, more preferably 0.1 to 150 parts by mass, even more preferably 1 to 100 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). When the amount of the filler (J) is more than 200 parts by mass, the viscosity of the composition is increased, the printability is lowered, or the cured product is brittle, which is not preferable. Further, the photocurable thermosetting resin composition of the present invention is intended to improve the dryness of the touch, improve the workability, and the like, and a binder polymer can be used. For example, a polyester-based polymer, a polyamino phthalate-based polymer, a polyester-amine phthalic acid S-based polymer, a polyamine-based polymer, a polyester amide-based polymer, propylene, a polymer, A cellulose polymer, a polylactic acid polymer, a stupid oxygen polymer or the like. The above-mentioned binder polymer can be used singly or as a mixture of the above-mentioned types, and the photocurable thermosetting resin composition of the present invention can be used for the purpose of improving flexibility, brittleness of a cured product, and the like. Elastomer. 2. A polyester elastomer, a polyurethane elastomer, a polyester 2-base phthalate elastomer, a polyamide-based elastomer, a polyester amide-based elastomeric acrylic elastomer, or the like can be used. These elastomers may be used singly or as a mixture of two or more. In addition, the photocurable thermosetting resin composition of the present invention is adjusted by the synthesis or composition of the carboxyl group-containing resin (A), or used for the viscosity adjustment of the coated substrate or the carrier film. An organic solvent can be used.方面 The organic solvent may, for example, be a ketone or an aromatic hydrocarbon, or a phthalic acid, an alcohol, an aliphatic tobacco or a fluorene. A more succinct 'can be exemplified by methyl ethyl ketone, cyclohexyl ketone, etc., aromatic hydrocarbons such as mono-toluene, tetramethylbenzene, etc.; 赛珞苏〇s〇ive, methyl 赛苏苏, butyl race珞Su, carbitol, methyl carbitol: butyl carbitol, propylene glycol monomethyl ketone, dipropylene glycol monomethyl: dipropylene ether, triethylene glycol monoethyl ether, etc. Ethyl esters such as esters, ethyl sulphide, propylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol acetate, propylene glycol butyl acetate, etc.; alcohols such as ethanol and diol; Aliphatic hydrocarbons such as octane and decane; ^ 1丨 油 oil naphtha), hydrogenated petroleum brain, solvent oil, etc. Such an organic solvent may be used singly or as a mixture of two or more. In general, when a large amount of a polymer material starts to oxidize, it undergoes oxidative degradation in a chain, and the function of the polymer material is lowered. Therefore, in the photocurable thermosetting resin composition of the present invention, In order to prevent oxidation, a U radical scavenger may be added to invalidate the radicals which have been generated and/or (2) an antioxidant such as a peroxide decomposer (κ_2) (Κ) The agent (κ_2) decomposes the peroxide which has been produced into a harmless substance, and does not generate new radicals. Especially in the composition of the butadiene-based elastomer used in the present invention, an antioxidant (κ) is used. When the PCT resistance is improved and the peeling or discoloration at the time of HAST is small, it is extremely effective. In the case of the antioxidant (K-1) which acts as a radical scavenger, the specific compound may, for example, be hydroquinone or 4- to tertiary. Butyl catechol, 2-tertiary butyl hydroquinone, hydrogen pro-monomethylhydrazine, 2,6-di-tributyl-pair, 2,2-methylene-bis(4-mercapto- 6-tertiary butyl phenol), 1,1,3-cis (2-mercapto-4-hydroxy-5-tributylphenyl)butane, 1,3, 5-trimium _2, 4, 6-parade (3, 5-ditributyl-4-hydroxybenzyl) benzene, 1,3, 5-paran (3,5,2-di-tert-butyl-4_benzyl Base)-S-III. Qin 2, 4, 6-(1Η, 3Η, 5Η) triketones, etc., phenolic compounds such as phenolic, formazan, benzoquinone, etc., double (2, 2, 6, 6- Amino compound such as tetramethyl-4-piperidinyl)-sebacate, thiophene 34 201102405 (Phenothiazine), etc. Free radical scavenger (K-1) can be commercially available , for example, Adecastab AO-30, Adecastab AO-330, Adecastab AO-20, Adecastab LA-77, Adecastab LA-57, Adecastab LA-67, Adecastab LA-68, Adecastab LA-87 (above, ADEKA, Trade name), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (manufactured by Ciba Japan K.K., trade name), etc. As the antioxidant (K-2) of the agent, a specific compound may be exemplified by a filling compound such as triphenylphosphite, tetralauryl thiopropionate, tetralauryl thiodipropionate or lauric acid dilaurate. Ester, two Aliphatic acyl 3, 3'-thiodipropionate, etc. The sulfur-based compound. The peroxide decomposing agent (K-2) may also be a commercially available one, and may, for example, be exemplified by

