TW201102754A - Photocurable thermosetting resin composition - Google Patents

Abstract

Disclosed is a photocurable thermosetting resin composition which is capable of forming a cured coating film having PCT resistance, HAST resistance, electroless gold plating resistance and thermal shock resistance, which are important to a solder resist for semiconductor packages. Also disclosed are a dry film and cured product of the photocurable thermosetting resin composition, and a printed wiring board wherein a cured coating film such as a solder resist is formed from one of the photocurable thermosetting resin composition, the dry film and the cured product. Specifically disclosed is a photocurable thermosetting resin composition which can be developed with an aqueous alkaline solution and contains a carboxyl group-containing resin (excluding carboxyl group-containing resins using an epoxy resin as a starting material), a photopolymerization initiator, and a functional group-containing elastomer. Preferably, the carboxyl group-containing resin contains no hydroxyl group, but additionally contains a photosensitive group. The functional group-containing elastomer is preferably a butadiene derivative.

Description

201102754 VI. Description of the Invention: [Technical Fields According to the Invention] The photohardenability of a film which can be developed by an aqueous alkaline solution is related to the composition of ultraviolet light exposure or laser exposure; [The prior art] and the use of such a hardened film to form a hardened film. [Previously used in a part of the printed wiring board for the people's livelihood and most of the solder resists used in the chapter's high precision, high density.吏(4) type 烊 photoresist, which is exposed to ultraviolet light, surface, and is finally processed by heat and/or light and hardened.

Hey.丄f ’ Due to environmental concerns, an alkaline aqueous solution is used as the L Ϊ main for the manufacture of actual printed wiring boards. On ί; Second print illusion? : Tr commission (electronic equipment) is light and thin, and it is high-density for the 庳 ^ 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线 线More questions. That is, compared to the conventional thermosetting type and solvent:

^Sexuality, etc.: Inability to test, water resistance T:, infiltration of liquid medicine, *, water vapor, etc., and to reduce the adhesion between the film and steel. As a result, it is necessary to be resistant to damp heat 3 201102754 1 i (pressure cooker test). However, the current situation is that alkaline solder resists can only last for several hours to about ten hours under such stringent conditions. In addition, in the HAST test (highly accelerated life test) in the state where the alkaline development type photo solder resist is applied under the humidification condition, it is confirmed that the migration is performed in a few hours in the case of the Big Eight (migrati〇n). The occurrence caused by the failure. Further, in recent years, with the shift in surface assembly and the concern about the ring, the use of lead-free antimony tin tends to be applied to the sealing degree, which is very high. Along with this, the temperature of the inside and the outside of the package becomes higher, and the conventional liquid photosensitive photoresist has a thermal shock and the coating film is cracked, or the substrate or the sealing material is peeled off. Improvement. On the one hand, 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. A report on a solder resist composition, which is composed of a photosensitive resin, a photopolymerization initiator, a diluent, and an epoxy compound, is disclosed in Japanese Laid-Open Patent Publication No. S61-243869 (Patent Document No.). The photosensitive resin is a reaction product of an acid anhydride = a novolac type epoxy compound and an unsaturated monobasic acid (m〇n〇 basic add). Japanese Patent Publication No. 3_25〇〇12 (Patent Document 2) discloses a solder resist composition composed of a photosensitive resin, a photopolymerization initiator, an organic solvent, or the like, which is attached to salicylaldehyde (Salicylic aldehyd). ^) A reaction product with a monovalent phenol, which is obtained by adding an (meth)acrylic acid to an epoxy resin obtained by the epoxy gas propane 1 to further react a polybasic carboxylic acid or an anhydride thereof. . However, the use of an enemy-based resin which is conventionally used in the solder resist composition has poor properties. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [Problem to be Solved by the Invention] The present invention has been made in view of the problems of the prior art described above, and its main object is to provide a photocurable thermosetting resin composition which can form a hardened film. The cured film has PCT resistance, HAST resistance, electroless gold plating resistance, and thermal shock resistance which are extremely important in soldering resistance for a semiconductor package. Further, an object of the present invention is to provide a dry film and a cured product which are excellent in the above-mentioned properties, which are obtained by using such a photocurable thermosetting resin composition, and a printed wiring board using the same A hard film such as a solder resist is formed by a dry film or a cured product. [Means for Solving the Problem] 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) (wherein The epoxy resin is a carboxyl group containing a starting material, a photopolymerization initiator (B), and a functional group-containing elastomer (c). It should be noted that the carboxyl group-containing resin (A) is preferably free from hydroxyl groups, and more preferably has saltiness. ^, the functional group-containing elastomer (c) is preferably a butadiene derivative. In a suitable aspect, the photocurable thermosetting resin composition of the present invention further contains a thermosetting component (D). It is preferable to further contain a photocurable thermosetting resin composition for a colorant photoresist. Further, according to the present invention, a dry film can be provided which is characterized in that the resin composition of the dry film is coated. == The invention can also provide a cured product which is applied to the substrate of the light hard boat. The heat-curable resin composition or the coating film may be obtained by laminating the resin composition of the dry film, preferably at a wavelength of 350 nm to 4 μm. The hardened material obtained by first hardening the image into a pattern is obtained. 201102754 m = Further, according to the present invention, a printed wiring board having a -minute L, the hardening film is composed of the photocurable thermosetting resin @ The coating film obtained on the soil material and dried, or the dry film by the active energy ΐ:: It is preferred that the direct line of the material line will be light-hardened into a sulphate:: wide? Further, the hardened wire board of the present invention may be obtained by bonding the resin composition layer of the dry film to the material and performing photohardening by irradiation with an energy ray, and then thermally hardening the film. The active energy ray is more than the [effect of the invention] ^ the photohardenable thermosetting tree of the invention The composition, because it is a component that can be used as a component of ϊ ϊ ϊ 1 ' 系 使用 使用 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂The combination of the ruthenium-containing resin (4) and the π 1 & elastomeric elastomer (C) can improve the softness of the hardened coating film, not only the crack resistance of the heat-resistant cycle, but also the adhesion of the heat-resistant cycle. The effect of the PCT resistance is obtained. Therefore, the curing can be formed by using the photocurable thermosetting resin composition ', which has the PCT resistance of the semiconductor body. HAST, resistance to electroless gold, cold and thermal shock resistance [Embodiment] This is a characteristic material of a photocurable thermosetting resin composition / 5 · A resin containing a certain amount of resin (A) The photopolymerization initiator (B) and the functional group-containing elastomer (c). In the case of the carboxyl group-containing resin which does not use an epoxy resin as a starting material, the conventionally known various contents include Carboxyl resins are used, especially 'with ethyl in the molecule The light-reducing resin containing a saturated double bond is preferred in terms of photocurability or development resistance. Further, the saturated double bond of the bath is preferably acrylic acid or mercapto (10) acid, and the wire is from the & raw 6 201102754 In order to use a slow-base resin which does not have an ethylenically unsaturated double bond, and to form a photocurable one, it is necessary to use a compound having one or more ethylenically unsaturated groups as described later (photosensitive) The specific compound used in the carboxyl group-containing resin of the present invention is preferably the following compound (may be either an oligomer or a polymer). S, sclerosing varnish type resin, condensate of this (10), naphthalene (tetra) _, dihydronaphthalene and Lai's shrinkage & matter and other compounds with two or more phenolic hydroxyl groups in the two molecules; A reaction product obtained by an epoxy-derived reaction such as oxime, reacts with an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid, and produces a reaction such that maleic anhydride or tetrahydrophthalic anhydride is obtained. , 丨, 2,4_benzene triphthalic anhydride, pyromellitic acid needle, adipic acid, etc. A carboxyl group-containing photosensitive resin obtained by the reaction of a meta-anhydride. (2) a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule; and a cyclic carbonate compound such as ethyl carbonate or propylene carbonate to react an unsaturated group-containing monocarboxylic acid 'The carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride. (3) 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 polyolefin-based polyalcohol, an acrylic polyalcohol, a bisphenol fluorene alkylene oxide adduct (diol), a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group ( The polyaddition reaction results in a terminal-containing urethane resin which is obtained by reacting an acid anhydride at the end of the amino phthalic acid. (4) 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 di-methylbutyric acid; a terminally (meth)-acrylated carboxyl group-containing urethane resin having a hydroxyl group and one or more (fluorenyl) propylene fluorenyl groups in a molecule such as a hydroxyl (meth) acrylate or the like . 201102754 (5) In the synthesis of a carboxycarbamate-containing resin resulting from the addition polymerization of a diisocyanate, a slow-group diol-containing compound, and a diol compound, 'addition of an isonic acid to isophora and triacrylate Equivalent molar reactants such as vinegar, etc. 'Carboxyamino phthalate resin having a terminal (meth) acrylated compound having one isocyanate group and one or more (meth) acrylonitrile groups in the molecule . (6) Copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid or an unsaturated group-containing compound such as styrene, α-mercaptostyrene, lower alkyl (fluorenyl) acrylate or isobutylene a carboxyl group-containing resin. # (7) A polyfunctional oxetane resin to be described later, which reacts a di-oroxic acid such as adipic acid, citric acid or hexahydro- succinic acid to a primary sulfhydryl group which has been produced, and is added with phthalic anhydride and tetrahydrogen. In a carboxyl group-containing polyester resin of a dibasic acid anhydride such as phthalic anhydride or hexahydrophthalic anhydride, a glycidyl (meth)acrylate or an α-mercapto-glycidyl (meth)acrylate is added, one molecule A carboxyl group-containing photosensitive resin having a compound having one epoxy group and one or more (meth) acrylonitrile groups. (8) A carboxyl group-containing photosensitive resin containing a compound having a cyclic ether group and a (fluorenyl) acryl group in one molecule in the carboxyl group-containing resin of the above (1) to (7). " Further, in this specification, acrylate means acrylate, acrylate and the collective term of these mixtures, and the same is true for the second. The containing resin (4)' used in the butterfly-like watch has a feature that the content of the south compound is very small because it does not use an epoxy resin. Ϊί = two bases j. Generally, it has excellent characteristics such as improved durability, but it is obvious that the density is higher than that of the general photoresist used in the tan. Hereinafter, the excellent deodorant wax of the money-based resin of the present invention, the phenolic novolak resin having an airless component can be contained in a % by weight. The partial substitution of the phenol resin modified by the alkylation oxide (alky 1 oxide) and the introduction of the acid anhydride can be obtained by the equivalent of 3〇〇~55〇,=40 in the double bond. A resin having a hydroxyl group in the range of ~120 mgKOH/g. On the one hand, the entire epoxy group of the resin synthesized from a similar phenolic novolak resin is acrylated, and when the acid anhydride is introduced into the whole: the acid value in the equivalent amount of 400 to 500 in the double bond is extremely large; It is also impossible to obtain a coating film having developability after light. Further, due to the acid value, the water resistance is poor, and the insulation reliability and the PCT resistance are remarkably lowered. It is also very difficult to completely eliminate the radicals by a similarly derived phenolic novolac type epoxy resin. The amino phthalate resin can also be used to The equivalent of the isocyanate group is uniform, and the resin containing no hydroxyl group can be easily synthesized. Preferably, it is an isocyanate compound which does not use phosgene as a starting material, and a carboxyl group-containing resin having a gas ion impurity amount of ～30 ppm which is not synthesized from a raw material of epihalohydrin is more preferably theoretically not contained. From the viewpoint of the tree in which the hydroxyl group is synthesized, the carboxyl group-containing resins (1) to (5) previously represented by specific examples can be particularly suitably used. Further, with respect to the carboxyl group-containing resin (6) obtained by copolymerization with an unsaturated group-containing compound as previously shown, a mercaptoacrylic acid having a cyclic ether group and a (methacryl fluorenyl compound) in one molecule is obtained. 3, 4-epoxycyclohexylmethyl gram-containing slow-acting photosensitive resin 'Because alicyclic epoxy group is used, chlorine is less than impurities, and it can be suitably used. 'On the one hand, it contains Wei-based resin. (6) 'The reaction of a mercaptopropionic acid epoxidizing compound having a cyclic bond group with a (fluorenyl) acryl fluorenyl group in one molecule, or a methyl propyl group containing an unsaturated group-containing compound The acid epoxime g will be considered to have a large amount of chloride ion impurities. In addition, when synthesizing a urethane carboxylic acid resin, a propylene glycol vinegar vinegar modified raw material may be used. Impurity infiltration can be used from the viewpoint of controlling the quality of chloride ions, etc. 'Lil 201102754 As described in the month of the U-containing resin (A) 'Because of the back bone · the side chain of the character It has a majority of carboxyl groups, so it can be developed by an alkaline aqueous solution. The acid value of the carboxyl group-containing resin (Α) is desirably in the range of ～150 mgKOH/g, preferably in the range of 40 to 130 mgKOH/g. When the acid value of the carboxyl group-containing resin (A) is less than 40 mgKOH/g, alkali development On the other hand, when it exceeds 150 mgKOH/g, in order to carry out the dissolution of the exposed portion by the developer, the line is made thinner than necessary. Depending on the case, the film is developed by not distinguishing between the exposed portion and the unexposed portion. It is not suitable because the drawing of the normal photoresist pattern is difficult, and the weight average molecular weight of the carboxyl group-containing resin (A) varies depending on the resin skeleton, but it is generally preferably 2,000 to 150. 〇〇〇, and further preferably in the range of ~100,000. The weight average molecular weight is less than 2, and when it is ruthenium, the tack free performance is poor. Therefore, the moisture resistance of the coating film after exposure is improved. When the film is developed, the film becomes thinner and the resolution is greatly deteriorated. On the other hand, when the average molecular weight exceeds 150, the developability is remarkably deteriorated, and the amount of the carboxyl group-containing resin (A) is stored in the whole. The composition is 2〇~6〇% by mass, preferably 30~50 When the amount is less than the above range, it is not preferable because the coating film strength is lowered. On the other hand, when the amount of the compound is larger than the above range, the viscosity is high, or the coating property is lowered. In the case of a photopolymerization initiator (Β), it is preferred to use an oxime ester-based photopolymerization initiator (Β1) selected from the group represented by the following general formula (I); (a) a group of α-aminoethyl hydrazide-based photopolymerization (Β2); and a cerium oxide-based initiator (Β3) having a group represented by the following formula (in) More than one kind of photopolymerization of bamboo shoots [Chemical Formula 1] " (I) 201102754 ——C=N—0—C—R2 I ii R1 °

