KR101419161B1 - Photocurable/thermosetting resin composition, dry film thereof and cured substance therefrom, and printed circuit board using same - Google Patents

Abstract

The present invention relates to a photocurable thermosetting resin composition which can be developed by an aqueous alkaline solution to form a cured coating film having a PCT resistance, HAST resistance, electroless gold plating resistance and cold / , (A) a carboxyl group-containing resin (excluding a carboxyl group-containing resin starting from an epoxy resin), (B) a photopolymerization initiator, and (C) a naphthalene ring-containing epoxy resin. The carboxyl group-containing resin preferably contains no hydroxyl group, and more preferably has a photosensitive group. By using such a photo-curable thermosetting resin composition or a dry film thereof, it is possible to provide a printed wiring board in which a cured film such as a solder resist is formed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photo-curable thermosetting resin composition, a dry film and a cured product thereof, and a printed circuit board using the same. BACKGROUND OF THE INVENTION [0001]

The present invention relates to a photo-curable thermosetting resin composition which can be developed by an aqueous alkali solution, particularly a composition for a solder resist which is photo-cured by ultraviolet exposure or laser exposure, a dry film thereof and a cured product thereof, .

At present, solder resists of some commercial printed circuit boards and most industrial printed circuit boards are subjected to ultraviolet ray irradiation, ultraviolet irradiation, development, and image formation, and liquid phase development (final curing) by heat and / A solder resist is used, and in consideration of environmental problems, a photo-solder resist of an alkali development type which uses an alkali aqueous solution as a developer is the mainstream and is used in large quantities in the production of an actual printed wiring board. In addition, in response to the increase in the density of the printed wiring board due to the thinning and shortening of electronic devices in recent years, workability and high performance of the solder resist are also required.

However, the current alkali-developing type photo-solder resist still has a problem in terms of durability. That is, the alkali resistance, water resistance, heat resistance, and the like are lower than those of the conventional thermosetting and solvent developing type. This is because alkali-developing type photo-solder resists have a hydrophilic group as a main component in order to enable alkali development, and chemical solution, water, water vapor and the like are likely to permeate, resulting in deterioration of chemical resistance or adhesion of the resist film to copper . As a result, alkali resistance as chemical resistance is weak. Particularly, in a semiconductor package such as a BGA (Ball Grid Array) or CSP (Chip Scale Package), a pressure cooker test Pressure cooker test resistance) is required, but under such a severe condition, it is only a few hours to several hours. Further, in the HAST test (High Accelerated Stress Test) under the condition of applying the voltage under the humidifying condition, in most cases, defects due to the occurrence of migration were confirmed in several hours.

Recently, the temperature applied to the package tends to become very high, such as the transition to surface mounting and the use of lead-free solder in consideration of environmental problems. As a result, the temperature at the inside and the outside of the package becomes remarkably high, and in the conventional liquid photosensitive resist, there is a problem that the coating film deteriorates or the characteristics change due to thermal history, peeling occurs, and the PCT or HAST resistance as described above deteriorates , And his improvement is required.

On the other hand, an epoxy acrylate-modified resin derived from the modification of an epoxy resin is generally used as the carboxyl group-containing resin used in the conventional solder resist. For example, Japanese Patent Application Laid-Open No. 61-243869 (Patent Document 1) discloses a photosensitive resin in which an acid anhydride is added to the reaction product of a novolac epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound Has been reported as a solder resist composition. Japanese Unexamined Patent Publication (Kokai) No. 3-250012 (Patent Document 2) discloses a method in which (meth) acrylic acid is added to an epoxy resin obtained by reacting epichlorohydrin with the reaction product of salicylaldehyde and monovalent phenol, There is disclosed a solder resist composition comprising a photosensitive resin obtained by reacting a polybasic carboxylic acid or an anhydride thereof, a photopolymerization initiator, an organic solvent, and the like.

The above-mentioned epoxy acrylate-modified resin has a problem that a large amount of hydroxyl groups derived from epoxy acrylate remains and the water resistance is originally poor.

Japanese Patent Application Laid-Open No. 61-243869 Japanese Patent Application Laid-Open No. 3-250012

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art as described above, and its main object is to provide a solder resist for a semiconductor package which requires thermal history at a high temperature and which is excellent in PCT resistance, HAST resistance, electroless gold plating resistance, Curable thermosetting resin composition capable of forming a cured film having impact resistance.

It is also an object of the present invention to provide a dry film and a cured product excellent in various properties obtained by using such a photo-curable thermosetting resin composition as described above, and a printing process in which a cured film such as a solder resist is formed by the above- And to provide a wiring board.

In order to achieve the above object, according to the present invention, there is provided an alkaline aqueous solution containing a carboxyl group-containing resin (excluding a carboxyl group-containing resin starting from an epoxy resin as a starting material), a photopolymerization initiator and a naphthalene ring- A thermosetting resin composition capable of being developed by a photopolymerization initiator is provided.

It is preferable that the carboxyl group-containing resin has a photosensitive group.

According to the present invention, there is also provided a photocurable thermosetting dry film obtained by applying and drying the above-mentioned photocurable thermosetting resin composition to a carrier film, and a photocurable thermosetting resin composition or a dry film obtained by photocuring, A cured product obtained by photo-curing a patterned image with a light source of 410 nm is provided.

According to the present invention, there is also provided a printed wiring board having a cured coating obtained by photo-curing the photo-curable thermosetting resin composition or the dry film in a patterned state by irradiation of an active energy ray, preferably by direct irradiation of ultraviolet rays / RTI >

The photo-curable thermosetting resin composition of the present invention contains a carboxyl group-containing resin which does not use an epoxy resin as a starting material and contains a naphthalene ring-containing epoxy resin in combination with the epoxy resin as a component capable of being developed by an aqueous alkali solution, Not only the toughness and heat resistance of the cured coating film are improved but also the physical properties at the time of thermal history of the coating film and during curing are small. More surprisingly, it was found that even if the thermosetting temperature is low, the thermosetting resin has good curability, and even when a thermal history is applied at a high temperature, the physical properties are not changed and good properties are maintained. Therefore, by using the photocurable thermosetting resin composition of the present invention, it is possible to form a cured coating having PCT resistance, HAST resistance, electroless gold plating resistance, and excellent heat resistance, which are important as solder resists for semiconductor packages.

As described above, the features of the photocurable thermosetting resin composition of the present invention are characterized by containing a carboxyl group-containing resin, a photopolymerization initiator and a naphthalene ring-containing epoxy resin, which do not comprise an epoxy resin as a starting material.

As the carboxyl group-containing resin, any of conventionally known various carboxyl group-containing resins may be used as long as it is a carboxyl group-containing resin which does not use an epoxy resin as a starting material. Among them, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in its molecule is preferably photo- It is preferable in view of developability. Further, the unsaturated double bond thereof is preferably derived from acrylic acid or methacrylic acid or a derivative thereof. In the case of using only a carboxyl group-containing water having no ethylenically unsaturated double bond, in order to make the composition photocurable, it is necessary to use a compound (photosensitive monomer) having at least one ethylenic unsaturated group in the molecule as described later have.

As specific examples of the carboxyl group-containing resin that can be used in the present invention, compounds (which may be any of oligomers and polymers) listed below are preferable.

(1) A method for producing a polyfunctional epoxy resin composition, which comprises the steps of (1) mixing a mixture of bisphenol A, bisphenol F, bisphenol S, novolac phenol resin, poly-p- hydroxystyrene, condensate of naphthol and aldehyde, condensate of dihydroxynaphthalene and aldehyde A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with a monocarboxylic acid containing an unsaturated group such as (meth) acrylic acid, A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as maleic acid, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic anhydride.

(2) reacting a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, and then reacting the resultant monocarboxylic acid with an unsaturated group- A carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained with a polybasic acid anhydride.

(3) A process for producing a polyisocyanate compound, which comprises reacting a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate with a polycarbonate-based polyol, a polyether- , A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride at the terminal of a urethane resin by a heavy-chain reaction of a diol compound such as a bisphenol A-based alkylene oxide adduct diol, a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group .

(4) a method for producing a urethane resin comprising a carboxyl group-containing urethane resin, such as a hydroxyalkyl (meth) acrylate, during synthesis of a carboxyl group-containing urethane resin by a reaction of a diisocyanate and a carboxyl group-containing dialcohol compound such as dimethylolpropionic acid, dimethylolbutyric acid, (Meth) acryloyl group-containing urethane resin obtained by adding a compound having at least one hydroxyl group and at least one (meth) acryloyl group in the molecule.

(5) A process for producing a urethane resin comprising a carboxyl group-containing urethane resin, which comprises the reaction of a mixture of isophorone diisocyanate and pentaerythritol triacrylate in the presence of a diisocyanate, a carboxyl group-containing dialcohol compound and a diol compound, (Meth) acrylate obtained by adding a compound having an isocyanate group and at least one (meth) acryloyl group to a carboxyl group-containing urethane resin.