Adecastab TPP (product name, manufactured by ADEKA Co., Ltd.), Mark AO-412S (product name manufactured by ADEKA Co., Ltd.), sumiHzer_Tps (manufactured by Sumitomo Chemical Co., Ltd., trade name), and the like. The antioxidant (K) may be used alone or in combination of two or more. In addition, in general, the photocurable thermosetting resin composition of the present invention is prepared by decomposing and degrading light, and the photocurable thermosetting resin composition of the present invention is prepared in addition to the antioxidant (κ) in order to stabilize the ultraviolet rays. In addition, an ultraviolet absorber (L) can be used. The ultraviolet absorber (L) may, for example, be a benzophenone derivative benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative or a cinnamate derivative. An anthracene benzoate derivative, a dimethane decane derivative or the like. Specific examples of the benzophenone derivative may, for example, be 28-benzyloxybenzophenone, 2-carbyl-4-n-butylbenzoic acid, 2,2,-dipyrimyl-4-a Mercaptobenzophenone and 2,4-dihydroxydiphenylhydrazine. Specific examples of the benzoic acid vinegar derivative may be exemplified by 35 201102405 2-ethylhexyl salicylate, phenyl salicylate, salicylic acid to tert-butyl phenyl ester, 2, 4- 2 3 Butylphenyl-3,5-ditributyl-4-hydroxybenzoate and hexadecyl-3,5-ditributyl-4-acetate. Specific examples of the benzotriazine derivative include 2-(2'-hydroxy-5'-tertiary butylphenyl)benzotriazole and 2-(2'-radio-5'-oxime. Benzophenyl)benzotriazine, 2-(2,-trans-yl-3'-tertiary butyl-5'-mercaptophenyl)-5-chlorobenzotrix, 2-(2'- Benzyl-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-nonylphenyl)benzotriazole and 2-(2 '-Hydroxy-3', 5'-ditripentylpentyl)benzotriazole and the like. Specific examples of the triazine derivative may be exemplified by benzotrizene, bisethylhexyloxy oxyphenyl triterpene or the like. The ultraviolet absorber (L) aspect can be a commercially available one, and for example, for example,

TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, Ciba Japan K.K., trade name) . The ultraviolet ray absorbing agent (L) may be used alone or in combination of two or more. When used in combination with the antioxidant (K), the molded article obtained by the photocurable thermosetting resin composition of the present invention can be stabilized. Chemical. In the photocurable thermosetting resin composition of the present invention, in order to improve interlayer adhesion, adhesion, or adhesion between the photosensitive resin layer and the substrate, a clindy adhesive can be used. Specific examples include, for example, benzimidazole, benzoxazole, benzothiazole, 2-hydrothiobenzimidazole, 2-hydrothiobenzoxazole, 2-hydrogenthiobenzoxazole, and the like. Kawaguchi Chemical Industry Co., Ltd. Accel M), 3_昧琳methylphenyl-oxazolone foot (10), 5-amino group _3_昧琳methyl-carbazole 1 sulfur = 2-hydrogenthio Antimony bismuth, tris, tetras, benzotriazine, slow benzobisoxazole, amino-containing benzotriazole, decane coupling agent, and the like. Further, in the photocurable thermosetting resin composition of the present invention, a touch modifier such as pulverized silica, bentonite (Bent〇nit=), smectite or hydrotalcite may be added as needed. . As a time-changing agent, the time-stabilization stability is preferably Bentonite or hydrotalcite 36 201102405 (hydrotalcite). In particular, hydrotalcite has excellent electrical properties. Further, a thermal polymerization inhibitor, a silicone, a fluorine-based or a polymer-based foaming agent and/or a leveling agent, an imidazole-based, a thiazole-based or a triazole-based decane coupling agent may be mixed. Further, a rust removing agent may be used, and a conventionally used additive such as a bisphenol-based or triazine thiol-based anti-two oxidizing agent (copper inhibitor) may be mixed. The thermal polymerization inhibitor can be used to prevent thermal polymerization or time-varying polymerization of the polymerizable compound. The thermal polymerization inhibitor may, for example, be 4-oxophenol, hydrogen, calcined or aryl substituted brewing, tertiary butyl catechin, gallnut, 2-pass _, 4-oxo Copper-2-hydroxydiphenyl, copper (I) (copper (I) chloride), Phenothiazine, chlorine gas, naphthylamine, β-naphthene, 2, 6-two Tertiary butyl-4-indole, 2, 2,-arylene di(4·fluorenyl-6-tertiary butyl phenol), pyridine, nitrobenzene, dinitro'benzene, picric acid ), 4-nonylaniline, methylene blue, copper and organic chelating agent reactants, decyl salicylate, and phenothiazine, nitroso compounds, nitroso compounds and aluminum chelation. The photocurable thermosetting resin composition of the present invention is, for example, adjusted in viscosity to be suitable for coating by the organic solvent, by a dip coating method, a flow coating method, a coating method, or a rod coating method. A method such as a screen printing method or a curtain coating method is applied to a substrate. Next, the organic solvent contained in the composition is subjected to volatilization drying (temporary drying) at a temperature of about 60 to 1 Torr (i.e., to form a coating film which is tackless). Thereafter, by contact type (or non-contact mode) through the mask that has been patterned, exposed by selective active energy lines' or direct pattern exposure by laser direct exposure machine, the unexposed part of the empirical aqueous solution (such as 0.3 ~3% 3% carbonate aqueous solution) is developed to form a photoresist pattern. Further, when the composition containing the thermosetting component (E) is contained, for example, by heating to about 14 〇 to 180 C The temperature is thermally hardened, and the enemy group containing the