KR20100106235A

KR20100106235A - Photocurable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using the same

Info

Publication number: KR20100106235A
Application number: KR1020100025117A
Authority: KR
Inventors: 도우꼬 시이나; 마사오 아리마
Original assignee: 다이요 잉키 세이조 가부시키가이샤
Priority date: 2009-03-23
Filing date: 2010-03-22
Publication date: 2010-10-01
Also published as: CN101846882B; CN102636954B; JP5377020B2; TWI398458B; KR101073792B1; JP2010224168A; CN102636954A; TW201105695A; CN101846882A

Abstract

This invention is excellent in the heat resistance of a dry coating film, electroless gold plating resistance, electrical insulation, etc., The photocurable thermosetting resin composition, its dry film especially which can prevent the disconnection of the fine pitch circuit by coarse particle of an insoluble content, and The printed wiring board which hardened | cured material and hardened films, such as a soldering resist, are formed by these is provided.
According to this invention, it is a composition containing (A) epoxy resin, (B) carboxyl group-containing resin, and (C) photoinitiator, The said epoxy resin (A) is bifunctional biphenyl epoxy which has a structure represented by following General formula (1). At least 1 having an epoxy equivalent of 180 to 300 at a softening point of 40 to 100 ° C. selected from the group consisting of resin (A-1), a bisphenol A epoxy resin, a bisphenol A novolac epoxy resin and a biphenol novolac epoxy resin It is a mixture of epoxy resin (A-2) of a species, The ratio of said epoxy resin (A-1) and (A-2) is (A-1) <(A-2), The alkali developable sight A chemical conversion thermosetting resin composition is provided.
<Formula 1>

Wherein R represents H or CH ₃

Description

PHOTOCURABLE THERMOSETTING RESIN COMPOSITION, DRY FILM AND CURED PRODUCT THEREOF, AND PRINTED WIRING BOARD USING THE SAME}

The present invention is a photocurable thermosetting resin composition which can be developed by an aqueous alkali solution, in particular, a print having a composition for soldering resist photocured by ultraviolet or laser exposure, a dry film and cured product thereof, and a cured coating film formed using the same. It relates to a wiring board.

Conventionally, the alkali developing photosensitive resin composition was used a lot as a soldering resist for printed wiring boards. Solder resist is used for the purpose of protecting the surface layer circuit of a printed wiring board, and high solder heat resistance and electrical insulation property are calculated | required. Moreover, in recent years, the densification of printed wiring boards is remarkable, and since the circuit has a minimum line of 10 micrometers and a space of 10 micrometers, the insulation reliability higher than before is calculated | required.

Conventional alkali developing solder resists are composed of an acid-modified epoxy acrylate, a photopolymerization initiator, a reactive diluent, an epoxy resin, and a filler. Especially among these components, an epoxy resin plays the important role which improves heat resistance, an electrical property, and adhesiveness. In particular, among the epoxy resins, crystalline epoxy resins are important components in terms of specific heat resistance and optical properties (see Patent Document 1).

However, with the recent increase in the density of printed boards, insoluble substances (inorganic fillers, crystalline epoxy resins, etc.) exist as particles between fine pattern circuits, causing short circuits between circuits. In addition, in the step of laminating a dry film obtained by applying and drying the photocurable thermosetting resin composition on a carrier film on a substrate on which various circuit patterns are formed, a particle of an insoluble substance is a cause of lamination failure. In particular, it also caused a decrease in the yield of the fine pattern substrate fabrication requiring high film thickness control. Therefore, various dispersion treatments are performed during the manufacture of the solder resist or filtration is performed to remove coarse particles of insoluble components. However, most of the crystalline epoxy resins have affinity with organic solvents and other resins, and are dispersed. It is partially dissolved by the temperature change of the process and recrystallized to become coarse particles. In addition, when filtering, the temperature must be lowered, and it is difficult to obtain a high viscosity composition.

Japanese Patent Application Laid-Open No. 1-1141904 (claims)

This invention is made | formed in view of the prior art as mentioned above, and is excellent in the heat resistance of a dry coating film, electroless gold plating resistance, electrical insulation, etc., and especially prevents disconnection of the fine pitch circuit by coarse particle of an insoluble content. It is an object to provide a photocurable thermosetting resin composition for forming a cured film such as a solder resist.

Moreover, the objective of this invention is the dry film and hardened | cured material excellent in the various characteristics and smoothness mentioned above obtained by using such a photocurable thermosetting resin composition, and the hardened film, such as a soldering resist, is formed by the said dry film or hardened | cured material. It is providing the printed wiring board which becomes.

In order to achieve the above object, according to the present invention, there is provided a composition containing (A) an epoxy resin, (B) a carboxyl group-containing resin, and (C) a photopolymerization initiator, wherein the epoxy resin (A) is represented by the following formula (1): Epoxy equivalent at a softening point of 40 to 100 ° C. selected from the group consisting of a bifunctional biphenyl epoxy resin (A-1) having a bisphenol A epoxy resin, a bisphenol A novolac epoxy resin and a biphenol novolac epoxy resin It is a mixture of at least 1 sort (s) of epoxy resin (A-2) which is 180-300, and the ratio of the said epoxy resin (A-1) and (A-2) is (A-1) <(A-2) An alkali developable photocurable thermosetting resin composition is provided.

Wherein R represents H or CH ₃

In a preferred embodiment, the carboxyl group-containing resin (B) has an acid value of 40 to 120 mgKOH / g, with respect to 100 parts by mass of the mixture of (A-1) and (A-2) is 20 to 60 parts by mass, 1 The photocurable thermosetting resin composition containing the photosensitive monomer (E) which has a 2 or more ethylenically unsaturated group in a molecule | numerator can be used suitably as a soldering resist.

Moreover, according to this invention, the dry film obtained by apply | coating and drying the said photocurable thermosetting resin composition on a carrier film, the dry obtained by apply | coating and drying the said photocurable thermosetting resin composition or this photocurable thermosetting resin composition to a carrier film Cured products obtained by photocuring and / or thermosetting a film, in particular cured products obtained by photocuring on copper, and cured products obtained by photocuring in a pattern form are also provided.

According to the present invention, there is also provided a printed wiring board comprising a cured film obtained by photocuring the cured product, in particular, the photocurable thermosetting resin composition or the dry film in a pattern form, followed by thermosetting.

The photocurable thermosetting resin composition of this invention is a composition containing (A) epoxy resin, (B) carboxyl group-containing resin, and (C) photoinitiator, Comprising: The said epoxy resin (A) has a structure represented by the said General formula (1). Epoxy equivalent is 180 at the softening point of 40-100 degreeC selected from the group which consists of bifunctional biphenyl epoxy resin (A-1), bisphenol-A epoxy resin, bisphenol-A novolak-type epoxy resin, and biphenol novolak-type epoxy resin. It is a mixture of at least 1 type epoxy resin (A-2) which is -300, and the ratio of the said epoxy resin (A-1) and (A-2) is (A-1) <(A-2), It is characterized by the above-mentioned. Therefore, it is possible to form a cured film that is excellent in stability over time with respect to crystallization of the epoxy resin mixture, is excellent in solder heat resistance, electroless gold plating resistance, electrical insulation, and the like, and particularly has high insulation reliability between fine patterns. .

Therefore, the photocurable thermosetting resin composition of this invention can be advantageously applied to hardened film formation, such as a soldering resist of a printed wiring board and a flexible printed wiring board.

As mentioned above, the characteristic of the photocurable thermosetting resin composition of this invention is a composition containing (A) epoxy resin, (B) carboxyl group-containing resin, and (C) photoinitiator, The said epoxy resin (A) is a said chemical formula Softening point 40-chosen from the group which consists of bifunctional biphenyl epoxy resin (A-1) which has a structure represented by 1, a bisphenol-A epoxy resin, a bisphenol-A novolak-type epoxy resin, and a biphenol novolak-type epoxy resin It is a mixture of at least 1 type epoxy resin (A-2) whose epoxy equivalent is 180-300 at 100 degreeC, and the ratio of the said epoxy resin (A-1) and (A-2) is (A-1) <(A It is characterized by -2).

According to the researches of the present inventors, the bifunctional biphenyl epoxy resin (A-1) having the structure represented by the formula (1) among the components (A) is an epoxy resin excellent in heat resistance, electroless gold plating resistance, electrical insulation, etc. In particular, it is an important component because of excellent insulation reliability between fine patterns, while having high crystallinity in a resin component or an organic solvent, recrystallization easily occurs due to factors such as temperature change, and particles are coarsened in the mixture. This may cause a short circuit between circuits. Furthermore, the dry film obtained by apply | coating and drying the photocurable thermosetting resin composition containing a bifunctional biphenyl epoxy resin (A-1) on a carrier film is laminated on the board | substrate which formed various circuit patterns, and a printed circuit board is In the manufacturing process, the coarse particle which generate | occur | produced became a cause of lamination defect, and also the cause which the yield of the fine pattern board | substrate manufacture which especially requires high film thickness control fell.

Accordingly, the present inventors have conducted diligent research, and as a result, the bifunctional biphenyl epoxy resin (A-1), the bisphenol A type epoxy resin and the bisphenol A novolac, in which the epoxy resin (A) has the structure represented by the above formula (1) A mixture of at least one epoxy resin (A-2) having an epoxy equivalent of 180 to 300 at a softening point of 40 to 100 ° C. selected from the group consisting of a type epoxy resin and a biphenol novolak type epoxy resin, A-1) <(A-2), in the case of the mixture which micronized or melt | dissolved the particle | grains of bifunctional biphenyl epoxy resin (A-1) by methods, such as stirring, kneading, and heating, heat resistance and electroless gold Since plating resistance is excellent and generation | occurrence | production of the coarse particle resulting from a bifunctional biphenyl epoxy resin (A-1) can be prevented, the short circuit between circuits can be prevented, it has the outstanding electrical insulation, and the photocurable thermosetting resin composition Carrier fill A dry film obtained by coating and drying on the discovery that it is possible to prevent failure of the laminate when the laminate, will be reached to complete the present invention.

Hereinafter, each structural component of the photocurable thermosetting resin composition of this invention is demonstrated in detail.

First, in the epoxy resin (A) which comprises the alkali developable photocurable thermosetting resin composition of this invention, as bifunctional biphenyl epoxy resin (A-1), it is Japan's epoxy resin YL-6056, YX4000, YX4000K, Bixylenol type or biphenol type epoxy resins, such as YX4000H, YX4000HK, YL6121, YL6121H, YL6640, and YL6677 (all are brand names), or a mixture thereof can be used.

Next, a bisphenol A type epoxy resin, a bisphenol A novolak type epoxy resin, and / or a biphenol novolak type epoxy resin having an epoxy equivalent of 180 to 300 at a softening point of 40 to 100 ° C. in the epoxy resin (A). For example, JER834 manufactured by Japan Epoxy Resin Co., Ltd., Epikron 860 manufactured by Dainippon Ink & Chemicals Co., Ltd., Efotot YD-134 manufactured by Toto Kasei Co., Ltd., DER337 manufactured by Dow Chemical Co., Ltd. (all Bisphenol A epoxy resin; Bisphenol A novolac-type epoxy resins such as JER157S manufactured by Japan Epoxy Resin Co., Ltd., and Epikron N-865 (both trade names) manufactured by Dainippon Ink & Chemicals, Ltd .; Although biphenol novolak-type epoxy resins, such as NC-3000, NC-3000H, NC-3000L, and NC-3100 (brand name) by a Nippon Kayaku Co., Ltd., etc. are mentioned, It is not limited to these. These epoxy resins can be used individually or in combination of 2 or more types.

The compounding ratio of the said epoxy resin (A-1) and (A-2) is (A-1) <(A-2). When the blending ratio of (A-1) exceeds the blending ratio of (A-2), the solubility in the composition of (A-1) is lowered and the stability over time for crystallization of the mixture is lowered.

The compounding quantity of the said epoxy resin (A-1) and (A-2) is 10-100 mass parts with respect to 100 mass parts of carboxyl group-containing resin (B), for example, Preferably the range of 20-60 mass parts is suitable. . When the compounding quantity of an epoxy resin (A-1) and (A-2) is too much larger than the said range, alkali developability will fall and it will become easy to produce a defective resolution and a developing residue. On the other hand, when less than 10 mass parts, since the solder heat resistance of the obtained cured coating film is impaired, it is not preferable.

Moreover, other epoxy resin can also be used in combination with the said epoxy resin (A-1) and (A-2). As other epoxy resin, a well-known conventional epoxy resin can be used, without particular limitation. As such an epoxy resin, the compound which has at least 2 or more epoxy groups in a molecule | numerator, ie, a polyfunctional epoxy compound, is mentioned, for example.