(6) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene,? -Methylstyrene, lower alkyl (meth) acrylate or isobutylene.

(7) reacting a polyfunctional oxetane resin as described below with a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid, and reacting the produced primary hydroxyl group with phthalic anhydride, tetrahydrophthalic anhydride, Containing polyester resin in which a dibasic acid anhydride such as phthalic acid is added is added to an epoxy group-containing polyester resin in which one epoxy group in one molecule such as glycidyl (meth) acrylate and? -Methyl glycidyl (meth) (Meth) acryloyl group is further added to the photosensitive resin.

(8) A photosensitive resin containing a carboxyl group in which a compound having a cyclic ether group and a (meth) acryloyl group in one molecule is added to the carboxyl group-containing resin of the above (1) to (7).

Further, in the present specification, the term (meth) acrylate is generically referred to as acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin used in the present invention does not use an epoxy resin as a starting material, it has a feature that the content of the halide is very small. The content of the chloride ion impurity in the carboxyl group-containing resin used in the present invention is 0 to 100 ppm, more preferably 0 to 50 ppm, and still more preferably 0 to 30 ppm.

In addition, a resin containing no hydroxyl group can be easily obtained from the carboxyl group-containing resin used in the present invention. In general, the presence of a hydroxyl group has excellent properties such as an improvement in adhesion due to hydrogen bonding, but it is known that the moisture resistance is significantly deteriorated. Hereinafter, the superior merits of the carboxyl group-containing resin of the present invention as compared with the epoxy acrylate-based modified resin used in general solder resists will be described.

Phenol novolac resins without chlorine are readily available. It is possible to obtain a resin which does not have a hydroxyl group theoretically in a range of double bond equivalence of 300 to 550 and acid value of 40 to 120 mgKOH / g by partial acrylation of the alkylene oxide-modified phenol resin and introduction of acid anhydride.

On the other hand, when an epoxy group of an epoxy resin synthesized from a similar phenol novolac resin is entirely acrylated and an acid anhydride is introduced into all the hydroxyl groups, the acid value becomes very large at a double bond equivalent of 400 to 500. Thus, . Further, since the acid value is high, the water resistance is deteriorated, and insulation reliability and PCT resistance are significantly lowered. Namely, it is very difficult to completely eliminate the hydroxyl groups from the epoxy acrylate-based modified resin derived from the similar phenol novolak type epoxy resin.

As described above, the conventional epoxy acrylate-based modified resin inevitably has a hydroxyl group, but the presence of a hydroxyl group affects not only the water absorption but also the reactivity with the epoxy resin and the acid. That is, it is known that the hydroxyl group promotes the reaction between the acid and the epoxy group. However, the presence of the hydroxyl group is expected to accelerate the curing process until the cured product forms the gelation, but it is expected that the promoting effect after the gelation of the reaction system is insufficient. That is, it is considered that the reaction of an acid and an epoxy in a system in which a hydroxyl group is abundant is delayed in the end point of the reaction instead of accelerating the reaction initiation. It is not preferable from the standpoint of the time of use of the composition or the development life of the solvent until drying and development, and further, since the gelation is formed at an early stage, a high temperature and long time are required until the reaction is completed do. Since the composition of the present invention is a reaction in the absence of a hydroxyl group, the reaction may be said to be a mild reaction. As a result, it is considered that the lifetime to development is long and the reaction is likely to be completed. As a result, it is considered that excellent reliability is obtained. This phenomenon was conspicuous when a naphthalene ring-containing epoxy resin described later was used. It is considered that this is because the naphthalene ring of the naphthalene ring-containing epoxy resin has a planar structure, so that it has a low melt viscosity and a high reactivity.

In addition, the urethane resin can easily synthesize a resin not containing a hydroxyl group by adjusting the equivalents of hydroxyl group and isocyanate group. A preferable resin is a carboxyl group-containing resin having a chlorine ion impurity content of 0 to 30 ppm synthesized from an isocyanate compound which does not use phosgene as a starting material or a raw material which does not use epihalohydrin, more preferably a hydroxyl group- It is a resin synthesized not to include.

From this viewpoint, the carboxyl group-containing resins (1) to (5) shown above as specific examples can be particularly preferably used.

In addition, it is also possible to use, as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule, a 3,4-epoxycyclohexylmethyl methacrylate Is also used because the alicyclic epoxy is used because the carboxyl group-containing photosensitive resin is reacted with the carboxyl group-containing photosensitive resin.

On the other hand, a resin obtained by reacting a carboxyl group-containing resin (6) with glycidyl methacrylate as a compound having a cyclic ether group and a (meth) acryloyl group in one molecule or a copolymer obtained by copolymerizing glycidyl methacrylate as an unsaturated group- The chlorine ion impurity amount may increase. Further, an epoxy acrylate modifying raw material may be used as the diol compound in the synthesis of the urethane resin. It is possible to use it in that chlorine ion impurities are mixed, but the amount of chlorine ion impurities can be controlled.

Since the carboxyl group-containing resin as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with an aqueous alkaline solution becomes possible.

The acid value of the carboxyl group-containing resin is preferably in the range of 40 to 150 mgKOH / g, and more preferably in the range of 40 to 130 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, the alkali development becomes difficult. On the other hand, when the acid value exceeds 150 mgKOH / g, dissolution of the exposed portion by the developer proceeds, It is not preferable because it is dissolved and peeled off as a developing solution without distinction between the light portion and the unexposed portion, rendering normal resist pattern drawing difficult.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. If the weight average molecular weight is less than 2,000, the tackfree performance may be deteriorated, the moisture resistance of the coated film after exposure may be poor, the film may be reduced during development, and the resolution may be significantly lowered. On the other hand, if the weight average molecular weight exceeds 150,000, the developability may be markedly deteriorated and the storage stability may be poor.

The blending amount of the carboxyl group-containing resin is 20 to 60 mass%, preferably 30 to 50 mass%, in the total composition. When the amount is smaller than the above range, the coating film strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity is increased or the coating property is lowered.

When the resin composition of the present invention is produced from a photo-curing resin composition or a photo-curable thermosetting resin composition, a photo-polymerization initiator may be added. As a preferable initiator, at least one photopolymerization initiator selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an? -Aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator may be used.

As the oxime ester-based photopolymerization initiator, CGI-325, Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919 and NCI-831 manufactured by Ciba Japan Co., Ltd. are commercially available. Further, a photopolymerization initiator system having two oxime ester groups in the molecule can be preferably used. Specifically, an oxime ester compound having a carbazole structure represented by the following formula can be given.

(Wherein X represents 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 (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms) Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms, or an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), anthryl group, pyridyl group, benzofuryl group or benzothienyl group, Ar is a bond, To 10 carbon atoms, such as alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, furylene, 2,5- , 4,2'-styrene diyl, and n is 0 or an integer of 1)

In particular, it is preferable that X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, Ar is a bond, or phenylene, naphthylene, thiophene or thienylene.

The blending amount of such oxime ester-based photopolymerization initiator is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the above-mentioned carboxyl group-containing resin. When the amount is less than 0.01 part by mass, the photocuring property is insufficient and the coating film is peeled off and the coating film properties such as chemical resistance are deteriorated. On the other hand, if it exceeds 5 parts by mass, the light absorption at the surface of the coating film becomes severe, and the deep portion curability tends to be lowered. More preferably 0.5 to 3 parts by mass.

Specific examples of the? -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone, N, N-dimethylaminoacetophenone, and the like. Commercially available products include Irgacure 907, Irgacure 369 and Irgacure 379 manufactured by Shiba &

Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6- 2, 4, 4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lucirin TPO manufactured by BASF, Irgacure 819 manufactured by Shiba Japan Ltd., and the like.

It is preferable that the blending amount of the? -Aminoacetophenone-based photopolymerization initiator and the acylphosphine oxide-based photopolymerization initiator is 0.01 to 15 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin. If the amount is less than 0.01 part by mass, the photocurability on copper is similarly insufficient, resulting in peeling of the coating film and deterioration of coating film properties such as chemical resistance. On the other hand, if it is more than 15 parts by mass, the effect of reducing the outgas is not obtained, and the light absorption at the surface of the coating film becomes severe, and the deep portion curability tends to be lowered. More preferably 0.5 to 10 parts by mass.

Examples of the photopolymerization initiator, photoinitiator and sensitizer that can be preferably used in the resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, 3 A quaternary amine compound and a xanthone compound.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.

Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone. .

Specific examples of the anthraquinone compound include 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone.

Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and the like. .

Specific examples of the ketal compound include acetophenone dimethyl ketal, benzyl dimethyl ketal, and the like.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl- Benzoyl-4'-propyldiphenyl sulfide and the like.

Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure such as 4,4'-dimethylaminobenzophenone (Nissocure MABP manufactured by Nippon Soda Co., Ltd.), 4 , 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), and dialkylaminobenzophenone such as 7- (diethylamino) -4-methyl-2H-1-benzopyran- Dimethylaminobenzoate (Kaya Cure (registered trademark) EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (available from International Bio Co., Ltd.) (Quantacure DMB manufactured by Shinseitics Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Biosynthesis Inc.), p-dimethylaminobenzoic acid isoamyl ethyl ester Manufactured by Kayacure DMBI), 4-dimethylaminobenzoic acid 2- Teal is cyclohexyl and the like (Van Dyke (solrol (Esolol) 507 to Van Dyk) Co., Ltd.), 4,4'-diethylamino-benzophenone (G is manufactured by Hodogaya Chemical Co., EAB).

Of these, thioxanthone compounds and tertiary amine compounds are preferred. Particularly, it is preferable that a thioxanthone compound is included in view of deep curability. Among them, it is preferable to include thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone .

The amount of the thioxanthone compound is preferably 20 parts by mass or less based on 100 parts by mass of the carboxyl-containing resin. If the blending amount of the thioxanthone compound exceeds 20 parts by mass, the thick film hardening property is lowered and the cost of the product is increased. More preferably 10 parts by mass or less.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable. Among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, Particularly preferred.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone has low toxicity and is preferable. Since the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet region, it is possible to provide a coloring film which is less colored, reflects the color of the coloring pigment itself by using a coloring pigment as well as a colorless transparent photosensitive composition It becomes possible. Particularly, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferred.

The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin. When the compounding amount of the tertiary amine compound is less than 0.1 part by mass, there is a tendency that sufficient increase or decrease effect can not be obtained. If it exceeds 20 parts by mass, the deep curing property tends to be lowered. More preferably 0.1 to 10 parts by mass.

These photopolymerization initiators, photoinitiators and sensitizers may be used alone or as a mixture of two or more.

The total amount of the photopolymerization initiator, photoinitiator and sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When the amount exceeds 35 parts by mass, the deep curing property tends to be lowered due to the light absorption.

In addition, since these photopolymerization initiators, photoinitiator and sensitizer absorb specific wavelengths, the sensitivity is lowered in some cases, and they sometimes function as an ultraviolet absorber. However, they are not used for the purpose of improving the sensitivity of the composition. It absorbs light of a specific wavelength as needed so as to increase the photoreactivity of the surface and change the line shape and opening of the coating film in the vertical, tapered, and reverse tapered forms, and improve the line width and machining accuracy of the aperture .

Particularly preferred among the above photopolymerization initiators are at least one photopolymerization initiator selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an? -Aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. Among them, the oxime ester-based initiator is preferable since it is effective in improving the initiator efficiency and effective in improving the sensitivity even in a small amount because it is effective in reducing contamination and volatilization due to outgas during the heat treatment after the resist film is formed and warping of the coating film . The thioxanthone type and coumarin type sensitizers are preferable because they are effective in adjusting the cross-sectional shape of the resist. Especially preferred is a combination of both.

The naphthalene ring-containing epoxy resin used in the photo-curable thermosetting resin composition of the present invention is not only excellent in reactivity and quick completion of reaction as described above, but also has a coating film with high heat resistance strong against thermal history, (Hereinafter abbreviated as CTE) of the solder resist is low, and is very effective for relieving stress at the time of curing the solder resist. Examples of such naphthalene ring-containing epoxy resins include HP-4032 (manufactured by DIC Corporation), HP-4700 (manufactured by DIC Corporation), ESN-355 (manufactured by Dotogasei Corporation), ESN-375 Kasei Co., Ltd.) and NC-7300 (manufactured by Nippon Kayaku Co., Ltd.). Among them, polyfunctional epoxy or derivatives thereof having a naphthalene skeleton, an aralkyl structure and the like are particularly preferable.

The blending amount of the naphthalene ring-containing epoxy resin is suitably 5 parts by mass to 60 parts by mass, 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. If the amount is less than 5 parts by mass, the effect of the naphthalene ring-containing epoxy resin can not be confirmed. On the other hand, if it exceeds 60 parts by mass, deterioration in the tackiness of the coating film and poor development may occur.

Further, a thermosetting component may be added to the photo-curable thermosetting resin composition of the present invention to impart heat resistance. Examples of the thermosetting component used in the present invention include a block isocyanate compound, an amino resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, A thermosetting resin for a known purpose such as a thermosetting resin, a feed resin and a melamine derivative. Among them, a preferable thermosetting component is a thermosetting component having at least two cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule. These thermosetting components having a cyclic (thio) ether group are commercially available in many types, and can impart various properties depending on their structure.

The thermosetting component having at least two cyclic (thio) ether groups in the molecule is a compound having at least two of the cyclic ether group or the cyclic thioether group of 3, 4 or 5-membered rings in the molecule, A compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having two or more thioether groups in the molecule, Episulfide resins, and the like.

Examples of the polyfunctional epoxy compound include jER 828, jER 834, jER1001, jER1004 manufactured by Japan Epoxy Resin Co., Ltd., epiclone (registered trademark) 840 manufactured by DIC, epiclon 850, epiclon 1050, YD-013, YD-127, YD-128 manufactured by Dot Chemical Industries, Ltd., DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Aralidite 6084, Araldite GY250, Araldite GY260, SUMI EPOXY ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Bisphenol A type epoxy resins such as AER330, AER331, AER661, AER664 (all trade names) manufactured by Teijin; JERYL903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152 manufactured by DIC Corporation, Epiclon 165, Epototo YDB-400, YDB-500 manufactured by Toko Kasei Co., DER542 manufactured by Dow Chemical Co., Aramidite 8011, Sumi-epoxy ESB-400 manufactured by Sumitomo Chemical Industry Co., Ltd., ESB-700, AER711 manufactured by Asahi Kasei Kogyo Co., and AER714 (all trade names); JER152, jER154 manufactured by Japan Epoxy Resin Co., DEN431, DEN438 manufactured by Dow Chemical Company, Epiclon N-730 manufactured by DIC, Epiclon N-770, Epiclon N-865, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, manufactured by Nippon Kayaku Co., Ltd., EPPN (registered trademark) -201, EOCN (manufactured by Nippon Kayaku Co., Ltd.), YDCN- ESCN-220 manufactured by Sumitomo Chemical Co., Ltd., AERECN-235 manufactured by Asahi Chemical Industry Co., Ltd., ECN-299 manufactured by Asahi Kasei Corporation, and the like (All trade names) novolak-type epoxy resins; Epothilone YDF-170, YDF-175, YDF-2004 manufactured by Toko Kasei Co., Ltd., Araldite XPY306 manufactured by Shiba Japan Co., Ltd. (all trade names), Epiclon 830 manufactured by DIC Corporation, jER 807 manufactured by Japan Epoxy Resin Co., Bisphenol F type epoxy resin; Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007 and ST-3000 (trade name) manufactured by Tokuga Seisakusho; JER604 manufactured by Japan Epoxy Resin Co., Ltd., Ephoto YH-434 manufactured by Toko Kasei Co., Araldite MY720 manufactured by Shiba Japan Ltd., SUMI EPOX ELM-120 manufactured by Sumitomo Chemical Co., Ltd. A sidylamine type epoxy resin; Hidanto-type epoxy resin such as Aralidite CY-350 (trade name) manufactured by Shiba & (Trade name) manufactured by Daicel Chemical Industries, Ltd., Araldite CY175 and CY179 (all trade names) manufactured by Ciba Japan Co., Ltd., alicyclic epoxy resins; YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T.E.N. produced by Dow Chemical Co., EPPN-501, EPPN-502 (all trade names), trihydroxyphenylmethane type epoxy resin; A biscylenol type or biphenol type epoxy resin such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Japan Epoxy Resins, or a mixture thereof; Bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Corporation and EXA-1514 (trade name) manufactured by DIC Corporation; Bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd.; JERYL-931 manufactured by Japan Epoxy Resin Co., Ltd., Araldite 163 manufactured by Shiba Japan Co., Ltd. (all trade names), tetraphenylol ethane type epoxy resin; Araldite PT810 (trade name), manufactured by Ciba Japan Ltd., and TEPIC (registered trademark), manufactured by Nissan Chemical Industries, Ltd.; Diglycidyl phthalate resins such as Bremmer (registered trademark) DGT manufactured by Nippon Oil Polymer Co., Ltd.; Tetraglycidylcylenoyl ethane resins such as ZX-1063 manufactured by Toko Chemical Co., Ltd.; ESN-190, ESN-360 manufactured by Shinnittsu Chemical Co., Ltd., HP-4032, EXA-4750 and EXA-4700 manufactured by DIC Corporation; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Co., Ltd.; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.) and CTBN-modified epoxy resins (e.g., YR-102 and YR-450 manufactured by Tokuga Seisakusho Co., Ltd.) , But are not limited thereto. These epoxy resins may be used alone or in combination of two or more. Of these, novolac-type epoxy resins, modified novolak-type epoxy resins, heterocyclic epoxy resins, biquilene-type epoxy resins, and mixtures thereof are particularly preferable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (P-hydroxystyrene), cardo-type bisphenols, calixarene, calix resorcinarene, or a mixture of oxalic alcohol and novolak resin, poly And ether compounds with a hydroxyl group-containing resin such as sesquioxane. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

Examples of the episulfide resin having two or more cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Japan Epoxy Resin Co., Ltd., YSLV-120TE manufactured by Tokto Kasei Co., . An episulfide resin in which the oxygen atom of the epoxy group of the novolac epoxy resin is substituted with a sulfur atom can also be used by using the same synthetic method.

The amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is preferably in the range of 0.6 to 2.5 equivalents, more preferably 0.8 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the carboxyl group-containing resin. When the blending amount of the thermosetting component having two or more cyclic (thio) ether groups in the molecule is less than 0.6 equivalent, a carboxyl group remains in the solder resist film, and heat resistance, alkali resistance, electrical insulation, etc. are lowered. On the other hand, when the amount is more than 2.5 equivalents, a cyclic (thio) ether group having a low molecular weight remains in the dried coating film, and the strength or the like of the coating film is lowered.

Examples of thermosetting components which can be preferably used include melamine derivatives, benzoguanamine derivatives and the like. For example, methylolmelamine compounds, methylolbenzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. The alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound, and the alkoxymethylated urea compound may be used in combination with the respective methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds, and methylol urea compounds Methylol group into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Particularly, a melamine derivative having a formalin concentration of 0.2% or less is desirable for human body and environment.

As commercial products thereof, for example, CYMEL (registered trademark) 300, Copper 301, Copper 303, Copper 370, Copper 325, Copper 327, Copper 701, Copper 266, Copper 267, Copper 238, Copper 1141, Copper Copper 272 202, 1056, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by Mitsui Cyanamid Co., Ltd.), Nigalak (registered trademark) Mx-750, copper Mx- 30, Mw-30HM, Mw-30, Mw-30, Mw-30, Mw-30, Mw- Copper Mw-390, copper Mw-100LM, copper Mw-750LM (manufactured by Sanwa Chemical Co., Ltd.).

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

Further, a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule may be added to the photo-curable thermosetting resin composition of the present invention in order to improve the curability of the composition and the toughness of the resulting cured film. Such a compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or a compound having two or more blocked isocyanate groups in one molecule, i.e., a block isocyanate compound .

As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Examples of the above-mentioned isocyanate compounds include adduct, burette and isocyanurate.

The blocked isocyanate group contained in the block isocyanate compound is a group in which the isocyanate group is protected by a reaction with the blocking agent and is temporarily inactivated. When heated to a predetermined temperature, the block agent dissociates to produce an isocyanate group.

As the block isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent is used. Examples of the isocyanate compound capable of reacting with the block agent include isocyanurate type, buret type, and adduct type. As the isocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate block agent include phenolic block agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam-based blocking agents such as? -caprolactam,? -valerolactam,? -butyrolactam and? -propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; But are not limited to, methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Alcohol-based blocking agents such as butyl acetate, diacetone alcohol, methyl lactate and ethyl lactate; Oxime-based blocking agents such as formaldehyde scavengers, acetal aldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol and ethyl thiophenol; Acid amide type block agents such as acetic acid amide, benzamide and the like; Imide block agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine blockers such as methylene imine and propylene imine, and the like.

Block isocyanate compounds may be commercially available, for example Sumitur TM BL-3175, BL-4165, BL-1100, BL-1265, Dismodur TM TPLS-2957, TPLS-2062 (Trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Colonate (registered trademark) 2512, Colonate 2513, Colonate 2520 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), TPLS-2078, TPLS-2117, (Trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (Trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.). Further, SMILDIR BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a block agent.

The above-mentioned compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule may be used alone or in combination of two or more.

The compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in the molecule is preferably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the blending amount is less than 1 part by mass, sufficient toughness of the coating film can not be obtained, which is not preferable. On the other hand, if it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable.

In the photo-curable thermosetting resin composition of the present invention, a urethane-forming catalyst may be added to accelerate the curing reaction between a hydroxyl group and a carboxyl group and an isocyanate group. As the urethanization catalyst, it is preferable to use at least one urethane-forming catalyst selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfate salts, amine compounds and / or amine salts.

Examples of the tin-based catalyst include organotin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

Examples of the metal chloride include chlorides of metals such as Cr, Mn, Co, Ni, Fe, Cu, or Al, such as cobalt chloride, nickel chloride and ferric chloride.

The metal acetylacetonate salt is an acetylacetonate salt of a metal containing Cr, Mn, Co, Ni, Fe, Cu or Al, and examples thereof include cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, .

Examples of the metal sulfate include metal sulfate such as Cr, Mn, Co, Ni, Fe, Cu, or Al, and copper sulfate, for example.

Examples of the amine compound include triethylenediamine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) N, N ", N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, Aminopyridine, triazine, N'- (2-hydroxyethyl) -N, N, N'-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, (2-hydroxyethyl) -N, N ', N ", N" -tetramethyldiamine, N- N, N'-trimethyl-N '- (2-hydroxyethyl) -N, N'-tetramethyldiethylenetriamine, N- ) Propane diamine, N, N'-bis (N, N-dimethylaminopropyl) amine, bis Aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1- (2'-hydroxy Propyl imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole, 1- Imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (3'-aminopropyl) imidazole, 1- , N, N-dimethylaminopropyl-N '- (2-hydroxyethyl) imidazole, 1- (3'- (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ', N'-bis (2-hydroxypropyl) amine, (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ', N'-bis (2-hydroxypropyl) amine, melamine or / And benzoguanamine.

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

The amount of the urethanization catalyst to be used is usually in a suitable quantitative ratio, and is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10.0 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A).

When a thermosetting component having at least two cyclic (thio) ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as imidazole, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., U-CAT DBU, U-CATSA102, U-CAT5002 (all of bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, and may be a catalyst for accelerating the reaction between a thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group and a carboxyl group, or may be used alone or in combination have. Further, it is also possible to use at least one selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, isocyanuric acid Or an S-triazine derivative such as an adduct may be used. Preferably, a compound that also functions as such an adhesion-imparting agent is used in combination with the above-mentioned thermosetting catalyst.

The compounding amount of these thermosetting catalysts is usually sufficient in a usual quantitative ratio and is preferably 0.1 to 20 parts by mass, for example, based on 100 parts by mass of the thermosetting component having two or more cyclic (thio) ether groups in the carboxyl group- More preferably 0.5 to 15.0 parts by mass.

The photo-curable resin composition of the present invention may contain a colorant. As the colorant, publicly known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments may be used. Specifically, the color index (CI. Issued by The Society of Dyers and Colors) is given as follows. However, it is preferable that it does not contain a halogen in terms of environmental load reduction and human influence.

Red colorant:

Examples of the red colorant include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. And the same color index (CI) issued by The Society of Dyers and Colourists.

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

Disazo system: Pigment Red 37, 38, 41.

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 pigments: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224, Pigment Red 174, Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, .

Diketopyrrolopyrrole-based pigments: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

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

Quinacridone pigments: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

Examples of the blue colorant include a phthalocyanine type and anthraquinone type, and a pigment type is a compound classified as a pigment. Specific examples thereof include 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.

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 Etc. may be used. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Green colorant:

Examples of the green colorant include phthalocyanine type, anthraquinone type and perylene type. Specific examples include Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20 and Solvent Green 28 . In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Yellow colorant:

Examples of the yellow colorant include a monoazo system, a disazo system, a condensed azo system, a benzimidazolone system, an isoindolinone system, and an anthraquinone system, and specific examples include the following.

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

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

Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone pigments: 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.

Disazo system: 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.

Illustratively, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C.I. Pigment Orange 1, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 16, C.I. Pigment Orange 17, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 51, C.I. Pigment Orange 61, C.I. Pigment Orange 63, C.I. Pigment Orange 64, C.I. Pigment Orange 71, C.I. Pigment Orange 73, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Black 1, C.I. Pigment Black 7 and so on.

The mixing ratio of the colorant as described above is not particularly limited, but is preferably 0 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin.

The compound having two or more ethylenically unsaturated groups in the molecule used in the photo-curable thermosetting resin composition of the present invention is photo-cured by irradiation with active energy rays and is capable of insolubilizing or insolubilizing the carboxyl-containing resin in an aqueous alkali solution will be. Examples of such compounds include polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate and epoxy Specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol and tris-hydroxyethylisocyanurate, or ethylene oxide adducts thereof, propylene oxide adducts, or? -Caprolactone adducts Polyhydric acrylates; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; The present invention is not limited to the above. The polyol such as polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene and polyester polyol may be directly acrylated or acrylated with urethane acrylate through diisocyanate and melamine acrylate , And / or the respective methacrylates corresponding to the acrylate.

In addition, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolak type epoxy resin with acrylic acid, or an epoxy acrylate resin obtained by reacting a hydroxy acrylate such as pentaerythritol triacrylate with an isophorone di And an epoxy urethane acrylate compound obtained by reacting a half urethane compound of a diisocyanate such as isocyanate. Such an epoxy acrylate resin can improve photo-curability without deteriorating the touch-dry composition.

The compounding amount of the compound having two or more ethylenically unsaturated groups in the molecule is 5 to 100 parts by mass, more preferably 1 to 70 parts by mass, based on 100 parts by mass of the carboxyl-containing resin. When the blending amount is less than 5 parts by mass, the photocurability is lowered, and pattern formation becomes difficult due to the alkali development after irradiation with active energy rays, which is not preferable. On the other hand, if it exceeds 100 parts by mass, the solubility in an aqueous alkaline solution is lowered and the coating film becomes weak, which is not preferable.

In the photocurable thermosetting resin composition of the present invention, a filler may be added if necessary in order to increase the physical strength and the like of the coating film. As such a filler, inorganic or organic fillers for publicly known generations can be used, and particularly barium sulfate, spherical silica and talc are preferably used. Further, metal hydroxide such as titanium oxide, metal oxide, and aluminum hydroxide may be used as extender pigment filler in order to obtain white appearance and flame retardancy. The blending amount of these fillers is preferably 200 parts by mass or less, more preferably 0.1 to 150 parts by mass, and particularly preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the blending amount of the filler exceeds 200 parts by mass, the viscosity of the composition is increased, the printing property is lowered, or the cured product becomes fragile.

In addition, the photo-curable thermosetting resin composition of the present invention may use a binder polymer for the purpose of improving tackiness and handling properties. For example, a polyester polymer, a polyurethane polymer, a polyester urethane polymer, a polyamide polymer, a polyester amide polymer, an acrylic polymer, a cellulose polymer, a polylactic acid polymer and a phenoxy polymer can be used. These binder polymers may be used alone or as a mixture of two or more thereof.

In addition, the photo-curable thermosetting resin composition of the present invention may contain a hydroxyl group-containing elastomer or other elastomer for the purpose of imparting flexibility and improving the fragility of a cured product. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyester amide elastomer, an acrylic elastomer, and an olefin elastomer can be used. Further, a resin obtained by modifying an epoxy group of part or all of the epoxy resin having various skeletons with both terminal carboxylic acid modified butadiene-acrylonitrile rubbers can also be used. Further, an epoxy-containing polybutadiene-based elastomer and an acrylic-containing polybutadiene-based elastomer may be used. These elastomers can be used singly or as a mixture of two or more kinds.

The photo-curable thermosetting resin composition of the present invention can be used for the synthesis of the carboxyl group-containing resin, the adjustment of the composition, or the viscosity adjustment for the application to the substrate or the carrier film.

Examples of such organic solvents include 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; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether And the like; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents are used alone or as a mixture of two or more kinds.

In general, most of the polymeric materials are oxidatively deteriorated successively one after the start of oxidation, resulting in deterioration of the function of the polymer material. Therefore, in the photo-curable thermosetting resin composition of the present invention, ) And / or (2) an antioxidant such as a peroxide decomposition agent which decomposes the generated peroxide into a harmless substance to prevent generation of new radicals.

Specific examples of the antioxidant that functions as a radical scavenger include hydroquinone, 4-t-butyl catechol, 2-t-butyl hydroquinone, hydroquinone monomethyl ether, 2,6- , 2-methylene-bis (4-methyl-6-t-butylphenol), 1,1,3-tris -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'- Based compounds such as phenol-based, metaquinone, benzoquinone, etc., bis (2,2,6,6-tetramethylpiperidine) 6-tetramethyl-4-piperidyl) sebacate, phenothiazine, and the like.

Radical scavengers may be commercially available, for example, ADEKA STAP (registered trademark) AO-30, ADEKA STAB AO-330, ADEKA STAB AO-20, ADEKA STAB LA- -57, Adeka Staff LA-67, Adeka Staff LA-68, Adeka Staff LA-87 (trade name, manufactured by Adeka Co., Ltd.), IRGANOX 1010, Irganox 1035, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (trade names, manufactured by Ciba Japan Ltd.) .

Specific examples of the antioxidant functioning as a peroxide releasing agent include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetra lauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3'-t- And sulfur compounds such as octyl propionate.

The release of the peroxide may be a commercially available one, and examples thereof include Adekastab TPP (trade name, manufactured by Adeka), Mark AO-412S (trade name, manufactured by Adeka Agusuga) (Trade name, manufactured by Sumitomo Chemical Co., Ltd.).

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

In addition, in general, since the polymer material absorbs light and causes decomposition or deterioration thereof, the photo-curable thermosetting resin composition of the present invention may contain an ultraviolet absorbent in addition to the antioxidant .

Examples of ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives. Specific examples of benzophenone derivatives include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy- , 4-dihydroxybenzophenone, and the like. Specific examples of the benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di- -Hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, . Specific examples of the triazine derivatives include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.

Examples of ultraviolet absorbers that may be used include commercially available products such as Tinuvin PS, Tinuvin 99-2, Tinuvin 109, Tinuvin 384-2, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 400, Nubin 405, Tinuvin 460, and Tinuvin 479 (all trade names, manufactured by Shiba, Japan).

The ultraviolet absorber can be used singly or in combination of two or more. By using the ultraviolet absorber in combination with the antioxidant, the molded article obtained from the photo-curable thermosetting resin composition of the present invention can be stabilized.

To improve the sensitivity of the photo-curable thermosetting resin composition of the present invention, known chain transfer agents such as N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as a chain transfer agent. Specific examples of the chain transfer agent include chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; Chain transfer agents having a hydroxyl group such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropane diol, mercaptobutanediol, hydroxybenzene thiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylene dioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan , Propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

Further, a multifunctional mercaptan-based compound can be used and is not particularly limited. Examples thereof include hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethyl alcohol Aliphatic thiols such as xylylene dimethacrylate and feed, aromatic thiols such as xylylene dimercaptan, 4,4'-dimercaptodiphenylsulfide and 1,4-benzenedithiol; (Mercaptoacetate), ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylol ethane tris Poly (mercaptoacetates) of polyhydric alcohols such as mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), dipentaerythritol hexakis (mercaptoacetate); (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate) , Trimethylol ethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis - mercapto propionate); poly (3-mercaptopropionates) of polyhydric alcohols; 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- 3H, 5H) -triene, and pentaerythritol tetrakis (3-mercaptobutyrate).

Examples of commercially available products thereof include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEMPIC (manufactured by Sakai Chemical Industry Co., Car lens MT-BD1 and Car lens -NR1 (manufactured by Showa Denko K.K.).

Examples of the heterocyclic compound having a mercapto group functioning as a chain transfer agent include mercapto-4-butyrolactone (alias: 2-mercapto-4-butanololide), 2-mercapto- 4-butyrolactone, 2-mercapto-4-butyrolactone, 2-mercapto-4-butyrolactam, N-methoxy- 2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N- 2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto- Mercapto-5-valerolactone, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam Mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole Mercapto-5-methylthio-thiadiazole, 2-mercapto-6-hexanolactam, 2,4,6-trimercapto-s-triazine (Trade name: Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., 6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd., trade name: Disnet AF).

Particularly, as a heterocyclic compound having a mercapto group which is a chain transfer agent which does not impair the developability of the photocurable thermosetting resin composition, mercapto benzothiazole, 3-mercapto-4-methyl-4H-1,2,4- Sol, 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferable. These chain transfer agents may be used alone or in combination of two or more.

In the photocurable thermosetting resin composition of the present invention, an adhesion promoter may be used to improve adhesion between layers or adhesion between the photosensitive resin layer and the substrate. Specific examples thereof include benzoimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi Kagaku Kogyo ) Manufactured by Arc Cell M), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole- Methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

The photocurable thermosetting resin composition of the present invention may further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, and hydrotalcite, if necessary. The aging stability as a thixotropic agent is preferably organic bentonite or hydrotalcite, and particularly hydrotalcite has excellent electrical properties. In addition, thermal polymerization inhibitors, defoaming agents such as silicone, fluorine, and high molecular weight and / or leveling agents, silane coupling agents such as imidazole, thiazole, and triazole, rheological agents, and further, bisphenol, Antioxidants, anti-corrosive agents for copper, and the like.

The thermal polymerization inhibitor may be used to prevent thermal polymerization or aging polymerization of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy- Benzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine,? -Naphthol, 2,6-di-t-butyl-4-cresol, 2,2'- butylphenol), reactants such as pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agents, methyl salicylate, phenothiazine, nitroso compounds, And the like.

The photo-curable thermosetting resin composition of the present invention can be prepared, for example, by adjusting the viscosity with a suitable viscosity for the coating method with the above-mentioned organic solvent, and coating on the substrate by an immersion coating method, a flow coating method, a roll coating method, a bar coater method, Coating method and the like, and then the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 60 to 100 ° C, whereby a tack-free coating film can be formed. Thereafter, by a contact type (or noncontact type), the resist film is selectively exposed to an active energy ray through a photomask having a pattern formed thereon, or directly pattern-exposed by a laser direct exposure apparatus, and the unexposed portion is exposed in an alkali aqueous solution For example, 0.3 to 3% aqueous sodium carbonate solution) to form a resist pattern. Further, in the case of a composition containing a thermosetting component, for example, by heating at a temperature of about 130 to 180 캜 to thermoset, the carboxyl group of the carboxyl group-containing resin and at least two cyclic ether groups and / A thermosetting component having an ether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, electrical characteristics and the like. In addition, even when the thermosetting component is not contained, the thermal treatment is performed to thermally radical polymerize the ethylenically unsaturated bonds of the photo-curing component remaining in the unreacted state during exposure to improve the film properties, (Heat curing).

In addition to the printed wiring board and the flexible printed wiring board which have been formed in advance, the above substrate may be formed of a resin such as a paper-phenol resin, a paper-epoxy resin, a glass cloth-epoxy resin, a glass-polyimide, a glass cloth / (FR-4 or the like), polyimide film, PET film, glass substrate, ceramic substrate, wafer plate or the like using a composite material such as synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester Can be used.

The volatile drying performed after the application of the photocurable thermosetting resin composition of the present invention is carried out by a hot air circulating drying furnace, a hot plate, a convection oven or the like (the hot air in the dryer A method of countercurrent contact with the support and a method of spraying onto the support by a nozzle).

After the photocurable thermosetting resin composition of the present invention is applied and volatilized and dried as described below, the resulting coating film is exposed (irradiated with active energy rays). The coating film is cured by the exposure part (the part irradiated by the active energy ray).

Examples of the exposure apparatus used for the irradiation of the active energy ray include a direct imaging apparatus (for example, a laser direct imaging apparatus for directly drawing an image with a laser by CAD data from a computer), an exposure apparatus equipped with a metal halide lamp, A direct exposure apparatus equipped with a mercury short arc lamp, or a direct drawing apparatus using an ultraviolet lamp such as a (super) high pressure mercury lamp can be used. As the active energy ray, either a gas laser or a solid laser may be used if laser light having a maximum wavelength in the range of 350 to 410 nm is used. The amount of exposure differs depending on the film thickness and the like, but can be generally in the range of 5 to 500 mJ / cm ² , preferably 10 to 300 mJ / cm ² . As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech Co., Ltd. or manufactured by FANUC Corporation may be used, and any apparatus may be used as long as it is an apparatus for emitting laser light having a maximum wavelength of 350 to 410 nm.

As the developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, have.

The photocurable thermosetting resin composition of the present invention may be used in the form of a dry film having a solder resist layer formed by applying and drying a solder resist to a film such as polyethylene terephthalate in advance, The case where the photocurable thermosetting resin composition of the present invention is used as a dry film will be described below.

The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film, which is used as needed, are laminated in this order. The solder resist layer is a layer obtained by applying and drying an alkali developing photocurable thermosetting resin composition onto a carrier film or a cover film. A dry film can be obtained by laminating a cover film on the carrier film after forming the solder resist layer thereon, or by forming a solder resist layer on the cover film and laminating the laminate on the carrier film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 mu m is used.

The solder resist layer is formed by uniformly applying an alkali developable photocurable thermosetting resin composition to a carrier film or a cover film by a blade coater, a lip coater, a comma coater, a film coater or the like to a thickness of 10 to 150 mu m and drying the same.

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

In order to manufacture a protective film (permanent protective film) on a printed wiring board using a dry film, the cover film is peeled off, the solder resist layer and the circuit-formed substrate are superimposed and bonded together using a laminator or the like, Layer. When the exposed solder resist layer is exposed, developed, and heat cured as described above, a cured coating film can be formed. The carrier film may be peeled off either before or after exposure.

<Examples>

The present invention will be described in more detail with reference to the following examples and comparative examples, but it goes without saying that the present invention is not limited to the following examples. In the following, &quot; parts &quot; and &quot;% &quot; are based on the whole mass unless otherwise specified.

Synthesis Example 1

119.4 parts of a novolak type cresol resin (trade name: "SCORNOL CRG951", trade name, manufactured by Showa Kobunshi Co., Ltd., OH equivalent: 119.4) was added to an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device, 1.19 parts of potassium and 119.4 parts of toluene were charged, and the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Subsequently, 63.8 parts of propylene oxide was gradually added dropwise, and the reaction was carried out at 125 to 132 캜 and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature. To the reaction solution, 1.56 parts of 89% phosphoric acid was added and mixed to neutralize the potassium hydroxide, and a propylene oxide reaction solution of a novolac cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / &Lt; / RTI &gt; This means that an average of 1.08 mole of alkylene oxide per equivalent of phenolic hydroxyl group was added.

293.0 parts of the alkylene oxide reaction solution of the novolac cresol resin thus obtained, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone and 252.9 parts of toluene were fed into a reactor equipped with a stirrer, a thermometer and an air blowing tube, Air was blown at a rate of 10 ml / min and reacted at 110 ° C for 12 hours with stirring. The water produced by the reaction was 12.6 parts of water as an azeotropic mixture with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off by replacing toluene with 118.1 parts of diethylene glycol monoethyl ether acetate as an evaporator to obtain a novolak type acrylate resin solution. Subsequently, 332.5 parts of the obtained novolak type acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, blowing air at a rate of 10 ml / min, 60.8 parts of phthalic anhydride was slowly added, and the mixture was reacted 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 and a nonvolatile content of 71% was obtained. Hereinafter, this is referred to as varnish A-1.

Synthesis Example 2

Liter separable flask equipped with a stirrer, a thermometer, a stirrer and a reflux condenser was charged with 1,245 parts of polycaprolactone diol (PLACCEL208, manufactured by Daicel Chemical Industries, Ltd., molecular weight 830) as a polymer polyol, (Meth) acrylate having a hydroxyl group, 119 parts of 2-hydroxyethyl acrylate, furthermore, p-methoxyphenol and di-t-butyl-diisocyanate as a polyisocyanate, And 0.5 parts of hydroxytoluene, respectively. With stirring, the mixture was heated to 60 DEG C and stopped, and 0.8 part of dibutyltin dilaurate was added. When the temperature in the reaction vessel starts to decrease, the mixture is heated again, and stirring is continued at 80 ° C. It is confirmed that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group is lost in the infrared absorption spectrum and the reaction is terminated. To obtain a urethane acrylate compound. The nonvolatile content was adjusted to 50% by mass using carbitol acetate. To obtain a resin solution of urethane (meth) acrylate compound having a carboxyl group of 47 mg KOH / g of solid matter and 50% of nonvolatile content. Hereinafter, this is referred to as a varnish A-2.

Synthesis Example 3

A 2-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 900 parts of diethylene glycol dimethyl ether as a solvent and 10 parts of t-butylperoxy 2-ethylhexanoate ( 21.4 parts of perbutyl O, manufactured by Nippon Oil Co., Ltd.) was added and the mixture was heated to 90 占 폚. After heating, 309.9 parts of methacrylic acid, 116.4 parts of methyl methacrylate, and 109.8 parts of lactone-modified 2-hydroxyethyl methacrylate (Flacxel FM1, manufactured by Daicel Chemical Industries, Ltd.) Was added dropwise over 3 hours with 21.4 parts of polyoxyethylene (4-t-butylcyclohexyl) peroxydicarbonate (trade name, manufactured by NIPPON BUSINESS CO., LTD .; Perillo TCP), and the mixture was further aged for 6 hours, To obtain a resin. The reaction was carried out in a nitrogen atmosphere.

Subsequently, 363.9 parts of 3,4-epoxycyclohexylmethyl acrylate (trade name: CYROMER-A200, manufactured by Daicel Chemical Industries, Ltd.), 3.6 parts of dimethylbenzylamine as a ring opening catalyst, , 1.80 parts of hydroquinone monomethyl ether was added, and the mixture was heated to 100 占 폚 and stirred to carry out a ring-opening addition reaction of epoxy. After 16 hours, a resin solution having a solid acid value of 108.9 mgKOH / g, a weight average molecular weight of 25,000, and a solid content of 54% was obtained. Hereinafter, this is referred to as a varnish A-3.