fluorene-based resin (A) is reacted with a thermosetting j-forming component (E) having two or more cyclic ether groups and/or cyclic thioether groups in the molecule, that is, A cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed. In addition, even if it is $37 201102405 light 2::, it is a thermal radical polymerization at the time of exposure. , increased by 20%: the heart is heat treated (thermal hardening). • Use can also be flexible == external = ί = printed wiring board or glass cloth - epoxy La, glass epoxy f grease, grease, glass cloth / paper - epoxy resin, synthetic fiber cloth is not t fiber cloth - Private oxygen tree ^ grease. Poly (10) - material purpose, make = gas, etc.) Copper (copper brain) laminate, Juyue ^ ^ (^4 glass substrate, ceramic substrate, wafer board, etc..溥 、 , , , , , , , , , , , , , , , , , , ί 本 ί ί ί ί 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Spray one g) of the light). The coating film is an exposure machine for hardening the exposed portion (directly irradiated by the "heart" line of the active energy line), and a direct drawing device can be used (for example, a laser from a computer to directly scan a laser surface of a 4D surface) Direct imaging, equipped with a metal machine, an exposure machine equipped with a (super) high-pressure mercury lamp, a direct-drawing device equipped with a water === exposure machine, or an ultraviolet lamp such as a (super) high-pressure mercury lamp. In terms of the energy line, any one of a gas laser and a solid laser may be used as long as it can use a laser beam having a maximum wavelength in the range of 35 〇 to 410 nm. Further, the exposure amount varies depending on the film thickness, etc., but generally Preferably, it is in the range of 5 to 200 mJ/cm 2 , preferably 5 to 1 μm/cm 2 , more preferably 5 to 50 mJ/cm 2 . For the direct drawing device, for example, 38 201102405 can be used by Orbotech, Japan. , pentay gossip, ^, clothing remax company, etc., as long as it can be carried out = long 350 ~ 41 〇 nm laser light oscillating device can be used any device. = can use the dipping method, washing method, Spray method, brush ^ method special 'in the shirt 'A hydroxide solution, sodium hydroxide, carbon, sodium, potassium carbonate, sodium phosphate, sodium citrate, ammonia, or an amine solution can be used. The photocurable thermosetting resin composition of the present invention is Ϊ = other than the Γϊ method In the case where the photocurable thermosetting resin composition of the present invention is used as a dry film, the film is bonded to the film and dried to form a solder resist layer. A structure having a structure in which a carrier film, a solder resist layer, and a peelable cover film which can be used in accordance with the order are laminated. i-resistance light-curing thermosetting resin composition coating = drying The layer is formed by forming a solder resist layer on the cover film, and laminating the film on the film or forming a solder resist layer on the heat layer 2 to 15. The thickness of the layer of the polyester film is developed. Sex photohardenability

= 曰汲 (4) knife coater, Libian coater (lipeQ machine (C〇mmac〇ater), film coater, etc., coated on a carrier film or cover film with 1〇~ = two cloth, and dried In terms of shape/dimension uniform film, although a polyethylene film can be used, it is preferable to use a dry film to make a _cover film on the printed wiring board, and to superimpose the photoresist layer. It is formed on the substrate of the solder resist layer by using a laminator or the like, and is formed on the substrate of the solder resist layer. Only for exposure and development of the film is formed; 39 201102405 , hardening by heat, can form a hard film, can be peeled off before or after exposure. 纟 film. Carrier 溥 [Examples] Illustrative examples and comparative examples According to the present invention - the first is not limited In the following examples: "Minutes" and "%" are indicated, unless otherwise notified, all of them are referred to in Synthesis Example 1 and filled with o-cresol novolak-type epoxy resin (DIC (N-695, softening temperature) 95. (:, epoxy equivalent 214, ^ P 7.6) 1070 g (epoxypropyl number (total number of aromatic rings): 5 〇 $ 琴. Material) And Hydrogen L5...Ethylene glycol monol ethyl ether) ether = 600g, heated to 100 C and disturbed 'to be uniformly dissolved. Also, charged with 4.3 g of diphenyl scales, heated to 110 C, and reacted for 2 hours, then heated to The reaction was carried out for 12 hours at 120 ° C. 4i5g of aromatic hydrocarbons (s〇ivess〇i5〇) and 456.0g of tetrahydrouric anhydride (3.0 moles) were added to the obtained reaction liquid, and 4 was carried out at 11 °c. The hourly reaction 'after cooling' was obtained as a resin solution having a solid acid value of 89 mgKOH/g and a solid content of 65°/❶. Hereinafter, this is called varnish A-1. Synthesis Example 2 Incorporation of a nonylphenol novolak type epoxy resin (Nippon) Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent 220) 2200 parts, 134 parts of dihydroxypropionic acid, 648.5 parts of acrylic acid, 4.6 parts of methylhydroquinone, carbitol acetic acid 1131 parts of ester and 484.9 parts of solvent oil, heated to 90 ° C and stirred to dissolve the reaction mixture. Further, the reaction solution was cooled to 60 ° C. [13.8 parts of triphenylphosphine was charged and heated to 1 (8) ° C to make the reaction about 32. In an hour, a reactant having an acid value of 0.5 mgKOH/g was obtained. Further, 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate, and 58.8 parts of solvent oil were added thereto. The mixture was heated to 95 ° C for about 6 hours, and cooled to obtain a resin solution containing a carboxyl group-containing photosensitive resin having a solid acid value of 40 mg KOH/g and a non-201102405 volatile component of 65%. Hereinafter, this is called varnish A-2. Example 3 400 parts of bisphenol F-type solid epoxy resin having an epoxy equivalent of 800 and a softening temperature of 79 ° C was dissolved in 925 parts of epichlorohydrin and 462.5 parts of dimethyl hydrazine, and then mixed at 703⁄4 by 1 〇〇. 81.2 parts of 98.5% NaOH was added in minutes. After the addition, the reaction was carried out at 70 ° C for 3 hours. Further, most of the unreacted epichlorohydrin and disulfoxide are distilled off under reduced pressure, and a reaction product containing a by-produced salt and dimethyl sulfite is dissolved in 750 parts of methyl isobutyl ketone, and further 10 parts of 30% NaOH was added and reacted at 70 ° C for 1 hour. After the reaction was completed, it was washed twice with 200 parts of water. After the separation of the oil and water, the sulfhydryl isobutyl ketone was distilled and recovered by an oil layer to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 29 Å and a softening temperature of 62 °C. 2900 parts (10 equivalents) of the obtained epoxy resin (a_1), 720 parts (1 〇 equivalent) of acrylic acid, 2.8 parts of methylhydroquinone, 195 parts of carbitol acetate, and heated to 90 ° C, stirred , dissolve the reaction mixture. Further, the reaction liquid was cooled to 60 ° C, and 16.7 parts of triphenylphosphine was charged, and the mixture was heated to 100 ° C to carry out a reaction for about 32 hours to obtain a reaction product having an acid value of 1. 〇 mg K 〇 H / g. Further, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were charged here, and the mixture was heated to 95 ° C, and reacted for about 6 hours to obtain a solid acid value of 100 mgKOH/g and a solid content of 65%. Resin solution. The following 'this is called varnish A-3. Synthesis Example 4 A vacuum cleaner type cresol resin (product name "Shonol CRG951", OH equivalent: 119.4) Li9.4g, 1.19 g of potassium hydroxide, and 119.4 g of toluene were substituted with nitrogen while stirring, and heated to increase the temperature. Further, 63.8 g of propylene oxide was gradually dropped, and the reaction was carried out for 16 hours at i25 to 132 ° C and 〇 to 4.8 kg/cm 2 . After that, it was cooled to room temperature, 201102405 Adding force: 89% of the acid acid L56g in the reaction solution, and mixing, neutralizing potassium hydroxide, obtaining a volatile component of 62%, a hydroxyl group i82 2g / equivalent of novolac type resin A propylene oxide reaction solution. This is 1 equivalent per phenolic hydroxyl group, and the average alkylene oxide is added to .08 moles. Further, 'the obtained alkylene oxide type phenolic resin alkylene oxide reaction solution 293.0^, 43 2g of acrylic acid, sulfonate sulfonate u 53g, methylhydroquinone 7 and benzene 252.9g were charged with a mixer, a thermometer and air. The reactor which was blown into the tube was blown with air at a rate of 10 ml/min, and stirred at 11 (rc for 12 hours. Water formed by the reaction, as azeotrope with toluene, '12.6 g of water). The mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35 35 g of a +15% aqueous sodium hydroxide solution, followed by washing with water. Thereafter, the toluene was replaced with 1,181 g of diethylene glycol monoethyl ether acetate in an evaporator while removing the toluene. 'Acquired acid varnish type acrylate resin solution. Further, 332 5 g of the obtained varnish type acrylate resin solution and 122 g of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer and an air blowing tube at 1 〇 ml/ At a sub-speed, air was blown, and 60.8 g of tetrahydrophthalic anhydride was gradually added thereto while stirring, and reacted at 95 to 1 〇 rc for 6 hours to obtain an acid value of 88 mg K〇H/g of a solid matter and 71% of a nonvolatile component. Resin solution of carboxyl photosensitive resin Hereinafter, this is called varnish A-4. Synthesis Example 5, a polycaprolactone diol in which a polymer polyol is charged in a 5 liter separable flask equipped with a thermometer, a stirrer, and a circulation cooler (Daicd Chemical Industry Co., Ltd.) Production of PLACEL 208, molecular weight 830) 1,245 g, dihydroxyl-propionic acid having a carboxyl group, dimethylglycolic acid 2 〇 ig, polyisocyanate isophorone diisocyanate 777 g, and hydroxyl group (fluorenyl) acrylic acid The ester of 2-hydroxyethyl acrylate vinegar 119g' is further charged with p-methoxyphenol and di-tert-butyl hydroxytoluene. 5g, heated to 6 搅拌 while stirring and stopped, and added dibutyl laurate Tin salt 0.8g. If the temperature in the reaction vessel begins to decrease, reheating 'continuously stirring at 80 ° C, confirming the absorption spectrum (2280 cm -1 ) of the isocyanate group 42 201102405 by infrared absorption spectrum to complete the reaction, and obtain a viscous liquid A urethane acrylate compound, adjusted to a nonvolatile content = 50% by mass using carbitol acetate, and an amino acid decanoic acid having a carboxyl group value of 47 mg KOH/g and a nonvolatile content of 50%. Ester A resin solution of an acrylate compound. Hereinafter, this is called varnish A-5. Synthesis Example 6 A 2-liter separable flask equipped with a scrambler, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and a solvent added thereto Ethylene glycol dimethyl sulfonate 9 〇〇g, and a polymerization initiator of tertiary butyl peroxy 2-ethylhexanoate (trade name: Nippon Oil Co., Ltd. 'trade name; over butyl 0) 21.4g 'and heated To 90 ° C. After heating, add 309.9 g of methacrylic acid, 4 16 g of isopropyl methacrylate i16, and modified by 2-carboethyl propyl citrate (Piaxei FM1 : Daicel Chemical Industry Co., Ltd.) (manufactured by the company), 〇 9.8 g, and bis (4-tributylcyclohexyl) peroxydicarbonate (manufactured by Oyster Sauce Co., Ltd., trade name TCP) 21.4 g The mixture was diluted for 3 hours, and then the resin containing the ruthenium-based copolymer was obtained by aging for 6 hours. Further, the reaction was carried out under a nitrogen atmosphere. Further, in the buffer-containing copolymer resin to be added, acrylic acid 3, 'epoxycyclohexyl hydrazine vinegar (manufactured by Daicel Chemical Industry Co., Ltd., trade name: ^^ A^0) 363.9 g, and open-loop catalyst were added. 36 g of amine and 36 g of the polymerization inhibitor were heated to 1 Torr (rc, and stirred to carry out an epoxy group to open m: after 16 *, a solid acid i 108.9 mg KOH / g, weight average molecular weight 25, _, fat solution. Hereinafter, this is called varnish A-6. Tree reference example using the resin solution obtained in each of the above synthesis examples, fish composition. Root (four) A "===== 43 201102405 The flask was burned and treated with ion chromatography to quantify the amount of the compound (the total of chlorine and bromine). The results are shown in Table 1. 3 Å [Table 1] Composition (parts by mass) Reference data

Varnish A-6 185 photopolymerization initiator ethyl ketone, 1-[9-ethyl-6-(2-toluamyl)-9H-indazol-3-yl]-1,1-(0-acetamidine肟) (Irgacure OXE 02 : Ciba Japan Κ·Κ.) Vinyl elastomer pole Β 3 6 0 0 (Daicel Chemical Industry Co., Ltd.) Hydrogen thiol compound Accel M (Kawaguchi Chemical Industry Co., Ltd.) Halogen content (ppm) 20 20 20 20 20 20 0.1 0.1 0.1 0.1 0-1 0.1 261 304 338 12 25 21 From the results shown in Table 1, it is apparent that the surface acid resin oxyresin as a starting material Photocurable thermosetting resin composition (see ==, 4 == 44 201102405 ί = data 1, reference data 2, reference examples 1 to 13 and comparative examples 1 to 3 using the above-mentioned resin solution, When it is mixed with the following (Table 2), it is mixed with the mixture, and after mixing by the mixer, it is kneaded, and the photosensitive resin composition for soldering photoresist is prepared. The dispersity of the photosensitive resin composition is evaluated by the measurement of the particle size of the grind meter, for example, the following coat is _____ [Table 2] The varnish photopolymerization initiator is hot and hard. Chemical composition 1 Γ Example: part) 1 2 3 4 5 6 7 8 9 10 A-1 A-2 A-3 A-4 141 141 141 141 141 141 141 141 141 85 A-5 - 80 A-6 (B- 1Γ 15 (B- 2)*2 1 (B- 3Γ 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (E- I)*4 15 (E- 2)*5 15 15 15 15 15 15 15 10 15 15 Comparative Example 12 62 92 1.5 15 13 77 77 1.5 15 2 77 77 154 141 1.0 20 20 5 1.0 1.0 20 20 20 45 201102405

Poly bd*6 20 PB3600*7 25 25 25 25 25 25 25 25 25 25 25 25 25 Accel M*8 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Karenz MTBD1*9 1.0 Zisnet DB”0 1.0 Karenz MTIMRI*1 1 1.0 Zisnet F*12 0.2 Karenz ΜΤΡΕΓ13 1.0 Benzoquinone Avianamine 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 Melamine 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 Colorant (Η -1)"4 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Colorant (Η-2)" 5 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.1 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 0.1 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 0.1 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 85 85 85 85 DHT-4A” 8 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Polyoxane defoamer 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Organic solvent 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 46 201102405 *19 DPHA·20 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 TPA-B80 E*21 17 Mw-IOOL M*22 10 10 47 201102405 Remark *1 : 2-methyl-1-(4- Methylthiophenyl)-2-mercaptopropan-1-one (Irgacure 907: manufactured by Ciba Japan KK) *2 : 2,4-diethyl 9-oxosulfide dOj dJ (KAYACURE DETX-S Nippon Kayaku Co) Ltd.) *3: Ethylketone, 1-[9-ethyl-6-(2-toluamyl)-9H-indazol-3-yl]-1,1-(0-acetamidine) (Irgacure OXE 02 : manufactured by Qba Japan KK) *4 : Phenolic novolak type epoxy resin (RE306CA90: manufactured by NipponKayaku Co., Ltd.) *5 : Dixylenol type epoxy resin (γχ-4000: Sakamoto Epoxy Co., Ltd. *6: Hydroxyl-terminated liquid polybutadiene (manufactured by Idemitsu Kosan Co., Ltd.) *7 : Epoxidized polybutadiene (Daicel Chemical Industry Co., Ltd.) *8 : 2_Hydrogen thiophene thiophene (made by Kawaguchi Chemical Industry Co., Ltd.) *9 : 1,4_bis(3-hydrothiobutane oxy)butane (made by Showa Denko Co., Ltd.) * 10 . 2 -Dibutylamino-4,6-dihydrothio-s-triazine (manufactured by Sankyo Chemical Co., Ltd.) : U5-parameter (domain thiobutoxy b' & 1,3,5-three 2, 4, 6 (m 3H (Showa Denko Co., Ltd.) ' *12 : 2,4,6-trihydrothio-s-triazine (manufactured by Sankyo Chemicals Co., Ltd.) *13 : Neopentyl alcohol oxime (3-hydrogen) Sulfuric acid vinegar) (Showa Denko Co., Ltd. *14: CI·Pigment Blue 15:3 *15 : CI Pigment Yellow 147 *16. Antioxidant (Qba Japan KK) *17 : B·30 (琢Chemical Company) (Stock) system *18: Hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd.) *19: Diethylene glycol monoethyl ether acetate *20: Dipentaerythritol hexaacrylate *21 · Isocyanate ( Asahi Kasei Chemicals Co., Ltd.) 22. Mercapylated melamine resin (Sanwa Chemical Co., Ltd., ------ Performance evaluation: &lt;Optimum exposure> 48 201102405 Copper thickness 18μπι The circuit pattern substrate was subjected to roughening treatment on a copper surface (Mec H bond CZ-8100 manufactured by Mec Co., Ltd.), and after water washing and drying, the photohardening of the examples and the comparative examples was comprehensively applied by screen printing. The thermosetting resin composition was dried in a hot air circulating drying oven at 8 Torr for 60 minutes. After drying, using an exposure apparatus equipped with a high-pressure mercury lamp, exposure was carried out via a stage exposure meter (Kodak No. 2), and development (3〇〇c, 0.2 MPa, lwtG/〇 sodium carbonate aqueous solution) was carried out for 60 seconds, and the remaining stage was The pattern of the exposure meter is 7 segments as the optimum exposure amount. &lt;Developability&gt; The photocurable thermosetting resin composition of the examples and the comparative examples was applied to a copper clad substrate by a screen printing method so that the film thickness after drying became It was dried at about 80 μm in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, development was carried out by an aqueous solution of iwt% sodium carbonate, and the time until the dried coating film was removed was measured by a horse. <maximum developing life> The composition of the examples and the comparative examples was completely coated by screen printing on the copper foil substrate formed at 8 Å. Dry the crucible and take out the substrate from 10 minutes to 80 minutes at 10 minutes, and let it cool to room temperature. 30 was placed on the substrate under the conditions of a squirting pressure of 2 MPa. (: lwt% sodium carbonate aqueous solution was developed for 6 sec seconds, so that the maximum allowable drying time without residue remained as the maximum development cycle. &lt;stickiness (^〇1(:)&gt; The composition of the examples and the comparative examples was completely coated on the copper foil substrate formed by the pattern, and dried by a hot air circulating method of TC for 30 minutes, and allowed to cool to room temperature. The negative film of PET was coated on the substrate. ^ The HMW-GW20 manufactured by ORC Co., Ltd. was pressed under a reduced pressure of 1 minute, and then the adhesive of the film was evaluated when the negative film was peeled off by the following criteria. 〇: When the film was peeled off, there was no resistance at all, and the film was coated. No trace residue 49 201102405 There is resistance, there are some traces on the film. When there is resistance in the film _4 film, there are obvious traces on the film. Characteristic test: The composition of the example and the comparative example is applied to the pen On the substrate, dry at 3G °C at 8G °C, and let it cool to room temperature. Use an exposure device equipped with a high-pressure mercury lamp to make the welding resistance (4) light at the optimum exposure, and make it under the pressure of UMPa. Exposure to lwt/〇 carbon k sodium aqueous solution for development for 9 sec seconds to obtain a photoresist pattern. Under the conditions of an exposure amount of 1000 mJ/cm 2 , the substrate was subjected to ultraviolet irradiation using a uv conveyor furnace, and then heated at 16 (rc) for 60 minutes. The obtained printed substrate (evaluation substrate) was as follows. (Jia's characteristic., &lt;acid resistance&gt; The substrate was immersed in a 10 vol% H2SO4 aqueous solution at room temperature for 30 minutes at room temperature to visually confirm infiltration or coating elution (elute), further confirming the band Peeling due to peeling. 〇: Unrecognized change Δ: only some changes X: swelling or swelling on the coating film &lt;figurability&gt; The evaluation substrate was immersed in a 10 vol% NaOH aqueous solution at room temperature for 30 minutes to visually observe Confirm the penetration of the permeation or coating, and confirm the peeling due to peeling. 〇: Confirm no change △: only some changes x: expansion or expansion on the coating film 50 201102405 &lt;solder heat resistance&gt; The evaluation substrate of the rosin flux was previously immersed in a solder bath set at 260 ° C, and the flux was washed with a modified alcohol, and then evaluated by visual expansion and peeling of the photoresist layer. The criteria for determination were as follows. 〇: Even 1 0 second immersion repeated three times or more and no peeling was confirmed. △: When 10 seconds of immersion was repeated three times or more, there was some peeling. x : 10 seconds of immersion within three times, the photoresist layer was expanded and peeled off. Golding> Using a commercially available electroless nickel bath and an electroless gold bath, plating was carried out under conditions of nickel 5 μm and gold 0.05 μm, and peeling of the photoresist layer was evaluated by tape peeling or After the penetration of the plating, the peeling of the photoresist layer was evaluated by strip peeling. The criteria for determination are as follows. ◎: No penetration or peeling was observed. 〇 : Some penetration after plating was confirmed, but there was no peeling after the tape was peeled off. △: A slight penetration after plating was observed, and peeling was also observed after the tape was peeled off. X: Peeling after plating. &lt;PCT resistance&gt;

The evaluation substrate on which the solder resist cured film was formed was treated at 240 ° C, saturated, 〇. 2 MPa for 240 hours using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by Espec Co., Ltd.). After the state of the coating film, the peeling was evaluated by peeling off the tape. The judgment base is as follows. ◎: No swelling, peeling, discoloration, or dissolution were observed, and peeling could not be completely confirmed even if the tape was peeled off. 〇: Although there is no swelling, peeling, discoloration, or dissolution, some peeling can be confirmed by stripping. 51 201102405 △: There are some swelling, peeling, discoloration, and dissolution, and peeling can be confirmed by peeling off the tape. X. Most swelling, peeling, discoloration, and dissolution were observed, and even peeling was confirmed even if the tape was peeled off. &lt;Cold and Thermal Shock Resistance&gt; A § parity substrate having a solder resist film formed by removing the □ and removing the 〇 pattern was produced. The obtained evaluation substrate was subjected to a heat-shock tester (manufactured by ETAC Co., Ltd.) at -55 〇C/30 minutes to 15 (TC/30 minutes as a cycle for a 1 〇〇〇 cycle resistance test. After the test The cured film after the treatment was visually observed to determine the occurrence of cracks on the basis of the following criteria: 0: The crack occurrence rate was less than 30% Δ: The crack occurrence rate was 30 to 50% x: The crack occurrence rate was 50% or more &lt; HAST Characteristics &gt; A solder resist cured film was formed on a BT substrate on which a comb-type electrode (line/space = 30 μm / 30 μm) was formed, and an evaluation substrate was produced. The evaluation substrate was placed in a 13 Å, The high-temperature and high-humidity tank at a humidity of 85% was subjected to a HAST test with a voltage of 5 V and 168 hours. The insulation resistance value of the tank after 168 hours was evaluated according to the following criteria. ◎ : 108 Ω or more ° : 107 ~108Ω △ ·· 1〇6 ～107ω χ: ι〇6ω or less [Table 3] Characteristics "Example Comparative Example 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 Optimum exposure 400 150 150 170 150 170 150 150 150 140 140 160 130 180 180 130 52 201102405

Light quantity (mJ/cm2) Developability (seconds) 32 34 33 35 32 35 33 34 32 32 31 33 40 32 35 45 Maximum development cycle (minutes) 60 60 60 50 60 50 60 60 60 60 60 60 50 60 60 40 Sticky Δ Δ △ △ Δ Δ Δ Δ Δ Δ Δ 〇 Δ △ 〇〇 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 acid 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 testability 〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇 Solder heat resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 resistance to no bond gold 〇 ◎ ◎ ◎ ◎ ◎ ◎ 〇〇〇〇〇〇〇〇〇 PCT resistance 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇〇 〇〇〇 XX resistance to thermal shock 〇〇〇〇〇〇〇〇〇〇〇〇〇 X Δ 〇 HAST characteristics ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ Δ Δ ◎ XX Implementation Examples 14 to 25 and Comparative Examples 4 to 6 Each of the compositions of Examples 2 to 13 and Comparative Examples 1, 2 and 3 prepared by mixing ratios shown in Table 2 was diluted with methyl ethyl ketone and applied onto a PET film. Dry at 80 ° C for 30 minutes to form a photosensitive film with a thickness of 20 μm The resin composition layer. Further, a cover film was bonded thereto, and a dry film was formed, and each of them was used as Examples 14 to 25 and Comparative Examples 4 to 6. &lt;Dry film evaluation&gt; 53 201102405 The film of the film of the film obtained from the above-mentioned method is made to be toughened with a film, and the film of the pattern film is evaluated. The body was thinned using this example and exposed under the same conditions. After exposure, the stripping load to m^U^TyilL 3〇〇C^ lwt〇/〇^s^ cumulative exposure is also 1 Λ: ~ get the photoresist pattern. After the uv conveyor belt is fired, it is. Under the conditions of mJ/cm2, the substrate was subjected to ultraviolet irradiation test 2 丨 6 〇 (: heating was performed for 60 minutes and hardened. The respective test methods and evaluation methods were carried out according to the obtained cured film 枰 #暴板'. Dry {bei or 殓. The results are shown in Table 4.

Sexual Examples Comparative Example 14 15 16 17 18 19 20 21 22 23 24 25 4 5 6 .150 150 170 150 170 150 150 150 140 140 150 130 180 180 130 36 35 38 35 37 35 37 35 36 34 37 43 35 37 49 〇0 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇f 〇〇〇〇〇〇〇0 〇〇〇〇〇〇〇:@ ◎ ◎ ◎ ◎ ◎ 〇〇〇〇〇〇〇〇〇 © © ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇〇 XX Γ 0 0 〇 0 〇〇〇〇〇〇〇〇 X Δ 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ △ Δ Δ XX XX 54 201102405 As apparent from the results shown in Tables 3 and 4, it is apparent that the photocurable thermosetting resin composition of the present invention is required to have a solder resist for a semiconductor package. It is extremely useful as a photocurable thermosetting resin composition because it is resistant to electroless gold plating, PCT resistance, thermal shock resistance, and HAST properties (electrical properties). 55

Claims (1)

201102405 VII. Patent application scope: 1. A photocurable thermosetting resin composition which can be developed by an aqueous alkaline solution, and is characterized by containing: a carboxyl group-containing resin (A), photopolymerization initiation y (B), and Vinyl elastomer (c), and thiol compound (9). The photocurable thermosetting resin composition according to the first aspect of the invention, wherein the monomer-containing resin (A) is used in an amount of 100 parts by mass, and the amount of the photopolymerization initiator (B) is 〇〇1 to 3 The blending amount of the vinyl-containing elastomer (C) is 5 to 60 parts by mass, and the amount of the hydrosulfide compound (D) is 0.01 to 10.0 parts by mass. The photocurable thermosetting resin composition according to claim 2, wherein the carboxyl group-containing resin (A) is mixed in an amount of from 20 to 60% by mass based on the composition. The photocurable thermosetting resin composition of claim 1 further comprising a thermosetting component (E) and a coloring agent. The photocurable thermosetting resin composition according to claim 1, wherein the terpene-containing resin (A) is not derived from an epoxy resin. The photocurable thermosetting resin composition of claim 1, wherein the acid-containing resin (A) has an acid value of from 4 〇 to 15 〇 mgKOH/g. The photocurable thermosetting resin composition of claim 1 wherein the weight-containing molecular weight of the base-containing resin (A) is 2,000 to 150,000 刀-knife... as in the first claim of the patent scope A photocurable thermosetting resin composition, wherein the photopolymerization initiator (B) is selected from the group consisting of an oxime ester photopolymerization initiator having the group represented by the following general formula (I) (B ^ has The α-aminoethyl ketone ketone polymerization initiator (Β2) of the group represented by the general formula (II); and the fluorenylphosphine-based photopolymerization initiator having the formula (πΐ) represented by the following formula (πΐ) (Β3) Photopolymerization initiator on one of the groups formed: ' 2. 3. 4. 5. 6. 8. 56 201102405 In the above, R1 represents a hydrogen atom; a phenyl group substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms; or a tooth atom; one substituted or unsubstituted with Shanghai soil and one or more intermediate groups in the alkyl chain; Oxygen shoulder or non-oxygen atomic hindrance number 1~2〇 of the alkyl group; carbon number $~丨 cycloalkyl; carbon number 2~20 alkane (alkan〇yl) group; or carbon #1~ a leuco group or a substituted or unsubstituted phenyl group: a stupid group substituted with a carbon number, a phenyl group or a heart = substituted, having more than one oxygen atom or having no more than one intermediate group or no intermediate group a -20 alkyl group of an oxygen atom; a cycloalkyl group having 5 to 8 carbon atoms; a decyl group having 2 to 2 carbon atoms; or a benzene substituted by a C 1 to 6 alkyl group or a phenyl group; Mercapto; 12 alkyl or depleted R3 and R4 represent each independently carbon number 1 ^ 炫; R5 and R6 represent an alkyl group independently of a hydrogen atom, or a cyclic alkyl ether group bonded with a diyl group; The linear chain R7 and R8 represent their respective carbon number 1, 57 201102405 branched chain alkyl, cyclohexyl, cyclopentyl, aryl, or self atom, alkyl or Alkoxy substituted aryl, wherein, R7 and 'of a foot 8 may represent R-C (= square) - group' and R is a group having the carbon Lu. i 9. 10. 11. 12. 13. 14. The photocurable thermosetting resin composition of claim 4, wherein the thermosetting component (E) has more than one molecule in one molecule A cyclic ether group and a cyclic thioether group, or two or more cyclic ether groups or cyclic thioether groups in one molecule/in total. 〃 Two kinds of dryness, characterized in that the resin composition layer of the dry film is applied to the film and dried by the photocurable thermosetting resin composition according to any one of the above claims 1 to 9. The winner. A cured product obtained by applying a photocurable thermosetting resin composition according to any one of claims 2 to 9 to a substrate and drying it to obtain a cured film. A cured product obtained by laminating a resin composition layer of a dry film of the first aspect of the patent application to a substrate and photocuring it is obtained. A printed wiring board having a cured film obtained by applying a photocurable thermosetting resin composition according to any one of claims 1 to 9 to a substrate and drying the film. The coating film is photohardened into a pattern by irradiation with an active energy ray, and then hardened by hydrazine. A printed wiring board having a cured film which is bonded to a substrate by a resin composition layer of a dry film according to claim 10 of the patent application, and is photohardened into a pattern by irradiation with an active energy ray. It is obtained by heat hardening. 58 201102405 IV. Designation of representative drawings: (1) The representative representative of the case is: (No). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: