TWI483982B - A photohardenable thermosetting resin composition, a dry film and a cured product, and a printed circuit board - Google Patents

Description

Photocurable thermosetting resin composition, dry film and cured product, and printed circuit board using same

The present invention relates to a photocurable thermosetting resin composition which can be developed with an aqueous alkali solution, in particular, a solder resist composition which is photocured by ultraviolet exposure or laser exposure, the dry film and cured product, and the use thereof. A printed circuit board of the formed hardened film.

At present, a part of the printed circuit board for the livelihood and the solder resist of almost all industrial printed circuit boards are formed by high-temperature and high-density, and are formed by ultraviolet light irradiation and development to form an image with heat and/or light. The liquid-developed solder resist of the final work hardening (true hardening) is carried out, and the photo solder resist which uses an alkali-based aqueous solution of the developing solution becomes a mainstream in consideration of environmental problems, on the actual printed circuit board. A large number of them are used in manufacturing. In addition, with the increase in density of printed circuit boards in which electronic devices are light and thin in recent years, solder resists are required to have workability and high performance.

However, current alkali-developing type photo solder resists have problems in terms of durability. That is, it is inferior in alkali resistance, water resistance, heat resistance, and the like as compared with those of the conventional thermosetting type and solvent developing type. It is considered that the alkali-developable photo-resist resist can be alkali-developed, and the hydrophilic base is a main component, and the chemical liquid, water, water vapor, and the like are easily impregnated, and the chemical resistance is lowered or the photoresist film is adhered to copper. reduce. As a result, the alkali resistance as a chemical resistance is weak, and in particular, in a semiconductor package such as a BGA (spherical matrix) or a CSP (wafer size package), PCT resistance (pressure cooker test resistance) called moist heat resistance is required, but it is as strict as this. Under severe conditions, it can only withstand the current situation of several hours to ten hours. Further, in almost all cases where a voltage state was applied under a humidification condition, the HAST test (highly accelerated life test) was confirmed to have a problem due to migration.

In recent years, it has gradually changed to surface mounting and environmental protection problems, and the use of lead-free materials has a tendency to increase the temperature on the packaging. As the temperature at the inside and the outside of the package is significantly higher, the conventional liquid photosensitive photoresist has a problem that the coating film is cracked by the heat and peeled off from the substrate or the sealing material, and the improvement is sought.

Further, the carboxyl group-containing resin used in the conventional solder resist generally uses an epoxy acrylate-modified resin derived by modification of an epoxy resin. For example, JP-A-61-243869 (Patent Document 1) discloses a photosensitive resin, a photopolymerization initiator, and a diluent for adding an anhydride to a reaction product of a novolac type epoxy compound and an unsaturated monobasic acid. A solder resist composition composed of an epoxy compound. Japanese Patent Publication No. 3-250012 (Patent Document 2) discloses an epoxy resin addition (meth)acrylic acid obtained by reacting a reaction product of salicylaldehyde with monovalent phenol with epichlorohydrin, and further A solder resist composition comprising a photosensitive resin obtained by a reaction of a carboxylic acid or an anhydride thereof, a photopolymerization initiator, an organic solvent, or the like.

Generally, an epoxy acrylate-modified resin, which is used as a raw material, contains almost a large amount of chlorine ion impurities, and it is very difficult to remove the epoxy acrylate after it is modified. Further, the insulating letter of the insulating material containing chloride ion impurities is a well-known fact.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-61-243869 (Patent Application)

[Patent Document 2] Japanese Patent Laid-Open No. Hei-3-250012 (Application No.)

The present invention has been made in view of the problems of the prior art described above, and its main object is to provide an important PCT resistance, HAST resistance, electroless gold plating resistance, and cold and heat resistance which can be formed as solder resist for semiconductor packaging. A photocurable thermosetting resin composition of a cured film.

Further, an object of the present invention is to obtain a dry film and a cured product having excellent properties described above, and a printed circuit of the cured film or a hardened film such as a solder resist by using a cured product, by using the photocurable thermosetting resin composition. board.

In order to achieve the above object, according to the present invention, there is provided a light which can be developed with an aqueous alkali solution containing a carboxyl group-containing resin (except for a carboxyl group-containing resin which is an epoxy resin as a starting material), a photopolymerization initiator, and a hydroxyl group-containing elastomer. A curable thermosetting resin composition.

The carboxyl group-containing resin is preferably a hydroxyl group-free resin, and further preferably has a photosensitive group. Further, the hydroxyl group-containing elastomer is preferably a butadiene or isoprene derivative. In the suitable aspect, the photocurable thermosetting resin composition of the present invention further contains a thermosetting component, and is preferably a solder resist containing a colorant.

Furthermore, according to the present invention, a photocurable thermosetting dry film obtained by applying the photocurable thermosetting resin composition to a film and drying the film, and the photocurable thermosetting resin composition or dried The film photohardening is preferably a cured product obtained by photohardening a light source having a wavelength of 350 to 410 nm into a pattern.

Furthermore, according to the present invention, it is also possible to provide a photocurable thermosetting resin composition or a dry film which is cured by an active energy ray, preferably by direct light curing of ultraviolet rays into a pattern, and then thermally cured. A printed circuit board that hardens the film.

In the photocurable thermosetting resin composition of the present invention, a component which can be developed by an aqueous alkali solution is used, and a carboxyl group-containing resin which does not use an epoxy resin as a starting material is used, and a chloride ion impurity is remarkably low, and the obtained hardened coating film is obtained. The electrical properties are improved, and in combination with the hydroxyl group-containing elastomer, not only the flexibility of the cured coating film is improved, but also the stress relaxation during the over-hardening of the coating film is greatly effective. Therefore, by using the photocurable thermosetting resin composition of the present invention, it is possible to form a cured film having PCT resistance, HAST resistance, electroless gold plating resistance, and cold and heat resistance which are important as solder resist for semiconductor packaging.

[Best Mode for Carrying Out the Invention]

As described above, the photocurable thermosetting resin composition of the present invention is characterized by containing a carboxyl group-containing resin, a photopolymerization initiator, and a hydroxyl group-containing elastomer which are not derived from an epoxy resin.

The carboxyl group-containing resin may be a carboxyl group-containing resin which does not use an epoxy resin as a starting material, and various conventional carboxyl group-containing resins in which a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in a molecule are photohardened may be used. The surface of the property or the development resistance is preferred. Next, the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof. In addition, when only the carboxyl group-containing resin having no ethylenic unsaturated double bond is used, in order to make the composition photocurable, it is necessary to use a compound having one or more ethylenically unsaturated groups in the molecule as described below (photosensitive monomer). ).

Specific examples of the carboxyl group-containing resin which can be used in the present invention are preferably the compounds exemplified below (any of an oligomer and a polymer).

(1) bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehyde, condensate of dihydroxynaphthalene and aldehyde, etc. a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with an epoxide such as ethylene oxide or propylene oxide, and reacting with an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid The carboxyl group-containing photosensitive resin obtained by reacting the reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride or adipic acid.

(2) a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, and a monocarboxylic acid containing an unsaturated group, and reacting the obtained product A carboxyl group-containing photosensitive resin obtained by reacting a 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 polyol, a polyether polyol, a polyester polyol, Polyaddition reaction of a diol compound such as a polyolefin-based polyol, a propylene-based polyol, a bisphenol A-based epoxide addition diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group in a urethane resin The terminal end contains a carboxyl group-containing urethane resin obtained by reacting with an acid anhydride.

(4) adding a hydroxyalkane to a synthesis of a carboxyl group-containing urethane resin which is subjected to a polyaddition reaction of a diisocyanate with a carboxy group-containing diol compound such as dimethylolpropionic acid or dimethylol-butyric acid and a diol compound; A terminal (meth)acrylonitrile-containing carboxyl group-containing urethane resin obtained by a compound having one hydroxyl group and one or more (meth)acryl fluorenyl groups in a molecule such as a (meth) acrylate.

(5) adding a mixture of a diisocyanate and a carboxyl group-containing carboxyl formate resin having a polyaddition reaction of a carboxyl group-containing diol compound and a diol compound, and adding a mixture of isophorone diisocyanate and pentaerythritol triacrylate. A terminal (meth)acrylonitrile-containing carboxyl group-containing urethane resin obtained by having a compound having one isocyanate group and one or more (meth)acryl fluorenyl groups in a molecule such as a reactant.

(6) a carboxyl group obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene Resin.

(7) A polyfunctional oxetane resin described later is reacted with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to form a first-stage hydroxyl group-added phthalic anhydride or tetrahydrophthalic anhydride. a carboxyl group-containing polyester resin such as hexahydrophthalic anhydride or the like, and further added to one molecule such as a glycidyl (meth) acrylate or an α-methyl propyl propyl (meth) acrylate. 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 having a cyclic ether group and a (meth) acrylonitrile group in one molecule of the carboxyl group-containing resin of the above (1) to (7).

In the present specification, (meth) acrylate means a general term for acrylate, methacrylate and a mixture thereof, and other similar expressions are also the same.

The carboxyl group-containing resin used in the present invention is characterized in that it has no halide content as a starting material and has a very low halide content. The carboxyl group-containing resin used in the present invention has a chloride ion impurity content of 100 ppm or less, more preferably 50 ppm or less, still more preferably 30 ppm or less.

Further, the carboxyl group-containing resin used in the present invention can easily obtain a resin containing no hydroxyl group. It is generally known that although the presence of a hydroxyl group is excellent in adhesion due to hydrogen bonding, the moisture resistance is remarkably lowered. The following is an explanation of the superiority of the carboxyl group-containing resin of the present invention in comparison with the epoxy acrylate-modified resin used in general solder resist.

Chlorine-free phenol novolac resin is readily available. By partially acrylating the alkyl oxide-modified phenol resin and introducing an acid anhydride, it is possible to obtain an equivalent amount of 300 to 550 in the double bond, an acid value of 40 to 120 mgKOH/g, and theoretically no hydroxyl group. Resin.

Further, all of the epoxy groups of the epoxy resin synthesized by the phenol novolak-like resin are all acrylated, and the acid anhydride is introduced into all the hydroxyl groups, and the double bond amount is 400 to 500, and the acid value becomes very large even after the exposure. It became impossible to obtain a coating film having developability. Further, due to the high acid value, the water resistance is poor, the insulation reliability, and the PCT resistance are remarkably lowered. That is, the epoxy acrylate-based resin derived from a similar phenol novolak type epoxy resin makes it extremely difficult to completely have no hydroxyl group.

Further, the urethane resin can be easily synthesized into a resin containing no hydroxyl group by combining the equivalent of a hydroxyl group and an isocyanate group. The preferred resin is an isocyanate compound which does not use phosgene as a starting material, a carboxyl group-containing resin having a chloride ion content of 30 ppm or less synthesized from a raw material which does not use an epihalohydrin, and further preferably theoretically contains no hydroxyl group. Synthetic resin.

From such a viewpoint, the carboxyl group-containing resins (1) to (5) shown in the above specific examples are particularly preferably used.

Further, the carboxyl group-containing resin (6) obtained by copolymerizing the above-mentioned unsaturated group-containing compound is used as a compound having a cyclic ether group and a (meth)acryl fluorenyl group in one molecule, so that 3,4- The carboxyl group-containing photosensitive resin reacted with epoxycyclohexylmethyl methacrylate is preferably used because it does not use an alicyclic epoxy group.

Further, the carboxyl group-containing resin (6) is reacted with a glycidyl methacrylate as a compound having a cyclic ether group and a (meth) acrylonitrile group in one molecule, or as a compound containing an unsaturated group. The copolymerization of glycidyl methacrylate has a concern that the mass of chlorine ions is increased. Further, in the synthesis of the urethane resin, an epoxy acrylate-modified raw material may be used as the diol compound. Although chloride ion impurities are mixed in, it can be used from the viewpoint of controlling the mass of chlorine ions.

As described above, the carboxyl group-containing resin can be developed into an aqueous alkali solution because the backbone ‧ polymer side chain has a plurality of free carboxyl groups.

Further, the acid value of the carboxyl group-containing resin is preferably in the range of 40 to 150 mgKOH/g, more preferably 40 to 130 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, alkali development becomes difficult. Further, when it exceeds 150 mgKOH/g, the exposure portion is dissolved by the developer, and the line becomes thinner than expected, and the exposure portion is caused by the situation. The unexposed portions cannot be distinguished, and the developer is dissolved and peeled off, making it difficult to draw a normal photoresist pattern, which is not preferable.

Further, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, and is usually 2,000 to 150,000, and more preferably in the range of 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the non-stick property may be deteriorated, and the moisture resistance of the coating film after exposure may be poor, and film thinning may occur during development, and the resolution may be greatly deteriorated. Further, when the weight average molecular weight exceeds 150,000, the developability is remarkably deteriorated, and the storage stability is poor.

The amount of the carboxyl group-containing resin to be used is 20 to 60% by mass, preferably 30 to 50% by mass, based on the total composition. When it is less than the above range, it is not preferable because the film strength is lowered. In addition, when it is more than the above range, the viscosity is high, and the coating property or the like is not preferable.

The photopolymerization initiator used in the present embodiment can be used as a photopolymerization initiator of an oxime ester group, a photopolymerization initiator of α-aminoethenyl photopolymerization initiator, and a mercaptophosphine oxide photopolymerization initiator. It is preferred to use at least one or more of these agents.

The oxime ester photopolymerization initiator may, for example, be CGI-325, IRGACUREOXE01, IRGACUREOXE02 manufactured by Ciba Specialty Chemicals Inc., N-1919 manufactured by ADEKA, ADEKA NCI-831, or the like.

Further, a photopolymerization initiator having two oxime ester groups in the molecule may be used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula.

【化1】

(wherein X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (alkyl group having 1 to 17 carbon atoms, and 1 to 8 carbon atoms) Alkoxy group, amine group, alkylamino group having a carbon number of 1 to 8 or substituted by a dialkylamino group), naphthyl group (alkyl group having 1 to 17 carbon atoms, carbon number 1 to 8) Alkoxy group, amine group, alkylamino group having a carbon number of 1 to 8 or substituted with a dialkylamino group), each of Y and Z is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and a carbon number 1 to 8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, an amine group, an alkyl group having 1 to 8 carbon atoms) a substituted alkylamino or dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amine group, an alkyl group having 1 to 8 carbon atoms) Alkylamino or dialkylamino substituted), mercapto, pyrimidinyl, benzofuranyl, benzothienyl, Ar is an alkylene group having a carbon number of 1 to 10, a vinyl group, a phenylene group, Biphenyl, pyridyl, naphthylene, thiophene, thiol, thienylene, furfuryl, 2,5-pyrrolyl-diyl, 4,4'-fluorene-diyl, 4,2'- Styrene-two Base, n is an integer of 0 or 1)

Particularly, in the formula, X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, and Ar is preferably a phenylene group, a naphthylene group, a thiophene group or a thienylene group.

The amount of the oxime ester-based photopolymerization initiator is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount is less than 0.01 parts by mass, the photocurability on the copper is insufficient, and the coating film properties such as chemical resistance are deteriorated in addition to the peeling of the coating film. On the other hand, when it exceeds 5 parts by mass, light absorption on the surface of the solder resist film becomes intense, and deep hardenability tends to decrease. More preferably, it is 0.5 to 3 parts by mass.

The α-aminoethenyl photopolymerization initiator is specifically, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2 -benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylbenzene) Methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoethyl benzene, and the like. Commercially available products are IRGACURE 907, IRGACURE 369, IRGACURE 379, etc., manufactured by Ciba Japan.

The mercaptophosphine oxide photopolymerization initiator may specifically be, for example, 2,4,6-trimethylbenzimidium diphenylphosphine oxide or bis(2,4,6-trimethylbenzhydrazide). )-Phenylphosphine oxide, bis(2,6-dimethoxybenzhydrazide)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include, for example, Lucirin TPO manufactured by BASF Corporation and IRGACURE 819 manufactured by Ciba Japan Co., Ltd., and the like.

The amount of the α-aminoethenyl photopolymerization initiator and the mercaptophosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount is less than 0.01 parts by mass, the photocurability on copper is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, when it exceeds 15 parts by mass, a sufficient outgassing effect cannot be obtained, and the light absorption on the surface of the solder resist film becomes intense, and the deep hardenability tends to be lowered. More preferably, it is 0.5 to 10 parts by mass.

Further, examples of the photopolymerization initiator, photoinitiator, and sensitizer which are suitably used in the photocurable resin composition of the present embodiment include a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxantate. A ketone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, and a xanthone compound.

The benzoin compound is specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or the like.

The acetophenone compound is specifically, for example, acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenylethyl benzene, 1, 1-di Chloroethyl benzene and the like.

Specifically, the hydrazine compound is, for example, 2-methylhydrazine, 2-ethylhydrazine, 2-t-butylhydrazine, 1-chloroindole or the like.

The thioxanthone compound is specifically, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone or the like.

The ketal compound is specifically, for example, acetophenone ketal, benzyl dimethyl ketal or the like.

The benzophenone compound is specifically, for example, benzophenone, 4-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzhydryl-4' - Ethyl diphenyl sulfide, 4-benzylidene-4'-propyl diphenyl sulfide, and the like.

The tertiary amine compound is specifically, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, and a commercially available product such as 4,4'-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Japan Soda Co., Ltd.) , 4,4'-diethylaminobenzophenone (EAB by HODOGAYA CHEMICAL CO., LTD.), etc., dialkylaminobenzophenone, 7-(diethylamino)-4 a dialkylamino group-containing coumarin compound such as methyl-2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin), 4 - dimethylamino benzoic acid ethyl ester (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl ester (Quantacure DMB manufactured by International Bio-Synthetics Co., Ltd.), 4-dimethylamino group Benzoic acid (n-butoxy)ethyl ester (Quantacure BEA, manufactured by International Bio-Synthetics Co., Ltd.), p-dimethylamino benzoic acid isoamylethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4 2-Ethylamino benzoic acid 2-ethylhexyl ester (Esolol 507, manufactured by Van Dyk Co., Ltd.) or the like.

Among these, a thioxanthone compound and a tertiary amine compound are preferred. In particular, deep sclerosing properties can be improved by the thioxanthone-containing compound.

The amount of the thioxanthone compound to be mixed is preferably 20 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When the amount of the thioxanthone compound is more than 20 parts by mass, the thick film hardenability is lowered and the product cost is increased. More preferably, it is 10 mass parts or less.

Further, the tertiary amine compound is preferably a compound having a dialkylaminobenzophenone compound, wherein the dialkylaminobenzophenone compound and the dialkylamine-based coumarin having a maximum absorption wavelength of 350 to 450 nm are used. Compounds and coumarins are particularly preferred.

The dialkylaminobenzophenone compound is preferred because of its low toxicity to 4,4'-diethylaminobenzophenone. The coumarin compound containing a dialkylamine group has a coloring solder which uses a coloring pigment and reacts with the color of the coloring pigment itself because the maximum absorption wavelength is in the ultraviolet field of 350 to 410 nm, and the photosensitive composition having less coloration and colorless transparency becomes available. Photoresist film. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one has an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The amount of the tertiary amine compound is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount of the tertiary amine compound is less than 0.1 part by mass, there is a tendency that a sufficient sensitizing effect cannot be obtained. In addition, when it exceeds 20 parts by mass, the light absorption on the surface of the coating film of the tertiary amine compound becomes intense, and the deep hardenability tends to be lowered. More preferably, it is 0.1 to 10 parts by mass.

These photopolymerization initiators, photoinitiating aids, and sensitizers may be used singly or in combination of two or more kinds.

The total amount of the photopolymerization initiator, the photoinitiating aid, and the sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When the amount is more than 35 parts by mass, there is a tendency that the light hardening is lowered and the deep hardenability is lowered.

Moreover, these photopolymerization initiators, photoinitiating aids, and sensitizers may have a sensitivity due to absorption of a specific wavelength, and may act as an ultraviolet absorber. However, these are not only used for the purpose of improving the sensitivity of the composition. It is necessary to absorb light of a specific wavelength to improve the photoreactivity of the surface, and to change the line shape and opening of the photoresist into a vertical, tapered, and reverse tapered shape, and at the same time, the processing precision of the line width or the opening diameter can be improved.

In the hydroxyl group-containing elastomer used for the photocurable thermosetting resin composition of the present invention, it is understood that not only the flexibility of the obtained cured coating film is improved, but also the stress relaxation during the solder resist overhardening is very effective, and the PCT resistance is excellent. The hydroxyl group-containing elastomer is preferably a compound having a hydroxyl group at a side chain or a terminal, and is not particularly limited, and examples thereof include a hydroxyl group-containing propylene elastomer, a hydroxyl group-containing polyester elastomer, and a hydroxyl group-containing polyester urethane system. An elastomer, a hydroxyl group-containing urethane-based elastomer, a cellulose-based derivative elastomer resin, a polylactic acid-based elastomer, or the like. Particularly suitable for the user, such as a polybutadiene-based elastomer, a polyisoprene-based elastomer or a derivative thereof.

Specific examples of the hydroxyl group-containing elastomer include hydroxyl terminated liquid polybutadiene (Poly bd, manufactured by Idemitsu Kosan Co., Ltd.), and hydroxyl terminated liquid isoprene (Poly ip, Idemitsu Kosan Co., Ltd.)羟基), a hydroxyl-terminated polyolefin-based polyol (made by Aiboer, Idemitsu Kosan Co., Ltd.), a hydroxyl-terminated liquid polybutadiene hydride (Bao Litai H, manufactured by Mitsubishi Chemical Corporation).

The amount of the hydroxyl group-containing elastomer is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When the amount is less than 5 parts by mass, the effect of the hydroxyl group-containing elastomer is not confirmed, and when it exceeds 60 parts by mass, the tackiness of the coating film is deteriorated, and development failure is poor.

Further, in order to impart heat resistance, the photocurable thermosetting resin composition of the present invention may be added with a thermosetting component. The thermosetting component used in the present invention may be, for example, a blocked isocyanate compound, an amine based resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, a polyfunctional epoxy compound, A known thermosetting resin such as a polyfunctional oxetane compound, an epoxy sulfide resin, or a melamine derivative. Among these, a thermosetting component is preferably a thermosetting component having a plurality of cyclic ether groups and/or cyclic thioether groups (hereinafter referred to as cyclic (thio)ether groups) in one molecule. These thermosetting components having a cyclic (thio)ether group are commercially available in a wide variety of types, and various characteristics can be imparted depending on their structures. Further, the hydroxyl group of the hydroxyl group-containing elastomer is reacted with a hydroxyl group formed by a reaction with a carboxyl group and a cyclic (thio)ether group (for example, an epoxy group), and the hydroxyl group thereof reacts with each other to be combined into a strong 3 dimensional network. Further, since the characteristics can be maximized, a cured product having remarkably softness can be obtained by using an amine-based resin or an isocyanate or a blocked isocyanate which is easily reacted with a hydroxyl group or a carboxyl group.

The thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is any one of a cyclic ether group having a plurality of 3, 4 or 5 membered rings or a cyclic thioether group in the molecule or 2 a compound of the type, such as a compound having at least a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having at least a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, A compound having a plurality of thioether groups in the molecule, that is, an epoxy sulfide resin.

The above polyfunctional epoxy compound, for example, jER828, jER834, jER1001, jER1004 manufactured by Japan Epoxy Resins Co., Ltd., EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055 manufactured by DIC Corporation, and EPOTOTEYD-011 and YD-013 manufactured by Dongdu Chemical Co., Ltd. YD-127, YD-128, DER317, DER331, DER661, DER664 by The Dow Chemical Company, Araldite 6071, Araldite6084, Araldite GY250, Araldite GY260 from Ciba Japan, Sumi-Epoxy ESA- by Sumitomo Chemical Industries Co., Ltd. 011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661, AER664, etc. (all are trade names) bisphenol A type epoxy resin manufactured by Asahi Kasei Industrial Co., Ltd.; Japan Epoxy Resins Co JERYL903 manufactured by Ltd., EPICLON 152, EPICLON 165 manufactured by DIC Corporation, EPOTOTEYDB-400 manufactured by Dongdu Chemical Co., Ltd., YDB-500, DER542 manufactured by The Dow Chemical Company, Araldite 8011 manufactured by Ciba Japan Co., Ltd., manufactured by Sumitomo Chemical Industries Co., Ltd. Sumi-Epoxy ESB-400, ESB-700, AER711, AER714, etc. (all are trade names) brominated epoxy resin manufactured by Asahi Kasei Kogyo Co., Ltd.; Japan Epoxy Resins Co., Ltd JER152, jER154, DEN431, DEN438, manufactured by The Dow Chemical Company, EPICLONN-730, EPICLONN-770, EPICLONN-865, manufactured by DIC Corporation, EPOTOTEYDCN-701, YDCN-704, Ciba Japan, manufactured by Toho Chemical Co., Ltd. Company's AralditeECN1235, AralditeECN1273, AralditeECN1299, AralditeXPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, manufactured by Sumitomo Chemical Industries Co., Ltd., Sumi-Epoxy ESCN-195X, manufactured by Sumitomo Chemical Industries, Ltd. ESCN-220, AERECN-235, ECN-299, etc. (all are trade names) made of phenolic varnish type epoxy resin manufactured by Asahi Kasei Industrial Co., Ltd.; EPICLON830 manufactured by DIC Corporation, jER807 manufactured by Japan Epoxy Resins Co., Ltd., Dongdu EPOTOTEY DF-170, YDF-175, YDF-2004, Araldite XPY306, which is manufactured by Ciba Japan Co., Ltd. (both trade names), bisphenol F-type epoxy resin; EPOTOTEST-2004, ST-2007 manufactured by Dongdu Chemical Co., Ltd. , hydrogenated bisphenol A type epoxy resin such as ST-3000 (trade name); jER604 manufactured by Japan Epoxy Resins Co., Ltd.; EPOTOTEYH-434 manufactured by Dongdu Chemical Co., Ltd., AralditeMY720 manufactured by Ciba Japan Co., Ltd., Sumitomo Chemical Industries Co., Ltd. Su Epoxypropylamine type epoxy resin such as mi-Epoxy ELM-120 (both trade names); urethane type epoxy resin such as Araldite CY-350 (trade name) manufactured by Ciba Japan Co., Ltd.; Daicel Chemical Industries Limited . Cellulose 2021 manufactured by the company, Araldite CY175 manufactured by Ciba Japan Co., Ltd., CY179, etc. (all are trade names) alicyclic epoxy resin; YL-933 manufactured by Japan Epoxy Resins Co., Ltd., TEN manufactured by The Dow Chemical Company , EPPN-501, EPPN-502 (all are trade names) of trishydroxyphenylmethane type epoxy resin; Japan Epoxy Resins Co., Ltd. YL-6056, YX-4000, YL-6121 (all Commodity name) such as bixylenol type or bisphenol type epoxy resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., and EXA-1514 (trade name) manufactured by DIC Corporation S-type epoxy resin; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resins Co., Ltd.; jERYL-931 manufactured by Japan Epoxy Resins Co., Ltd., manufactured by Ciba Japan Co., Ltd. Tetraphenylolethane type epoxy resin such as Araldite 163 (all are trade names); Araldite PT810 manufactured by Ciba Japan Co., Ltd. Heterocyclic epoxy resin such as TEPIC (both trade name) manufactured by Chemical Industry Co., Ltd.; diepoxypropyl phthalate resin such as Brahma DGT manufactured by Nippon Oil Co., Ltd.; ZX-1063 manufactured by Dongdu Chemical Co., Ltd. Tetraglycidyl xylenoyl ethane resin; Enagen-based epoxy resin manufactured by Nippon Steel Chemical Co., Ltd. ESN-190, ESN-360, HP-4032, EXA-4750, EXA-4700, etc.; HP-7200, HP manufactured by DIC Corporation Epoxy resin with dicyclopentadiene skeleton such as -7200H; epoxy methacrylate copolymerized epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd.; and cyclohexylmaleimide Copolymerized epoxy resin with epoxy propyl methacrylate; epoxy modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industries Limited), CTBN modified epoxy resin (for example) YR-102, YR-450, etc. manufactured by Dongdu Chemical Co., Ltd., etc., but are not limited thereto. These epoxy resins may be used singly or in combination of two or more kinds. Among these, a novolac type epoxy resin, a modified novolac type epoxy resin, a heterocyclic epoxy resin, a bixylenol type epoxy resin or a mixture thereof is preferable.

The aforementioned polyfunctional oxetane compound, such as bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy) Methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl)benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy) Methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxetanyl)methacrylate, (3-methyl 3-oxo-butyl-butyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or polyfunctional or oligomeric polymers thereof In addition to oxetane, there are oxetane and novolak resins, poly(p-hydroxystyrene), Cardo bisphenols, calixarenes, Calixresorcinarene, or sesquioxanes. An etherified product of a resin having a hydroxyl group. Further, for example, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate or the like can be mentioned.

An epoxy sulfide resin having a plurality of cyclic thioether groups in the above molecule, for example, YL7000 (bisphenol A type epoxy sulfide resin) manufactured by Japan Epoxy Resins Co., Ltd., or the like. Further, an epoxy sulfide resin obtained by substituting an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom by the same synthesis method may be used.

The amount of the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is preferably from 0.6 to 2.5 equivalents, more preferably from 0.8 to 2.0 equivalents, per equivalent of the carboxyl group of the carboxyl group-containing resin. range. When the amount of the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is less than 0.6, the carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, and the like are not preferable. In addition, when it exceeds 2.5 equivalents, the low molecular weight cyclic (thio)ether group remains in the dried coating film, and the strength of the coating film or the like is lowered.

Further, a thermosetting component suitable for use, such as a melamine derivative, a benzoguanamine derivative or the like. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, and the like. Further, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound, and the alkoxymethylated urea compound may each have a methylol melamine compound The hydroxymethyl benzoguanamine compound, the methylol glycoluril compound, and the methylol urea compound are converted into an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Especially for the human body or the environment, it is preferable to use a melamine derivative having a formaldehyde concentration of 0.2% or less.

Such commercial products, such as Cymel300, the same 301, the same 303, the same 370, the same 325, the same 327, the same 701, the same 266, the same 267, the same 238, the same 1141, the same 272, the same 202, the same 1156, the same 1158, the same 1123, the same 1170, the same 1174, the same UFR65, the same 300 (above, MITSUI CYANAMID (share) system), NIKALACMx-750, the same Mx-032, the same Mx-270, the same Mx-280, the same Mx-290 Same as Mx-706, same Mx-708, same Mx-40, same Mx-31, same Ms-11, same Mw-30, same Mw-30HM, same Mw-390, same Mw-100LM, same Mw-750LM (above, (share) Sanwa-chemical system) and so on.

These thermosetting components may be used alone or in combination of two or more.

Further, in the photocurable thermosetting resin composition of the present invention, in order to enhance the curability of the composition and the toughness of the obtained cured film, a compound having a complex isocyanate group or a blocked isocyanate group in one molecule may be added. The compound having an isocyanate group or a blocked isocyanate group in one molecule may, for example, be a compound having a complex isocyanate group in one molecule, that is, a polyisocyanate compound or a compound having a plurality of blocked isocyanate groups in one molecule. That is, a blocked isocyanate compound or the like.

As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, and naphthalene-1,5. - Diisocyanate, o- dimethyl dimethyl diisocyanate, m- benzene dimethyl diisocyanate and 2,4-methylphenylene dimer. Specific examples of the aliphatic polyisocyanate include, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methylene bis(cyclohexyl isocyanate). And isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include, for example, bicycloheptane triisocyanate. And the adduct-type, burette-type and isocyanurate bodies of the isocyanate compounds exemplified above.

The blocked isocyanate group contained in the blocked isocyanate compound is a group which is inactivated by the reaction of the isocyanate group with the block agent. Upon heating to a specific temperature, the blocker dissociates to form an isocyanate group.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent can be used. An isocyanate compound which can be reacted with a block agent, such as an isocyanurate type, a burette type, an adduct type, or the like. As the isocyanate compound, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate include, for example, the compounds exemplified above.

In the case of isocyanate block agents, for example, phenolic blockers such as phenol, cresol, xylenol, chlorophenol and ethylphenol; ε-caprolactam, δ-valeroguanamine, γ-butyrolactone and An internal mesylate block agent such as β-propionalamine; an active methylene block agent such as ethyl acetate and acetonitrile; methanol, ethanol, propanol, butanol, amyl alcohol, and B Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, glycolic acid Alcohol blockers such as ester, diacetone alcohol, methyl lactate and ethyl lactate; oxime systems such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, diethyl hydrazine monohydrate, cyclohexane hydrazine Blocking agent; thiol blocker such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol, ethyl thiophenol; acid such as decylamine or benzylamine Amidoxime blocker; a quinone imine blocker such as succinimide succinate or succinimide; an amine blocker such as guanamine, aniline, butylamine or dibutylamine; Imidazole blocker such as 2-ethylimidazole; Imine blockers such as imine and acrylimine.

The blocked isocyanate compound can be commercially available, for example, Smithica BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desa 2170, Dessam 2265 (above, Sumitomo Bayeramide Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, manufactured by Japan Polyurethane Industrial Co., Ltd., trade name), B-830 , B-815, B-846, B-870, B-874, B-882 (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name), TPA-B80E, 17B-60PX, E402-B80T (made by Asahi Kasei Chemical Co., Ltd., trade name) )Wait. Further, Smithjob BL-3175 and BL-4265 blockers were obtained by using methyl ethyl hydrazine.

The compound having a complex isocyanate group or a blocked isocyanate group in one molecule may be used singly or in combination of two or more kinds.

The amount of the compound having a complex isocyanate group or a blocked isocyanate group in one molecule is preferably from 1 to 100 parts by mass, more preferably from 2 to 70 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. . When the amount of the above-mentioned collocation is less than 1 part by mass, the toughness of a sufficient coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, it is not preferable because the storage stability is lowered.

In the photocurable thermosetting resin composition of the present invention, in order to promote a hardening reaction between a hydroxyl group or a carboxyl group and an isocyanate group, an ethyl urethane catalyst may be added. The urethane-based catalyst is one or more kinds of urethanes selected from the group consisting of tin-based catalysts, metal chlorides, metal acetoacetones, metal sulfates, amine compounds, or/and amine salts. Ethyl esterification catalyst is preferred.

The tin-based catalyst is, for example, an organotin compound such as Steiner Otley or dibutyltin dilaurate, or an inorganic tin compound.

The metal chloride is a chloride of a metal composed of Cr, Mn, Co, Ni, Fe, Cu or Al, such as cobalt chloride, nickel chloride, iron chloride or the like.

The metal acetoacetone salt is an ethyl acetonide salt of a metal composed of Cr, Mn, Co, Ni, Fe, Cu or Al, such as cobalt acetonitrile, nickel acetonitrile, iron acetonitrile or the like.

The metal sulfate is a sulfate of a metal composed of Cr, Mn, Co, Ni, Fe, Cu or Al, such as copper sulfate.

In terms of the aforementioned amine compound, for example, conventional triethylenediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, bis(2-dimethylaminoethyl)ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylethanolamine, dimorpholinodiethyl Ether, N-methylimidazole, dimethylaminopyridine, triazine, N'-(2-hydroxyethyl)-N,N,N'-trimethyl-bis(2-aminoethyl) Ether, N,N-dimethylhexanolamine, N,N-dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-(2-hydroxyethyl)ethene Amine, N-(2-hydroxyethyl)-N,N',N",N"-tetramethyldiethylenetriamine, N-(2-hydroxypropyl)-N,N',N",N "-Tetramethyldiethylenetriamine, N,N,N'-trimethyl-N'-(2-hydroxyethyl)propanediamine, N-methyl-N'-(2-hydroxyethyl) Piperazine, bis(N,N-dimethylaminopropyl)amine, bis(N,N-dimethylaminopropyl)isopropanolamine, 2-aminoquinine, 3-amine quinine Ning, 4-aminoquinine, 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1-(2'-hydroxypropyl)imidazole, 1-(2'-hydroxypropanol 2-methylimidazole, 1-(2'-hydroxyethyl) , 1-(2'-hydroxyethyl)-2-methylimidazole, 1-(2'-hydroxypropyl)-2-methylimidazole, 1-(3'-aminopropyl)imidazole, 1- (3'-Aminopropyl)-2-methylimidazole, 1-(3'-hydroxypropyl)imidazole, 1-(3'-hydroxypropyl)-2-methylimidazole, N,N-di Methylaminopropyl-N'-(2-hydroxyethyl)amine, N,N-dimethylaminopropyl-N',N'-bis(2-hydroxyethyl)amine, N,N -Dimethylaminopropyl-N',N'-bis(2-hydroxypropyl)amine, N,N-dimethylaminoethyl-N',N'-bis(2-hydroxyethyl An amine, N,N-dimethylaminoethyl-N', N'-bis(2-hydroxypropyl)amine, melamine or/and benzoguanamine.

Examples of the amine salt include an amine salt of an organic acid salt of DBU (1,8-diaza-bicyclo[5,4,0]undecene-7).

The ratio of the amount of the urethane-based catalyst to a normal amount is sufficient. For example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10.0 parts by mass, per 100 parts by mass of the carboxyl group-containing resin.

When a thermosetting component having a plurality of cyclic (thio)ether groups in the above molecule is used, it is preferred to use a thermosetting catalyst. The thermosetting catalyst, such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl Imidazole derivatives such as 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethyl Amines such as -N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine An antimony compound such as a compound, diterpene adipate or diammonium phthalate; a phosphorus compound such as triphenylphosphine or the like. In addition, as for the commercial products, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (trade name of imidazole-based compound) manufactured by Shikoku Chemical Industrial Co., Ltd., and U-CAT (registered trademark) manufactured by San-apro Co., Ltd. 3503N, U-CAT3502T (trade name of a block isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all bicyclic guanidine compounds and salts thereof). It is not particularly limited thereto, and may be a thermosetting catalyst for an epoxy resin or an oxetane compound or a reaction for promoting an epoxy group and/or an oxetanyl group and a carboxyl group, and may be used alone or in combination of two or more. Mixed use. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2 can also be used. ,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine, isomeric cyanuric acid adduct, 2,4-diamino-6-methyl An S-triazine derivative such as an acryloyloxyethyl-S-triazine/isocyanuric acid addition product, preferably a compound which can also serve as an adhesion imparting agent and the aforementioned thermosetting contact Media use.

It is sufficient that the amount of the thermosetting catalyst is a ratio of a normal amount, for example, it is preferably 100 parts by mass based on the carboxyl group-containing resin or the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule. 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass.

The photocurable resin composition of the present invention can be used in combination with a colorant. As the coloring agent, a conventional coloring agent such as red, blue, green, or yellow may be used, and any of a pigment, a dye, and a coloring matter may be used. However, it is preferable that the viewpoint of environmental load reduction and influence on the human body is halogen-free.

Red colorant:

Red coloring agents include monoazo, bisazo, Azo Lake, benzimidazolone, anthraquinone, pyrrolopyrroledione, condensed azo, anthraquinone, quinophthalone, etc. Such as the following Colour Index (CI; The Society of Dyers and Colourists issued) number.

Monoazo systems: Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269.

Bisazo: Pigment Red 37, 38, 41.

Single Azo Lake Series: Pigment Red 48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2 , 57:1, 58:4, 63:1, 63:2, 64:1, 68.

Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

The system is: 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.

Pyrrolopyrroledione: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

蒽醌: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

The blue coloring agent is a phthalocyanine system or a lanthanide system, and the pigment system is classified into a compound of a pigment. Specifically, as follows: Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60.

For the dye system Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 and so on. In addition to the above, a phthalocyanine compound which may be substituted with or without a metal may be used.

Green colorant:

The green colorant also has a phthalocyanine system, an anthraquinone system, and an anthraquinone system. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, or the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:

The yellow coloring agent may be a monoazo type, a bisazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type, an anthraquinone type, etc., specifically, the following.

Lanthanum: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone series: 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.

Bisazo series: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, a coloring agent such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.

Specific examples are Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CIPigment Orange 1, CIPigment Orange 5, CIPigment Orange 13, CIPigment Orange 14, CIPigment Orange 16, CIPigment Orange 17, CIPigment Orange 24, CIPigment Orange 34, CIPigment Orange 36, CIPigment Orange 38, CIPigment Orange 40, CIPigment Orange 43, CIPigment Orange 46, CIPigment Orange 49, CIPigment Orange 51, CIPigment Orange 61, CIPigment Orange 63, CIPigment Orange 64, CIPigment Orange 71, CIPigment Orange 73, CI color brown 23, CI color brown 25, CI color black 1, CI color black 7, and the like.

The ratio of the coloring agent is not particularly limited, and is preferably 10 parts by mass or less, and particularly preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin.

The compound having a plurality of 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, and the carboxyl group-containing resin is insolubilized in an aqueous alkali solution or helps to dissolve it. . As the compound, conventionally used polyester (meth) acrylate, polyether (meth) acrylate, ethyl urethane (meth) acrylate, carbonate (meth) acrylate, epoxy can be used. (meth) acrylate or the like, specifically, hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol a diacrylate of a glycol such as an alcohol or a propylene glycol; N,N-dimethylpropenylamine, N-methylolpropenylamine, N,N-dimethylaminopropylpropenylamine Ethyl amides such as N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate, etc.; hexane diol, a polyvalent alcohol such as trimethylolpropane, pentaerythritol, dipentaerythritol, cis-hydroxyethyl isocyanurate or the like, or an ethylene oxide adduct, a propylene oxide adduct, or ε-caprolactone Multivalent acrylates such as adducts; phenoxy acrylates, bisphenol A diacrylates, and ethylene oxide adducts or propylene oxide adducts of such phenols Polyvalent acrylates; glycerol diepoxypropyl ether, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, triepoxypropyl isocyanurate, etc. The polyvalent acrylate of the ether; not limited to the above, for example, direct acrylation or permeation of a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl terminated polybutadiene or a polyester polyol Diisocyanate and urethane acrylated acrylates and melamine acrylates, and/or methacrylates corresponding to the above acrylates.

Further, for example, an epoxy acrylate resin in which a polyfunctional epoxy resin such as a cresol novolac type epoxy resin and acrylic acid are reacted, or a hydroxyl group of the epoxy acrylate resin and a hydroxy acrylate such as pentaerythritol triacrylate may be used. An epoxy urethane acrylate compound or the like which is reacted with an ethyl melamine compound of a diisocyanate such as isophorone diisocyanate. The epoxy acrylate-based resin does not reduce the dryness of the touch, and the photocurability is improved.

The amount of the compound having a plurality of ethylenically unsaturated groups in the molecule is from 5 to 100 parts by mass, more preferably from 1 to 70 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the amount of the collocation is less than 5 parts by mass, the photocurability is lowered, and the alkali development after the irradiation with the active energy ray is difficult to form a pattern. On the other hand, when it exceeds 100 parts by mass, the solubility in the aqueous alkali solution is lowered, and the coating film becomes brittle.

The photocurable thermosetting resin composition of the present invention is used to improve the physical strength of the coating film and the like, and may be blended with a filler as necessary. As the filler, a conventionally known inorganic or organic filler can be used, but in particular, barium sulfate, spherical cerium oxide, and talc are preferably used. Further, in order to obtain a white appearance or flame retardancy, a metal hydroxide such as titanium oxide, metal oxide or aluminum hydroxide may be used as the extender pigment filler. The amount of the filler is preferably 200 parts by mass or less, more preferably 0.1 to 150 parts by mass, even more preferably 1 to 100 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the amount of the filler is more than 200 parts by mass, the viscosity of the composition becomes high, the printability is lowered, and the cured product becomes brittle.

Further, in the photocurable thermosetting resin composition of the present invention, a binder polymer can be used for the purpose of improving the dryness of the touch, improving the workability, and the like. For example, a polyester-based polymer, a polyurethane-based polymer, a polyester urethane-based polymer, a polyamine-based polymer, a polyester amide-based polymer, or a propylene-based polymer can be used. A cellulose polymer, a polylactic acid polymer, a phenoxy polymer, or the like. These binder polymers may be used singly or in combination of two or more kinds.

Further, in the photocurable thermosetting resin composition of the present invention, other elastomers may be used for the purpose of imparting flexibility, improving the brittleness of the cured product, and the like. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyester amide amine elastomer, or a propylene elastomer can be used. Olefin-based elastomer. Further, a resin having a partial or total epoxy group having an epoxy group of various skeletons and a carboxylic acid-modified butadiene-acrylonitrile rubber modified with both ends may be used. Further, an epoxy group-containing polybutadiene-based elastomer, an acryl-containing polybutadiene-based elastomer, or the like can also be used. These elastomers may be used singly or in combination of two or more kinds.

Further, the photocurable thermosetting resin composition of the present invention may be an organic solvent for the purpose of adjusting the synthesis or composition of the carboxyl group-containing resin or adjusting the viscosity of the substrate or the carrier film.

Such organic solvents are ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, and carbitol , glycol ketones, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate , esters of butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate; ethanol, propanol, ethylene glycol Alcohols such as propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, naphtha, hydrogenated naphtha, and petroleum-soluble petroleum spirit. These organic solvents can be used singly or in combination of two or more.

Since most of the polymer materials are oxidized and then oxidatively degraded continuously to reduce the polymer material, the photocurable thermosetting resin composition of the present invention can be added to generate free radicals in order to prevent oxidation. An invalidated radical scavenger or an antioxidant such as a peroxide decomposing agent that decomposes a peroxide into a harmless substance without generating a new radical.

As an antioxidant of a radical scavenger, specific compounds such as hydroquinone, 4-t-butylcatechol, 2-t-butyl hydroquinone, hydroquinone monomethyl ether, 2, 6-di-t-butyl-p-cresol, 2,2-methylene-bis(4-methyl-6-t-butylphenol), 1,1,3-para (2-methyl) 4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4-hydroxybenzyl) Benzo, 1,3,5-paran (3',5'-di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H.5H) A phenolic compound such as a triketone, an anthraquinone compound such as metaquinone or benzoquinone, an amine compound such as bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate or phenothiazine.

The radical scavenger may be a commercially available product such as ADEKA STAB AO-30, ADEKA STAB AO-330, ADEKA STAB AO-20, ADEKA STAB LA-77, ADEKA STAB LA-57, ADEKA STAB LA-67, ADEKA STAB LA -68, ADEKA STAB LA-87 (above, manufactured by Asahi Kasei Corporation, trade name), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, Ciba Japan Company system, product name, etc.

As an antioxidant of a peroxide decomposing agent, a specific compound such as a phosphorus compound such as triphenylphosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate or distearyl sulfonate A sulfur-based compound such as 3,3'-thiodipropionate.

The peroxide decomposing agent may be a commercially available product, for example, ADEKA STAB TPP (made by Asahi Kasei Co., Ltd., trade name), MarkAO-412S (made by AADEKA ARGUS CHEMICAL CO., LTD., trade name), SUMILIZERTPS (manufactured by Sumitomo Chemical Co., Ltd., Product name).

These antioxidants may be used alone or in combination of two or more.

In addition, in the photocurable thermosetting resin composition of the present invention, the ultraviolet curable agent can be used in addition to the above-mentioned antioxidant in order to prevent the deterioration of the ultraviolet ray.

Ultraviolet absorbers such as benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazolyl derivatives, cinnamate derivatives, o-amine benzoates Derivatives, benzamidine methane derivatives, and the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-dihydroxyl group. 4-methoxybenzophenone and 2,4-dihydroxybenzophenone. Specific examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, and 2,4-di-t-butyl. Phenylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include, for example, 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole and 2-(2'-hydroxy-5'-methylbenzene. Benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3' , 5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxyl -3',5'-di-t-pentylphenyl)benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.

The ultraviolet absorber may be a commercially available product such as TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, Ciba) Japan company, product name, etc.

The ultraviolet ray absorbing agent may be used singly or in combination of two or more kinds thereof, and the molded article obtained from the photocurable thermosetting resin composition of the present invention is stabilized by the use of the above-mentioned antioxidant.

In order to improve the sensitivity, the photocurable thermosetting resin composition of the present invention may be a conventionally used N-phenylglycine, phenoxyacetic acid, thiophenoxyacetic acid, mercaptothiazolyl or the like as a chain transfer agent. . Specific examples of the chain transfer agent, such as a chain transfer agent having a carboxyl group such as mercapto succinic acid, thioglycolic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof; mercaptoethanol, mercapto group a chain transfer agent having a hydroxyl group such as propanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate , methyl-3-mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propane mercaptan , butane thiol, pentane thiol, 1-octane thiol, cyclopentane thiol, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzene thiol, and the like.

Further, a polyfunctional thiol compound can be used, and it is not particularly limited, and for example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, or the like can be used. An aromatic thiol such as an aliphatic thiol such as mercapto diethyl sulfide, benzodimethyldithiol, 4,4'-dimercaptodiphenyl sulfide or 1,4-benzenedithiol; Diol bis(mercaptoacetate), polyethylene glycol bis(mercaptoacetate), propylene glycol bis(mercaptoacetate), glycerol ginseng (mercaptoacetate), trimethylolethane thiol (mercaptoacetate) Poly(mercaptoacetate) of polyvalent alcohols such as esters, trimethylolpropane ginsyl (mercaptoacetate), pentaerythritol ruthenium (mercaptoacetate), dipentaerythritol hexa(mercaptoacetate); Diol bis(3-mercaptopropionate), polyethylene glycol bis(3-mercaptopropionate), propylene glycol bis(3-mercaptopropionate), glycerol ginseng (3-mercaptopropionate), trihydroxyl Methylethane ginseng (mercaptopropionate), trimethylolpropane ginseng (3-mercaptopropionate), pentaerythritol bismuth (3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), etc. Poly(3-mercaptopropionate) of polyvalent alcohols; 1,4-bis(3-mercaptobutyloxy) butyl Alkane, 1,3,5-gin(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H.5H)-trione, pentaerythritol oxime (3 - mercaptobutyl ester) isomeric (mercaptobutyl ester).

Such commercially available products, such as BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (above, 堺Chemical Industries), KarenzMT-PE1, KarenzMT-BD1, and Karenz -NR1 (above, Showa Denko (share) system).

Further, a heterocyclic compound having a mercapto group as a chain transfer agent, such as mercapto-4-butyrolactone (alias: 2-mercapto-4-γ-butyrolactone), 2-mercapto-4-methyl-4-butyl Lactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butyl lactone, 2-mercapto-4-butylidene, N-methoxy-2-indenyl- 4-butylideneamine, N-ethoxy-2-mercapto-4-butylideneamine, N-methyl-2-mercapto-4-butylidene, N-ethyl-2-mercapto-4 - Butyrolactam, N-(2-methoxy)ethyl-2-mercapto-4-butylidene, N-(2-ethoxy)ethyl-2-indolyl-4-butene Amine, 2-mercapto-5-valerolactone, 2-mercapto-5-pentalinamide, N-methyl-2-indolyl-5-pentalinamide, N-ethyl-2-mercapto-5- Indoleamine, N-(2-methoxy)ethyl-2-indolyl-5-pentalinamide, N-(2-ethoxy)ethyl-2-indolyl-5-pentalinamide , 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-caprolactam, 2,4,6-trimethyl-s-triazine (III Chemical Co., Ltd.: the product name: 希希特特 F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sanxiehua Co., Ltd.: trade name: 希奈特DB), and 2 -anilino-4,6-dimercapto-s - Triazine (manufactured by Sankyo Chemical Co., Ltd.: trade name: Chitite AF).

A heterocyclic compound having a mercapto group which is particularly resistant to the developability chain transfer agent of the photocurable thermosetting resin composition, which is mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1, 2, 4 Triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole is preferred. These chain transfer agents may be used singly or in combination of two or more.

The photocurable thermosetting resin composition of the present invention may be an adhesion promoter in order to improve interlayer adhesion or adhesion of the photosensitive resin layer to the substrate. Specific examples are, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi Chemical Industry Co., Ltd.) Carrep M), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazolyl-2-thione, 2- Mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amine-containing benzotriazole, decane crosslinker, and the like.

In the photocurable thermosetting resin composition of the present invention, a shaker such as fine powder of ceria, organic bentonite, montmorillonite or magnesite may be added as needed. The stability of the shake change agent is preferably organic bentonite or magnesite, and the magnesia magnesite has excellent electrical properties. Further, it may be combined with a thermal polymerization inhibitor or an antifoaming agent such as an fluorenone, a fluorine or a polymer, a leveling agent, a decane crosslinking agent such as an imidazole type, a thiazole type or a triazole type, or a rust inhibitor. Further, there are known conventionally used additives such as a bisphenol-based or triazine thiol-based copper damage preventive agent.

The aforementioned thermal polymerization inhibiting agent can be used to prevent thermal polymerization or time-lapse polymerization of the aforementioned polymerizable compound. Examples of thermal polymerization inhibitors, such as 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, tetrachloroguanidine, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-methyl Phenol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic Chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelating compound of nitroso compound and A1, and the like.

The photocurable thermosetting resin composition of the present invention can be subjected to a dip coating method, a flow coating method, a roll coating method, or a bar coating method on a substrate by, for example, adjusting the viscosity of the coating method by the organic solvent. The method is applied by a method such as a screen printing method or a curtain coating method, and the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of about 60 to 100 ° C to form a non-stick coating film. Thereafter, in a contact (or non-contact manner), a pattern of the mask is formed by selective active energy line exposure, or a direct pattern exposure is performed by a laser direct exposure machine, so that the unexposed portion is treated with an aqueous alkali solution (for example, A 0.3 to 3% aqueous sodium carbonate solution was developed to form a photoresist pattern. Further, in the case of a composition containing no thermosetting component, for example, it is thermally cured by heating to a temperature of about 140 to 180 ° C, and the carboxyl group of the carboxyl group-containing resin has a plurality of cyclic ether groups and/or a ring in the molecule. The thermosetting component of the thioether group reacts to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. In addition, in the case where the thermosetting component is not contained, the thermal-radical polymerization of the photo-curable component remaining in the unreacted state during the exposure is accelerated by thermal polymerization to improve the coating film characteristics. It can also be heat treated (thermal hardened).

The above substrate may be made of paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimine, glass cloth/not, in addition to a printed circuit board or a flexible printed circuit board in which a circuit is formed in advance. Fiber cloth - epoxy resin, glass cloth / paper - epoxy resin, synthetic fiber - epoxy resin, fluororesin ‧ polyethylene ‧ PPO ‧ cyanate ester and other composite grades (FR-4, etc.) Copper laminate, polyimide film, PET film, glass substrate, ceramic substrate, wafer board, and the like.

The volatilization drying which is carried out after applying the photocurable thermosetting resin composition of the present invention can be carried out by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a heat source having a method of heating air by steam) The method of contacting the hot air in the dryer and the method of blowing the nozzle to the support are performed.

After the photocurable thermosetting resin composition of the present invention is applied and volatilized and dried, the obtained coating film is exposed (irradiation of active energy rays). The exposed portion of the coating film (the portion irradiated with the active energy ray) is hardened.

The exposure machine used for the active energy ray irradiation can use a direct drawing device (for example, a laser direct imaging device that directly draws a laser image by computer CAD data), an exposure machine equipped with a metal halide lamp, and a (super) high pressure mercury lamp. An exposure machine, an exposure machine equipped with a mercury short-arc lamp, or a direct drawing device using an ultraviolet lamp such as a (super) high-pressure mercury lamp. The active energy ray may be laser light having a maximum wavelength in the range of 350 to 410 nm, and may be a gas laser or a solid laser. Further, the exposure amount varies depending on the film thickness or the like, and is usually 5 to 200 mJ/cm ² , preferably 5 to 100 mJ/cm ² , and more preferably 5 to 50 mJ/cm ² . For the above-described direct drawing device, for example, a device manufactured by Orbotech Co., Ltd., manufactured by PENTAX Corporation, or the like, which emits laser light having a maximum wavelength of 350 to 410 nm, may be used, and any device may be used.

As the developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. For the developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, an amine or the like can be used. Aqueous aqueous solution.

The photocurable thermosetting resin composition of the present invention may be formed by directly applying a solder resist to a film such as polyethylene terephthalate or drying it, in addition to a method of directly applying a liquid to a substrate. The shape of the dry film of the solder resist layer is used. The photocurable thermosetting resin composition of the present invention is used as a dry film as follows.

The dry film is a structure having a sequentially laminated carrier film, a solder resist layer, and a peelable cover film which is used as necessary. The solder resist layer is a layer obtained by coating a base-developable photocurable thermosetting resin composition on a carrier film or a cover film and drying it. After the solder film is formed on the carrier film, the cover film is laminated thereon, or a solder resist layer is formed on the cover film, and the laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm can be used.

In the solder resist layer, the alkali-developable photocurable thermosetting resin composition is uniformly coated on a carrier film or a cover film with a thickness of 10 to 150 μm by a spray coater, a LIP Coater, a Comma Coater, a film coater or the like. And formed after drying.

As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but the adhesion to the solder resist layer is preferably smaller than that of the carrier film.

A protective film (permanent protective film) is formed on a printed circuit board by using a dry film, and the cover film is peeled off, and the solder resist layer and the substrate on which the circuit is formed are laminated, and laminated using a laminator or the like to form a circuit. A solder photoresist layer is formed on the substrate. The hardened coating film can be formed by performing exposure, development, and heat curing in the same manner as described above with respect to the formed solder resist layer. The carrier film may be peeled off before or after exposure.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. In addition, the following "parts" and "%" are quality standards without special restrictions.

Synthesis Example 1

A phenol novolak type cresol resin (product name "Shonol CRG951", OH equivalent: 119.4) 119.4 was added to an autoclave equipped with a thermometer, a nitrogen gas introduction device, an epoxide introduction device, and a stirring device. g, 1.19 g of potassium hydroxide and 119.4 g of toluene were subjected to nitrogen substitution in the system while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually dropped, and reacted at 125 to 132 ° C for 0 to 4.8 kg/cm ² for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution, and then potassium hydroxide was neutralized to obtain a ring of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl group value of 182.2 g/eq. Oxypropane reaction solution. This is an average addition of 1.08 moles per equivalent of epoxide to the phenolic hydroxyl group.

Next, 293.0 g of the epoxide reaction solution of the obtained novolac type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methyl hydroquinone, and 252.9 g of toluene were placed in a mixer, a thermometer, and an air blow. In the reactor which was introduced into the tube, air was blown at a rate of 10 ml/min, and the reaction was carried out at 110 ° C for 12 hours while stirring. The water formed by the reaction was distilled off as an azeotropic mixture with toluene to 12.6 g of water. Thereafter, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, followed by water washing. Thereafter, toluene was distilled off with 118.1 g of diethylene glycol monoethyl ether acetate as an evaporator to obtain a novolac type acrylate resin solution. Next, 332.5 g of the obtained novolac type acrylate resin solution and 1.22 g of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min while stirring. 60.8 g of tetrahydrophthalic anhydride was gradually added, and the reaction was carried out at 95 to 101 ° C for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having an acid value of 88 mgKOH/g of a solid matter and a nonvolatile content of 71% was obtained. Hereinafter, this is referred to as varnish A-1.

Synthesis Example 2

Into a 5 liter separable flask equipped with a thermometer, a stirrer, and a reflux condenser, polycaprolactone diol (PLACCEL 208, molecular weight 830 manufactured by Daicel Chemical Industries Limited.) having a polymer polyol was added as 1,245 g. 201 g of dihydroxymethylpropionic acid of a dihydroxy compound of a carboxyl group, 777 g of isophorone diisocyanate as a polyisocyanate, and 119 g of 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group, and further p-A 0.5 g of oxyphenol and di-t-butyl-hydroxytoluene. The mixture was heated to 60 ° C with stirring, and stopped, and 0.8 g of dibutyltin dilaurate was added. After the temperature in the reaction vessel began to decrease, the temperature was again heated, and stirring was continued at 80 ° C. After confirming that the isocyanate group absorption spectrum (2280 cm ^-1 ) disappeared by infrared absorption spectrum, the reaction was terminated to obtain a viscous liquid urethane acrylate compound. . The carbaryl alcohol acetate was used to adjust the nonvolatile content = 50% by mass. A resin solution of a carboxylic acid ethyl methacrylate (meth) acrylate compound having a carboxyl group having an acid value of 47 mg KOH/g and a nonvolatile content of 50% was obtained. Hereinafter, this is referred to as 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, a solvent of diethylene glycol dimethyl ether 900 g and a polymerization initiator t-butylperoxy 2 were added. 2-Ethyl acrylate (manufactured by Nippon Oil & Fats Co., Ltd., trade name; PERBUTYLO) 21.4 g, heated to 90 °C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 2-hydroxyethyl methacrylate modified by lactone (PLACCEL FM1: manufactured by Daicel Chemical Industries Limited.) were 109.8 g. It was added to 21.4 g of bis(4-t-butylcyclohexyl)peroxydicarbonate (manufactured by Nippon Oil & Fats Co., Ltd., trade name; PEROYLTCP), and the mixture was added dropwise for 3 hours, and further aged for 6 hours. A carboxyl group-containing copolymerized resin is obtained. Further, the reaction was carried out under a nitrogen atmosphere.

Next, 3,4-epoxycyclohexyl methacrylate (manufactured by Daicel Chemical Industries Limited., trade name; CYCLMER A200) 363.9 g, open-loop catalyst was added to the obtained carboxyl group-containing copolymer resin. 3.6 g of dimethylbenzylamine and 1.80 g of hydroquinone monomethyl ether of a polymerization inhibitor were heated to 100 ° C and stirred to carry out a ring-opening addition reaction of an epoxy group. After 16 hours, a resin solution having a solid content of 108.9 mgKOH/g, a weight average molecular weight of 25,000, and a solid content of 54% was obtained. Hereinafter, it is referred to as varnish A-3.

Comparative Synthesis Example 1

An ortho-cresol novolac type epoxy resin (made by DIC), EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average functional group number 7.6 was added to 600 g of diethylene glycol monoethyl ether acetate. 1070 g (epoxypropyl number (total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were heated and stirred to 100 ° C, and uniformly dissolved. Next, 4.3 g of triphenylphosphine was added, and after heating to 110 ° C, the reaction was carried out for 2 hours, and then the temperature was raised to 120 ° C, and further, the reaction was carried out for 12 hours. 415 g of an aromatic hydrocarbon (Solvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride 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 mg KOH / g was obtained. The solid solution is 65% resin solution. Hereinafter, this is called varnish R-1.

Comparative Synthesis Example 2

2,200 parts of cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent 220), 134 parts of dimethylolpropionic acid, 648.5 parts of acrylic acid, and methyl group were added. 4.6 parts of hydroquinone, 1131 parts of carbitol acetate, and 484.9 parts of petroleum-soluble petroleum spirit were heated to 90 ° C and stirred to dissolve the reaction mixture. Next, the reaction liquid was cooled to 60 ° C, 13.8 parts of triphenylphosphine was added, and the mixture was heated to 100 ° C, and the reaction was carried out for about 32 hours to obtain a reactant having an acid value of 0.5 mgKOH/g. Then, 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate, and 58.8 parts of coal-soluble petroleum spirit were added thereto, and heated to 95 ° C, and reacted for about 6 hours and cooled to obtain a solid acid value of 40 mgKOH. / g, a resin solution containing 65% of a carboxyl group-containing photosensitive resin. Hereinafter, this is called varnish R-2.

Comparative Synthesis Example 3

400 parts of bisphenol P type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C was dissolved in 925 parts of epichlorohydrin and 462.5 parts of dimethyl hydrazine, and then 98.5% NaOH 81.2 parts at 70 ° C under stirring. It takes 100 minutes to join. After the addition, the reaction was further carried out at 70 ° C for 3 hours. Then, the excess unreacted epichlorohydrin and dimethyl hydrazine were mostly distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl hydrazine was dissolved in 750 parts of methyl isobutyl ketone. Further, 10 parts of 30% NaOH was added, and the reaction was carried out at 70 ° C for 1 hour. After the reaction was terminated, the mixture was washed twice with 200 parts of water. After the oil-water separation, the methyl isobutyl ketone was distilled and recovered from the oil layer to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 °C. 2900 parts (10 equivalents) of the obtained epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methyl hydroquinone, 1950 parts of carbitol acetate, and heated to 90 ° C and stirred The reaction mixture was dissolved. Next, the reaction liquid was cooled to 60 ° C, 16.7 parts of triphenylphosphine was added, and the mixture was heated to 100 ° C to carry out a reaction for about 32 hours to obtain a reactant having an acid value of 1.0 mgKOH/g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were added thereto, and the mixture was heated to 95 ° C, and reacted for about 6 hours to obtain a solid acid value of 100 mgKOH/g and a solid content of 65%. Resin solution. Hereinafter, this is called varnish R-3.

Examples 1, 2 and Comparative Examples 1 to 3

The resin solution obtained by each of the above-mentioned synthesis examples was mixed with various components shown in the following Table 1 in the proportions (mass parts) shown in Table 1, and prepared by mixing with a stirrer, and then kneaded by three roller mills to prepare photocurability. A thermosetting resin composition. The obtained photocurable thermosetting resin composition was subjected to a JPCA-based flask combustion treatment ion chromatography to quantify the halide content (total of chlorine and bromine). The results are shown in Table 1.

As a result of the above-mentioned Table 1, it is understood that the photocurable thermosetting resin composition of Examples 1 and 2 using a carboxyl group-containing resin (A-1, A-2) which does not use an epoxy resin as a starting material and the use thereof In comparison with the photocurable thermosetting resin compositions of Comparative Examples 1 to 3 containing a carboxyl group-containing photosensitive resin (R-1, R-2, R-3) starting from an epoxy resin, the amount of halogen was apparently small. .

Examples 3 to 13 and Comparative Examples 4 to 6

The resin solution of the above-mentioned synthesis example was mixed with the components shown in the following Table 2 in the proportions (mass parts) shown in Table 2, and the mixture was prepared by mixing with a stirrer, and then kneaded by three roller mills to prepare a photosensitive film for solder resist. Resin composition. Here, the degree of dispersion of the obtained photosensitive resin composition was evaluated to be 15 μm or less by the particle size measurement of the Grind Meter manufactured by Erichsen.

[Remarks]

*1: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one (IRGACURE 907: manufactured by Ciba Japan Co., Ltd.)

*2: 2,4-Diethylthioxanthone (KAYACURE DETX-S: manufactured by Nippon Kayaku Co., Ltd.)

*3: Ethylketone, 1-[9-ethyl-6-(2-methylbenzhydrazide)-9H-carbazol-3-yl]-1,1-(O-acetamidine) (IRGACURE OXE02) :Ciba Japan company)

*4: Phenolic novolac type epoxy resin (RE306CA90: Nippon Chemical Co., Ltd.)

*5: bixylenol type epoxy resin (YX-4000: manufactured by JER)

*6: Hydroxyl-terminated liquid polybutadiene (made by Idemitsu Kosan Co., Ltd.)

*7: Hydroxyl-terminated liquid polyisoprene (manufactured by Idemitsu Kosan Co., Ltd.)

*8: Hydroxy-terminated liquid polyolefin (made by Idemitsu Kosan Co., Ltd.)

*9: Epoxidized polybutadiene (Daicel Chemical Industries Limited.)

*10: C.1.Pigment Blue 15:3

*11: C.I.Pigment Yellow 147

*12: 2-mercaptobenzothiazole

*13: Antioxidant (Ciba Japan)

*14: B-30 (堺化学(股) system)

*15: Magnesite Magnesite (Kyowa Chemical Industry Co., Ltd.)

*16: Diethylene glycol monoethyl ether acetate

*17: Dipentaerythritol hexaacrylate

*18: Block isocyanate (Asahi Kasei Chemicals Co., Ltd.)

*19: Methylated melamine resin (manufactured by Sanwa-chemical)

Performance evaluation: <Optimum exposure>

The circuit pattern substrate having a copper thickness of 18 μm was subjected to copper surface roughening treatment (MECetch BONDCZ-8100 manufactured by MEC Co., Ltd.), washed with water, and dried, and then the photocurable thermosetting resin composition of the above examples and comparative examples was subjected to a net. The printing method was carried out by a plate printing method, and dried in a hot air circulating drying oven at 80 ° C for 60 minutes. After drying, the exposure apparatus equipped with a high-pressure mercury lamp was exposed through a Step Tablet (Kodak No. 2), and the development (30 ° C, 0.2 MPa, 1 wt% aqueous sodium carbonate solution) was carried out for 60 seconds. The time is the best exposure.

<developability>

The photocurable thermosetting resin composition of the above-mentioned examples and the comparative examples was applied onto a copper solid substrate so as to have a film thickness after drying by a screen printing method of about 25 μm, and a hot air circulation type at 80 ° C. The drying oven was dried for 30 minutes. After drying, development was carried out with a 1 wt% aqueous sodium carbonate solution, and the time until the dried coating film was removed was measured by a stopwatch.

<maximum development life>

The composition of the above examples and comparative examples was applied to the copper foil substrate on which the pattern was formed by screen printing, and dried at 80 ° C, and the substrate was taken out every 10 minutes from 20 minutes to 80 minutes. To room temperature. On the substrate, a 1 wt% sodium carbonate aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 0.2 MPa for 60 seconds, and the maximum allowable drying time without remaining residue was the maximum development life.

<stickiness>

The composition of the above examples and comparative examples was applied to the copper foil substrate on which the pattern was formed by screen printing, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes, and allowed to cool to room temperature. A negative film made of PET was placed on the substrate, and the film was pressed under reduced pressure for 1 minute using HMW-GW20 manufactured by ORC Co., Ltd., and then the state of adhesion of the film when the negative film was peeled off was evaluated by the following criteria.

○: When the film was peeled off, there was no resistance at all, and there was no residue on the coating film.

△: A little resistance was observed when the film was peeled off, and the coating film was slightly traced.

×: There was resistance when the film was peeled off, and the coating film was markedly marked.

Characteristic test:

The compositions of the above examples and comparative examples were completely coated by screen printing on a copper foil substrate having a pattern, dried at 80 ° C for 30 minutes, and allowed to cool to room temperature. The substrate was exposed to a solder resist pattern at an optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp, and a 1 wt% sodium carbonate aqueous solution at 30 ° C was developed under a spray pressure of 0.2 MPa for 90 seconds to obtain a photoresist. Graphic type. The substrate was subjected to ultraviolet irradiation under the conditions of a cumulative exposure amount of 1000 mJ/cm ² in a UV conveyor belt furnace, and then heat-hardened at 150 ° C for 60 minutes. The obtained printed substrate (evaluation substrate) was evaluated for the following characteristics.

<acid resistance>

The evaluation substrate was immersed in a 10 vol% H ₂ SO ₄ aqueous solution at room temperature for 30 minutes to visually confirm the elution or the elution of the coating film, and the peeling of the tape peeling test was confirmed.

○: No change

△: Only a few changers

×: The film is swelled or swollen.

<Alkaline resistance>

The evaluation substrate was immersed in a 10 vol% aqueous NaOH solution at room temperature for 30 minutes, and the infiltration or the elution of the coating film was visually confirmed, and the peeling of the tape peeling test was confirmed.

○: No change

△: Only a few changers

×: The film is swelled or swollen and peeled off.

<Welding heat resistance>

The evaluation substrate coated with the rosin-based flux was immersed in a solder bath set at 260 ° C in advance, and after the flux was washed with a modified alcohol, the expansion and peeling of the photoresist layer were visually evaluated. The judgment criteria are as follows.

○: No peeling was confirmed even if the immersion was repeated three times or more in 10 seconds.

△: The immersion was repeated three times or more in 10 seconds with a slight peeling.

×: After immersing for 10 times in 10 seconds, the photoresist layer was swollen and peeled off.

<electroless gold plating resistance>

Electroplating was carried out under the conditions of nickel 5 μm and gold 0.05 μm using an electroless nickel plating bath and an electroless gold plating bath which were commercially available, and the presence or absence of peeling of the photoresist layer peeled off by the tape or plating infiltration was evaluated. After the presence or absence, the presence or absence of peeling of the photoresist layer peeled off by the tape was evaluated. The judgment criteria are as follows.

○: A certain amount of penetration was confirmed after plating, but no peeling occurred after the tape was peeled off.

△: A certain amount of penetration was confirmed after plating, and peeling was also observed after the tape was peeled off.

×: Peeling after plating.

<PCT tolerance>

The evaluation substrate on which the solder resist-hardening coating film was formed was subjected to a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Co., Ltd.) at 121 ° C, saturated, and 0.2 MPa for 168 hours to evaluate the state of the coating film. The judgment criteria are as follows.

○: no swelling, peeling, discoloration, dissolution

△: There are several expansion, peeling, discoloration, and dissolution

×: visible multiple expansion, peeling, discoloration, dissolution

<Cold and heat tolerance>

An evaluation substrate having a solder resist-cured coating film having a dot-notch and a dot-notch pattern was produced. The obtained evaluation substrate was subjected to a 1000-cycle tolerance test using a hot and cold sputum tester (manufactured by ETAC Co., Ltd.) at -55 ° C / 30 minutes to 150 ° C / 30 in 1 cycle. After the test, the cured film after the treatment was visually observed, and the occurrence of cracking was judged using the following criteria.

○: The incidence of cracks is less than 30%

△: The incidence of cracks is 30 to 50%.

×: The crack occurrence rate is 50% or more

<HAST characteristics>

A solder resist-curing coating film was formed on a BT substrate on which a comb-shaped electrode (line/space = 50 μm / 50 μm) was formed, and an evaluation substrate was produced. The evaluation substrate was placed in a high-temperature and high-humidity bath at an environment of 130 ° C and a humidity of 85%, and a voltage of 12 V was applied for 168 hours to carry out an in-tank HAST test. The insulation resistance value in the tank at the passage of 168 hours was evaluated by the following criteria.

○: 108 Ω or more

△: 106 to 108 Ω

×: 106 Ω or less

Examples 14 to 21 and Comparative Examples 7 to 9

Each of the compositions of Examples 3, 5, 6, 8, 9, 10, 11, 13 and Comparative Examples 4, 5, and 6 prepared in the proportions shown in Table 2 was diluted with methyl ethyl ketone in a PET film. After the upper coating, it was dried at 80 ° C for 30 minutes to form a photosensitive resin composition layer having a thickness of 20 μm. Further, a dry film was formed by laminating a cover film thereon, and each of them was used as Examples 14 to 21 and Comparative Examples 7 to 9.

<Dry film evaluation>

From the dry film peeling cover film obtained as described above, the film was thermally laminated on the copper foil substrate on which the pattern was formed, and then exposed under the same conditions as those of the substrate used for the evaluation of the coating film characteristics of the above examples. After the exposure, the carrier film was peeled off, and a 1 wt% sodium carbonate aqueous solution at 30 ° C was developed under the conditions of a spray pressure of 0.2 MPa for 90 seconds to obtain a photoresist pattern. The substrate was subjected to ultraviolet irradiation under the conditions of an accumulated exposure amount of 1000 mJ/cm ² in a UV conveyor belt furnace, and then heated and cured at 150 ° C for 60 minutes. The test substrate having the obtained hardened film was subjected to an evaluation test of each characteristic by the aforementioned test method and evaluation method. The results are shown in Table 4.

As is apparent from the results shown in the above Tables 3 and 4, the photocurable thermosetting resin composition of the present invention can be used as a PCT resistance, cold and heat resistance, and HAST characteristic (electricity) necessary for the solder resist for semiconductor packaging. A photocurable thermosetting resin composition of the characteristics).

Claims (5)

A photocurable thermosetting resin composition which can be developed with an aqueous alkali solution, characterized in that: (A) a compound having two or more phenolic hydroxyl groups selected from (A-1) 1 molecule is reacted with alkylene oxide The reaction product is reacted with a monocarboxylic acid containing an unsaturated group, and the carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride has two or more phenolicities in one molecule of (A-2). a carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting a hydroxy compound with a cyclic carbonate compound with a monocarboxylic acid containing an unsaturated group, and reacting the obtained reaction product with a polybasic acid anhydride, (A-3 a terminal carboxyl group-containing urethane resin obtained by a polyisocyanate compound and a polyaddition reaction with a diol compound at a terminal of a urethane resin and an acid anhydride, (A-4) a diisocyanate and a In the synthesis of a carboxyl group-containing urethane resin having a polyaddition reaction of a carboxy diol compound and a diol compound, a compound having one hydroxy group and one or more acryl fluorenyl groups or methacryl fluorenyl groups in the molecule is added. Got a carboxyl group-containing urethane resin having a terminal propylene oxime or methacryl oxime, (A-5) a carboxyl group-containing amino group in a polyaddition reaction of a diisocyanate and a carboxyl group-containing diol compound with a diol compound In the synthesis of an ethyl formate resin, a terminal propylene oxime or methacrylic acid obtained by adding a compound having one isocyanate group and one or more acryloyl fluorenyl groups or methacryl fluorenyl groups in the molecule is added. A carboxyl group-containing resin having at least one of a group consisting of a carboxyl group-containing urethane resin (except for a carboxyl group-containing resin excluding an epoxy resin), (B) photopolymerization initiation And the (C) side chain or an elastomer having a hydroxyl group at the end. The photocurable thermosetting resin composition of claim 1, wherein the carboxyl group-containing resin does not contain a hydroxyl group. A photocurable thermosetting dry film obtained by coating and drying a photocurable thermosetting resin composition of the above claim 1 or 2 on a film. A cured product characterized in that a photocurable thermosetting resin composition of claim 1 or 2 or a photocurable thermosetting resin composition is coated and dried on a film to obtain a dry film laminated on a substrate. The coating film obtained after the above is obtained by photohardening by irradiation with an active energy ray. A printed circuit board having a dry film obtained by coating and drying a photocurable thermosetting resin composition of claim 1 or 2 or a photocurable thermosetting resin composition on a film, which is active After the energy ray is irradiated and photohardened into a pattern, the hardened film obtained by thermal curing is obtained.