(I) R R

One c-

II (m) (wherein R1 represents a hydrogen atom, a phenyl group (which may be substituted by a carbon number of 1 to 6 or a phenyl group or a halogen atom), and an alkyl group having 1 to 20 carbon atoms (may be by a hydroxyl group, may have more than one oxygen atom in the middle of the alkyl chain), a cycloalkyl group having a number of 5 to 8 and an alkanoyl group of a benzoic acid having a carbon number of 2 to 20 (a carbon number of 1) 1-6 alkyl or stupid substituted); R2 represents phenyl (V is substituted by a carbon number of 1 to 烷基 alkyl, phenyl or substituted by a halogen atom), a number of 1 to 20 burnt base (can be a The above hydroxyl group is substituted, and there may be one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having a carbon number of 5 to 8, a graft base having a carbon number of 2 to 20, or a mercapto group (a carbon number of 1) -6 and phenyl are substituted) ' \ and R 6 represent an independent alkyl or aralkyl group having 1 to 12 carbon atoms; R and R 6 represent independent hydrogen atoms, and carbon number i to 6 An alkyl group, or a cyclic alkyl ether group bonded to a diyl group; and a linear or branched bond group of a group of Wei 1 to 1G, or a halogen atom, an alkyl group or a group thereof (4) Which has the base D shown by the general formula (1). In the case of (B1), preferred is a sulfonate-based photopolymerization initiator group of thiophene-9-keto, which is represented by the following general formula i^(IV). The compound represented by oxyimine A, the following general formula (VI) 201102754 is a compound of the formula (IV): 2-(ethyl oxime), wherein the value is more than a methylamine) thio 〇山〇星-9-ketone, and formula ( , ° [化2] αν) s [Chemical 3]

(V) (wherein R9 represents a hydrogen atom, a functional atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamidine group, and a carbon number of 2 to decane. An alkoxycarbonyl group having a fluorenyl group and a carbon number of from 12 to 12 (when the alkyl group number of the alkoxy group is 2 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. Hand), or the oxygen group, R10, R12 represent a separate phenyl group (which can be substituted by a phenyl group or a tooth atom of a carbon number of 1 to 6), and an alkyl group having a number of 1 to 20 (can be More than one hydroxyl group substituted, 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 20 or a benzoinyl group (a carbon number of 1) ～Alkyl or phenyl substituted); RU is a hydrogen atom, a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl 12 201102754 or a halogen atom), or an alkyl group having 1 to 20 carbon atoms. a base (which may be substituted by more than one hydroxyl group, or an oxygen atom of f in the middle of the alkyl chain), a cycloalkyl group having a carbon number of 5 to 8, an alkylene group having a number of 2 to 20 or a benzoyl group. Can be The substituted alkyl or phenyl number of 1~6)) [Formula 4]

R 16 R 15

C—c—R13 N—Ο— R18 R 17 Ο

(VI) RU)n (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 6 alkyl group; η represents 0 In the case of a commercial product of the oxime ester-based photopolymerization initiator (Β1) having a group represented by the general formula (I), CGI-325, Irgacure manufactured by Ciba Japan Co., Ltd. may be mentioned. OXE01, Irgacure OXE02, etc. These vinegar-based photopolymerization initiators (B1) may be used singly or in combination of two or more. The α-aminoethylbenzene-based photopolymerization initiator (Β2) having a group represented by the general formula (II) can be exemplified by 2-methyl-1-[4·(methylthio)phenyl ]_2_昧^ base (morpholino) acetone-1, 2-benzyl-2-dimethylamine group small...oral phenyl phenyl)-butan-1, ketone, 2-(dimethylamino) _2_[(4_methylphenyl)indolyl]_1[4 soil_(4_ morpholinyl)phenyl]_丨-butanone, n,N-dimethylaminophenone, etc. . As a commercial item, Ciba japan K.K's "jrgacure 907, Irgacure 369, Irgacure 379, etc. are mentioned. The bismuth oxide-based phosphine-based photopolymerization agent (B3) having the group represented by the general formula (III) can be exemplified by oxidation of 2, 4, 6·triphenylbenzene diphenyl scales, oxidation Bis(2,4,6-trisylbenzimidyl)-phenylphosphine, oxidized bis(2,6-di 13 201102754 benzhydryl)-2,4,4-tridecyl-pentanephosphine, and the like. For the commercial product, Lucinin TPO manufactured by BASF Corporation, 819 manufactured by Ciba Japan K.K., and the like can be exemplified.混合6 The amount of the photopolymerization initiator (B) to be added is preferably from 1 to 30 parts by mass, preferably in parts by mass, based on 100 parts by mass of the base of the base crystal (A). When the amount of the coating is less than 0.01 parts by mass, the photocurability of the solder resist film on copper is insufficient, the coating film is peeled off, or the coating property such as chemical resistance is lowered, which is not preferable. On the other hand, when the amount of the mixture exceeds 3 Å, the light absorption on the surface of the photoresist film of the photopolymerization initiator (B) is intense, which tends to lower the deep hardenability. Further, in the case of the oxime ester-based photopolymerization initiator (B1) having the group represented by the formula (I), the desired amount of the mixture is selected based on the mass fraction of the ruthenium-containing resin. It is preferably in the range of 0.01 to 20 parts by mass, more preferably 0 to 1 part by mass. The photopolymerization initiator (B), the photoinitiation aid, and the sensitizer which can be used in the photocurable thermosetting resin composition of the present invention may, for example, be a benzoin compound, an acetophenone compound or a hydrazine. A compound, a sulfonium sulfonate, a ketal compound, a ketone compound, a sin compound, a tertiary amine compound, and the like. Specific examples of the benzoin compound may, for example, be benzoic acid, benzoin ethyl ether or benzoin isopropyl ether. Specific examples of the ethyl benzene compound can be exemplified by ethyl benzene, 2, 2 bis phenyl benzene, 2, 2 dimethyl ethoxy phenyl phenyl benzene, and broth: Stuffed benzene. For example, 2-methyl group, %, 2-"w醌2_2nd-butyl butyl hydrazine, 1-chloro hydrazine. Specific examples of the 9 J oxy 7 wide-star compound may, for example, be exemplified. Κ 』 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 For example, B-dimethyl _, 201102754 benzyl dimethyl ketal. Specific examples of the benzophenone compound may, for example, be benzophenone, 4-benzylidene diphenyl sulfide, 4-benzoquinone. Indenyl_4'-mercaptodiphenyl sulfide, 4-benzylidene-4, ethyldiphenyl sulfide, 4-benzylidene-4,-propyldiphenyl sulfide. Specific examples of the amine-based compound include, for example, an ethanolamine compound, a compound having a dialkylamine benzene structure, for example, 4,4'-diamine benzophenone (Nissocure MABP manufactured by Nippon Soda Co., Ltd.), 4, 4'-two. Dialkylamine benzophenone, 7-(diethylamino)-4-methyl-2H-1-benzopipene-2-, such as diethylamine benzophenone (HODOGAYA CHEMICAL CO., LTD., EAB) Dialkylamine coumarin compound, 4-diguanamine, such as ketone (7-(diethylamino)_'methylcoumarin) Formic acid (Kayacure EPA, manufactured by Nippon Kayaku Co. Ltd.), 2-dimethylamidobenzoate (Quantacure DMB, manufactured by International Bio-synthetics), 4-dimethylamine benzoic acid (n-butoxy) Ester (Quantacure BEA, manufactured by International Bio-synthetics Co., Ltd.), p-amylamine benzoate (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-diamine acetal acid 2-ethylhexyl ester (Esolol 507 manufactured by Van Dyk Co., Ltd.), 4' 4'-diethylamine benzophenone (EAB manufactured by HODOGAYA CHEMICAL CO., LTD.). The above is preferably a 9-oxo sulfur d mountain aj compound and a tertiary amine compound. In the composition of the present invention, from the aspect of deep hardenability, it is preferred to contain a 9-oxosulfanyl d-star compound, wherein 2, 4-dimethylnonane 9 oxysulfonate is suitable for the comet. 2, 4_ Diethyl 9-oxo sulfur 0 mountain d star, 2-oxo thioxanthone (xanthone), 2, 4-diisopropyl 9-oxo sulphate, Yamaguchi, etc. Star compound. The amount of the 9-oxosulfur I] stellite compound is preferably 2 parts by mass or less, more preferably 1 part by mass or less, based on the mass of the carboxyl group-containing resin (A). ratio. When the amount of the compound of the 9-oxosulfanyl compound is too large, the decrease in the thick film hardenability is closely related to the increase in the cost of the product, and it is not suitable. In the case of a tertiary amine compound, preferred is a 201102754 compound having a dialkylaminobenzene structure, wherein a dialkylamine benzophenone compound is particularly preferred, and a dialkylamine coumarin compound having a maximum absorption wavelength of 350 to 410 nm is contained. . In terms of dialkylamine benzophenone compounds, the toxicity of 4,4'-diethylamine benzophenone is also low. The diamined 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 -benzopyrene (pyran)_2__ is excellent in sensitizing 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 1 to 20 parts by mass, more preferably from 〇j to 10 parts by mass, per 100 parts by mass of the fluorenyl group-containing resin (A). When the amount of the tertiary amine compound is less than 0 parts by mass, a sufficient sensitizing effect is not obtained. When the compounding amount exceeds 20 parts by mass, the light absorption on the surface of the dry 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 functional group-containing elastomer (C) used in the photocurable thermosetting resin composition of the present invention not only improves the flexibility of the obtained cured coating film, but also improves the crack resistance of the hot and cold cycle and further improves The adhesion of the solder resist is 'in particular, it improves the PCT resistance. In the case of such a compound, as long as it is a compound having a functional group in the skeleton, it is possible to use, without limitation, a '(mercapto) acryl fluorenyl group, an acid needle group, a slow group, an epoxy group. Base compound. Further, it is suitable for the butadiene derivative to impart the above characteristics to the skeleton of the elastomer. Specific examples of the elastomer (C) containing this group are shown below. Examples of the substance containing the acid needle base 201102754 include Ricon13〇MA8, Riconl30MA13, Riconl30MA20, Riconl31MA5 'Riconl31MA10>Riconl31MA17, Riconl31MA20, Riconl84MA6, Riconl56MA17 (the above-mentioned trade name of Sertomer Co., Ltd.), and the like. Further, the product having a (fluorenyl) acrylate group may, for example, be CN301, CN307 (trade name manufactured by Sertomer Co., Ltd.), or BAC-45 (trade name manufactured by Osaka Organic Chemical Industry Co., Ltd.). Further, as the substance having a carboxyl group, a carboxyl group-modified butadiene-acrylonitrile copolymer or the like can be used. Further, in the case of an epoxy group or a carboxyl group, one or a part of the epoxy groups having various skeletons may be used to modify the elasticity of the two-terminal carboxylic acid-modified butadiene-acrylonitrile copolymer. Body and so on. The compounding amount of the functional group-containing elastomer (C) is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more, based on the mass of the carboxyl group-containing resin (A). Below the mass. When the amount is less than 5 parts by mass, the effect of the functional group-containing elastomer can not be confirmed. On the other hand, when it exceeds 6 parts by mass, it may be unfavorable because the viscosity of the coating film is deteriorated and the development is poor. Further, in the photocurable thermosetting resin composition of the present invention, a thermosetting component (D) may be added in order to impart heat resistance. For use in the hardening component (D) of the present invention, a blocked isocyanate compound, an amine resin, a maleimide compound, an oxazine resin, a carbodiimide resin, or a ring can be used. A thermosetting resin which is conventionally used, such as a carbonate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, and an episulfide resin. The above-mentioned preferred thermosetting component (D) is a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter referred to as cyclic (thio)ether groups) in one molecule. The thermosetting component (D) having such a cyclic (thio)ether group is commercially available in a wide variety of properties which can be imparted by the structure. v A thermosetting component (D) having two or more cyclic (thio)ether groups in such a molecule, a cyclic ether group having a 3, 4 or 5 membered ring in the molecule, or a cyclic sulfur 17 201102754 ether group Any one of the compounds having two or more bases, for example, a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1); a compound having at least two or more oxetanyl groups, that is, a polyfunctional oxetane compound (D-2); a compound having two or more thioether groups in the molecule, that is, an episulfide resin (D- 3) Wait. Examples of the polyfunctional epoxy compound (D-1) include jER828, jER834, jER1001, and jER1004 manufactured by Nippon Epoxy Co., Ltd.; Epiclon 840, Epiclon. 850, and Epiclon 1050 manufactured by Otsuka Ink Chemical Industry Co., Ltd. Epiclon 2〇55; 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 of Ciba Japan KK 607 araldite 6084, araldite GY250, araldite GY260; Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Industries Co., Ltd.; AER330, AER331, AER66 manufactured by Asahi Kasei Industrial Co., Ltd. AER664 (all trade names) bisphenol A epoxy resin; JERYL903 manufactured by Japan Epoxy Resin Co., Ltd.; Epiclon 152, Epiclon 165 manufactured by Dainippon Ink and Chemical Industry Co., Ltd.; Epotohto YDB-made by Dongdu Chemical Co., Ltd. 400, YDB-500; DER542 manufactured by Dow Chemical Co., Ltd.; Araldite 8011 manufactured by Ciba Japan KK; Sumi-epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Industries Co., Ltd.; AER711 manufactured by Asahi Kasei Industrial Co., Ltd. Brominated epoxy resin such as AER714 (both trade names); jER152 and jER154 manufactured by Epoxy Epoxy Co., Ltd.; DEN431 and DEN438 manufactured by Dow Chemical Co., Ltd.; Epiclon N- manufactured by Dainippon Ink Chemical Industry Co., Ltd. 730, Epiclon N_770, Epiclon N-865; Epotot YDCN-7 manufactured by Dongdu Chemical Co., Ltd. (H, YDCN-704; araldite ECN1235, araldite ECN1273, araldite ECN1299, araldite XPY307 manufactured by Ciba Japan KK; EPPN-made by Nippon Kayaku Co., Ltd. 201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000H; Sumitomo Chemical 18 201102754 Sumi-epoxyESCN-195X, ESCN-220 manufactured by Industrial Co., Ltd.; AERECN-235 manufactured by Asahi Kasei Industrial Co., Ltd. ECN-299 (all of the trade names) are varnish-type oxy-resin, Epiclon 830 manufactured by Dainippon Ink Chemical Industry Co., Ltd.; jER807 manufactured by Sakamoto Epoxy Co., Ltd.; Epotohto YDF_170, YDF-175 manufactured by Dongdu Chemical Co., Ltd. YDF-2004; bisphenol F-type epoxy resin such as araldite XPY306 manufactured by Ciba Japan KK (both trade names); Epotohto ST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd. hydrogen Bisphenol A type epoxy resins; epoxy resins of the present jER604 said Corporation's; Ep〇t〇hto Tohto Kasei Co., Ltd. The YH-434;

Ciba Japan KK araldite MY720; Sumitomo Chemical Industries Co., Ltd. Sumi-epoxy ELM-120 (both trade names) epoxy propyl amine epoxy resin, Ciba Japan KK·araldite CY-350 (commodity Hydantoin type epoxy resin, etc.; made by Daicel Chemical Industry Co., Ltd.

Celloside 2021, an alicyclic epoxy resin manufactured by Ciba Japan KK araldite CIY175, CY179, etc. (all trade names); YL-933 manufactured by Sakamoto Epoxy Co., Ltd.; τ.Ε.Ν manufactured by Dow Chemical Co., Ltd. , EPPN-501, take -502, etc. (all are trade names) of trishydroxyphenyl decane type epoxy resin; YL 环氧树脂 环氧树脂 环氧树脂 4000 4000 4000 4000 4000 4000 4000 4000 4000 4000 4000 4000 4000 4000 4000 4000 4000 4000 Name) bisphenol phenol type or biphenol type epoxy resin or such mixture; EBPS_2 制 manufactured by Nippon Kayaku Co., Ltd.; PPX-^O manufactured by Asahi Kasei Kogyo Co., Ltd.; EXA_ manufactured by Dainippon Ink Chemical Industry Co., Ltd. 15 i 4 (trade name) special phenolic S-type epoxy resin; 曰 环氧树脂 epoxy resin metric d ^ A _ lacquer-type epoxy resin; Japan and resin public ^ 931; (four) Japan KK system - 163, etc. (All are tetraphenyl (phenyl 〇 1) phenyl epoxy resin; (10) 峋 (10) κ κ 脔 ^ 打 810; Nissan Chemical Industry Co., Ltd. butyl fertilizer, etc. (all ΪΓ ϊ ϊ 式 epoxy resin; Japanese oil company made such as - dirty 12,7 epoxy propyl ester resin; Dongdu Chemical Company's system 063 and gossip ίο 笨 纷 ( (Xylen〇lyl) B Resin; Nippon Iron & Steel Co., Ltd. E purchase 9G, ESN•fine, Dainippon Ink Chemical Industry Co., Ltd. 201102754 Γ本卜ΕΐΑ_175(), EXA., etc. Naphthalene-based epoxy resin; Sub-Industrial Co., Ltd. HP_7200, HP 7200H, etc. Epoxy resin with pentadiene skeleton, EXA-4816, £XA_48U series of soft and strong epoxy resin; 曰本油公司制制_,·5_, etc. The epoxy propylene acrylate copolymerized epoxy resin is exemplified by cyclohexyl maleimide and methacrylic acid or a combination of two or more. These are particularly suitable as ί=::heterocyclic epoxy Resin 'bis dimethyl phenanthrene epoxy resin, fs oxetane compound (D 2), exemplified by bis methoxy) fine, bis [(3 · ethyl _ 3 oxacyclobutane) ^土]本丨,4-bis[(3-ethyl-3-oxetanylmethoxy)indenyl 1 stupid, alkane) fluorenyl, methacrylic acid (3-mercapto_3_oxygen Heterocyclic butane) methyl ester,

Ϊΐϊί!: ethyl | oxequid) A or these oligomers or copolymers ε f oxetane, in addition to oxetane f-alcohol and novolac resin , poly(p-hydroxystyrene), cardo type bisphenol =, phenolic cyclic polymer (calixarene), phenolic resorcinol cyclic polymerization, (calix resorcin arene), or sesquiterpene oxygen An alkyl ether or a hydroxy group-containing resin, such as an ether compound of the hydroxy group, and a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate. In the case of the episulfide resin (D-3) having two or more cyclic thioether groups in the molecule, for example, YL7〇(9) (bisphenol A type episulfide resin) manufactured by Nippon Epoxy Co., Ltd., or Dongdo can be mentioned. Chemical company (share) system yslv_i2〇t^, etc.: The same synthesis method can be used, and an episulfide resin or the like can also be used, and the oxygen atom in the epoxy group of the novolac type epoxy resin is replaced with a sulfur atom. 20 201102754 two or more cyclic ethers (ethyl sulphate) in the molecule relative to the carboxyl group equivalent of the carboxyl group-containing resin (A) ) Jiajia is 0.6~2.5 equivalents, more preferably ο., ^2Λ成量; ^ When the mixing amount is less than 0·6, the base is left in the tapping knife (D), which is alkaline and electrically insulated. Sexuality is not appropriate. Second, reduce heat resistance, resistance (ethyl sulphide exposure = when coated = j polychlorinated compound, hydroxyf-benzoic guanamine amine) and ? = compounds, etc. :: poly ΐ compound, calcined methylated benzoguanamine compound, oxyalkyl thiolated b == alkoxymethylated urea compound, by the respective meglumines: toluene and guano The amine compound, the hydroxymethylacetylene urea compound, and the methyl group are converted into a calcined oxygen methyl group per methylurea compound. The type of the alkoxy group is not particularly limited, and may be, for example, methoxymethyl or ethoxy group. Methyl, propyloxymethyl, butoxycarbonyl, etc.. Particularly preferred is a melamine derivative having a milder concentration of 0.2% or less to the human body or the environment. These commercially available products can be exemplified by, for example, Saimel 3 〇〇, the same 3〇1,同303,同37G,同325,fi]327,同七〇1,同266,同267,同238,同1141,同272,同202,同1156,同1158, the same 1123, the same 1170, the same 1174, the same UFR65, the same 300 (the above is Mitsui Cyanamid company), Nikalac Mx-750, the same Mx-032, the same Mx-270, the same Mx-280, the same 290, Same as Mx-706, same Mx-708, same Mx-40, same Mx-31, same Ms-H, same Mw-30, same Mw-30HM, same Mw-390, same Mw-l〇〇LM, same Mw -750LM, (the above is manufactured by Sanwa Chemical Co., Ltd.). The above-mentioned thermosetting component may be used singly or in combination of two or more. Further, in the photocurable thermosetting resin composition of the present invention, in order to improve the hardenability of the composition and the toughness of the obtained cured film, it is possible to add a 21 201102754 molecule having two or more isocyanate groups or blocked isocyanates. Base compound (E). The compound (E) 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 (E-1); A compound having two or more blocked isocyanate groups in one molecule, that is, a blocked isocyanate compound (E-2). As the polyisocyanate compound (E-1), for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate include 4,4,-dibenzopyrene diisocyanate, 2,4-methyl tolylene ester, and diisocyanate 2, 6-methylphenylene ester, naphthalene diisocyanate, 5-ester, o-diphenylene diisocyanate, m-dimethyl isopropyl diisocyanate and 2,.4-methyl benzene ( 1〇1丫卜1^) Dimer. Specific examples of the aliphatic polyisocyanate include butyl butyl diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, and trimethyl hexamethylene diisocyanate. , 4-methylene bis(cyclohexyl isocyanate) and diisocyanate isophor vinegar. Specific examples of the alicyclic polyisocyanate may be exemplified by the triisocyanate of triisocyanate. And an adduct of an isocyanate compound, a biuret and an isocyanurate as exemplified above. a blocked isocyanate group contained in the blocked isocyanate compound (E-2), which is protected by a reaction with a blocking agent and temporarily inert. Foundation. The capping agent dissociates and forms an isocyanate group upon heating to a set temperature. In the case of the blocked isocyanate compound (E 2 ), an addition reaction product of the isocyanate compound (c) and the isocyanate blocking agent (d) is used. The isocyanate compound (c) obtained by the reaction with the blocking agent may, for example, be an iso-cyanate type, a biuret type or an adduct type. As the isocyanate compound (c), for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic cyanate can be used. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate may, for example, be a compound of the above-mentioned Joe. 22 201102754 Isocyanate end-capping agent (d), for example, phenolic terminal blocking agents such as phenol, indophenol, xylenol, chlorophenol and ethylphenol; ε-caprolactam, δ-pentanetanamide (Valerolactam , γ-butyrolactam and (3_propiolactam, etc. endoamine-based blocking agent; active ethylidene-based blocking agent such as ethyl acetate and acetamidine; sterol , ethanol, propanol, butanol, pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monoterpene ether, benzyl ether, hydroxyl Alcohol-based blocking agent such as decyl acetate, butyl acetate, diacetone alcohol, decyl lactate and ethyl lactate; aldehyde oxime, acetaldoxime, acetoxime, acetophenone oxime, Terpene blocking agent such as diethyl hydrazine monochloride or cyclohexane hydrazine; thiol end capping of butyl mercaptan, hexyl mercaptan, tertiary thiol, thiophenol, thiophenol, ethyl thiophenol, etc. An acid amine amide-based blocking agent such as decylamine or benzoguanamine; an imide-based blocking agent such as a guanidinium succinate and a guanidinium maleate; Xylidine), An amine-based terminal blocking agent such as an amine, butylamine or dibutylamine; an imidazole-based terminal blocking agent such as amid, 2-ethylimidazole or the like; an imide-based blocking agent such as an imide and an imine. The normal isocyanate compound (E-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 Sumitomo Bayeramine citrate) , trade name), Coronet 2512, Coronet 2513, Coronet 2520 (the above is a product of the polyamine phthalate industrial company, trade name), B-830, B-815, B-846, B-870, B- 874, B-882 (the above is a product name manufactured by Mitsui Takeda Chemical Co., Ltd.), 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 (E) 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. a compounding amount of the compound (E) having two or more isocyanate groups or blocked isobaric 23 201102754 acid ester groups in one molecule, relative to the mass portion of the slow-base resin (A) 1 () () A ratio of 1 to 100 parts by mass, more preferably 2 to 70 parts by mass, is suitable. 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 it exceeds 1 part 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 amino formate catalyst (F) can be added. In terms of the amide phthalate catalyst (F), it is preferred to use a catalyst selected from the group consisting of tin-based catalyst (F-1), metal chloride (F-2), metal acetoacetate (f_3), and metal sulphuric acid. One or more kinds of amino phthalate catalysts of the group consisting of a salt (F-4), an amine compound (F-5), and/or an amine salt (F-6). The tin-based catalyst (F-1) may, for example, be an organotin compound such as stannous octoate or a dibutyltin laurate or a tin-tin compound. ... the metal vapor (F-2) aspect can be exemplified by a chloride of a metal composed of chromium, fibrate, tin, nickel, iron, copper or quartz, such as chlorinated diamond (III) (cobaltic = 1〇nde) , nickel chloride, ferric iron (ferric chl〇ride). The metal acetoacetate (F_3) may, for example, be a metal pyruvate composed of chromium, manganese, cobalt, ', iron, copper or sulphate, and may, for example, be acetonitrile-cobalt cobalt salt. , acetonitrile nickel pyruvate, acetonitrile pyruvate iron salt and the like. The metal sulfate (F_4) aspect has a sulfate of a metal composed of chromium, manganese, cobalt, nickel, iron, or s3 aluminum, and examples thereof include copper sulfate. The amine compound (F_5) may, for example, be a conventionally known tris(R) N'_tetramethyl 6-hexanediamine, bis(2-m-based) fluorene, N'', N" Diethylenetriamine, N-mercaptopurine, Ν· 乙 dimethylethanolamine, diterpene diethyl ether, 甲米嗤, , pyridine, triazine, Ν'_(2_hydroxyethyl )_Ν,Ν,Ν,_三methyl_双(2_ NN Ν_二曱hexylamine, hydrazine, Ν_dimethylamine ethoxyethanol, ' '-dimethyl Ν Ν'-(2- Ethyl) Ethylenediamine, ν-(2-Ethyl)·Ν, 24 201102754 N',N,',N"-Tetramethyl Diethyl B = Face χτ ^ 扣田Α - You/一吐It amine, Ν-(2_propyl)·Ν,Ν,,Ν,,,Ν,'-tetramethyl-ethylenediamine, hydrazine, hydrazine, hydrazine, amine, hydrazine-methyl-hydrazine, - (2-ethyl) hexaamine, bis(Ν' Ν·dimethylaminopropyl) isopropyl; US) cholyl propyl) imi, H3, _ hydroxypropyl 二Amine propyl-specific (2_ethyl)amine, N,N-di-r-r2, _bis(2-ethyl)amine, N,N-diguanamine propyl-N, N, _ ί N, methymidine ethyl _N,, N, · bis (2-ethylidene) amine, and 'bird i~JiBase N, N, bis (2 propyl) amine, melamine and / or benzoquinone + ίί i (F'6) aspects can be exemplified * DBU (1,8-two 丫-bicyclo[5, 4, 〇] hexene-7) an organic salt of an organic acid salt or the like. The amount of the mixture of the yoghurt and the catalyzed catalyst (F) is such that the ratio of the amount of the amount of the fluorene is 100 parts by mass of the carboxyl group-containing resin (A), preferably 〇.1 to 20, More than ^ 〇 5~1〇〇 parts by mass. When a hard or more cyclic ether (ethyl sulfide) is used, -T (1)), and it contains a thermosetting catalyst. Such heat-hardened nails, σ t! such as imidazole, 2_imidazole, 2 - ethylimidazole, 2-ethyl-4-cyanide 2, 2' stupid alpha sitting, 4-benzene flavor also, 1 -|L-ethyl-2-phenylidene, 1-(2-yy-1) ethyl imidazole and the like imidazole derivatives; dicyanoguanamine, di-, 4-(diamine) ) Ν Ν Ν 曱 曱 曱 苄 benzylamine, 4-methoxy-N, N-^ a & amine, 4-methyl-N, N-dibenzyl benzylamine and other amine compounds, An anthracene compound such as diterpene sebacate; a phosphating system such as triphenylphosphine; and a 'commercial aspect of the product' can be exemplified by, for example, 4MZ-A, 2MZ-OK of Shikoku Chemical Industry Co., Ltd. 2PHZ, 2P4BHZ, 2P4MHZ (both are the trade names of the spectroscopy compound); U-CAT (registered by 25 201102754) 3503N, U-CAT3 5〇2Τ manufactured by San-apro Co., Ltd. a trade name of a blocked isocyanate compound, DBU, DBN, U-CATSA102, U-CAT5002 (both f-ring oxime compounds and salts thereof), etc. In particular, it is not limited to these, as long as it is an epoxy resin or an oxygen a thermosetting catalyst for a cyclobutane compound, or may promote an epoxy group and/or an oxetane group and a carboxyl group The reaction product can be used alone or in combination of two or more. It is also possible to use guanamine, acetaminophen, benzoguanamine, melamine, 2,4-diamino-6- Mercaptopropenyl oxyethyltriazine, 2·ethylene-2,4-diaminotriazine, 2-ethylene-4,6-diamino-s-triazine·iso-cyanuric acid adduct An S-triazine derivative such as a 2,4-diamino-6-methylpropionyloxyethyl-S-tributive/isocyano cyanate adduct is preferably used as a functional system. The compound to which the adhesion agent is added is used in combination with the heat-curing catalyst. The amount of the heat-curing catalyst is sufficient in a normal amount ratio, for example, two or more in the carboxyl group-containing resin (A) or in the molecule. The thermosetting component (D) i by mass of the cyclic ether (ethyl sulfide) group is preferably 0.1 to 20 parts by mass, more preferably 5 to 15.0 parts by mass. The photocurable resin of the present invention. The composition may be mixed with a coloring agent (G). For the coloring agent, a conventionally known coloring agent such as red (G-1), blue (G-2), green (G-3), or yellow (G-4) may be used. It can also be any of pigments, dyes, and pigments. From the viewpoint of environmental load reduction and human influence, 'it should be halogen-free. Red colorant (G-1): Red colorant, monoazo, diazo, azolake Examples, benzimidazolone-based, fluorene-based, diketopyrrolopyrrole 0, condensed azo-based, fluorene-based, quinacridone, etc., specifically, the following With the color index (CI; The Society of Dyers and Colourists issued) number. Monoazo system: Pigment red 1, 2, 3, 4, 5, 6, 8, 9, 12, 26 201102754 14, 15, 16, 17, 2, 22, 23, 3, 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: 1, 52: 1, 52: 2, 53: 1, 53 : 2, 57 : 1, 58 : 4, 63 : Bu 63 : 2, 64 : Bu 68. Benzimidazolone type: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208. Lanthanide: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224. The diketone group has a ratio of p to each of the respective groups: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, and Pigment Red 272. Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242. Lanthanide: Pigment Red 168, Pigment Red 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 2 〇 2, a pigment red 206, a pigment red 207, and a pigment red 209. 'Blue coloring agent (G-2): A blue coloring agent is a phthalocyanine type or a lanthanoid type, and a pigment system is classified into a pigment (Pigment), and specifically, the following substance blue 15 , pigment blue 15 : 1, pigment blue 15 : 2, color tone g ^ plain blue 15: 4, pigment blue 15: 0, pigment blue 16, pigment blue 6 〇. ·, color dye system' can use Solvent Blue 3 5, Solvent Blue 6 3: Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 7〇^二' In addition to the above, a metal-substituted or unsubstituted phthalocyanine/product can also be used. Γ 27 201102754 Green coloring agent (G-3): For green coloring agents, there are also phthalocyanines, lanthanides, and lanthanides. In fact, pigment greens 7, pigment greens 36, and solvent greens can be used. Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like. In addition to the foregoing, a metal-substituted or unsubstituted phthalocyanine compound can also be used. Yellow coloring agent (G-4): ^ In the case of yellow coloring agents, there are monoazo, diazo, condensed azo, benzo 11 mactone, isoindolinone, 蒽g The Kunming system, etc., can be exemplified by the following. Lanthanide: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow! 93, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202. Isoindolinone: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185. Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180. Benzimidazolone: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181. Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 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 may also add a coloring agent such as purple, orange, brown, or black for the purpose of adjusting the color tone. Specific examples are pigment purple 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, CI pigment orange 1, CI pigment orange 5, CI pigment orange 13, CI pigment orange 14, CI pigment orange 16, CI pigment orange 17, CI pigment orange 24, CI pigment orange 34, CI pigment orange 36, CI pigment orange 38, CI pigment 28 201102754 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 (G) is not particularly limited, and is preferably a ratio of 〇 to mass parts, particularly preferably 0.1 to 5 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). The compound having two 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 make the carboxyl group-containing resin (A) Insoluble in an alkaline aqueous solution or contribute to insolubilization. For such a compound, a conventionally known polyester (mercapto) acrylate, polyether (meth) acrylate, amino decanoate (meth) acrylate, carbonate (meth) acrylate can be used. And (meth)acrylic acid epoxy ester, etc., specifically, 2-hydroxyethyl acrylate, propylene 2-acrylic acid acetonitrile, glycerin, glycerin, ethylene glycol, methoxytetraethyl : Diacrylates of ethylene glycol such as alcohol, polyethylene glycol, propylene glycol; N,N-decylamine, N_(tetra)acrylamide, N,N-dimethylaminopropylpropionic acid=Special acrylamide Aminoalkyl acrylates such as N,N-dimethylamine ethyl acrylate and guanamine propyl acrylate; hexane diol, trimethylol, alkane, neopentyl alcohol, dipentaerythritol, ginseng a polyvalent propylene lysine such as an oxyethyl iso-trioxide oxidized ethyl ester adduct or a propylene oxide adduct; acrylic acid benzene si or didienoic acid vinegar: and the like Polyvalent acrylates such as ketopropane, bismuth, bismuth, etc.; glycerol bicyclopolycyanide bismuth, bis, trioxane, trioxyethylene ether, and iso-three Diluted acid hydrazine; not limited to linalool direct propylene _, or, via a chaperone, and / or corresponding to the aforementioned yttrium yt 29 201102754 esters, etc. s further, may be exemplified in cresol novolac a multifunctional epoxy resin such as an epoxy resin, an epoxy acrylate resin which reacts with an acrylic acid, or a hydroxyl group of the epoxy acrylate resin, and a hydroxy acrylate such as neopentyl glycol triacrylate An epoxy urethane acrylate compound reacted with a hemi-aminoglycolate compound of a diisocyanate such as isophorone diisocyanate, etc. Such a oxy acrylate resin does not cause dry touch (dry-to- The photohardenability can be improved by lowering the touch. In the past, the compound (H) having two or more ethylenically unsaturated groups in the molecule is 5 to 1 by mass based on 1 part by mass of the carboxyl group-containing resin (A). The quality of the enamel is preferably from 1 to 70 parts by mass. The amount of the mixture is less than 5 masses, the photohardenability is lowered, and the alkaline development after irradiation with the active energy ray is formed into a pattern, so Suitable. On the other hand, the amount of mixing exceeds 1〇〇 In the case of the balance, the solubility of the aqueous solution is lowered, and the coating film becomes brittle, which is unfavorable. The photocurable thermosetting resin composition of the present invention is used to increase the physical strength and the like, so that the filler can be mixed as needed. (1) In terms of such π^(Ι), it is possible to use a conventional inorganic or organic filler, and it is preferable to use barium sulfate, spheroidal cerium oxide and talc, and further, it is difficult or desirable to obtain a H color. For flammability, titanium oxide or metal oxide or metal ruthenium oxide hydroxide can be used as a primer filler. ^ Filling amount of filler (1) relative to the mass of the carboxyl group-containing resin (A) = helmet is preferably 200 parts by mass or less, more preferably 1.1 to 150 parts by mass, special ', and 1 to 100 parts by mass. The amount of the filler (1) is more than 2 parts by mass of the viscosity of the composition It becomes higher, the printability is lowered, or the hardened material becomes brittle and is not suitable. Further, the photocurable thermosetting resin composition of the present invention is used for the purpose of improving dryness and improving the handling material, and it is possible to use a binder polymerization such as a compound, a polyaminocarbamic acid, or a polymer. Polyacetate soil S-based polymer, polyamido-based polymer, polyester amide-based polymer, 30 201102754 acrylic polymer, cellulose polymer, polylactic acid polymer, phenoxy ruthenium polymer Wait. These binder polymers may be used singly or as a mixture of two or more. Further, the photocurable thermosetting resin composition of the present invention can be used for the adjustment of the synthesis or composition of the carboxyl group-containing resin (A) or for the viscosity adjustment of the substrate or the carrier film. Solvent. The organic solvent may, for example, be a ketone, an aromatic hydrocarbon, an ethylene glycol bond, a glycol ether acetate, an ester, an alcohol, an aliphatic hydrocarbon or a sulphuric acid solvent. More specifically, an aromatic hydrocarbon such as acetophenone, cyclohexanone or the like, benzene, xylene, tetradecene benzene, etc.; cellosolve, thiol acesulfame, Glycol ether of butyl acesulfame, carbitol, methyl carbitol, butyl carbitol, propylene glycol monoterpene ether, dipropylene glycol monoterpene ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Ethyl acetate, butyl acetate, dipropylene glycol oxime ether acetate, propylene glycol oxime ether acetate, propylene glycol diethyl ether acetate, propylene glycol butyl ether acetate, etc.; ethanol, propanol, ethylene glycol An alcohol such as propylene glycol; an aliphatic hydrocarbon such as octane or decane; a petroleum solvent such as petroleum ether, naphtha, hydrogenated petroleum brain or solvent oil. Such an organic solvent can be used singly or as a two. In general, most polymer materials are oxidatively degraded in a chain when they start to oxidize, and the photocurable thermosetting resin composition of the present invention is added to the polymer material according to the present invention. 1) Free radical trapping "", in order to invalidate the free radicals that have been produced and/or (2) the decomposition of the peroxide decomposing agent into a non-infective substance does not create new free and effective. k with 'and HAST The peeling or discoloration is less, and it is extremely effective in the action of the antioxidant σ·υ which acts as a radical scavenger. Specific compound 31 201102754 may, for example, be hydroquinone, 4-tert-butyl catechol, or 2-tributyl. Hydroquinone, hydroquinone monomethyl ether, 2,6-di-tributyl-p-cresol, 2,2-methylene•bis(4-mercapto-6-tertiary butylphenol), 1,1 , 3-paran (2-mercapto-4-hydroxy-5.tributylphenyl)butane, 1,3,5-trimethyl-2,4,6-para (3,5-two Butyl-4-hydroxybenzyl)benzene, 1,3,5-(3,5,2-di-tert-butyl-4-hydroxybenzyl)-S-triazine-2, 4, 6- (1Η, 3H, 5H) ketones such as ketones, hydrazines, benzoquinones, etc., bis(2, 2, 6, 6-tetradecyl-4_α Amine compounds such as sebacate, phethoxazine, etc. The radical scavenger (J-1) may 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 CORPORATION, trade name), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135 , TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, 11 hunger; ¥ 5100 (above (: ^^仏? &11匕1:., trade name), etc. The anti-oxidant (J-2) of the decomposition agent may, for example, be a linonic compound such as triphenylphosphite, tetralauryl thiopropionate, tetralauryl thioacetate or thiodipropionic acid. A sulfur-based compound such as dilauryl ester or distearyl 3,3'-thiodipropionate. The peroxide decomposing agent (J-2) may also be a commercially available one, and may, for example, be Adecastab. TPP (made by ADEKA CORPORATION, trade name;), Mark AO-412S (made by ADEKA CORPORATION) Name), sumilizer-TPS (SUMITOMO Chemical Co "Ltd., trade name) and so on. The above-mentioned antioxidants (J) may be used alone or in combination of two or more. In addition, in the photocurable thermosetting resin composition of the present invention, in addition to the antioxidant (7), the photocurable thermosetting resin composition of the present invention is generally used for the purpose of suppressing the stabilization of ultraviolet rays. , can be used on 2011-02754 UV absorber (κ). The ultraviolet absorber (Κ) may, for example, be a benzophenone derivative, a benzoic acid derivative, a benzotristrile derivative, a tripod derivative, a benzopyrene derivative or a cinnamate. a derivative, an anthraquinone derivative, a diphenyl fluorenyl derivative, or the like. Specific examples of the benzophenone derivative include 2-shoe-based 4-decyloxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2,-dihydroxy-4. -Methoxybenzophenone and 2,4-di-diphenylbenzene 1 and the like. Specific examples of the benzoic acid vinegar derivative can be exemplified by 2-ethylhexyl salicylate phenyl salicylate, salicylic acid to tert-butylphenyl ester, and 2,4-di-tributyl butyl. Phenyl-3, 5-ditributyl-4-hydroxybenzoate and hexadecyl-3,5-ditributyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2-(2'-hydroxy-5'-tertiary butylphenyl)benzotriazole and 2-(2'-hydroxy-5'-methyl group. Phenyl)benzotriazole, 2-(2'-hydroxy-3'-tertiary butyl-5'-nonylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 ',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tolyl)benzotriazole and 2-(2'-trans-based- 3', 5'-di-triphenylpentyl) benzotriazine and the like. Specific examples of the tripod derivative include hydroxybenzenetriazine, bisethylhexoxyphenol oxime oxyphenyltriazine, and the like. In the case of the ultraviolet absorber (K), it may be a commercially available one, and for example, for example,

TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TimjVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, Ciba Japan K.K., trade name) . The ultraviolet ray absorbing agent (K) may be used singly or in combination of two or more kinds, and by using the antioxidant (J) together, the molded article obtained by the photocurable thermosetting resin composition of the present invention can be stabilized. Chemical. In the photocurable thermosetting resin of the present invention, in order to improve the sensitivity, a known conventionally used phthalic acid, a lactoacetic acid, a thiophenoxyacetic acid, or a sulfur can be used as a key transfer agent. Say*»Sit and wait. The chain transfer agent may, for example, be hydrogen sulfide succinic acid, hydrogen thioacetic acid, hydrogen thiopropionic acid, hydrazine 33 201102754 thiline, cyst (10) (eystine), thioresidic acid and its enchantment 2 turns. Ϊ; hydrogen thioethanol, hydrogen thiopropanol, hydrogen thiocyanate, Ϊ妒ίί multiple agents; butyl mercaptan, butyl winter hydrogen thiopropionic acid: 荨二巧,,, 2,2-(ethylene oxide) Diethyl mercaptan, diethyl brittle dimethyl toluene, alcohol, t-thiol, propanethiol, butanol, pentyl mercaptan, 1-octyl mercaptan, cyclopentane; brewing, cyclohexyl mercaptan, sulfur glycerol 4, 4-thiobisbenzenethiol and the like.乂"L, and a polyfunctional thiol compound can be used, but for example, it can be used, for example, 6-dithiol, Wei, 1 (^=疋丄) alcohol 2 4 hydrogen?: 2, sulfide, etc. Aliphatic thiols,: one methyl monosulfide, 4,4 dihydrothiodiphenyl sulfide, aromatic aromatic thiol; ethylene glycol bis (gas sulphuric acid hydrazine alcohol 1L cone. sulphur Ethyl sulphuric acid vinegar), glycerin ginseng (nitrogen sulphide-L sulphonyl sulphate (sodium sulphuric acid g), tris-methyl propyl hydrazine), multiple Gil sulphur B (tetra), dipentaerythritol ( Hydrogen thioacetate ί ί acetate series; ethylene glycol bis(3·hydrothiopropionate), poly(1)-(3·虱 thiopropionate), propylene glycol bis(3_hydrothiopropionate) Oil ginseng (3-hydrothiopropionate), trihydrocarbyl ethane sulfonate (hydrothiopropionate), trimethylpropane f (3-hydrothiopropionate), neopentyl quinone oxime (3_ Polythiopropionic acid, dipentaerythritol, tert-(3-hydrothiopropionate), poly(l-hydrothiophene); 1,4-bis(3-hydrothiobutane) Alkane, anthracene, 3, 5_parade (3_hydrothiobutane ethyl)-1,3,5-triazine-2, 4, 6(1H,3H, 5H)-trione, pentaerythritol肆(34 thiobutyrate) (Hyperthiobutyrate). For the above-mentioned commercial products, for example, BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (manufactured by Seiko Chemical Industry Co., Ltd.) Calends MT-PE1, Calends MT-BD1, and Calends-NRl (manufactured by Showa Denko Co., Ltd.), etc. Further, in the case of a heterocyclic compound having a hydrogenthio group as a chain transfer agent, for example, hydrogen sulfur can be exemplified 4-butyrolactone (other names: 2-hydrothio group 4 butanolide), 2-hydrothio-4-indolyl-4-butyrolactone, 2-hydrogenthio 34 201102754 -4-ethyl-4-butene, 2-residue; g* and (butyro-thiolactone), 2-hydrogen sulfide or 4 butyl sulphate thiol-4-butylan, N-B is: hydrogen; 2 amine, Ν·methoxy 2 -hydro-2-hydrothio-4-butylide, N-ethyl 2 AI indoleamine, N_methyl field I ^ 虱thio-4-butylidene, N-(2-methoxy)ethyl-2-indolyl-4-butylan, ethyl ethion-4-butylide, 2 -Hetthiosyl_5_pentane gt, = amine, N-methyl-2-hydrothio-5-valeroinamide = decylamine, N-(2-methoxy)ethyl, benzyl-5 _pent = thio) ethyl-2- Sulfur-5-pentane amine, 2· vermiculite * lean, political and technical oxygen "Tian Jing ^ λ, z wind sulfur benzene sputum saliva, 2-argon-based - _ nail thiazole, 2 - thiol_6-ε_caprolactam, 2 4 6_di-s-triazine (tri-co-formed by the company: trade name Zis: one, ^ 2-aminoamine-4,6- Dihydrothio group _8•三唪(二协^