As said polyfunctional epoxy compound, jER828, jER1001, jER1004 by Japan Epoxy Resin Co., Ltd., Epikron 840, Epikron 850, Epikron 1050, Epikron 2055, and Epto Co., Ltd. make YD-011, YD-013, YD-127, YD-128, DER317, DER331, DER661, DER664 made by Dow Chemical, Araldide 6071, Araldide 6084, Arald made by Ciba Specialty Chemicals Co., Ltd. DERID GY250, Araldide GY260, Sumitomo Chemical Co., Ltd.Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661 manufactured by Asahi Kasei Kogyo Co., Ltd. Bisphenol A epoxy resins such as (all trade names) AER664; JERYL903 made in Japan epoxy resin company, epicron 152 made in DIC company, epicron 165, dopot Kasei Co., Ltd. YPOD YDB-400, YDB-500, Dow Chemical company's DER542, Ciba specialty chemicals company Brominated epoxy resins such as Araldide 8011, Sumitomo Kagaku Kogyo Co., Ltd. Sumi-Epoxy ESB-400, ESB-700, Asahi Kasei Kogyo Co., Ltd. AER711, AER714 and the like (both trade names); JER152, jER154 manufactured by Japan epoxy resin company, DEN431, DEN438 manufactured by Dow Chemical Company, epicron N-730, epicron N-770, manufactured by DIC Corporation, epicron N-865, manufactured by Toto Kasei Co., Ltd. YDCN-701, YDCN-704, Araldide ECN1235, Araldide ECN1273, Araldide ECN1299, Araldide XPY307 manufactured by Ciba Specialty Chemicals, EPPN-201, EOCN-1025 manufactured by Nihon Kayaku Co., EOCN- Furnace of 1020, EOCN-104S, RE-306, Sumitomo Kagaku Kogyo Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo AERECN-235, ECN-299 (all brand names) Ballac type epoxy resins; Epiclon 830 manufactured by DIC Corporation, JER807 manufactured by Japan Epoxy Resin Corporation, Efotot YDF-170, YDF-175, YDF-2004 manufactured by Tohto Kasei Co., Ltd., Araldide XPY306 manufactured by Ciba Specialty Chemicals, Inc. (all brand names) Bisphenol F type epoxy resin; Hydrogenated bisphenol A epoxy resins, such as Efotot ST-2004, ST-2007, and ST-3000 (brand name) by a Toto Kasei company; JER604 made in Japan epoxy resin company, Etoport YH-434 made by Toto Kasei Co., Ltd. Araldide MY720 made by Ciba specialty chemicals company, Sumitomo Kagaku Kogyo Co., Ltd. sumi-epoxy ELM-120 (all brand names) Glycidyl amine epoxy resins; Hydantoin type epoxy resins, such as Araldide CY-350 (brand name) by the Ciba Specialty Chemicals company; Alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd., Araldide CY175 manufactured by Ciba Specialty Chemicals, and CY179 (both trade names); Trihydroxyphenylmethane type epoxy resins such as YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T.E.N., EPPN-501, EPPN-502, etc. manufactured by Dow Chemical Company; Bisphenol S type epoxy resins, such as Nippon Kayaku Co., Ltd. EBPS-200, Asahi Denka Kogyo Co., Ltd. EPX-30, and DIC Corporation EXA-1514 (brand name); Tetraphenylolethane type epoxy resins, such as jERYL-931 by the Japan epoxy resin company, Araldide 163 by Ciba Specialty Chemicals, Inc. (all are brand names); Heterocyclic epoxy resins, such as Araldide PT810 by Ciba Specialty Chemicals Co., Ltd. and TEPIC by Nissan Chemical Industries, Ltd. (all are brand names); Diglycidyl phthalate resins such as Bremmer DGT manufactured by Nippon Yushi Corporation; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; Naphthalene group-containing epoxy resins such as Shin-Netsu Chemical Co., Ltd. ESN-190, ESN-360, DIC Corporation HP-4032, EXA-4750, EXA-4700; Epoxy resins having a dicyclopentadiene skeleton, such as HP-7200 and HP-7200H manufactured by DIC Corporation; Glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Corporation; Copolymerized epoxy resins of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (e.g., YR-102, YR-450, manufactured by Toto Kasei Co., Ltd.), etc. It is not limited to these. These epoxy resins can be used individually or in combination of 2 or more types. Especially among these, a novolak-type epoxy resin, a heterocyclic epoxy resin, a bisphenol-A epoxy resin, or a mixture thereof is preferable.

It is preferable that the compounding quantity of the said other epoxy resin shall be 75 mol% or less when the usage-amount of the whole epoxy resin shall be 100 mol%. When used exceeding 75 mol%, there exists a possibility that the characteristic derived from bifunctional biphenyl epoxy resin (A-1) may not fully be obtained. The more preferable usage-amount of other epoxy resin is 50 mol% or less.

As said carboxyl group-containing resin (B), the conventionally well-known various carboxyl group-containing resin which has a carboxyl group in a molecule | numerator can be used for the purpose of providing alkali developability. In particular, carboxyl group-containing photosensitive resin (B ') which has an ethylenically unsaturated double bond in a molecule | numerator is more preferable at the point of photocurability and developability. In addition, the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or derivatives thereof. In addition, when using only the carboxyl group-containing resin which does not have an ethylenically unsaturated double bond, in order to make a composition photocurable, it is necessary to use together the photosensitive monomer (E) which has one or more ethylenically unsaturated groups in the molecule mentioned later. .

As a specific example of carboxyl group-containing resin (B), the compound (it may be any of an oligomer and a polymer) listed below is preferable.

(1) Carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated group containing compounds, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

(2) diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid; and polycarbonate-based polyols and polyethers. Carboxyl group containing by polyaddition reaction of diol compounds, such as a compound polyol, a polyester type polyol, a polyolefin type polyol, an acryl type polyol, a bisphenol A alkylene oxide adduct diol, a compound which has a phenolic hydroxyl group and an alcoholic hydroxyl group, etc. Urethane resin.

(3) difunctional isocyanates, bifunctional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins, and biphenol type epoxy resins The photosensitive carboxyl group-containing urethane resin by the polyaddition reaction of the (meth) acrylate or its partial acid anhydride modified substance, carboxyl group-containing dialcohol compound, and diol compound.

(4) In the synthesis | combination of the resin of said (2) or (3), the compound which has one hydroxyl group and one or more (meth) acryl groups in molecule | numerators, such as hydroxyalkyl (meth) acrylate, is added, and a terminal (meth ) Acrylic photosensitive carboxyl group-containing urethane resin.

(5) Compounds having one isocyanate group and one or more (meth) acryl groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate, during synthesis of the resin of the above (2) or (3) Photosensitive carboxyl group-containing urethane resin which was added and terminal (meth) acrylated.

(6) Photosensitive carboxyl group-containing resin which made (meth) acrylic acid react with the bifunctional or more than one polyfunctional (solid) epoxy resin mentioned later, and added dibasic acid anhydride to the hydroxyl group which exists in a side chain.

(7) (meth) acrylic acid is made to react with the polyfunctional epoxy resin further epoxidized by epichlorohydrin and the hydroxyl group of the bifunctional (solid) epoxy resin mentioned later, and dibasic acid anhydride is added to the produced hydroxyl group. Photosensitive carboxyl group-containing resin.

(8) The carboxyl group-containing polyester resin which made dicarboxylic acid react with the bifunctional oxetane resin as mentioned later, and added dibasic acid anhydride to the produced | generated primary hydroxyl group.

(9) Photosensitive carboxyl group-containing resin formed by adding the compound which has one epoxy group and one or more (meth) acryl groups in 1 molecule further to resin of said (1)-(8).

In addition, in this specification, (meth) acrylate is a term which generically mentions acrylate, methacrylate, and a mixture thereof, and is the same also about another similar expression.

Since carboxyl group-containing resin (B) mentioned above has many free carboxyl groups in the side chain of a frame | skeleton and a polymer, image development by a rare alkali aqueous solution is attained.

Moreover, the acid value of the said carboxyl group-containing resin (B) is the range of 40-200 mgKOH / g, More preferably, it is the range of 45-120 mgKOH / g. If the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, if it exceeds 200 mgKOH / g, dissolution of the exposed portion by the developing solution proceeds, so that the line becomes thinner than necessary or in some cases. It is not preferable because it dissolves and peels off with a developer without distinguishing between the exposed portion and the unexposed portion, and drawing of a normal resist pattern becomes difficult.

Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (B) changes with resin frame | skeleton, it is preferable to exist in the range of 2,000-150,000 normally, and also 5,000-100,000. If the weight average molecular weight is less than 2,000, the tack-free performance may decrease, the moisture resistance of the coating film after exposure deteriorates, the film decreases at the time of image development, and the resolution may fall large. On the other hand, when a weight average molecular weight exceeds 150,000, developability may deteriorate remarkably and storage stability may fall.

The compounding quantity of such carboxyl group-containing resin (B) is 20-80 mass% in the whole composition, Preferably the range of 30-60 mass% is suitable. When the compounding quantity of carboxyl group-containing resin (B) is less than the said range, since film strength falls, it is unpreferable. On the other hand, when more than the said range, since the viscosity of a composition becomes high, applicability | paintability, etc. fall, it is not preferable.

These carboxyl group-containing resins (B) can be used without being limited to what was enumerated above, and can also be used in 1 type or in mixture of 2 or more types.

Examples of the photopolymerization initiator (C) include an oxime ester photopolymerization initiator (C1) having a group represented by the following general formula (2), an α-aminoacetophenone series photopolymerization initiator (C2) having a group represented by the following general formula (3), and / or the following general formula (4) It is preferable to use at least 1 type of photoinitiator selected from the group which consists of an acylphosphine oxide type photoinitiator (C3) which has group represented by.

(Wherein R ¹ is a hydrogen atom, a phenyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, the middle of the alkyl chain) May have one or more oxygen atoms), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (which may be substituted with an alkyl or phenyl group having 1 to 6 carbon atoms),

R ² may be substituted with a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and at least one oxygen atom in the middle of the alkyl chain; May be substituted), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),

R ³ and R ⁴ each independently represent an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,

R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkylether group bonded to two,

R ⁷ and R ⁸ each independently represent a C1-C10 linear or branched alkyl group, cyclohexyl group, cyclopentyl group, aryl group, or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, provided that , One of R ⁷ and R ⁸ may represent an R′-C (═O) -group, where R ′ may represent a hydrocarbon group of 1 to 20 carbon atoms

As an oxime ester type photoinitiator which has group represented by the said Formula (2), Preferably, 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by following formula (5), the compound represented by following formula (6), and the following formula The compound represented by 7 is mentioned.

(Wherein R ⁹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, and a carbon having 2 to 12 carbon atoms). An alkoxycarbonyl group (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), or a phenoxycarbonyl group ,

R ¹⁰ and R ¹² are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups, and in the middle of the alkyl chain) May have one or more oxygen atoms), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (which may be substituted with an alkyl or phenyl group having 1 to 6 carbon atoms),

R ¹¹ is a hydrogen atom, a phenyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (may be substituted with one or more hydroxyl groups, and one in the middle of the alkyl chain) Or an oxygen atom), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group)

(In formula, R <^13> , R <^14> and R <^19> respectively independently represents a C1-C12 alkyl group,

R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

M represents O, S or NH,

m and p each independently represent an integer of 0 to 5)

Among the oxime ester photopolymerization initiators, the compounds represented by 2- (acetyloxyiminomethyl) thioxanthene-9-one represented by the formula (5) and the formula (6) are more preferable. Examples of commercially available products include CGI-325 manufactured by Ciba Specialty Chemicals, Irgacure-OXE01, Irgacure-OXE02, N-1919 manufactured by Adeca. These oxime ester photoinitiators can be used individually or in combination of 2 or more types.

Examples of the α-aminoacetophenone-based photopolymerization initiator having a group represented by the above formula (3) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) Phenyl] -1-butanone, N, N-dimethylaminoacetophenone, etc. are mentioned. Examples of commercially available products include Irgacure-907, Irgacure-369 and Irgacure-379 manufactured by Ciba Specialty Chemicals.

As an acyl phosphine oxide type photoinitiator which has group represented by the said Formula (4), 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6- trimethyl benzoyl) -phenylphosphine oxide, bis ( 2, 6- dimethoxy benzoyl) -2, 4, 4- trimethyl- pentyl phosphine oxide, etc. are mentioned. As a commercial item, Lucirin TPO by BASF Corporation, Irgacure-819 by Ciba Specialty Chemicals Corporation, etc. are mentioned.

The compounding quantity of such a photoinitiator (C) is 0.01-30 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B), Preferably the range of 0.5-15 mass parts is suitable. If the compounding quantity of a photoinitiator (C) is less than 0.01 mass part, since the photocurability on copper is inadequate, a coating film peels off or coating film properties, such as chemical resistance, fall, it is unpreferable. On the other hand, when it exceeds 30 mass parts, since the light absorption in the soldering resist coating film surface of a photoinitiator (C) becomes intense and deep-curing property tends to fall, it is unpreferable.

In addition, in the case of the oxime ester type photoinitiator which has a group represented by the said Formula (2), the compounding quantity becomes like this. Preferably it is 0.01-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B), More preferably, it is 0.01-5 mass Negative ranges are preferred.

In addition, as a photoinitiator, a photoinitiator, and a sensitizer which can be used suitably for the photocurable thermosetting resin composition of this invention, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound And xanthone compounds, tertiary amine compounds and the like.

As a specific example of a benzoin compound, it is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, for example.

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

As an example of an anthraquinone compound, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, and 1-chloro anthraquinone are mentioned, for example.

As a specific example of a thioxanthone compound, it is 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, 2, 4- diisopropyl thioxanthone, for example.

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

As a specific example of a benzophenone compound, for example, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyl diphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4-benzoyl -4'-propyldiphenylsulfide.

As a specific example of a tertiary amine compound, For example, an ethanolamine compound, the compound which has a dialkylaminobenzene structure, for example, 4,4'- dimethylamino benzophenone (Nisso Cure MABP by Nippon Soda Co., Ltd.), 4,4 ' -Dialkylaminobenzophenones such as diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (di Dialkylamino group-containing coumarin compounds such as ethylamino) -4-methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure manufactured by International Bio-Synthetics Co., Ltd.) (Quantacure) DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics Co., Ltd.), isoamylethyl ester of p-dimethylaminobenzoic acid (Kayakyuer DMBI manufactured by Nippon Kayaku Co., Ltd.) , 4-dimethylaminobenzoic acid 2-ethylhexyl (manufactured by Van Dyk) Esolol 507) and 4,4'-diethylaminobenzophenone (EAB by Hodogaya Chemical Co., Ltd.).

Among the above compounds, thioxanthone compounds and tertiary amine compounds are preferable. It is preferable that the thioxanthone compound is contained in the composition of the present invention from the viewpoint of deep hardening, and in particular, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2 Thioxanthone compounds, such as a 4-4-isoiso thioxanthone, are preferable.

As a compounding quantity of such a thioxanthone compound, Preferably it is 20 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin (B), More preferably, the ratio of 10 mass parts or less is suitable. When the compounding quantity of a thioxanthone compound is too large, since thick film sclerosis | hardenability will fall and it will lead to the cost increase of a product, it is unpreferable.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As a dialkylamino benzophenone compound, 4,4'- diethylamino benzophenone is preferable at the point of low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has little coloration because the maximum absorption wavelength is in the ultraviolet region, and reflects the color of the colored pigment itself using a color pigment as well as a colorless transparent photosensitive composition. It is possible to provide a colored solder resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

As a compounding quantity of such a tertiary amine compound, Preferably it is 0.1-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B), More preferably, it is the ratio of 0.1-10 mass parts. When the compounding quantity of a tertiary amine compound is less than 0.1 mass part, there exists a tendency for sufficient sensitization effect to not be acquired. On the other hand, when it exceeds 20 mass parts, there exists a tendency for the light absorption in the surface of the dry soldering resist coating film by a tertiary amine compound to become severe, and core part hardenability falls.

These photoinitiators, photoinitiator, and sensitizer can be used individually or as a mixture of 2 or more types.

It is preferable that the total amount of such a photoinitiator, a photoinitiation adjuvant, and a sensitizer is 35 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin (B). When it exceeds 35 mass parts, there exists a tendency for deep-part sclerosis | hardenability to fall by these light absorption.

In addition to the said epoxy resin, a thermosetting resin can be added to the photocurable thermosetting resin composition of this invention in addition to the said epoxy resin. Especially preferred are thermosetting components (D) having at least two cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in the molecule.

The thermosetting component (D) having two or more cyclic (thio) ether groups in such a molecule has two or more of any one or two of three, four or five member cyclic cyclic ether groups, or cyclic thioether groups in the molecule. A compound having at least two or more oxetanyl groups in a molecule, that is, a polyfunctional oxetane compound (D-1), a compound having two or more thioether groups in a molecule, that is, an episulfide resin (D-2), and the like. Can be mentioned.

Examples of the polyfunctional oxetane compound (D-1) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1 , 4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3- Oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl methacrylate and oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly (p-hydroxystyrene), cardo-type bisphenols, calix arenes and calyx rezos And etherified resins of resins having hydroxyl groups such as lecinarene or silsesquioxane. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As a compound (D-2) which has two or more cyclic thioether group in the said molecule | numerator, bisphenol-A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned, for example. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used using the same synthesis method.

The compounding amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents, more preferably cyclic (thio) ether groups relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (B). Preferably the range is 0.8 to 2.0 equivalents. When the compounding quantity of the thermosetting component (D) which has two or more cyclic (thio) ether group in a molecule | numerator is less than 0.6, since a carboxyl group remains in a soldering resist film and heat resistance, alkali resistance, electrical insulation, etc. fall, it is unpreferable. On the other hand, when it exceeds 2.5 equivalent, since low-molecular-weight cyclic (thio) ether group remains in a dry coating film, since the intensity | strength of a coating film, etc. fall, it is unpreferable.

It is preferable that the photocurable thermosetting resin composition of this invention contains a thermosetting catalyst. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole Imidazole derivatives such as 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, 4-methyl-N, N-dimethylbenzylamine Hydrazine compounds, such as a compound, adipic dihydrazide, and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. Moreover, as what is marketed, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole compound) by Shikoku Kasei Kogyo Co., Ltd., U-CAT (all are registered) Trademark) 3503N, U-CAT3502T (all are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all bicyclic amidine compounds and salts thereof) and the like. It does not specifically limit to these, The thermosetting catalyst of an epoxy resin or an oxetane compound, or may promote the reaction of an epoxy group and / or an oxetanyl group, and a carboxyl group, may be used individually or in mixture of 2 or more types. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid S-triazine derivatives, such as an adduct, can also be used, Preferably, the compound which functions also as these adhesive imparting agents is used together with the said thermosetting catalyst.

The compounding quantity of these thermosetting catalysts is sufficient in a normal quantitative ratio, For example, Preferably it is 100 mass parts of thermosetting components (D) which have two or more cyclic (thio) ether groups in a carboxyl group-containing resin (B) or a molecule | numerator. 0.1-20 mass parts, More preferably, it is 0.5-15.0 mass parts.

The photosensitive monomer (E) which has two or more ethylenically unsaturated groups in the molecule | numerator used for the photocurable thermosetting resin composition of this invention is photocured by active energy ray irradiation, and the said ethylenically unsaturated group containing carboxyl group-containing resin (B) Insolubilization in an aqueous alkali solution or to aid insolubilization. As such a compound, Diacrylates of glycol, such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, propylene glycol; Polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts or propylene oxide adducts thereof; Polyhydric acrylates, such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; And melamine acrylate and / or each methacrylate corresponding to the said acrylate etc. are mentioned.

Moreover, hydroxyacrylates, such as pentaerythritol triacrylate, and isophorone diisocyanate to the epoxy acrylate resin which made acrylic acid react with polyfunctional epoxy resins, such as a cresol novolak-type epoxy resin, and the hydroxyl group of this epoxy acrylate resin. Epoxy urethane acrylate compounds, etc. which reacted the half urethane compounds of diisocyanate, such as these, are mentioned. Such epoxy acrylate-based resin can improve photocurability without deteriorating the touch dryness.

The compounding quantity of the photosensitive monomer (E) which has two or more ethylenically unsaturated groups in such a molecule | numerator is 100 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin (B), More preferably, the ratio of 5-70 mass parts is suitable. . When the said compounding quantity is less than 5 mass parts, since photocurability falls and pattern formation becomes difficult by alkali development after active energy ray irradiation, it is unpreferable. On the other hand, when it exceeds 100 mass parts, since solubility to aqueous alkali solution falls and a coating film becomes weak, it is unpreferable.

The photocurable thermosetting resin composition of this invention can mix | blend a coloring agent (F). As the colorant, conventionally known colorants such as red (F-1), blue (F-2), green (F-3), and yellow (F-4) can be used, and any one of a pigment, a dye and a pigment may be used. It may be. However, it is preferable not to contain a halogen from a viewpoint of reducing environmental load and an influence on a human body.

Red Colorant (F-1):

Examples of the red colorant include monoazo, disazo, monoazolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone and quinacridone. It can be mentioned.

Monoazo series: 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 meter: Pigment Red 37, 38, 41.

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

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

Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224 .

Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensation azo system: 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 series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant (F-2):

Examples of the blue colorant include phthalocyanine-based and anthraquinone-based pigments, and pigments include compounds classified as pigments, specifically those having the following color index numbers issued by The Society of Dyers and Colourists. May be: 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.

As dye system, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 122, solvent blue 136, solvent blue 67, solvent blue 70 may be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Green Colorant (F-3):

Examples of the green colorant include phthalocyanine series, anthraquinone series, and perylene series, and specifically, pigment green 7, pigment green 36, solvent green 3, solvent green 5, solvent green 20, solvent green 28, and the like can be used. . In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Yellow Colorant (F-4):

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone and the like. 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 series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

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

Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Monoazo series: 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, coloring agents, such as purple, orange, brown, and black, can also be added for the purpose of adjusting a color tone.

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

Although the mixing | blending ratio of a coloring agent (F) as mentioned above does not have a restriction | limiting in particular, Preferably it is 0-10 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (B), Especially preferably, the ratio of 0.1-5 mass parts is sufficient. Do.

The photocurable thermosetting resin composition of this invention can mix | blend a filler as needed in order to raise the physical strength of the coating film, etc. As such a filler, well-known conventional inorganic or organic filler can be used, but especially barium sulfate, spherical silica, and talc are used preferably. In addition, metal hydroxides such as titanium oxide, metal oxides and aluminum hydroxide can also be used as extender pigment fillers in order to obtain a white appearance and flame retardancy. The compounding quantity of a filler becomes like this. Preferably it is 75 mass% or less of a composition whole quantity, More preferably, it is the ratio of 0.1-60 mass%. When the compounding quantity of a filler exceeds 75 mass% of the whole composition, since the viscosity of an insulating composition becomes high, application | coating and moldability fall, or hardened | cured material becomes weak, it is unpreferable.

Moreover, the organic solvent can be used for the photocurable thermosetting resin composition of this invention for the synthesis | combination of the said carboxyl group-containing resin (B), manufacture of a composition, or viscosity adjustment for apply | coating to a board | substrate or a carrier film.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, Ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Cellosolve, 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 Glycol ethers such as these; 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 solvents 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.

The photocurable thermosetting resin composition of the present invention may further contain, if necessary, known thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, finely divided silica, organic bentonite, Known conventional thickeners such as montmorillonite, antifoaming agents and / or leveling agents such as silicone, fluorine and polymers, silane coupling agents such as imidazoles, thiazoles and triazoles, antioxidants and rust inhibitors It can mix.

The photocurable thermosetting resin composition of this invention is adjusted to the viscosity suitable for an application | coating method with the said organic solvent, for example, and it is immersion coating method, flow coating method, roll coating method, bar coater method, screen printing method, It is apply | coated by methods, such as a curtain coating method, and a tack free coating film can be formed by volatilizing (temporarily drying) the organic solvent contained in a composition at the temperature of about 60-100 degreeC. Moreover, a resin insulating layer can be formed by apply | coating the said composition on a carrier film, drying, and bonding what wound up as a film on a base material. Thereafter, by contact type (or non-contact method), exposure is performed by an active energy ray selectively through a photomask in which a pattern is formed, or directly by a laser direct exposure machine, and the unexposed portion is diluted with an aqueous alkali solution (e.g., For example, 0.3 to 3% by weight aqueous solution of sodium carbonate) to form a resist pattern. Further, for example, by heating at a temperature of about 140 to 180 ° C. and thermosetting, two or more cyclic ether groups and / or cyclic thio in the carboxyl group of the carboxyl group-containing resin (B) and the epoxy resin (A) or the molecule. The thermosetting component (D) which has an ether group reacts, and the cured coating film excellent in various characteristics, such as heat resistance, chemical resistance, hygroscopicity, adhesiveness, and electrical characteristics, can be formed.

Examples of the substrate include paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth / nonwoven fabric-epoxy resin, glass cloth / paper-epoxy, in addition to a printed wiring board or a flexible printed wiring board formed in advance. Copper clad laminates of all grades (FR-4, etc.) using composite materials such as resins, synthetic fiber-epoxy resins, fluororesins, polyethylene, PPO and cyanate esters, polyimide films, PET films, glass substrates, ceramic substrates, wafer boards Etc. can be used.

Volatilization drying performed after apply | coating the photocurable thermosetting resin composition of this invention is a hot-air circulation type drying furnace, IR, hotplate, a convection oven, etc. (The thing equipped with the heat source of the air heating system by steam is used in the dryer. And a method of spraying hot air onto the support from a nozzle).

After apply | coating the photocurable thermosetting resin composition of this invention and making it volatilize as follows, exposure (irradiation of an active energy ray) is performed with respect to the obtained coating film. An exposed part (part irradiated with an active energy ray) hardens | cures a coating film.

As an exposure machine used for the said active energy ray irradiation, a direct drawing apparatus (for example, the laser direct imaging apparatus which draws an image with a laser directly by CAD data from a computer), the exposure machine equipped with the metal halide lamp, (super) high pressure mercury A direct drawing apparatus using ultraviolet lamps such as an exposure machine equipped with a lamp, an exposure machine equipped with a mercury short arc lamp, or a (ultra) high pressure mercury lamp can be used. As the active energy ray, any one of a gas laser and a solid laser may be used as long as the laser beam having a maximum wavelength in the range of 350 to 410 nm is used. Moreover, although the exposure amount changes with film thickness etc., it can generally be in the range of 5-200 mJ / cm <2>, Preferably it is 5-100 mJ / cm <2>, More preferably, it is 5-50 mJ / cm <2>. As the direct drawing apparatus, for example, those manufactured by Nippon Orbotech Co., Ltd. and Pantax Co., Ltd. may be used, and any apparatus may be used as long as it is an apparatus that oscillates a laser beam having a maximum wavelength of 350 to 410 nm.

As the developing method, a dipping method, a showering method, a spraying method, a brush method, or the like can be carried out. As the developing solution, aqueous alkali solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines can be used. have.

The photocurable thermosetting resin composition of this invention can be used in the form of a dry film which has a soldering resist layer formed by apply | coating and drying a soldering resist to films, such as polyethylene terephthalate, in addition to the method of apply | coating directly to a base material in liquid form. The case where the photocurable thermosetting resin composition of this invention is used as a dry film is shown below.

A dry film has a structure which the carrier film, the soldering resist layer, and the peelable cover film used as needed are laminated | stacked in this order. A soldering resist layer is a layer obtained by apply | coating and drying alkali developable photocurable thermosetting resin composition to a carrier film or a cover film. After forming a soldering resist layer in a carrier film, a cover film is laminated | stacked on it, a soldering resist layer is formed in a cover film, and this laminated body is laminated | stacked on a carrier film, and a dry film is obtained.

As a carrier film, thermoplastic films, such as a polyester film with a thickness of 2-150 micrometers, are used.

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

Although a polyethylene film, a polypropylene film, etc. can be used as a cover film, It is preferable that adhesive force with a soldering resist layer is smaller than a carrier film.

In order to produce a protective film (permanent protective film) on a printed wiring board using a dry film, a cover film is peeled off, a soldering resist layer and a circuit-formed base material are piled up and bonded using a laminator etc., and a soldering resist is formed on a circuit-formed base material. Form a layer. When it exposes, develops, and heat-cures in the same manner to the above about the formed soldering resist layer, a cured coating film can be formed. The carrier film may be peeled off at any time before or after exposure.

[Example]

Although an Example and a comparative example are shown to the following and this invention is demonstrated concretely, this invention is not limited to the following Example. In addition, below "part" and "%" are mass references | standards unless there is particular notice.

Synthesis Example 1 (Synthesis of carboxyl group-containing resin)

Cresol novolak-type epoxy resin (manufactured by Nihon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent 220) in a 2 L separate flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube. 660 g, carbitol acetate, 421.3 g, and solvent naphtha 180.6 g were introduced, and the mixture was heated and stirred at 90 ° C to dissolve it. Then, it cooled to 60 degreeC once, 216 g of acrylic acid, 4.0 g of triphenylphosphines, and 1.3 g of methylhydroquinone were added and reacted at 100 degreeC for 12 hours, and the reaction product which has an acid value of 0.2 mgKOH / g was obtained. 241.7 g of tetrahydrophthalic anhydride was added to this, and it heated at 90 degreeC and made it react for 6 hours. This obtained the solution of the photosensitive carboxyl group-containing resin of 50 mgKOH / g of acid value, 400 of double bond equivalent (g weight of resin per mol of unsaturated groups), weight average molecular weight 7,000, and solid content concentration 65%. Hereinafter, the solution of this photosensitive carboxyl group-containing resin is called B1 varnish.

Synthesis Example 2 (synthesis of carboxyl group-containing resin)

After dissolving 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide, 400 parts of bisphenol F-type solid epoxy resins of epoxy equivalent 800 and softening point of 79 degreeC were added, and 88.5 parts of 98.5% NaOH over 70 minutes were stirred at 70 degreeC under stirring over 100 minutes. After addition, the reaction was further conducted at 70 ° C. for 3 hours. Subsequently, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product containing byproduct salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and 10 parts of 30% NaOH. The mixture was further added and reacted at 70 ° C. for 1 hour. After completion of the reaction, water washing was performed twice with 200 parts of water. Methyl isobutyl ketone was distilled off from the oil layer after oil-water separation, and 370 parts of epoxy resins (A-0) of an epoxy equivalent of 290 and a softening point of 62 degreeC were obtained.

Subsequently, 2900 parts (10 equivalents) of obtained epoxy resin (A-0), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone, and 1950 parts of carbitol acetate were added, and heated and stirred to 90 ° C to dissolve the reaction mixture. . Subsequently, the reaction solution was cooled to 60 ° C, 16.7 parts of triphenylphosphine was added thereto, heated to 100 ° C, and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mgKOH / g. Then, 786 parts of succinic anhydride (7.86 mol) and 423 parts of carbitol acetate were added to this, and it heated at 95 degreeC and made it react for about 6 hours. This obtained the solution of the photosensitive carboxyl group-containing resin of 65% of solid content concentration whose acid value of solid content is 100 mgKOH / g. Hereinafter, the solution of this photosensitive carboxyl group-containing resin is called B2 varnish.

Examples 1-5 and Comparative Examples 1-3

The various components of Table 1 were mix | blended in the ratio (mass part) shown to each compounding example, and pre-mixed with the stirrer, it put into the sealed container, and heated for 60 minutes with the hot air circulation type dryer of 100 degreeC. After confirming that the obtained composition was in a completely dissolved state, the mixture was stirred with a stirrer and left at room temperature for 2 hours, and after confirming that the mixture had returned to room temperature, the mixed solution was filtered using a 5 µm filter to obtain an A liquid. When the obtained liquid A was measured for particle size using an erycksen company grinder and the dispersion degree was evaluated, it was 5 micrometers or less. After leaving this solution A for 5 hours at 5 ° C., particle size was measured using an erycksen company grinder to evaluate the degree of dispersion.

Table 2 shows the evaluation results of the degree of dispersion.

As shown in Table 2, in Examples 1 to 5 using the epoxy resins of (A-1) and (A-2) and Comparative Example 3 without using the A-1 component according to the present invention, the dispersion degree was 5 µm. Compared to the following, in the comparative examples 1 and 2 which did not use the epoxy resin of (A-1) and (A-2) by the ratio prescribed | regulated by this invention, the coarse particle which the A-1 component considers the cause generate | occur | produced. , Dispersion degree drastically decreased.

Example 6

A liquid was adjusted using 20 parts of Kayayad TMPTA (trimethylolpropanetriacrylate, manufactured by Nihon Kayaku Co., Ltd.) in place of DPHA of the compounding example 1-4, and dispersed in the same manner as in Example 4. Evaluation of the figure showed that dispersion degree was 5 micrometers or less.

Example 7

A liquid was adjusted using 20 parts of NK ester A-DCP (dimethyloltricyclodecane diacrylate, manufactured by Shin-Nakamura Chemical Industries, Ltd.) in place of the DPHA of the compounding example 1-4, and Example 4 and Similarly, the dispersion degree was evaluated and the dispersion degree was 5 micrometers or less.

Example 8

A liquid was adjusted using 20 parts of aronix M-350 (trimethylolpropane EO modified triacrylate, manufactured by Toagosei Co., Ltd.) instead of DPHA of the compounding example 1-4, and dispersed in the same manner as in Example 4. Evaluation of the figure showed that dispersion degree was 5 micrometers or less.

Example 9

A liquid was adjusted using 20 parts of TMPTMA (trimethylolpropane trimethacrylate, manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.) instead of DPHA of the compounding example 1-4, and the dispersion degree was the same as that of Example 4. As a result of evaluation, dispersion degree was 5 micrometers or less.

Example 10

A liquid was adjusted using 20 parts of NK ester BPE-500 (ethoxylated bisphenol A dimethacrylate, manufactured by Shin-Nakamura Chemical Industries, Ltd.) in place of DPHA of the compounding example 1-4, and Example 4 and Similarly, the dispersion degree was evaluated and the dispersion degree was 5 micrometers or less.

Examples 11-13 and Comparative Example 4

After using the carboxyl group-containing resin solution B1 varnish of the said synthesis example, the thing other than barium sulfate slurry among the various components shown in the compounding example 2 of Table 3 was mix | blended in the ratio (mass part) shown in Table 3, and pre-mixed with a stirrer, It knead | mixed with the triaxial roll mill. Next, the barium sulfate slurry was added to this composition in the ratio (mass part) shown in Table 3, and it stirred with the stirrer. This composition was filtered using the 5 micrometer filter and B liquid was adjusted. When the obtained liquid B was measured for particle size using an erycksen company grinder and the dispersion degree was evaluated, it was 5 micrometers or less. Subsequently, after leaving this composition at 5 degreeC for 24 hours, particle size measurement was carried out with the Grix meter manufactured by Eriksen Co., Ltd., and the dispersion degree was evaluated, and it was 5 micrometers or less.

Subsequently, the various components shown in the compounding example 3 of Table 4 were mix | blended in the ratio (mass part) shown in Table 4, and pre-mixed with the stirrer, it knead | mixed with the triaxial roll mill, and C liquid was adjusted. The obtained C liquid was measured for particle size using a Grix meter manufactured by Eriksen Co., and the dispersion degree was evaluated.

After mixing B liquid of the compounding example 2, and C liquid of the compounding example 3, respectively, it mixed by the stirrer and obtained the photocurable thermosetting resin composition. After diluting this photocurable thermosetting resin composition suitably with methyl ethyl ketone, and fully stirring with a stirrer, particle size measurement was performed with the erycksen company grinder and the dispersion degree was evaluated, The dispersion degree of C liquid is 15 micrometers or less Despite being less than 5 μm. This is considered to be because coarse particles of 5 µm or more of C liquid were dissolved when mixed with B liquid. Subsequently, after drying this liquid with an applicator, it is apply | coated to PET film (FB-50 by Toray Co., Ltd .: 16 micrometers) so that a coating film may be set to 50 micrometers, and it dries for 30 minutes in an 80 degreeC hot air circulation type drying furnace, and it is 24 at 15 degreeC. Allowed to cool for hours. This plate was observed with an optical microscope to evaluate the presence or absence of coarse crystal grains. Judgment criteria are as follows.

(Circle): No crystalline coarse particle.

(Triangle | delta): Some occurrence of crystal | crystallization is observed.

X: Many crystal coarse particles generate | occur | produce.

After buffing the patterned copper foil substrate, the dry coating film observed above was pressed using a vacuum laminator (MVLP-500, manufactured by Meisei Seisakusho Co., Ltd.). : It was heat-laminated under the condition of 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer.

This substrate was observed with an optical microscope and evaluated using the following criteria. The evaluation results are shown in Table 5.

(Circle): The surface state after lamination is smooth.

(Triangle | delta): Unevenness generate | occur | produces in part by lamination defect.

X: Unevenness | corrugation generate | occur | produces in the whole surface by lamination defect.

As shown in Table 5, in Examples 11 to 13 using the epoxy resins of (A-1) and (A-2) according to the present invention, the photocurable thermosetting resin composition obtained by mixing B liquid and C liquid was When the mixture was properly diluted with methyl ethyl ketone and sufficiently stirred with a stirrer, all of the coarse particles were dissolved, and even after 24 hours of drying, coarse particles believed to be caused by the A-1 component did not occur in the dry coating film. Moreover, smoothness was obtained even if this coating film was laminated. In contrast, in the case of Comparative Example 4, all the coarse particles were dissolved after dilution and stirring with methyl ethyl ketone, but after drying, coarse particles, which are thought to be caused by the A-1 component, were generated, resulting in a coating film on the substrate after lamination. It also became uneven.

Example 14

Instead of the B1 varnish of the compounding example 2, B liquid was adjusted using 155 parts of B2 varnishes, and the dry film was produced and surface conditions were evaluated by the method similar to Example 11. The result was the same as in Example 11.

Example 15

Liquid B was adjusted using 222 parts of cyclomer-P (ACA) Z250 (carboxyl group-containing resin, 45 mass% of solid content by Daicel Cytec Co., Ltd.) instead of B1 varnish of the compounding example 2, and a dry film was carried out by the method similar to Example 11 The fabrication and evaluation of the surface state were performed. The result was the same as in Example 11.

Examples 16-20, Comparative Examples 5-7

The various components shown in the compounding example 4 of Table 6 were mix | blended in the ratio (mass part) shown in the compounding example 4, and pre-mixed with the stirrer, it knead | mixed with the triaxial roll mill, and D liquid was adjusted. The dispersion degree of the obtained composition was 15 micrometers or less when it evaluated by the particle size measurement by the Grix meter manufactured by Eriksen.

Example 21, Comparative Example 8

The various components shown in the compounding example 5 of Table 7 were mix | blended in the ratio (mass part) shown in the compounding example 5, and pre-mixed with the stirrer, it knead | mixed with the triaxial roll mill, and E liquid was adjusted. The dispersion degree of the obtained composition was 15 micrometers or less when it evaluated by the particle size measurement by the Grix meter manufactured by Eriksen.

Subsequently, the A liquid, the E liquid, and the D liquid were mixed in the combinations shown in Table 8, followed by stirring with a stirrer to obtain a photocurable thermosetting resin composition. In addition, after liquid, A liquid and E liquid were left to stand at 15 degreeC for 7 days, and the liquid was used.

Performance rating:

The photocurable thermosetting resin compositions of Examples 16 to 21 and Comparative Examples 5 to 8 were applied to a glass plate so that the coating film was 50 μm after drying with an applicator, and dried for 30 minutes in a hot air circulation drying furnace at 80 ° C. for 24 hours at room temperature. Allowed to cool. This plate was observed with an optical microscope to evaluate the presence or absence of coarse crystal grains. Judgment criteria are as follows.

(Circle): No crystalline coarse particle.

(Triangle | delta): Some occurrence of crystal | crystallization is observed.

X: large number of crystal grain coarse particles

The photocurable thermosetting resin compositions of Examples 16 to 21 and Comparative Examples 5 to 8 were subjected to buff roll polishing of a circuit pattern substrate having a copper thickness of 35 μm, washed with water, dried, and then applied to the entire surface by screen printing. It dried for 60 minutes in the hot air circulation drying furnace of 80 degreeC. After drying, an exposure apparatus equipped with a high pressure mercury lamp (short arc lamp) was used to expose through a step tablet (Kodak No. 2), and development (30 ° C., 0.2 MPa, 1 wt.% Na ₂ CO ₃ aqueous solution) was carried out. The optimum exposure amount was set when the pattern of the step tablet which remains when it performed for the second time is seven steps.

Characteristic test:

The compositions of each of Examples 16 to 21 and Comparative Examples 5 to 8 were coated on the entire surface of the film-formed copper foil substrate so that the film thickness after drying was 20 µm, dried at 80 ° C for 30 minutes, and allowed to cool to room temperature. The substrate is exposed to a solder resist pattern at an optimum exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and developed for 30 seconds under a spray pressure of 0.2 MPa using a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. Was carried out to obtain a resist pattern. This board | substrate was irradiated with ultraviolet-ray on the conditions of the integrated exposure amount of 1000 mJ / cm <2> in a UV conveyor, and it heated and hardened | cured at 150 degreeC for 60 minutes. The characteristic was evaluated as follows about the obtained printed circuit board (evaluation board | substrate).

Solder Heat Resistance

The evaluation board | substrate with which the rosin type flux was apply | coated was immersed in the solder tank previously set to 260 degreeC, and the flux was wash | cleaned with denatured alcohol, and the expansion and peeling of the resist layer by visual observation were evaluated. Judgment criteria are as follows.

(Double-circle): Peeling is not observed even if it immerses 6 times or more for 10 second.

(Circle): Peeling is not observed even if immersion is repeated 3 times or more for 10 second.

(Triangle | delta): When it immerses 3 times or more for 10 second, it peels a little.

X: There exist expansion and peeling in a resist layer within 3 times of immersion for 10 second.

Electroless Gold Plating Resistance

Plating was carried out using commercially available electroless nickel plating baths and electroless gold plating baths under conditions of 0.5 µm of nickel and 0.03 µm of gold. Judgment criteria are as follows.

(Double-circle): Penetration and peeling are not observed.

(Circle): Penetration is confirmed a little after plating, but it does not peel after tape peeling.

(Triangle | delta): Penetration is observed very little after plating, and peeling is also observed after tape peeling.

X: There exists peeling after plating.

An evaluation substrate was produced under the above conditions using a comb electrode pattern of line / space = 20/20 μm instead of the copper foil substrate, and a bias voltage of DC 10 V was applied to 10 pieces of the comb electrode, and 130 ° C. and 85% The insulation resistance value was measured in tank by RH. During the measurement, the comb-shaped electrode whose resistance value became 10 ⁴ Ω or less was determined as a short, and the number of comb-shaped electrodes not shorted after 100 hours was calculated.

Example 22

Each of the photocurable thermosetting compositions of Example 16 was appropriately diluted with methyl ethyl ketone, and then applied to a PET film (FB-50 manufactured by Toray Co., Ltd .: 16 μm) so that the film thickness after drying was 20 μm using an applicator. And dried at 80 degreeC for 30 minutes, and obtained the dry film.

Board production

After buffing the patterned copper foil substrate, the dry film produced by the above method was subjected to a vacuum laminator (MVLP-500, manufactured by Meisei Seisakusho Co., Ltd.) at a pressure of 0.8 MPa, 70 ° C., 1 minute, and vacuum degree. : It was heat-laminated under the condition of 133.3 Pa to obtain a substrate (unexposed substrate) having an unexposed solder resist layer.

About the test board | substrate which has the obtained hardened film, each evaluation test was done by the said test method and an evaluation method.

Table 9 shows the results of the above evaluation tests.

As shown in Table 9, in Examples 16 to 22 of the present invention, compared to Comparative Examples 5 to 8, without the coarse particles on the dry coating film, it is excellent in solder heat resistance, electroless gold plating resistance, electrical properties It was.

On the other hand, in the case of the comparative example 5 which does not contain A-2 component sufficiently, although the decrease of the coarse particle of a crystalline phase was observed, it was not able to prevent occurrence of recrystallization completely. Moreover, in the comparative examples 6 and 8, the fall of the electrical characteristic considered to be caused by the generation | occurrence | production of many coarse particles was observed. In Comparative Example 7, coarse particles did not occur, but deterioration of solder heat resistance and electrical properties was observed.

Claims

Bifunctional biphenyl epoxy resin (A-1) which is a composition containing (A) epoxy resin, (B) carboxyl group-containing resin, and (C) photoinitiator, and the said epoxy resin (A) has a structure represented by following General formula (1) And at least one epoxy resin having an epoxy equivalent of 180 to 300 at a softening point of 40 to 100 ° C. selected from the group consisting of a bisphenol A epoxy resin, a bisphenol A novolak epoxy resin and a biphenol novolak epoxy resin. It is a mixture of A-2), The ratio of the said epoxy resin (A-1) and (A-2) is (A-1) <(A-2), The alkali developable photocurable thermosetting resin composition characterized by the above-mentioned.
<Formula 1>

Wherein R represents H or CH ₃

The photocurable thermosetting resin composition according to claim 1, wherein the epoxy resin (A) is mixed in a dissolved state.

The said carboxyl group-containing resin (B) has an acid value of 40-120 mgKOH / g, The mixture of the said epoxy resin (A-1) and (A-2) is 20-60 with respect to 100 mass parts thereof. It is a mass part, The photocurable thermosetting resin composition.

The photocurable thermosetting resin composition according to claim 1, further comprising (E) a liquid photosensitive monomer having two or more ethylenically unsaturated groups in one molecule.

The photocurable thermosetting resin composition according to any one of claims 1 to 4, which is for forming a solder resist.

The dry film obtained by apply | coating and drying the photocurable thermosetting resin composition of any one of Claims 1-4 to a film.

Laminating on the base material the dry coating film obtained by apply | coating and drying the photocurable thermosetting resin composition of any one of Claims 1-4 on a base material, or the dry film obtained by apply | coating and drying the said photocurable thermosetting resin composition to a film on a base material. Hardened | cured material obtained by photocuring and / or thermosetting the dry coating film obtained by making.

The printed wiring board which has the hardened | cured material of Claim 7.