Synthesis Example 4

To 650 parts of diethylene glycol monoethyl ether acetate, 1070 parts of an orthocresol novolac epoxy resin (EPICLON N-695 manufactured by DIC Corporation, softening point 95 占 폚, epoxy equivalent 214, average functional group number 7.6) (Total number of aromatic rings): 5.0 moles), 360 parts of acrylic acid (5.0 moles) and 1.5 parts of hydroquinone were charged and stirred at 100 DEG C to dissolve uniformly. Subsequently, 4.3 parts of triphenylphosphine was added, and the mixture was heated to 110 DEG C and reacted for 2 hours. Then, 1.6 parts of triphenylphosphine was further added, and the mixture was heated to 120 DEG C and reacted for 12 hours. 525 parts of an aromatic hydrocarbon (Solvesso 150) and 608 parts (4.0 mol) of tetrahydrophthalic anhydride were added to the obtained reaction solution, and the reaction was carried out at 110 ° C for 4 hours. Further, 142.0 parts (1.0 mol) of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was carried out at 115 DEG C for 4 hours to obtain a resin solution having a solid content of 77 mgKOH / g and a solid content of 65%. Hereinafter, this is referred to as varnish R-1.

Synthesis Example 5

To 600 parts of diethylene glycol monoethyl ether acetate were added 1070 parts of an orthocresol novolac epoxy resin (Epiclon N-695, manufactured by DIC Corporation, softening point 95 占 폚, epoxy equivalent 214, average number of functional groups: 7.6) (Total number of aromatic rings): 5.0 moles), 360 parts of acrylic acid (5.0 moles) and 1.5 parts of hydroquinone were charged and stirred at 100 DEG C to dissolve uniformly. Then, 4.3 parts of triphenylphosphine was added, and the mixture was heated to 110 DEG C and reacted for 2 hours, then heated to 120 DEG C and reacted for 12 hours. 415 parts of an aromatic hydrocarbon (Solvesso 150) and 456.0 parts (3.0 mol) of tetrahydrophthalic anhydride were added to the reaction solution obtained and reacted at 110 DEG C for 4 hours. After cooling, the mixture was allowed to have a solid content of 89 mgKOH / g, 65% of a resin solution was obtained. Hereinafter, this is referred to as varnish R-2.

Synthesis Example 6

2200 parts of cresol novolac epoxy resin (EOCN-104S, softening point 92 占 폚, epoxy equivalent 220), 134 parts of dimethylol propionic acid, 648.5 parts of acrylic acid, 4.6 parts of methylhydroquinone, And 484.9 parts of solvent naphtha were charged and heated to 90 DEG C and stirred to dissolve the reaction mixture. Subsequently, the reaction solution was cooled to 60 占 폚, triphenylphosphine 13.8 parts was added, and the mixture was heated to 100 占 폚 for about 32 hours to obtain a reaction product having an acid value of 0.5 mgKOH / g. Subsequently, 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate and 58.8 parts of solvent naphtha were charged and heated at 95 DEG C for about 6 hours to effect a reaction. The mixture was cooled to obtain a copolymer having a solid content of 40 mgKOH / g and a nonvolatile content of 65% Whereby a resin solution of a carboxyl group-containing photosensitive resin was obtained. Hereinafter, this is referred to as a varnish R-3.

Synthesis Example 7

925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide were dissolved in 400 parts of bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 DEG C, and 81.2 parts of 98.5% NaOH was added thereto at 70 DEG C over 100 minutes while stirring. After the addition, the reaction was further carried out at 70 ° C for 3 hours. Subsequently, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide was distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethylsulfoxide was dissolved in 750 parts of methyl isobutyl ketone, 10 parts of 30% NaOH The reaction was further carried out at 70 DEG C for 1 hour. After completion of the reaction, the reaction mixture was washed twice with 200 parts of water. After water separation, methyl isobutyl ketone was distilled off 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 캜. 2900 parts (10 equivalents) of the obtained epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone and 1950 parts of carbitol acetate were added and heated to 90 DEG C and stirred to dissolve the reaction mixture. Subsequently, the reaction solution was cooled to 60 캜, 16.7 parts of triphenylphosphine was added, and the mixture was heated to 100 캜 and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Subsequently, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were added thereto, and the mixture was heated to 95 DEG C and reacted for about 6 hours to obtain a resin solution having a solid content of 100 mgKOH / g and a solid content of 65%. Hereinafter, this is referred to as varnish R-4.

Examples 1 to 13 and Comparative Examples 1 to 3

Using the resin solution of the above synthesis example, the various components shown in the following Table 1 were mixed together at the ratio (parts by mass) shown in Table 1, preliminarily mixed with a stirrer, kneaded with a three-roll mill, A composition was prepared. The degree of dispersion of the obtained photosensitive resin composition was evaluated by particle size measurement by a grindmeter manufactured by Ericensa and found to be 15 占 퐉 or less.

Performance evaluation:

<Optimum exposure dose>

The circuit pattern substrate having a copper thickness of 18 占 퐉 was washed with water after copper surface roughening treatment (Mck etch bond CZ-8100 manufactured by Mack Co., Ltd.) and dried. Thereafter, the photocurable thermosetting resin compositions of the above- And dried in a hot-air circulation type drying furnace at 80 캜 for 60 minutes. After drying, the resist film was exposed to light through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a high-pressure mercury lamp, and then developed (30 ° C, 0.2 MPa, 1 wt% sodium carbonate aqueous solution) When the pattern of the step tablet is 7, the optimum exposure amount is set.

<Developability>

The photo-curable thermosetting resin compositions of the above Examples and Comparative Examples were coated on a copper front substrate by a screen printing method so as to have a film thickness of about 25 mu m after drying and dried for 30 minutes in a hot air circulating type drying furnace at 80 deg. After drying, development was carried out with a 1 wt% aqueous sodium carbonate solution, and the time until the dry coating film was removed was measured by a stop watch.

<Maximum Phenomenon Life>

The compositions of the above Examples and Comparative Examples were applied on the entire surface by screen printing on the patterned copper foil substrate, dried at 80 占 폚 and taken out at intervals of 10 minutes from 20 minutes to 80 minutes, followed by cooling to room temperature. The substrate was developed with a 1 wt% aqueous solution of sodium carbonate at 30 DEG C under a spray pressure of 0.2 MPa for 60 seconds, and the maximum permissible drying time at which no residue remained was taken as the maximum developing life.

<Tachung>

The compositions of the above examples and comparative examples were coated on the entire surface by screen printing on the patterned copper foil board, dried for 30 minutes in a hot air circulation type drying furnace at 80 캜, and cooled to room temperature. The substrate was struck with a PET negative film, pressed with HMW-GW20 manufactured by ORC Corporation under a reduced pressure condition for 1 minute, and then the film was peeled off and evaluated for the following criteria.

○: There is no resistance when peeling off the film, and no trace is left on the film.

△: There is some resistance when peeling off the film, and a little trace remains on the film.

X: There is resistance when peeling off the film, and there is a clear trace on the film.

Characteristic test:

The compositions of the above Examples and Comparative Examples were applied on the entire surface by screen printing on the patterned copper foil substrate, dried at 80 캜 for 30 minutes, and then cooled to room temperature. The substrate was exposed to a solder resist pattern at an optimal exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp, and developed for 90 seconds under the conditions of a 1 wt% sodium carbonate aqueous solution at 30 DEG C and a spray pressure of 0.2 MPa to obtain a resist pattern. The substrate was irradiated with ultraviolet rays under the conditions of an integrated exposure dose of 1000 mJ / cm ² with a UV conveyer, and then cured by heating at 150 ° C for 60 minutes. The properties of the obtained printed board (evaluation board) were evaluated as follows.

<Acid resistance>

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

○: Change is not recognized.

△: Very slightly changed.

X: The coating film has swelling or swelling or dropping.

<Alkali resistance>

The evaluation substrate was immersed in a 10% by volume aqueous solution of NaOH at room temperature for 30 minutes to visually confirm seepage and elution of the coating film, and peeling by tape peeling was confirmed.

○: Change is not recognized.

△: Very slightly changed.

X: The coating film has swelling or swelling or dropping.

&Lt; Soldering heat resistance &

The evaluation substrate coated with the rosin-based flux was immersed in a soldering tank set at 260 占 폚 in advance, and the flux was washed with denatured alcohol, and then the expansion and peeling of the resist layer by visual inspection were evaluated. The criteria are as follows.

○: No peeling was observed even if immersion for 10 seconds was repeated 3 times or more.

?: Slightly peeled if the immersion for 10 seconds was repeated 3 times or more.

X: Expansion and peeling occurred in the resist layer within 3 times of immersion for 10 seconds.

<Electroless gold plating resistance>

Plating was carried out under the conditions of nickel of 5 占 퐉 and gold of 0.05 占 퐉 using a commercially available electroless nickel plating bath and electroless gold plating bath to evaluate the presence or absence of peeling of the resist layer and the impregnation of the plating by tape peeling, The peeling of the resist layer was evaluated by tape peeling. The criteria are as follows.

○: A little seeping was confirmed after plating, but no peeling after tape peeling.

?: A little seeping was confirmed after plating, and peeling was observed after tape peeling.

X: Peeling occurred after plating.

<PCT Resistance>

The evaluation substrate on which the solder resist cured coating film was formed was treated at 121 占 폚 and saturation at 0.2 MPa for 168 hours using a PCT apparatus (HAST SYSTEM TPC-412 MD, manufactured by Espec Co., Ltd.) Respectively. The criteria are as follows.

○: No swelling, peeling, discoloration, or elution.

?: A little swelling, peeling, discoloration, elution.

X: Expansion, peeling, discoloration, and a lot of dissolution appear.

<Resistance to cold and heat shock>

An evaluation board having a solder resist cured coating film on which a removal pattern and a removal pattern were formed was prepared. The obtained evaluation substrate was subjected to an immunity test for 1000 cycles with one cycle of -55 占 폚 / 30 minutes to 150 占 폚 / 30 minutes with a cold / impact tester (manufactured by ETAC Co., Ltd.). After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged based on the following criteria.

○: Less than 30% crack occurrence rate.

?: Crack generation rate 30 to 50%.

X: The crack occurrence rate exceeds 50%.

<HAST characteristics>

A solder resist cured coating film was formed on a BT substrate on which a comb electrode (line / space = 50 占 퐉 / 50 占 퐉) was formed to prepare an evaluation substrate. The evaluation substrate was placed in a high-temperature, high-humidity bath at 130 캜 and a humidity of 85%, charged at a voltage of 12 V, and subjected to a HAST test in a bath for 168 hours. The internal insulation resistance value at the elapsing time of 168 hours was evaluated according to the following criteria.

○: exceeds 10 ⁸ Ω.

?: 10 ⁶ to 10 ⁸ Ω.

×: Less than 10 ⁶ Ω.

The results of the above evaluation tests are shown in Table 2 below.

Characteristic test:

The composition of Example 13 and Comparative Example 1 was coated on the entire surface by screen printing on the patterned copper foil substrate, dried at 80 캜 for 30 minutes, and allowed to cool to room temperature. A solder resist pattern was exposed at an optimum exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp mounted on this substrate, and development was carried out for 90 seconds under the conditions of a 1 wt% sodium carbonate aqueous solution at 30 캜 and a spray pressure of 0.2 MPa to obtain a resist pattern Example 14 and Comparative Example 4 were used. The substrate was irradiated with ultraviolet rays under the conditions of an integrated exposure dose of 1000 mJ / cm ² with a UV conveyer and cured by heating at 130 캜, 140 캜, 150 캜, 160 캜, 170 캜, 180 캜 or 190 캜 for 60 minutes. The properties of the obtained printed board (evaluation board) were evaluated as follows. The results are shown in Tables 3 and 4.

<Tg measurement>

A 3 mm x 10 mm cured film was subjected to a tensile test at a temperature raising rate of 0 ° C to 260 ° C at a constant heating rate while applying a load of 10 g with TMA6100 manufactured by Seiko Instruments Inc. The extrapolated point was calculated and the glass transition temperature Tg.

<CTE measurement>

A tensile test was performed at a constant temperature raising rate in a temperature range of 0 占 폚 -260 占 폚 while applying a load of 10 g with a TMA6100 manufactured by Seiko Instruments Inc. under a load of 3 mm 占 10 mm. The cured film against temperature calculated the linear thermal expansion coefficient CTE from the elongation.

Examples 15 to 22 and Comparative Examples 5 to 7

The compositions of Examples 1, 3, 4, 6, 7, 8, 9, 11 and Comparative Examples 1, 2, and 3 prepared in the blend ratios shown in Table 1 were diluted with methyl ethyl ketone, And dried at 80 캜 for 30 minutes to form a photosensitive resin composition layer having a thickness of 20 탆. Further, a cover film was laminated thereon to prepare a dry film, which were Examples 15 to 22 and Comparative Examples 5 to 7, respectively.

&Lt; Evaluation of dry film &

The cover film was peeled from the dry film obtained as described above, and the film was thermally laminated on the patterned copper foil substrate. Subsequently, the substrate was exposed under the same conditions as those used for evaluating the coating film characteristics of the above examples. After the exposure, the carrier film was peeled off and development was carried out for 90 seconds under the conditions of a 1 wt% sodium carbonate aqueous solution at 30 DEG C and a spray pressure of 0.2 MPa to obtain a resist pattern. The substrate was irradiated with ultraviolet rays under the conditions of an integrated exposure dose of 1000 mJ / cm ² with a UV conveyer, and then cured by heating at 150 ° C for 60 minutes. The test substrates having the obtained cured coatings were subjected to the evaluation tests of the respective characteristics by the above-described test method and evaluation method. The results are shown in Table 5.

&Lt; Evaluation of dry film &

The cover film was peeled off from the dry film obtained as described above using the composition of Example 1 and Comparative Example 1, and the film was thermally laminated on the patterned copper foil substrate. Subsequently, And exposed under the same conditions. After the exposure, the carrier film was peeled off and development was carried out for 90 seconds under the conditions of a 1 wt% sodium carbonate aqueous solution at 30 캜 and a spray pressure of 0.2 MPa to obtain a resist pattern, which was used in Example 23 and Comparative Example 8, respectively. The substrate was irradiated with ultraviolet rays under the conditions of an integrated exposure dose of 1000 mJ / cm ² with a UV conveyer and cured by heating at 130 캜, 140 캜, 150 캜, 160 캜, 170 캜, 180 캜 or 190 캜 for 60 minutes. The test substrates having the obtained cured coatings were subjected to the evaluation tests of the respective characteristics by the above-described test method and evaluation method. The results are shown in Tables 6 and 7.

As is clear from the results shown in Tables 6 and 7, the photocurable thermosetting resin composition of the present invention is a thermosetting thermosetting resin composition having a PCT resistance, a cold shock resistance and a HAST characteristic (electric characteristic) It has been recognized that it is useful as a resin composition.

By using the photocurable thermosetting resin composition of the present invention, it is possible to form a cured film excellent in PCT resistance, HAST resistance, electroless gold plating resistance, heat resistance, and the like. Therefore, a solder resist such as a printed wiring board or a flexible wiring board, It can be suitably used for forming a solder resist.

Claims (6)

A carboxyl group-containing resin (except for a carboxyl group-containing resin having an epoxy resin as a starting material),
A photopolymerization initiator, and
In a composition containing an epoxy resin having a planar naphthalene ring,
The above-mentioned carboxyl group-containing resin
(1) reacting a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in a molecule with an alkylene oxide, with a monocarboxylic acid containing an unsaturated group, and reacting the resultant reaction product with a polybasic acid anhydride, Suzy;
(2) a carboxyl group obtained by reacting a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in a molecule with a cyclic carbonate compound, with a monocarboxylic acid containing an unsaturated group, and reacting the resultant reaction product with a polybasic acid anhydride Containing photosensitive resin;
(3) a terminal carboxyl group-containing urethane resin which is obtained by reacting an acid anhydride at the terminal of a urethane resin by a heavy-chain reaction between a diisocyanate compound and a diol compound;
(4) A method for producing a polyester resin composition, which comprises reacting a diisocyanate, a carboxyl group-containing dialcohol compound, and a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin- A compound having at least one hydroxyl group and at least one (meth) acryloyl group in the molecule during the synthesis of a carboxyl group-containing urethane resin by a partial reaction with a diol compound selected from compounds having a hydroxyl group or an alcoholic hydroxyl group And a terminal (meth) acrylated carboxyl group-containing urethane resin; And
(5) A process for producing a polyisocyanate composition, which comprises reacting a diisocyanate, a carboxyl group-containing dialcohol compound, a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, A compound having one isocyanate group and at least one (meth) acryloyl group in the molecule during the synthesis of a carboxyl group-containing urethane resin by a heavy-chain reaction with a diol compound selected from compounds having a hydroxyl group or an alcoholic hydroxyl group (Meth) acrylated carboxyl group-containing urethane resin
Wherein the photo-curable thermosetting resin composition is at least one of the following: delete delete A photocurable thermosetting dry film obtained by applying the photocurable thermosetting resin composition according to claim 1 to a carrier film and drying the same. A cured product obtained by photo-curing the photo-curable thermosetting resin composition according to claim 1, or a dry film obtained by applying and drying the photo-curable thermosetting resin composition to a carrier film. A photocurable thermosetting resin composition as set forth in claim 1, or a dry film obtained by applying and drying the photocurable thermosetting resin composition to a carrier film is photocured into a patterned state by irradiation of an active energy ray and thermally cured to obtain a cured film .