ZisnetAF) # 〇 ( - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Sulphur thiobenzazole, 3-hydrothio- 4-methyl-4H-1,2,4-triazole, 5-methyl-j,3,4-thiadiazole-2-thiol, 丨_benzene The _5_hydrogen sulphur diene transfer agent may be used singly or in combination of two or more. The photocurable thermosetting resin composition of the present invention is used in order to improve interlayer adhesion or a photosensitive resin layer. For the adhesion of the substrate, a splicing promoting agent can be used. Specific examples include, for example, benzimidazole, benzopyrene, benzothiazole, 2-hydrothiobenzimidazole, and 2-hydrothiobenzene. And carbazole, 2-hydrogen sulfide = open thiazole (trade name: AccelM manufactured by Kawaguchi Chemical Industry Co., Ltd.), 3_ mouth methyl-1-phenyl-triazole·2-thione (thi〇ne), 5_Amino_3_昧昧曱基_, oxazolidine-2-thione, 2-hydrothio group_5_methylthio-thiadiazole, triazole, tetrazole, benzodiazole, carboxybenzotriene An azole, an amino-containing benzotriazole, a decane coupling agent, etc. The photohardening thermosetting of the present invention The composition of the chemical resin may further be added to a touch modifier such as Pulverized Silica, Bentonite, Bertite, Hydrotalcite, etc. as a tactile modifier 35 201102754 The stability of the change is preferably Bentonite or hydrotalcite. Especially the hydrotalcite has excellent electrical properties. Further, it can be mixed with a thermal polymerization inhibitor, or a polysilicon system, a fluorine system, or a high A defoaming agent and/or a leveling agent such as a molecular system, a shovel system, a sigh system, a trisaloid, etc., a rust removing agent, and a bisphenol system or a triazine sulphate. A conventionally used additive such as an alcohol-based copper oxidizing agent or the like. The thermal polymerization inhibitor can be used to prevent thermal polymerization or time-varying polymerization of the polymerizable compound. For example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, tertiary butyl tea, gallic phenol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxydiphenyl Ketone, copper (I) (copper (I) chloride), homogenized morphine (phenothiaz) Ine), tetrachlor chloranil, naphthylamine, β-naphthol, 2, 6-di-tert-butyl -4-indolol, 2, 2, _ fluorenyl bis(4-indenyl) 6-tertiary butyl phenol), pyridine, nitrobenzene, dinitro 'benzene, picric acid, 4-nonanilide, methylene blue, copper and organic chelating agent reactants, salicylic acid, and Phenometh (phen〇thiazine), sub-; 6 Schechyl compound, arginyl compound and chelated. The photocurable thermosetting resin composition of the present invention is, for example, adjusted in viscosity to be suitable for the coating method by the organic solvent, by a dipping coating method, a flow coating method, a roll 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. Then, at about 6〇~1〇〇. The temperature of the crucible is such that the organic solvent contained in the composition is volatilized and dried (temporarily dried) to form a tackfree coating film. Thereafter, the contact type (or the non-contact side forming mask) is subjected to a direct-exposure exposure by a selective active energy ray, and a non-hσ aqueous solution (for example, 3.3~3% sodium carbonate (s〇dium 八八中中1一-彳^,·,、,硬^, and the carboxyl group of the carboxyl group-containing resin (A), and 2 VIII reverse; upper cyclic sulfhydryl group And/or the thermosetting knife of the cyclic thioether group forms a hard thermosetting component (D) which is excellent in properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. By 敎step =. In addition, 'the photohardenability remaining even in the unreacted state: ☆ diluted == thermal polymerization, which improves the film properties and bonds into heat treatment (thermosetting). • Use can also be applied to the above-mentioned substrate, except that the electro-flexible printed wiring board is formed in advance. 'Paper can be used _ Pan: Can, glass cloth - epoxy resin; Glass · Polyimine, glass cloth / No Fiber cloth epoxy epoxy eucalyptus month: glass cloth / paper epoxy resin, synthetic fiber _ epoxy resin, used to fluorocarbon · pp0f All grades of composite materials such as nitrous acid vinegar (fr·4), copper, pom laminates, polyimine films, ρΕτ films, glass substrates, ceramic substrates, wafer boards, etc. After the photocurable thermosetting resin composition of the present invention is volatilized and dried, a hot air circulating drying furnace, an IR furnace, a hot plate, a convection oven (convection 0ven), or the like can be used (air heating by using steam) The heat source of the method is carried out by a method of countercurrent contacting the hot air in the dryer and a method of sprinkling the nozzle on the support. As described below, the photocuring thermosetting of the present invention is applied. After the resin composition is evaporated and dried, the obtained coating film is exposed (irradiation of active energy rays). The coating film is a cured exposed portion (portion irradiated by the active energy ray). It is used in the aforementioned active energy ray. For the exposure machine, a direct drawing device (for example, a laser direct imaging device that draws a laser directly from a computer with CAD data) can be used, and a metal is mounted. An exposure machine for a lamp, an exposure machine equipped with a (super) high-pressure mercury lamp, an exposure machine equipped with a mercury short-arc lamp, or a direct drawing device using an ultraviolet lamp such as a (ultra) high-pressure mercury lamp. In terms of active energy rays, As long as the laser light having a maximum wavelength in the range of 350 to 410 nm can be used, it may be either a gas laser or a solid laser. Further, the exposure amount varies depending on the film thickness, etc., but generally it is 5 ～200mJ/cm2, preferably 5~100mJ/cm2, more preferably 5~37 201102754 50mJ/cm2. For the direct drawing device, for example, it can be made by Orbotech Co., Ltd., Pentax, etc., as long as it is A device that can perform laser oscillation with a maximum wavelength of 350 to 410 nm can be used in any device. In the development method, a dipping method, a rinsing method, a spraying method, a washing method, or the like can be used. In the developer solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, or the like can be used. An alkaline aqueous solution of ammonia, amines, and the like. The photocurable thermosetting resin composition of the present invention has a method in which a liquid photoresist is directly applied to a substrate, and a solder resist can be applied to a film of polyacid B in advance and dried. Soldering the photoresist layer f. When the photocurable thermosetting resin composition of the present invention is used as a dry film, it is as follows. The dry film system has 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 of the film are laminated. I-resistance The photocurable thermosetting resin composition is applied to a carrier film or a cover film and dried to obtain a layer. When a solder resist layer is formed thereon or a solder resist is formed on the carrier film, a film can be obtained. In the case of the carrier ruthenium film, a 2 to 150 thermoplastic film is used.炙笊 炙笊 溥 溥 寻 寻

S. sinensis developability photocuring thermosetting property = 曰 composition is coated with a knife coater, a press coater (lipeQ machine, a film coater, etc.) at 1 〇 to i5 7 = two Deployed on a carrier film or a cover film, and dried and shaped. The uniformity of the film is uniform. Although a polyethylene film can be used, it is better to use the wire layer than the wire layer. Using dry film on the printed wiring board, it is used as a protective film (permanent protective film) to pay for the secret cover film 'heavy welding photoresist layer using a laminating machine ( Laminator), etc., the substrate formed by the & p\electrode, and the soldering photoresist layer is formed on the substrate formed by the circuit 38 201102754. As with the formed solder resist layer, as long as the above The hardened coating film can be formed by exposure, development, and heat hardening. The carrier film can be peeled off before or after exposure. [Examples] Exemplary embodiments and comparative examples are specifically described according to the present invention. As follows, the present invention is not limited to the following examples at the outset. """"""""""""""""""""""""""""""""""""""""""""""""""""""""""""" Resin (trade name "Shonol CRG951" manufactured by Showa Polymer Co., Ltd., OH equivalent: 119.4) 119 4. Potassium hydroxide 1.19 g and nail stupid 119.4 g, and the inside of the system was replaced with nitrogen § while stirring, f· The temperature was raised by heating. Further, 63 g of propylene oxide was slowly dropped, and the reaction was carried out for 16 hours at 125 to 132 ° C and 0 to 4.8 kg/cm 2 . Thereafter, it was cooled to room temperature, and then added = 89% phosphoric acid L 56 g The reaction solution is mixed and neutralized with hydrogen peroxide to obtain a non-volatile component of 62.1%, a hydroxyl group of i82.2 g/eq., and a phenolic styrene reaction solution of the phenolic varnish type. The addition of alkylene oxide to an average of 1.08 moles. Further, the obtained alkylene oxide type cresol resin obtained from the reaction of alkylene oxide 293.0, acrylic acid 43.2 g, methanesulfone acid 1153 g, mercaptohydroquinone 18 g and hydrazine 252.9 g of benzene was charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube. The air was blown at a rate of 10 ml/min, and the mixture was reacted at 11 ° C for 12 hours while stirring. The water formed by the reaction was distilled as azeotrope with toluene, and 12.6 g of water was distilled off. Thereafter, it was cooled to The resulting reaction solution was neutralized with 35 35 g of a 15% aqueous sodium hydroxide solution at room temperature, followed by washing with water. Thereafter, the terpene was replaced with 1,181 g of diethylene glycol monoethyl ether acetate in an evaporator and distilled off. a novolak type acrylate resin solution. Further, the obtained novolac type acrylate resin solution 332# and triphenylphosphine 1.22g 39 201102754 ^ into a reactor of a scrambler, a thermometer and an air blown tube, to l〇ml /degree / under-into air' - while stirring, slowly add tetrahydrophthalic anhydride ~ 1 〇 1 ° C reaction for 6 hours. A resin bath containing a carboxyl group-containing photosensitive resin having an acid value of a solid content of 71% and a nonvolatile content of 71% was obtained. Hereinafter, this is called varnish Λ-1. Synthesis Example 2, a 5-liter separable flask equipped with a thermometer, a stirrer, and a circulation cooler, and a polycaprolactone diol charged with a polymer polyol (Daicd Chemical Industry Co., Ltd. (PLACCEL 208, molecular weight 830) 1,245 g 2 〇 ig of dihydroxymethylpropionic acid having a dihydroxy group of a carboxyl group, 777 g of isophorone diisocyanate of polyisocyanate, and 2-hydroxyethyl propyl group having a (meth) acrylate of a hydroxyl group Dilute vinegar 119g' and then put 5g of p-methoxyphenol and di-tertiary butyl hydroxy hydrazine benzene. Heated to 6 (rc and stopped while stirring, and added dibutyltin dilaurate. 0.8g. When the temperature in the reaction vessel began to decrease, the mixture was heated again to continue stirring at 80 C, and the absorption spectrum of the isocyanate group (2280 cm-1) was confirmed by infrared absorption spectrum to complete the reaction, thereby obtaining a viscous liquid amino phthalate acrylate compound. Using carbitol acetate to adjust to a nonvolatile content = 50% by mass. A urethane (mercapto) acrylate compound having a carboxyl group having an acid value of 47 mg K 〇 H / g and a nonvolatile content of 50% having a carboxyl group was obtained. Resin solution. Below, this It is called varnish A_2. Synthesis Example 3 In a 2 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, 9 g of diethylene glycol dimethyl ether was added as a solvent, and polymerization was initiated. 31.4 butyl peroxy-2-ethylhexanoate (manufactured by Nippon Oil Co., Ltd., trade name; butyl butyl 0) 21.4 g, and heated to 9 〇. 加热. After heating, methyl group was added thereto. 309.9 g of acrylic acid, 116.4 g of decyl decyl acrylate, and 2-hydroxyethyl decyl acrylate modified by lactone (Piaxei FM1: manufactured by Daicel Chemical Industry Co., Ltd.) 〇 9.8 g 'and a polymerization initiator Bis(4-tert-butyl butyl 201102754 cyclohexyl) peroxydicarbonate g (Nippon Oil Co., Ltd., 〇. TCP) 21.4g - dripped for 3 hours, and then obtained by 6: two Per〇yl a carboxyl group-containing copolymer resin. Further, the reaction is carried out under a nitrogen atmosphere, and the resulting carboxyl group-containing copolymer resin is added with 1% hexyl decyl acrylate (Daicel Chemical Industry Co., Ltd.). σ : clothing oxygen ring A200) 363.9g ^ ^ ^ ^ ^ ^ f 3.6g, methyl ether L8 〇 g ' by heating to the boot, and stirring to open = ring Addition reaction. After 16 hours, Huiji 々 动 mobility mgK0H / g, weight average molecular weight of 25, "fat solution. Hereinafter, this is called varnish A-3. The secret comparison of synthesis example 1 charged o-nonylphenol Novolac type epoxy resin (manufactured by Dainippon Oil Co., Ltd., EHCLON N-695, softening temperature 9n: J winter f 214, average functional group number 7.6) 1070 g (epoxypropyl number (aromatic / s moir), Acrylic acid 360g (5.0 moles), and hydroquinone l5g in two ^ two) Xue set 0 diethyl ether acetate 600g, heated to l〇〇t and stirred 'to be; ^ again 'filled with diphenylphosphine 4.3g, heated to Ll 〇 °c, the reaction was carried out for 2 hours, and the field was further subjected to a reaction for 12 hours. 415 g of aromatic cigarette (^150) and 456.0 g of tetrahydrophthalic anhydride (3.0 mol) were added to the obtained reaction liquid, and the reaction was carried out at 110 ° C for 4 hours, and after cooling, a solid acid value of 89 mgKOH/g was obtained. , 65% resin solution of solids. Hereinafter, it is called varnish R-1. Comparative Synthesis Example 2 Ingot phenolic novolac type epoxy resin (Japan Chemicals Co., Ltd. EOCN-104S, softening point 92 〇C, epoxy equivalent 220) 22 parts, di-m-propionic acid 134 parts, acrylic acid 648.5 parts 4 parts of mercaptohydroquinone, 1131 parts of carbitol acetate vinegar and 484.9 parts of solvent oil 'heated to 9 (TC and mixed, dissolved reaction mixture. Further, the reaction liquid was cooled to 60 ° C, charged with triphenyl Phosphine 13 8 41 201102754 parts, heated to 100 ° C, and allowed to react for about 32 hours to obtain a reactant of acid value 〇 5 mg KOH / g. Further, 364.7 parts of tetrahydrophthalic anhydride and carbitol acetate 137.5 were added thereto. 58.8 parts of the solvent oil and the solvent oil were heated to 95 ° C, and the reaction was carried out for about 6 hours, and the mixture was cooled to obtain a resin solution of a carboxyl group-containing photosensitive resin having a solid acid value of 40 mgKOH/g and a nonvolatile content of 65%. Varnish R_2. Comparative Synthesis Example 3 400 parts of bisphenol F-type solid epoxy resin having an epoxy equivalent of 800 and a softening temperature of 791 was dissolved in 925 parts of surface alcohol and 462.5 parts of disulfoxide, and then scrambled at 70°. C. 81.2 parts of 98.5% NaOH was added over 100 minutes. After the addition, the reaction was further carried out at 70 ° C for 3 hours. Most of epichlorohydrin and dimethyl hydrazine are distilled off under reduced pressure, and a reaction product containing a by-produced salt and disulfoxide is dissolved in 75 parts of decyl isobutyl ketone, and then 30% NaOH is added. The reaction was completed at 70 ° C for 1 hour, and after completion of the reaction, the mixture was washed twice with 200 parts of water. After the separation of the oil and water, the methyl isobutyl ketone was distilled and recovered by the oil layer to obtain an epoxy equivalent of 29 Å and a softening temperature. 370 parts of the epoxy resin (al). The obtained epoxy resin (a_1) 29 parts (1 〇 equivalent), 720 parts (1 〇 equivalent) of acrylic acid, 28 parts of hydrazinohydroquinone, card Alcohol acetate 195 was injured, heated to 90 C, mixed and dissolved in the reaction mixture. Further, the reaction solution was cooled to 60 ° C, charged with 16 parts of triphenylphosphine, heated to cut. c, into the 彳The reaction was carried out for 32 hours to obtain a reactant of acid value i 〇 mg K 〇 H / g. Further, here, amber was charged. acysage 786 parts (7.86 mol), 423 parts of carbitol acetate, and heated to 95 C, The reaction was carried out for about 6 hours to obtain a resin solution having a solid acid value of 100 mgKOH/g and a solid content of 65%. Hereinafter, this is referred to as varnish R-3. Examples 1, 2 and Comparative Examples 丨 ~3 The resin solution obtained in each of the synthesis examples is mixed and mixed with the ratio (parts by mass) shown in Table 1 at the respective points shown in Table 1 below, and the mixture is kneaded by a scrambler, and then kneaded by a two-roll mill. Modification of photocurable thermosetting resin 42 201102754 Composition. The obtained photocurable thermosetting resin composition is subjected to flask combustion treatment ion chromatography according to the JPCA specification, thereby quantifying the halide content (chlorine and bromine) total). The results are shown in Table 1. [Table 1] Composition (parts by mass) Example Comparative Example 1 2 1 2 3 Varnish Α-1 141 Varnish Α-2 200 Varnish R-1 154 Varnish R-2 154 Varnish R-3 154 Photopolymerization initiator ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1, ι-(ο-acetyl) (Irgacure OXE 02 * Ciba Japan KK 1 1 1 1 1 Maleic acid modified polybutadiene Riconl 30MA8 (manufactured by Sartomer) 5 5 5 5 5 Halide content (ppm) ------- 8 21 256 298 332 As is apparent from the results shown in Table 1, the halogen (10) was used as the composition of the present invention as compared with the photocurable thermosetting tree test product in which (4) the epoxy resin was made into the epoxy resin. Examples 3 to 13 and Comparative Examples 4 to 6 43 201102754 The resin solution of the above-mentioned synthesis example was mixed with the various components shown in Table 2 below at a ratio (parts by mass) shown in Table 2, and after preliminary mixing by a stirrer, The composition was kneaded by a three-roll mill, and a photosensitive resin composition for soldering photoresist was prepared. Here, the degree of dispersion of the obtained photosensitive resin composition was 15 μm or less as measured by particle size measurement by a grind meter manufactured by Eriksen Co., Ltd. 44 201102754 [Table 2] Composition (parts by mass) f Example Comparative Example 3 4 5 6 7 8 9 10 11 12 13 4 5 6 Varnish A-1 141 141 141 141 141 141 141 141 99 99 85 141 A-2 60 A-3 56 R-1 62 77 R-2 77 R-3 154 Photopolymerization initiator (B-1)* 1 15 (B-2)* 2 1 (Β-3)Φ 3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Thermosetting component (Dl)* 4 15 15 15 15 15 15 15 (D-2)* 5 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Riconl30MA 8*6 7.5 10 22 10 15 15 15 15 15 20 15 Riconl31MA 5” 22 CN301*8 22 CN307*9 15 Poly bd*10 10 PB3600*11 20 20 17 17 17 17 15 Benzoguanamine 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 45 201102754 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 Colorant (G-1)”2 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 ( G-2)*13 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 morpholidine 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 0.2 0.1 0.1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 2 2 2 2 2 2 2 2 2 barium sulfate"6 80 80 80 80 80 80 80 80 80 80 80 80 80 80 DHT-4A·17 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Defoamer 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Organic solvent <18 5 5 5 5 5 5 5 5 5 5 5 5 5 5 DPHA*19 15 15 15 15 7.5 10 15 15 15 15 15 15 15 15 TPA-B80E*20 17.5 17.5 Mw-IOOLM* 21 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 46 201102754 Remarks *1 : 2-Methyl-1-(4-indolethiophenyl)-2-indole propane -1-ketone (Irgacure 907: manufactured by Ciba Japan KK) *2 : 2,4-diethyl 9-oxosulfide clU nJ (made by KAYACURE DETX-S Nippon Kayaku Co., Ltd.) *3 : Ethyl ketone ' l -[9-ethyl-6-(2-indolyl)-9H-carbazol-3-yl]-1,1-(〇_乙肟肟) (Irgacure OXE 02 : Ciba Japan KK) : Phenolic novolak type epoxy resin (RE306CA90: manufactured by Sakamoto Chemical Co., Ltd.) *5 : Dixyxylene (biXylen〇l) type epoxy resin (γχ_4〇) 〇〇: Japan Epoxy Resin Co., Ltd.) *6 · Maleic acid modified polybutylene dichloride (manufactured by Sartomer Co., Ltd.) *7. Butadiene diacid modified polybutylene dichloride (manufactured by Sartomer Co., Ltd.) *8. Dimethyl acrylate dibutyl vinegar (manufactured by Sartomer Co., Ltd.) *9: Dibutyl acrylate polybutylate (manufactured by Sartomer Co., Ltd.) *10 *11 *12 *13 *14 *15 *16 *17 *18 *19 *20 *21 Hydroxy-terminated liquid polybutadiene (manufactured by Idemitsu Kosan Co., Ltd.) Epoxidized polybutadiene (Daicel Chemical Industry Co., Ltd.) CI Pigment Blue 15 : 3 CI Pigment Yellow 147 2-Hydroxythiobenzothiazole Antioxidant (Ciba Japan KK) B_3〇 (manufactured by Seiko Chemical Co., Ltd.) Hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd.) Diethylene glycol monoethyl ether Acetate penta-propionic acid dipivalol ester block isocyanate (made by Asahi Kasei Chemicals Co., Ltd.) Methylated di- melamine resin (manufactured by Sanwa Chemical Co., Ltd.) Performance evaluation: <Optimum Exposure amount> A circuit pattern substrate having a copper thickness of 18 μm was subjected to roughening treatment on a copper surface (Mec H bond CZ-8100 manufactured by Mec Co., Ltd.), washed with water, dried, and then fully coated by screen printing. Examples and Comparative Examples of light curable thermosetting resin composition to 80¾ circulating hot air drying oven 6047201102754 minutes. After drying, the exposure apparatus equipped with a high-pressure mercury lamp was exposed through a staged exposure meter (Kodak No. 2), and developed (3 〇, 0.2 MPa, 1 wt% sodium carbonate 7 JC solution) for 60 seconds, and remained. The pattern of the staged exposure meter has 7 segments as the optimum exposure amount. <Developability> The photocurable thermosetting resin composition of the examples and the comparative examples was applied to a copper clad substrate by a screen printing method to make the film thickness after drying 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 obstructing the sodium acid aqueous solution, 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, and the formed copper foil substrate was dried at 80 ° C from 20 minutes to 80 minutes. The substrate was taken out by the mother Pwj for 10 minutes, and allowed to cool to room temperature. On the substrate, a 1 wt% sodium carbonate aqueous solution at 30 ° C was developed for 6 sec under the conditions of a squeezing pressure of 2 MPa, and the maximum allowable drying time without residual residue was taken as the maximum development period. <Tack> The compositions of the examples and the comparative examples were completely coated on a copper foil substrate formed of a type by screen printing to 80. (: The hot air circulating drying oven was dried for 3 3 minutes, and allowed to cool to room temperature. The negative film made of PET was coated on the substrate, and the HMW-GW20 manufactured by RC Corporation was pressed under a reduced pressure of 1 minute, and eight or less. The reference ^ evaluates the adhesion state of the film when the negative film is peeled off. 〇 · When the film is peeled off, there is no resistance at all, and no trace remains on the film. △: When the film is peeled off, there is a slight resistance, and the film has some Traces X. When the film is peeled off, there is resistance, and there is a clear trace on the film. Characteristic test: 48 201102754 丨 Printed on the screen, fully coated with the composition of the examples and comparative examples in Figure ΐC 0 minutes, let cool to room temperature.

In the "substrate to carry a 5 pressure mercury lamp exposure I to weld light resistance ® (four) light, under the side pressure G. 2MPa exposure lwt% sodium carbonate aqueous solution for development 9 sec seconds to obtain a photoresist exposure amount lOOmmJ / cm2 The substrate was subjected to ultraviolet irradiation using a ϋν conveyor furnace, and then cured at 60 Torr: 60° and hardened. The obtained printed substrate (evaluation substrate) was evaluated as follows; Characteristics: <Acid resistance> The evaluation substrate was immersed in a 10 vol% H 2 S 4 aqueous solution at room temperature for 30 minutes to visually confirm infiltration or eiute of the coating film, and further confirm the peeling of the coating layer. Peeling: 〇: Unrecognized change △: only some changes X: swelling or swelling on the coating film < and the testability> The substrate was immersed in a 10 vol% aqueous NaOH solution for 30 minutes at room temperature to visually confirm the penetration. Or the elution of the coating film, and further confirm the peeling due to peeling. 〇: Confirmation of no change △: only some changes X: expansion or swelling on the coating film <solder heat resistance> The rosin-based flux is applied ( Flux evaluation substrate, pre-impregnated in the setting The solder bath of 260 , was cleaned with a modified alcohol, and then evaluated by visual observation of expansion and peeling of the photoresist layer. The criteria for determination are as follows. 49 201102754 〇: No peeling was observed even if the immersion was repeated three times or more in 10 seconds. △: There was some peeling when the 10 second immersion was repeated three times or more. X : 10 seconds of immersion within three times, the photoresist layer was expanded and peeled off. <Caidian Refractory Gold > Commercially available electroless nickel plating The bath and the electroless gold bath were subjected to mineralization under the conditions of nickel 5 μm and gold 0.05 μm, and tape peeling was used to evaluate the peeling of the photoresist layer or the presence or absence of plating, and the tape was peeled off. The peeling of the photoresist layer was evaluated. The criterion was as follows: ◎: No penetration or peeling was observed. 〇: Some penetration after plating was confirmed, but no peeling occurred after peeling off the tape. △: plating was observed. A little penetration after application, and peeling after peeling off. X: Peeling after plating. <PCT resistance> Using PCT device (HAST SYSTEM TPC-412MD manufactured by Espec Co., Ltd.) at 121〇 C, saturated, 〇. 2MPa conditions will be shaped The evaluation substrate of the solder resist cured film was treated for 168 hours, and the state of the coating film was evaluated. The criteria for determination are as follows. ' ' 〇: no expansion, peeling, discoloration, or dissolution Δ: some expansion, peeling, discoloration, dissolution x ····································································································· The obtained evaluation substrate was -55 by a thermal shock tester (manufactured by ETAC Co., Ltd.). (: / 30 minutes ~ 150 ° C / 30 minutes as a ^ ring to carry out a 1 〇〇〇 cycle of resistance test. After the test 'visual observation of the treatment ^ hardening 50 201102754 film, quasi-judgment of the occurrence of cracks. Cracking rate is less than 30% △. Cracking rate is 30~50% X. Cracking rate is 50% or more <HAST characteristics> There are ^(C〇mb) type electrodes (line/space = 30 μm /3〇micron) Respiratory beauty 3 = photoresist hardened coating film 'and the evaluation substrate. The tank with a high voltage of 5V, 168 hours and HAST H in the tank at 130C and 85% humidity is placed. The internal insulation resistance value was evaluated according to the following criteria. 〇: 108 Ω or more △ : 1 〇 6 to 108 Ω χ: ιο6 ω or less [Table 3]

Characteristic Examples Comparative Example—------ 3 4 5 6 7 8 9 10 11 12 13 4 5 6 Optimum Exposure (mJ/cm2) 400 150 150 150 150 150 150 150 120 120 150 150 150 100 33 35 33 32 30 31 27 27 35 33 36 33 35 48 Maximum development cycle (minutes) 70 60 60 60 60 60 60 60 60 60 60 60 60 40 Viscosity ------ XXXXXXXXXXX Δ 〇X Acid resistant _·} Health - ---~~_ 〇〇〇〇〇〇0 〇〇〇〇〇〇〇Testability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 无 无 〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇 〇 〇 PCT resistance PCT 〇 51 51 51 51 201102754

Examples 4 to 21 and Comparative Examples 7 to 9 The compositions of Examples 3, 4, 6, 8, 1〇, 11, 12, 13 and Comparative Examples 4, S, and C were prepared on a PET film. , * The composition was diluted with methyl ethyl ketone, and a photosensitive resin composition layer. Further, a film of /f3G indexing 2 was used as Example 14 = two-two-coated film to prepare a dry <dry film evaluation> copper = enamel peeling cover film, and a pattern-type coating subtraction was formed. Further, the exposure was carried out under the same conditions as those of the earth plate of the embodiment. After the exposure, the carrier was stripped, and the thief's lwt% sodium carbonate was developed under the condition of G.2Mpa to obtain a photoresist pattern. The substrate was subjected to ultraviolet irradiation at 16 ° C for 6 并 minutes and hardened under a UV conveyor belt furnace at a light setting of OO mJ/cm 2 . According to the obtained hardened film test substrate, the evaluation test of each characteristic was carried out by using the above test method and evaluation method. The results are shown in Table 4. [Table 4] Comparison of characteristic examples ί 14 15 16 17 18 19 20 21 7 8 9 Optimum exposure (mJ/cm2) 400 150 150 150 150 120 120 150 150 150 100 Developability (seconds) 35 37 35 33 39 38 35 38 35 38 51 52 201102754

Acid resistance, economy, solder, heat resistance, resistance to electric clock, gold 〇 〇〇 〇〇 〇〇〇〇〇Δ 〇 resistance to PCT 〇〇〇〇〇〇〇 △ 〇 XX cold thermal shock 〇〇〇〇〇〇〇〇 X Δ 〇 HAST characteristic 〇〇〇 Δ 〇〇〇 Δ 〇 XX as the table 3 and the results shown in Table 4, it is apparent that the photocurable thermosetting resin composition of the present invention has both PCT resistance, thermal shock resistance, and HAST characteristics (electrical characteristics) which are necessary for soldering photoresist for a semiconductor package. ) is extremely useful as a photocurable thermosetting resin composition. 53

Claims (1)

201102754 VII 1. 2. 4. δ δ Green Patent Range: ^ ^ Photocurable 埶 曰 composition developed by alkaline aqueous solution, characterized by containing ♦ · ",, hardenable tree elastic g) based resin (4) , photopolymerization initiation _), and functional group-containing carboxyl group-containing resin (A) does not include the use of ring gas starting materials containing the county lion. (4) I as a photo-curing thermal product of the first item Wherein the slow-base resin (4) has a mass of 100 f = === (8) of 〇.01 to 30 mass; and the amount of the elastomer (C) is 5 to 60 parts by mass. The light-hardening thermosetting resin group ίοΐ'ί曰. The compounding amount of the resin (eight) is 20 to 60 mass of the composition. /〇. For applying the full-length light-hardening thermosetting resin composition of the first item, The carboxyl group-containing resin (Α) is a photocurable thermosetting resin composition according to the first aspect of the invention, wherein the carboxyl group-containing resin (Α) is a photosensitive resin group. The acid value is 4〇15〇m K〇H/g. 6. The composition of the photocurable thermosetting resin according to item 1 of the patent application scope The weight average molecular weight of the slow-setting resin (A) is 2, 〇〇〇 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 And the photopolymerization initiator (B) is selected from the group consisting of a photopolymerization initiator (B1) having a group represented by the general formula (I); having the following general formula (II); a group of α-amino-bromophenone-based photopolymerization initiators (Β2); and a group having a group represented by the following formula (III): a sulfonylphosphine-based photopolymerization initiator (Β3) More than one type of photopolymerization initiator: 54 201102754 —C=N—〇—C—R2 II R1 O (Π) R7, 〇, II R8〆〇(m) wherein R1 represents a hydrogen atom; a phenyl group substituted or unsubstituted with an alkyl group having 1 to 碳, a benzene or an S atom; Or unsubstituted and having more than one oxygen atom in the middle of the alkyl chain; an alkyl group having 1 to 20 carbon atoms without an oxygen atom; a fluorinated group having a carbon number of 5 to 8 ♦ a number of 2 to 20 calcined (aikan〇) a yl) group; or a benzyl group substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms; or a substituted or unsubstituted benzene group having an alkyl group having 1 to 6 carbon atoms, a phenyl group or a tooth atom; a group of carbon atoms having 1 to 20 carbon atoms which are substituted or unsubstituted by one or more hydroxyl groups and having one or more oxygen atoms or no oxygen atoms in the middle of the alkyl chain; a cycloalkyl group having 5 to 8 carbon atoms; 2 to 2 〇 醯 ;; or a phenyl group substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms; R 3 and R 4 each independently an alkyl or aralkyl having 1 to 12 carbon atoms; Base; R and R are not independent hydrogen atoms, alkyl 1 to 6 carbon nanotubes, or cyclic alkyl ether groups bonded with a diradical; R7 and R8 represent independent carbon numbers 1 ～1〇的直链状或55 201102754 is a aryl group, a hexyl group, a pentyl group, an aryl group, or a aryl group substituted with a dentate atom or an alkoxy group, wherein R7 and R8 are One may represent a RC(=0)- group, and R is a hydrocarbon group of a carbon number. 0 8. 9. 10. 11. 12. 13. 14. 15. Photocuring thermosetting as in claim 1 A resin-containing composition in which the functional group-containing elastomer (C) is a butadiene derivative. The photocurable thermosetting resin composition according to the first aspect of the invention, further comprising a thermosetting component and a coloring agent (6). The photocurable thermosetting resin composition according to claim 9 of the patent scope, Wherein the thermosetting component (D) has two or more cyclic ether groups and cyclic thioether groups in one molecule, or two or more cyclic ether groups or cyclic thioethers in one molecule/min. base. The film of the dry film is characterized in that the resin composition layer of the dry film is applied to a film and dried by a photocurable cerium hardening resin composition according to any one of the items i i 1G. A cured product obtained by applying a coating film obtained by applying a glazing 5-hardening thermosetting resin composition to a substrate and drying it as in the application of the above-mentioned Patent Application No. 1-3 to the present invention. A cured product obtained by laminating a resin composition layer as in the above-mentioned U.S. Patent Application No. 5 on a substrate and photohardening. And having a hardened film which is applied to a substrate and dried according to any one of the first to tenth aspects of the patent scope, and is cured by light irradiation with == The patterned rear wiring board 'haves a hardened film'. The hardened film is photohardened by the resin composition layer 2 of the dry film of SC. The figure is shown in Fig. 56. 201102754 4. Designated representative figure: (1) Representative figure of the case For: the (none) map. (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: 2 201102754 Patent description of the invention (The format and order of this manual, please do not change it, ※ mark part ※Application No.: W丨. ※Application date: Classification: 1. Name of the invention: (Chinese/English) Photocurable thermosetting resin composition, dry film using the composition, and printing using the materials The present invention provides a photocurable thermosetting resin composition composition, a dry film and a cured product using the composition, and a printed wiring board in which the photohardenable heat hardening is provided. The resin composition can form a hardened film which is extremely important in semiconductor package soldering resistance, such as PCT resistance, HAST resistance, electroless gold plating, and thermal shock resistance, and the printed wiring board These materials are used to form a cured film such as a solder resist. The solution of the present invention is through an alkaline aqueous solution. A photocurable thermosetting resin composition comprising: a carboxyl group-containing resin (A) (excluding a ruthenium-containing resin using % Oxygen ruthenium as a starting material), and a photopolymerization initiator (B) And a functional group-containing elastomer (C). It is preferable to further contain a thermosetting component (D), and further preferably further contain a coloring agent (G). The carboxyl group-containing resin (A) is not a base. More preferably, the functional group-containing elastomer (C) is preferably a butadiene derivative. III. English Abstract: 201102754 Invention Patent Specification (The format, order of the specification, please do not change, ※ Marking part ※Application number: W丨. ※Application date: Classification: 1. Name of the invention: (Chinese/English) Photocurable thermosetting resin composition, dry film using the composition, and use of the material The present invention provides a photocurable thermosetting resin composition composition, a dry film and a cured product using the composition, and a printed wiring board in which the photohardening is provided. The thermosetting resin composition can form a hardened film which is extremely important in semiconductor package soldering resistance, such as PCT resistance, HAST resistance, electroless gold plating, and thermal shock resistance, and the printing is performed. The wiring board is formed by using these materials to form a cured film such as a solder resist. The solution of the present invention is a photocurable thermosetting resin composition which can be developed by an aqueous alkaline solution, and contains a carboxyl group-containing resin ( A) (except for the ruthenium-containing resin containing % oxygen tree ruthenium as a starting material), a photopolymerization initiator (B), and a functional group-containing elastomer (C). It is suitable to further contain thermosetting property. Component (D) preferably further contains a coloring agent (G). The above-mentioned carboxyl group-containing resin (A) is not a substituent, and more preferably has a photosensitive group. Further, the functional group-containing elastomer (C) is preferably a butadiene derivative. III. English Abstracts: 201102754 IV. Designation of Representative Representatives: (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: