TW201621461A - Photocuring and thermosetting resin composition, dry film, cured product and printed circuit board - Google Patents

Abstract

Disclosed are a photocuring and thermosetting resin composition containing (A) carboxylic resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, (D) a thermosetting component and (E) a thermal base-generating agent, a dry film, a cured product, and a printed circuit board.

Description

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

The present invention relates to a photocurable thermosetting resin composition which is soluble in a dilute aqueous alkali solution, a dry film and a cured product thereof, and a printed circuit board having a cured product formed using the same.

At present, a photocurable thermosetting resin composition for a solder resist for a part of a consumer printed circuit board and most industrial printed circuit boards is formed by development using ultraviolet rays from the viewpoint of high precision and high density. A photocurable thermosetting resin composition for a liquid development type solder resist which is finally cured (completely cured) by heat and/or light irradiation. Among them, a photocurable thermosetting resin composition for an alkali-developing type solder resist using a dilute aqueous solution as a developing solution has become a mainstream, and has been widely used in the manufacture of an actual printed circuit board. See Japan Special Open 2013-539072).

Usually, the photocurable thermosetting resin composition for a solder resist contains a thermosetting catalyst. Thereby, the thermosetting reaction of the carboxyl group-containing resin and the thermosetting component is promoted, and various characteristics are exhibited.

However, when a thermosetting catalyst having high activity is used, there is a problem that the curing reaction proceeds at normal temperature and the storage stability is lowered. On the other hand, when a thermosetting catalyst having low activity is used, although the storage stability is good, it is difficult to exhibit various properties such as solder heat resistance. In particular, in recent years, lead-free solder or the like has been used in connection with environmental concerns. Therefore, the temperature applied to the solder resist tends to be extremely high, and therefore high solder heat resistance is required.

Therefore, an object of the present invention is to obtain a cured product excellent in various properties such as good storage stability and solder heat resistance.

The inventors of the present invention have conducted intensive studies and succeeded in obtaining a cured product excellent in storage stability and resistance to soldering heat resistance by using a compound which generates a base by heating as a thermosetting catalyst, and completed the present invention.

That is, according to the present invention, there is provided a photocurable thermosetting resin composition comprising: (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, and (D) thermosetting property. Ingredients, and (E) thermal base generator.

Here, the alkali-based starting temperature of the above (E) thermal base generator is preferably 40 ° C or higher, and more preferably 90 ° C or higher. In the case of 40 ° C or more, the storage stability is further improved. In addition, in the case of 90° C. or higher, the drying temperature of the photocurable thermosetting resin composition is higher than that of the conventional photocurable thermosetting resin composition. Therefore, it is possible to suppress the shortening of the drying management range.

On the other hand, the alkali-starting temperature of the above (E) thermal base generator is preferably 150 ° C or lower, more preferably 140 ° C or lower. In the case of 150 ° C or less, even when the heating temperature at the time of heat curing is low, an alkali can be generated, and a cured product excellent in solder heat resistance or the like can be obtained. Further, in the case of 150 ° C or lower, the heating temperature at the time of thermal curing can be lowered, so that energy saving and manufacturing cost of the printed circuit board can be reduced.

Further, the photocurable thermosetting resin composition of the present invention is preferably used for forming a cured film of a printed circuit board, more preferably for forming a permanent film, and particularly preferably for forming a solder resist film.

Moreover, according to the present invention, a photocurable thermosetting dry film obtained by applying the photocurable thermosetting resin composition onto a carrier film and drying it is provided.

Further, according to the present invention, there is provided a cured product obtained by photocuring the above-mentioned photocurable thermosetting resin composition or the above dry film and thermally curing the film.

Further, according to the present invention, there is provided a printed circuit board having the aforementioned cured product.

According to the present invention, it is possible to obtain a cured product having excellent storage stability and excellent properties such as solder heat resistance.

The present invention is a photocurable thermosetting resin composition containing There are: (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, (D) a thermosetting component, and (E) a thermal base generator.

In the (A) carboxyl group-containing resin in the photocurable thermosetting resin composition of the present embodiment, a known resin containing a carboxyl group in the molecule for imparting alkali developability can be used. From the viewpoint of photocurability and development resistance, a carboxyl group-containing resin having an ethylenically unsaturated double bond in a molecule is particularly preferable. Further, the unsaturated double bond is more preferably derived from acrylic acid or methacrylic acid or a derivative thereof. As the (A) carboxyl group-containing resin, a carboxyl group-containing resin having an epoxy resin as a starting material, a carboxyl group-containing polyurethane resin having a urethane skeleton, a carboxyl group-containing copolymer resin having a copolymerization structure, and a phenol compound as a starting point are preferable. a carboxyl group-containing resin of the raw material.

Specific examples of the carboxyl group-containing resin are shown below.

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

(2) A diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, or a carboxyl group-containing diol such as dimethylolpropionic acid or dimethylolbutanoic acid. a compound and a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, and a phenolic hydroxyl group; A carboxyl group-containing polyurethane resin obtained by addition polymerization of a diol compound such as an alcoholic hydroxyl group compound.

(3) Passing a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate a compound, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, and a phenolic hydroxyl group A polycondensation reaction of a diol compound such as a compound having an alcoholic hydroxyl group to obtain a polyurethane resin, and a terminal carboxyl group-containing polyurethane resin obtained by reacting a terminal of the polyurethane resin with an acid anhydride.

(4) Passing diisocyanate, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol phenol epoxy resin, A carboxyl group-containing photosensitive polyurethane resin obtained by addition polymerization of a (meth) acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing diol compound, and a diol compound of a bifunctional epoxy resin such as a biphenol-type epoxy resin .

(5) A compound having one hydroxyl group and one or more (meth)acrylonyl groups in a molecule such as a hydroxyalkyl (meth)acrylate is added to the synthesis of the resin of the above (2) or (4). A terminal (meth)acrylonitrile-containing carboxyl group-containing polyurethane resin.

(6) In the synthesis of the resin of the above (2) or (4), an isocyanate group and one or more (methyl) are added to the molecule such as isophorone diisocyanate and pentaerythritol triacrylate. A carboxy-containing polyurethane resin having a terminal (meth) propylene oxime formed by a compound of an acrylonitrile group.

(7) reacting a bifunctional or bifunctional or higher polyfunctional epoxy resin as described later with (meth)acrylic acid to form a hydroxy group present in the side chain, phthalic anhydride, tetrahydroortylene A carboxyl group-containing photosensitive resin obtained by using a dibasic acid anhydride such as formic anhydride or hexahydrophthalic anhydride. Here, the polyfunctional epoxy resin is preferably a solid.

(8) The hydroxyl group of the bifunctional epoxy resin as described later is further epoxidized with epichlorohydrin to obtain a polyfunctional epoxy resin, and the polyfunctional epoxy resin is reacted with (meth)acrylic acid to form a hydroxyl group. A carboxyl group-containing photosensitive resin obtained by adding a dibasic acid anhydride. Here, the bifunctional epoxy resin is preferably a solid.

(9) A cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate is added to a polyfunctional phenol compound such as a novolac, and the obtained hydroxyl group is partially esterified with (meth)acrylic acid to make the remaining A carboxyl group-containing photosensitive resin obtained by reacting a hydroxyl group with a polybasic acid anhydride.

(10) Further adding to the (1) to (9) resins, a molecule such as glycidyl (meth)acrylate or α-methylglycidyl (meth)acrylate has one epoxy group and one or more molecules. A carboxyl group-containing photosensitive resin comprising a (meth)acryloyl group-containing compound.

(A) The carboxyl group-containing resin may be used without being limited to these, and may be used singly or in combination of two or more.

It should be noted that (meth) acrylate herein refers to the terms collectively referred to as acrylate, methacrylate, and a mixture thereof, and the following other similar expressions are also the same.

(A) The carboxyl group-containing resin has a large amount of free carboxyl groups in the side chain of the main chain polymer, so development by a dilute aqueous alkali solution is possible.

Further, the acid value of the carboxyl group-containing resin is preferably 40 to 200 mgKOH/g. (A) When the acid value of the carboxyl group-containing resin is from 40 mgKOH/g to 200 mgKOH/g or less, the adhesion of the cured film can be obtained, the alkali development becomes easy, and the dissolution of the exposed portion by the developer is suppressed, and the line is not Will be as detailed as necessary On the top, the drawing of the normal resist pattern becomes easy. More preferably, it is 45-120 mgKOH/g.

Further, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, and is usually preferably from 2,000 to 150,000. When it is in the range of 2,000 to 150,000, the non-stick property is good, and the cured film after exposure is excellent in moisture resistance, and film formation is less likely to occur during development. Moreover, in the range of the above-mentioned weight average molecular weight, the resolution is improved, the developability is good, and the storage stability is good. More preferably, it is 5,000 to 100,000.

The compounding amount of the (A) carboxyl group-containing resin is suitably 20 to 80% by mass in the photocurable thermosetting resin composition. When it is 20% by mass or more and 80% by mass or less, the film strength is good, and the viscosity of the composition can be lowered, and the coating property and the like are excellent. More preferably, it is 30-60 mass %.

The (B) photopolymerization initiator which can be suitably used in the photocurable thermosetting resin composition of the present invention can be suitably selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, and an alkylbenzene. One or more of the group consisting of a photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, a fluorenylphosphine oxide photopolymerization initiator, and a titanocene photopolymerization initiator Photopolymerization initiator.

For the oxime ester-based photopolymerization initiator, CGI-325, IRGACURE OXE01, IRGACURE OXE02 manufactured by BASF Japan Ltd., N-1919 manufactured by ADEKA Co., Ltd., NCI-831, and the like are exemplified. In addition, a photopolymerization initiator having two oxime ester groups in the molecule may be suitably used, and specifically, an oxime ester compound having a carbazole structure may be mentioned.

The commercially available product of the alkyl phenyl ketone photopolymerization initiator may, for example, be an α-hydroxyalkyl phenyl ketone type such as IRGACURE 184, Dalocure 1173, IRGACURE 2959 or IRGACURE 127 manufactured by BASF Japan Ltd.

Specific examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1, 2 -benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylbenzene) Methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone and the like. As a commercial item, IRGACURE907, IRGACURE369, IRGACURE379, etc. by BASF Japan Ltd. are mentioned.

Specific examples of the fluorenylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzimidium diphenylphosphine oxide and bis(2,4,6-trimethylbenzhydrazide). ——Phenylphosphine oxide, bis(2,6-dimethoxybenzhydrazide)-2,4,4-trimethyl-pentylphosphine oxide, and the like. As a commercial item, LUCIRIN TPO by BASF Corporation, IRGACURE 819 by BASF Japan Ltd., etc. are mentioned.

In addition, as the photopolymerization initiator, a titanocene-based photopolymerization initiator such as IRGACURE 389 or IRGACURE 784 manufactured by BASF Japan Ltd. can be suitably used.

The compounding amount of the photopolymerization initiator is preferably 0.1 to 25 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the compounding amount is 0.1 to 25 parts by mass, it is excellent in photocurability and resolution, and the adhesion and PCT resistance are also improved, and the electroless gold plating resistance is further improved. A cured film excellent in chemical resistance. In particular, when the compounding amount is 25 parts by mass or less, the effect of reducing the exhaust gas can be obtained, and further, the light absorption on the surface of the coating film can be suppressed to be severe, and the deep curability can be lowered.

As the photocurable thermosetting resin composition, a photoinitiator or a sensitizer can be used in addition to the photopolymerization initiator. Examples of the photopolymerization initiator, photoinitiation aid, and sensitizer which can be suitably used in the photocurable thermosetting resin composition include a benzoin compound, an acetophenone compound, an anthraquinone compound, and a thioxantate. A ketone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, and a xanthone compound.

These photopolymerization initiators, photoinitiation aids, and sensitizers can be used singly or in the form of a mixture of two or more. The total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When it is 35 parts by mass or less, it is possible to suppress a decrease in deep curability due to light absorption thereof.

As the (C) photosensitive monomer, a compound having two or more ethylenically unsaturated groups in a molecule, a compound obtained by adding an α,β-unsaturated carboxylic acid to a polyhydric alcohol, and a glycidyl group-containing compound are used. A compound obtained by forming an α,β-unsaturated carboxylic acid or the like.

Examples of the compound having two or more ethylenically unsaturated groups in the molecule include diacrylates of diols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; and hexanediol. Polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, trishydroxyethyl isocyanurate or their ethylene oxide adducts or propylene oxide adducts; phenoxy Acrylate, bisphenol A diacrylate, and these phenols a polybasic acrylate such as an ethylene oxide adduct or a propylene oxide adduct; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate a polyacrylate of a glycidyl ether such as an acid ester; and a melamine acrylate, and/or each methacrylate corresponding to the above acrylate.

Examples of the compound obtained by adding an α,β-unsaturated carboxylic acid to a polyhydric alcohol include ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene glycol. Diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, butanediol diacrylate, pentanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane diacrylate, three Hydroxymethylpropane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, glycerin diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol An acrylate or the like and/or each methacrylate corresponding to the above acrylate. Further, examples of the compound obtained by adding an α,β-unsaturated carboxylic acid to a glycidyl group-containing compound include ethylene glycol diglycidyl ether diacrylate and diethylene glycol diglycidyl ether diacrylate. , trimethylolpropane triglycidyl ether triacrylate, bisphenol A glycidyl ether diacrylate, diglycidyl diglycidyl diacrylate, glycerol polyglycidyl ether polyacrylate, and the like; 2-bis(4-propenyloxydiethoxyphenyl)propane, 2,2-bis-(4-propenyloxypolyethoxyphenyl)propane, 2-hydroxy-3-propene oxime A propyl acrylate, and/or each methacrylate corresponding to the above acrylate. These photosensitive monomers can be used singly or in combination of two or more. use.

The amount of the photosensitive monomer to be added is preferably 5 to 100 parts by mass, more preferably 10 to 90 parts by mass, even more preferably 15 parts by mass to 85 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. By setting it as the range of the compounding amount mentioned above, photocurability improves, pattern formation becomes easy, and the intensity|strength of a cured film can also be improved.

As the (D) thermosetting component, a blocked isocyanate compound, an amine resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, a polyfunctional epoxy compound, or the like can be used. A known thermosetting resin such as a polyfunctional oxetane compound, an episulfide resin, or a melamine derivative. A particularly preferable thermosetting component is a thermosetting component having two or more cyclic ether groups and/or a cyclic thioether group (hereinafter simply referred to as a cyclic (thio)ether group) in one molecule. These thermosetting components having a cyclic (thio)ether group are commercially available in a wide variety of types, and various properties can be imparted depending on the structure.

The thermosetting component having two or more cyclic (thio)ether groups in the molecule is any one of a cyclic ether group or a cyclic thioether group having two or more three, four or five-membered rings in the molecule. The compound of the two groups may, for example, be a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1); and having at least two or more oxetanyl groups in the molecule. The compound, that is, the polyfunctional oxetane compound (D-2); a compound having two or more thioether groups in the molecule, that is, an episulfide resin (D-3) or the like.

Examples of the polyfunctional epoxy compound (D-1) include jER828, jER834, and jER1001 manufactured by Nippon Epoxy Resin Co., Ltd. JER1004, EPICLON840, EPICLON850, EPICLON1050, EPICLON2055 manufactured by Dainippon Ink and Chemicals Co., Ltd., EPOTOHTO YD-011, YD-013, YD-127, YD-128 manufactured by Tosho Kasei Co., Ltd., DER317 manufactured by Dow Chemical Co., Ltd. DER331, DER661, DER664, Araldite 6071, Araldite6084, Araldite DY250, Araldite DY260 from Ciba Specialty Chemicals Inc., Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA- manufactured by Sumitomo Chemical Industries, Ltd. 128. AER330, AER331, AER661, AER664, etc. (all are trade names) bisphenol A type epoxy resin manufactured by Asahi Kasei Kogyo Co., Ltd.; jERYL903 manufactured by Nippon Epoxy Co., Ltd., Dainippon Ink Chemical Industry Co., Ltd. EPICLON 152, EPICLON 165, manufactured by Tosoh Chemical Co., Ltd., EPOTOHTO YDB-400 manufactured by Toshiro Kasei Co., Ltd., YDB-500, DER542 manufactured by Dow Chemical Co., Ltd., Araldite 8011 manufactured by Ciba Specialty Chemicals Inc., and Sumi-epoxy manufactured by Sumitomo Chemical Industries, Ltd. ESB-400, ESB-700, AER711, AER714, etc. manufactured by Asahi Kasei Kogyo Co., Ltd. Brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin Co., Ltd., DEN431, DEN438 manufactured by The Dow Chemical Co., Ltd., EPICLONN-730, EPICLONN-770, EPICLONN manufactured by Dainippon Ink Chemical Industry Co., Ltd. 865, EPOTOHTO YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., Araldite ECN1235 manufactured by Ciba Specialty Chemicals Inc., Araldite ECN1273, Araldite ECN1299, Araldite XPY307, EPPN-201, EOCN-1025 manufactured by Nippon Kayaku Co., Ltd. , EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemicals Sumi-epoxy ESCN-195X, ESCN-220, manufactured by Asahi Kasei Kogyo Co., Ltd., AERECN-235, ECN-299, etc. (all are trade names), novolak-type epoxy resin; Dainippon Ink Chemical Industry Co., Ltd. EPICLON 830 manufactured by the company, jER807 manufactured by Nippon Epoxy Co., Ltd., EPOTOHTO YDF-170, YDF-175, YDF-2004 manufactured by Tohto Kasei Co., Ltd., Araldite XPY306 manufactured by Ciba Specialty Chemicals Inc., etc. (all are trade names) Bisphenol F-type epoxy resin; hydrogenated bisphenol A type epoxy resin such as EPOTOHTO ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toshiro Kasei Co., Ltd.; jER604 manufactured by Japan Epoxy Resin Co., Ltd. EPOTOHTO YH-434 manufactured by Tohto Kasei Co., Ltd., Araldite MY720 manufactured by Ciba Specialty Chemicals Inc., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Industries, Ltd. (all are trade names) glycidylamine type epoxy resin; Ciba Ethene-urea type epoxy resin such as Araldite CY-350 (trade name) manufactured by Specialty Chemicals Inc.; CELLOXIDE 2021 and Ciba Specialty Chemi manufactured by Daicel Chemical Industry Co., Ltd. Araldite CY175, CY179, etc. (all trade name) alicyclic epoxy resin manufactured by cals Inc.; YL-933 manufactured by Japan Epoxy Resin Co., Ltd., TEN manufactured by Dow Chemical Co., Ltd., EPPN-501, EPPN-502 (all are trade names) trishydroxyphenylmethane type epoxy resin; yoke phenol type or joint such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Nippon Epoxy Resin Co., Ltd. Phenol-based epoxy resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., and EXA-1514 manufactured by Dainippon Ink and Chemicals Co., Ltd. Bisphenol S-type epoxy resin such as bisphenol-based epoxy resin; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Nippon Epoxy Resin Co., Ltd.; jERYL-931, Ciba Specialty Chemicals, manufactured by Nippon Epoxy Resin Co., Ltd. Araldite 163 (all are trade names) manufactured by Inc., tetrahydroxyphenylethane type epoxy resin; Araldite PT810 manufactured by Ciba Specialty Chemicals Inc., TEPIC manufactured by Nissan Chemical Industries, Ltd. (all are trade names), heterocyclic ring Epoxy resin; diglycidyl phthalate resin such as BLEMMER DDT manufactured by Nippon Oil & Fats Co., Ltd.; tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Toshiro Kasei Co., Ltd. ) Enagen-based epoxy resin such as ESN-190, ESN-360, manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink Chemical Industry Co., Ltd.; Epoxy resin having a dicyclopentadiene skeleton such as HP-7200 or HP-7200H manufactured by Industrial Co., Ltd.; glycidyl methacrylate such as CP-50S or CP-50M manufactured by Nippon Oil & Fats Co., Ltd. Copolymer epoxy resin; further copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivative (for example, PB manufactured by Daicel Chemical Industry Co., Ltd.) -3600 or the like), CTBN-modified epoxy resin (for example, YR-102, YR-450, manufactured by Tohto Kasei Co., Ltd.), etc., but is not limited thereto. These epoxy resins may be used singly or in combination of two or more. Among them, a novolac type epoxy resin, a modified novolak type epoxy resin, a heterocyclic epoxy resin, a bisphenol type epoxy resin, or a mixture thereof is particularly preferable.

The polyfunctional oxetane compound (D-2) can be exemplified Bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-double [ (3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, acrylic acid (3- Methyl-3-oxetanyl)methyl ester, (3-ethyl-3-oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methacrylate Polyfunctional oxetanes such as esters, (3-ethyl-3-oxetanyl)methyl methacrylate, oligomers or copolymers thereof, and oxetane and novolac An etherified product of a resin having a hydroxyl group such as a resin, a poly(p-hydroxystyrene), a Cardo type bisphenol, a calixarene, a resorcinol calixarene or a sesquioxane. Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate may, for example, be mentioned.

For example, YL7000 (bisphenol A type episulfide resin) manufactured by Nippon Epoxy Resin Co., Ltd., and Toyo Kasei Co., Ltd., may be used as the episulfide resin (D-3) having two or more cyclic thioether groups in the above-mentioned molecule. Manufactured YSLV-120TE and the like. Further, an episulfide resin obtained by replacing the oxygen atom of the epoxy group of the novolac type epoxy resin with a sulfur atom by the same synthesis method may be used.

(D) The compounding amount of the thermosetting component is preferably 10 to 100 parts by mass based on 100 parts by mass of the (A) carboxyl group-containing resin. In particular, the amount of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is such that the cyclic (thio)ether group is preferably 0.6 equivalent to 1 part by weight of the carboxyl group of the (A) carboxyl group-containing resin. It is a range of ~2.5 equivalents, more preferably 0.8 to 2.0 equivalents. When the compounding amount of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is in the above range, heat resistance, alkali resistance, electrical insulating properties, and the like are good.

The (E) thermal base generator may be any one or more of the following compounds of the formula (1), the formula (2), the formula (3), the formula (3-1), and the formula (3-2).

(In the formula (1), R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group or an aryl group, and Z is a Hammett. The equation specifies a substituent having a σ value of 0 or more, i+j=3 and i represents 1 or 2).

(In the formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group or an aryl group, Z is a substituent having a σ value of 0 or more as defined by the Hammett equation, i+j=3 and i represents 1 or 2).

In the compound represented by the formula (1) or (2), Z is a substituent having a σ value of 0 or more when specified by the Hammett equation. As a preferred substituent, an example Examples thereof include a group having an aromatic ring, an alkenylcarbonyl group, an aralkylcarbonyl group, an arylcarbonyl group, an alkyloxycarbonyl group, an alkenyloxycarbonyl group, an aryloxycarbonyl group, and an aralkyloxycarbonyl group. , alkyl sulfonyl, alkenyl sulfonyl, aralkyl sulfonyl, aryl sulfonyl, alkyl fluorenylene, alkenylene fluorenyl, aralkyl fluorenylene, aryl Sulfhydryl, halogen, nitro, or cyano.

More preferably, a group having an aromatic ring, an alkylcarbonyl group, an alkenylcarbonyl group, an aralkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, an alkenylsulfonyl group, an aralkylsulfonyl group, an aromatic group Substituents such as a sulfonyl group, an alkyl sulfinyl group, an alkenyl fluorenylene group, an aralkyl fluorenylene group, an aryl fluorenylene group, a halogen, a nitro group, or a cyano group. Further, in the formula (1), Z is preferably bonded to R ¹ or R ² to form a cyclic structure containing an aromatic ring, and in the formula (2), Z is preferably bonded to R ⁹ or R ¹⁰ to form an inclusion. The ring structure of the aromatic ring.

The aromatic ring is preferably a benzene ring, a naphthalene ring or an anthracene ring.

In the compound represented by the formula (1) or (2), R ¹ to R ^{10 are} preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 14 carbon atoms, or a carbon number of 1 to 20 carbon atoms. An alkenyl group, an aralkyl group having 7 to 20 carbon atoms, or a phenyl group, a naphthyl group or an aromatic heterocyclic ring.

The alkyl group, the alkenyl group, the aralkyl group and the aryl group represented by R ¹ to R ¹⁰ may have a substituent, and for example, an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an alkoxyalkyloxy group may be used. , alkenyloxy, aralkyloxy, aralkyloxyalkoxy, aryloxy, aryloxyalkoxy, alkylcarbonyl, alkenylcarbonyl, aralkylcarbonyl, aromatic Carbocarbonyl, alkyloxycarbonyl, alkenyloxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, aralkylcarbonyloxy, aromatic Alkylcarbonyloxy, alkylsulfonyl, alkenylsulfonyl, aralkylsulfonyl, arylsulfonyl, alkyl fluorenylene, alkenyl fluorenylene, aralkyl fluorenylene The substituent such as an arylsulfinyl group, a hydroxyl group, a halogen, a nitro group, or a cyano group is mono- or polysubstituted.

(In the formula (3), R ¹¹ and R ¹² are each independently hydrogen or an organic group, and may be the same or different. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure, or may contain a bond of a hetero atom. Wherein at least one of R ¹¹ and R ¹² is an organic group. Here, the organic group means a hydrocarbon group. R ¹³ is hydrogen, halogen, hydroxy, thiol, thioether, decyl, stanol, Nitro, nitroso, sulfinyl, sulfo, sulfonate, phosphino, phosphinyl, phosphono group, phosphonato group, or organic group. R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are hydrogen, halogen, hydroxy, decyl, thioether, methoxyalkyl, stanol, nitro, nitroso, sulfinyl, sulfo, sulfonate, phosphino, oxygen A phosphino group, a phosphono group, a phosphonato group, an amine group, an ammonium group or an organic group may be the same or different. R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may be among them. when two or more bonded to form a cyclic structure, the cyclic structure may contain a hetero atom bond. wherein, R ¹³ is ^{hydrogen, R 14, R 15, R} 16 and R ¹⁷² among Above bonded to form a cyclic structure, the cyclic structure may contain a hetero atom bond other than an oxygen atom).

n in the formula (3-1) is 1 or 2. R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ^{26 in the} formula (3-1) and the formula (3-2) are each selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a monovalent group in the group consisting of a cycloalkyl group, an aralkyl group, an aryl group, and a heterocyclic residue (each group may have one or more substituents), R ²¹ and R ²² , and R ²³ and R ²⁴ A nitrogen-containing heterocyclic ring which may be bonded to each other to form a five-membered or six-membered ring. Further, R ²⁵ and R ^{26 are} preferably a hydrogen atom, an alkyl group and an aryl group, and particularly preferably a hydrogen atom. Further, each group may have one or more substituents. The number of carbon atoms of the alkyl group, the alkenyl group and the alkynyl group is preferably any one of from 1 to 8.

Y is a monovalent group selected from the group consisting of an alkyl group, an aryl group, and a heterocyclic residue. Among these, an aryl group and a heterocyclic residue are preferable, and an aryl group is particularly preferable. Further, each group may have one or more substituents. Examples of the substituent which may be substituted with an aryl group are the same as those of the substituent of the above aryl group.

Specific examples thereof include the following compounds. Wherein the substituent Cx in the formula (3-7) represents a cyclohexyl group. Further, in the formulae (3-3) to (3-12), Ar represents an aryl group or an arylene group.

The starting alkali temperature of the (E) thermal alkali generator is preferably 40 ° C or higher, preferably 90 ° C or higher, and particularly preferably 110 ° C or higher. When the temperature is 40 ° C or higher, the storage stability is improved. In addition, in the case of 90° C. or higher, the drying temperature of the photocurable thermosetting resin composition is higher than that of the conventional photocurable thermosetting resin composition. Therefore, it is possible to suppress the shortening of the drying management range. On the other hand, the alkali-based starting temperature of the (E) thermal base generator is preferably 150 ° C or lower, more preferably 140 ° C or lower, and particularly preferably 130 ° C or lower. In the case of 150 ° C or less, even when the heating temperature at the time of heat curing is low, an alkali can be generated, and a cured product excellent in solder heat resistance and the like can be obtained. Moreover, when it is 150 degrees C or less, since the heating temperature at the time of thermo-hardening can be reduced, it can save energy, and can reduce the manufacturing cost of a printed circuit board.

Here, the base initiation temperature means that 1 mg of the thermal alkali generator is dissolved in 0.5 μL of deuterated dimethyl hydrazine in an NMR tube to prepare a 2 mg/mL NMR measurement solution, and a heated oil bath is used. It was heated for 10 minutes and the NMR, 10 mol% base generated temperature was determined.

(E) The compounding amount of the thermal alkali generator is sufficient, and is, for example, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin.

The photocurable thermosetting resin composition of the present invention is used for coating The physical strength of the film, etc., may be compounded as needed (F). As such a filler (F), a conventionally known inorganic or organic filler can be used, and barium sulfate, spherical cerium oxide and talc are particularly preferably used. Further, in order to obtain a white appearance and flame retardancy, a metal oxide such as titanium oxide or a metal hydroxide such as aluminum hydroxide may be used as the extender pigment filler. The amount of the filler (F) is preferably 200 parts by mass or less, more preferably 0.1 to 150 parts by mass, even more preferably 1 to 120 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin.

When the compounding amount of the filler (F) is 200 parts by mass or less, the printability is good, and a cured product having high strength can be obtained.

Further, the photocurable thermosetting resin composition of the present invention can use a binder polymer in order to improve the dryness of the touch, improve the handleability, and the like. For example, a polyester polymer, a polyurethane polymer, a polyester urethane polymer, a polyamide polymer, a polyester amide polymer, an acrylic polymer, or a cellulose polymer can be used. A polylactic acid-based polymer or a phenoxy polymer. These binder polymers may be used singly or in the form of a mixture of two or more.

Further, the photocurable thermosetting resin composition of the present invention may use another elastomer in order to impart flexibility, improve the brittleness of the cured product, and the like. For example, a polyester-based elastomer, a polyurethane-based elastomer, a polyester urethane-based elastomer, a polyamide-based elastomer, a polyester amide-based elastomer, an acrylic elastomer, or an olefin-based elastomer can be used. Further, a resin obtained by modifying a part or all of the epoxy group of the epoxy resin having various skeletons with a two-terminal carboxylic acid-modified butadiene-acrylonitrile rubber may be used. Further, an epoxy group-containing polybutadiene-based elastomer, an acryl-based group-containing polybutadiene-based elastomer, or the like may be used. These elastomers may be used singly or in the form of a mixture of two or more.

Further, the photocurable thermosetting resin composition of the present invention may be an organic solvent in order to prepare the composition of the above (A) carboxyl group-containing resin, to prepare a composition, or to adjust the viscosity so as to be applied onto a substrate or a carrier film.

Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, there are ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, and methyl carbene. Alcohol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, diethylene glycol diethyl ether Esters such as acid ester, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; octane An aliphatic hydrocarbon such as decane; a petroleum solvent such as petroleum ether, naphtha, hydrogenated naphtha or solvent naphtha. Such an organic solvent may be used singly or in the form of a mixture of two or more.

In general, most of the polymer materials are oxidatively degraded in a chain, and the function of the polymer raw material is lowered. Therefore, the photocurable thermosetting resin composition of the present invention can be added to prevent oxidation (1). The radical scavenger (G-1) or/and (2) which can cause the generated radical to be deactivated can decompose the generated peroxide into a harmless substance and does not generate An antioxidant (G) such as a new free radical peroxide decomposing agent (G-2).

Examples of the antioxidant (G-1) which functions as a radical scavenger include hydroquinone, 4-tert-butylcatechol, 2-tert-butylhydroquinone, and hydroquinone monomethyl ether. , 2,6-di-tert-butyl-p-cresol, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl- 4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, a phenolic system such as 1,3,5-tris(3',5'-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione An oxime compound such as methoquinone or benzoquinone, an amine compound such as bis(2,2,6,6-tetramethyl-4-acridinyl)-sebacate or phenothiazine, etc. .

The radical scavenger may also be a commercially available product, and examples thereof include ADEKASTAB AO-30, ADEKASTAB AO-330, ADEKASTAB AO-20, ADEKASTAB LA-77, ADEKASTAB LA-57, ADEKASTAB LA-67, ADEKASTAB LA-68, ADEKASTAB LA-87 (above, manufactured by Asahi Kasei Co., Ltd., trade name), IRDANOX 1010, IRDANOX 1035, IRDANOX 1076, IRDANOX 1135, TINUVIN 111 FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, Ciba Specialty Chemicals Inc. Manufacturing, trade name), etc.

The antioxidant (G-2) which functions as a peroxide decomposing agent may, for example, be a phosphorus compound such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate or dilauryl sulfur. A sulfur-based compound such as a dipropionate or a distearyl 3,3'-thiodipropionate.

The peroxide decomposing agent may be a commercially available product, and examples thereof include ADEKASTAB TPP (manufactured by Asahi Kasei Co., Ltd., trade name), and Mark. AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd., trade name), and the like.

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

In addition, in the photocurable thermosetting resin composition of the present invention, the photocurable thermosetting resin composition of the present invention can be used in addition to the above-mentioned antioxidant in order to carry out decomposition and deterioration. UV absorber (H).

Examples of the ultraviolet absorber (H) include a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, and an ortho An aminobenzoate derivative, a benzotrimethane derivative or the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-di. Hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone. Specific examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, p-tert-butylphenyl salicylate, and 2,4-di-tert-butyl. Phenylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and cetyl-3,5-di-tert-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole and 2-(2'-hydroxy-5'-methyl group. Phenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3' , 5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole and the like. Specific examples of the triazine derivative include hydroxy Phenyltriazine, bis-ethylhexyloxyphenol methoxyphenyl triazine, and the like.

The ultraviolet absorber (H) may be a commercially available product, and examples thereof include TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, and TINUVIN 405. TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Specialty Chemicals Inc., trade name) and the like.

The ultraviolet ray absorbing agent (H) can be used singly or in combination of two or more kinds, and the molded article obtained by the photocurable thermosetting resin composition of the present invention can be stabilized by being used in combination with the above-mentioned antioxidant (G). Chemical.

In the photocurable thermosetting resin composition of the present invention, in order to improve the sensitivity, a well-known conventional N-phenylglycine, phenoxyacetic acid, thiophenoxyacetic acid or sulfhydryl group can be used as the chain transfer agent. Thiazole and the like. Specific examples of the chain transfer agent include, for example, a chain transfer agent having a carboxyl group such as mercapto succinic acid, thioglycolic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof; a chain transfer agent having a hydroxyl group such as ethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxythiophenol, and derivatives thereof; 1-butyl mercaptan, butyl 3-mercaptopropionate, Methyl 3-mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanethiol, 4-methylthiophenol, dodecyl mercaptan, propanethiol, butanol , pentyl mercaptan, 1-octyl thiol, cyclopentyl mercaptan, cyclohexyl mercaptan, thioglycerol, 4,4-thiobisthiophenol, and the like.

In addition, polyfunctional thiol compounds can be used without particular limitation. For example, an aliphatic thiol such as hexane-1,6-dithiol, decane-1,10-dithiol, didecyl diethyl ether or dimercapto diethyl sulfide can be used, and benzoic acid can be used. Alcohol, 4,4'-dimercaptodiphenyl sulfide, 1,4-benzenedithiol and other aromatic thiols; ethylene glycol bis(mercaptoacetate), polyethylene glycol bis(mercaptoacetic acid) Ester), propylene glycol bis(mercaptoacetate), glycerol tris(mercaptoacetate), trimethylolethane tris(mercaptoacetate), trimethylolpropane tris(mercaptoacetate), pentaerythritol IV Poly(mercaptoacetate) of polyhydric alcohols such as (mercaptoacetate), dipentaerythritol hexa(mercaptoacetate); ethylene glycol bis(3-mercaptopropionate), polyethylene glycol bis (3- Mercaptopropionate, propylene glycol bis(3-mercaptopropionate), glycerol tris(3-mercaptopropionate), trimethylolethane tris(mercaptopropionate), trimethylolpropane tris(3) Poly(3-mercaptopropionate) of polyhydric alcohols such as -mercaptopropionate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate); 1,4-double ( 3-mercaptobutyloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H) -trione Pentaerythritol tetrakis (3-mercapto butyrate) and other (mercaptobutyrate) class.

Examples of the commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (above, 堺Chemical Industries, Ltd.), KARENZ MT-PE1, KARENZ MT- BD1 and KARENZ-NR1 (above, manufactured by Showa Denko KK).

Further, examples of the heterocyclic compound having a mercapto group which functions as a chain transfer agent include mercapto-4-butyrolactone (alias: 2-mercapto-4-butyrolactone), 2-mercapto-4-methyl group 4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-thiobutyrolactone, 2-mercapto-4-butylidene, N-methoxy Base-2-mercapto-4-butylidene, N-ethoxy-2-mercapto-4-butylidene, N-methyl-2-mercapto-4-butylidene, N-ethyl -2-mercapto-4-butylidene, N-(2-methoxy)ethyl-2-mercapto-4-butylidene, N-(2-ethoxy)ethyl-2-indenyl 4-butylidene, 2-mercapto-5-valerolactone, 2-mercapto-5-pentalinamide, N-methyl-2-indolyl-5-pentalinamide, N-ethyl- 2-mercapto-5-valeroinamide, N-(2-methoxy)ethyl-2-indolyl-5-pentalinamide, N-(2-ethoxy)ethyl-2-indenyl- 5-pentalinamide, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-caprolactam, 2,4,6-tridecyl-all three Pyrazine (manufactured by Sankyo Chemical Co., Ltd.: trade name: ZISNET F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Co., Ltd.: trade name ZISNET DB), and 2- Anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Co., Ltd.: trade name: ZISNET AF).

In particular, the heterocyclic compound having a mercapto group as a chain transfer agent which does not impair the developability of the photocurable thermosetting resin composition is preferably mercaptobenzothiazole or 3-mercapto-4-methyl-4H-1. 2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole. 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 in order to improve the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate. Specific examples thereof include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi Chemical Industry) Accelerator M), 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2 - mercapto-5-methylthio - thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amine-containing benzotriazole, decane coupling agent, and the like.

The photocurable thermosetting resin composition of the present invention may further contain a thixotropic agent such as fine powder of ceria, organic bentonite, montmorillonite or hydrotalcite as needed. From the viewpoint of stability over time as a thixotropic agent, organic bentonite and hydrotalcite are preferred, and hydrotalcite is particularly excellent in electrical properties. Further, an antifoaming agent such as a thermal polymerization inhibitor, a coloring agent, an organic oxime system, a fluorine system or a polymer system, and/or a leveling agent, a decane coupling agent such as an imidazole type, a thiazole type or a triazole type, or the like may be blended. A conventionally known additive such as a rust preventive agent, a copper-resistant agent such as a bisphenol system or a triazine thiol compound, or the like.

The aforementioned thermal polymerization inhibitor can be used to prevent thermal polymerization or time-lapse polymerization of the aforementioned polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, tert-butylcatechol, pyrogallol, 2-hydroxybenzophenone, and 4 -Methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2 a reaction product of '-methylenebis(4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and an organic chelating agent, Methyl salicylate, a phenothiazine, a nitroso compound, a chelate compound of a nitroso compound and Al, and the like.

The photocurable thermosetting resin composition of the present invention is adjusted to a viscosity suitable for a coating method by using the above organic solvent, for example, by dip coating, flow coating, roll coating, bar coating, or screen printing. And a method such as a curtain coating method is applied to the substrate, and the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of about 60 to 100 ° C, thereby forming a non-stick coating. membrane. Then, the active energy ray is selectively exposed by contact (or non-contact) through the patterned photomask, or direct pattern exposure is performed by a laser direct exposure machine, and the unexposed portion is treated with an aqueous alkali solution (for example, 0.3). Developed with ~3% aqueous sodium carbonate solution to form a resist pattern. Then, the thermosetting component is heated to a temperature of, for example, about 130 to 180 ° C to be thermally cured, whereby the (A) carboxyl group-containing resin reacts with the thermosetting component to form heat resistance, chemical resistance, and moisture absorption resistance. A cured coating film excellent in properties such as properties, adhesion, and electrical properties.

As the substrate, in addition to a printed circuit board or a flexible printed circuit board in which a circuit is formed in advance, a copper clad laminate, a polyimide film, a PET film, a glass substrate, a ceramic substrate, and a wafer can be used. Board and so on. The copper clad laminate is made of paper-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimine, glass cloth/non-woven fabric, epoxy resin, glass cloth/paper-ring Oxygen resin, synthetic fiber - epoxy resin, fluororesin. Polyethylene. PPO. A copper-clad laminate of all grades (FR-4, etc.) of a composite material such as cyanate ester.

The volatilization drying after the application of the photocurable thermosetting resin composition of the present invention can be carried out using a hot air loop type drying furnace, an IR furnace, a hot plate, a convection oven, or the like (using a heat source having a heat supply method using steam) The method of bringing the hot air in the dryer into contact with the flow and the method of blowing the nozzle to the support are performed.

The photocurable thermosetting resin composition of the present invention is applied as described below, and after evaporation and drying, the obtained coating film is exposed (irradiation of active energy rays). The exposed portion of the coating film (the portion irradiated with the active energy ray) is solid Chemical.

As the exposure machine used for the active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device that directly uses a laser to draw an image based on CAD data from a computer), an exposure machine equipped with a metal halide lamp, and the like can be used. An (extra) high-pressure mercury lamp exposure machine, an exposure machine equipped with a mercury short-arc lamp, or a direct drawing device using an ultraviolet lamp such as a (super) high-pressure mercury lamp.

As the developing method, a dipping method, a shower method, a spray method, a brushing method, or the like can be used. As the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, or ammonia can be used. An aqueous alkali solution such as an amine.

The photocurable thermosetting resin composition of the present invention may be coated with a photocurable heat on a film such as polyethylene terephthalate in addition to a method of directly applying a liquid to a substrate. The curable resin composition is used in the form of a dry film of a resin layer formed by drying. The case where the photocurable thermosetting resin composition of the present invention is used in the form of a dry film is shown below.

The dry film has a structure in which a carrier film, a resin layer, and a peelable cover film used as needed are laminated in this order. The resin layer is a layer obtained by applying an alkali-developable photocurable thermosetting resin composition onto a carrier film or a cover film and drying it. After the resin layer is formed on the carrier film, a cover film is laminated thereon, or a resin layer is formed on the cover film, and the laminate is laminated on the carrier film to obtain a dry film.

As the carrier film, heat such as a polyester film having a thickness of 2 to 150 μm is used. Plastic film.

In the resin layer, the photocurable thermosetting resin composition is uniformly coated on the carrier film or the cover film with a thickness of 10 to 150 μm by a knife coater, a lip coater, a comma coater, a film coater or the like. It is formed by coating and drying.

As the cover film, a polyethylene film, a polypropylene film, or the like can be used, and a cover film having a bonding strength to the resin layer smaller than that of the carrier film and the resin layer is preferable.

A protective film (permanent protective film) is formed on a printed circuit board by using a dry film, the cover film is peeled off, and the resin layer is superposed on the substrate on which the circuit is formed, and bonded by a laminator or the like to form a substrate on which a circuit is formed. A resin layer is formed thereon. The formed resin layer is exposed, developed, and cured in the same manner as described above to form a cured coating film. The carrier film may be peeled off before or after exposure.

The photocurable thermosetting resin composition of the present invention is suitable for use in forming a cured film of a printed circuit board, is more suitable for forming a permanent film, is particularly suitable for forming a solder resist film, and can be used for covering. The use of layers, interlayer insulating materials, solder dams.

Example

The present invention will be specifically described below by way of examples and comparative examples, but the present invention is by no means limited to the following examples. In addition, in the following, "part" and "%" all mean the quality standard, unless otherwise indicated.

Synthesis Example 1 (carboxyl-containing resin A-1)

An o-cresol novolac type epoxy resin [EPICLON N-695, manufactured by DIC Corporation, softening point 95 ° C, epoxy equivalent 214, average functionality 7.6] 1070 g was added to 600 g of diethylene glycol monoethyl ether acetate. (Glycidyl group number (total aromatic ring): 5.0 mol), acrylic acid 360 g (5.0 mol), and hydroquinone 1.5 g, and the mixture was heated and stirred to 100 ° C to be uniformly dissolved. Next, 4.3 g of triphenylphosphine was added, and the mixture was heated to 110 ° C for 2 hours, and then heated to 120 ° C for further 12 hours. 415 g of an aromatic hydrocarbon (SOLVESSO 150) and 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic anhydride were added to the obtained reaction liquid, and the reaction was carried out at 110 ° C for 4 hours to cool. Thereafter, a cresol novolac type carboxyl group-containing resin solution having a solid content of 89 mgKOH/g and a solid content of 65% was obtained. This is referred to as a carboxyl group-containing resin A-1.

Synthesis Example 2 (carboxyl-containing resin A-4)

Into a 5 liter separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 1245 g of polycaprolactone diol (PLACCEL 208 manufactured by Daicel Chemical Co., Ltd., molecular weight 830) as a polymer polyol was introduced as 201 g of dihydroxymethylpropionic acid as a dihydroxy compound of a carboxyl group, 777 g of isophorone diisocyanate as a polyisocyanate, and 119 g of 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group, and then sequentially put into a pair of 0.5 g of oxyphenol and di-tert-butyl-hydroxytoluene. The mixture was heated to 60 ° C while stirring, and stopped, and 0.8 g of dibutyltin dilaurate was added. After the temperature in the reaction vessel began to decrease, the temperature was again heated, and stirring was continued at 80 ° C. It was confirmed that the absorption spectrum (2280 cm ^-1 ) of the isocyanate group in the infrared absorption spectrum disappeared and the reaction was terminated to obtain a viscous liquid urethane acrylate compound. . The carbitol acetate was adjusted to a nonvolatile content = 50% by mass. A resin solution of a urethane (meth) acrylate compound having a carboxyl group of 47 mg KOH/g of a solid substance and 50% of a nonvolatile component was obtained. Hereinafter, this is referred to as a carboxyl group-containing resin A-4.

Synthesis Example 3 (carboxyl-containing resin A-5)

A novolac type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name "Shonol CRG951", OH equivalent: 119.4) 119.4 g was placed in an autoclave equipped with a thermometer, a nitrogen gas introducing device, an alkylene oxide introducing device, and a stirring device. 1.19 g of potassium hydroxide and 119.4 g of toluene were subjected to nitrogen substitution in the system while stirring, and the temperature was raised by heating. Subsequently, 63.8 g of propylene oxide was slowly added dropwise, and the mixture was reacted at 125 to 132 ° C for 0 to 4.8 kg/cm ² for 16 hours. Then, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain a ring of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. Oxypropane reaction solution. It is the product of an average of 1.08 moles of alkylene oxide per 1 equivalent of phenolic hydroxyl groups.

Next, 293.0 g of an alkylene oxide reaction solution of the obtained novolac type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone, and 252.9 g of toluene were placed in a stirring device, a thermometer, and air. In the reactor which was blown into the tube, air was blown at a rate of 10 ml/min, and the mixture was reacted at 110 ° C for 12 hours while stirring. Water produced by the reaction 12.6 g of water was distilled off in the form of an azeotropic mixture with toluene. Then, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, followed by washing with water. Then, toluene was distilled off with 118.1 g of diethylene glycol monoethyl ether acetate by an evaporator to obtain a novolac type acrylate resin solution. Next, 332.5 g of the obtained novolac type acrylate resin solution and 1.22 g of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min. 60.8 g of tetrahydrophthalic anhydride was slowly added thereto while stirring, and the mixture was reacted at 95 to 101 ° C for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having a solid value of 88 mg KOH/g and a nonvolatile content of 71% was obtained. Hereinafter, this is referred to as a carboxyl group-containing resin A-5.

Synthesis Example 4 (thermal base generator E-1, formula (4))

In a 100 mL flask, (triphenylphosphine) ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.56 (7.34 mmol) and 1'-hydroxy-2'-naphthyl ethyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.22 g. (7.34 mmol, 1.0 eq) was dissolved in 20 mL of toluene, and stirred at 80 ° C for 3 hours. After confirming the completion of the reaction by the thin layer chromatography, a saturated aqueous solution of ammonium chloride was added thereto, and the mixture was extracted with chloroform, washed with water and a saturated aqueous solution of ammonium chloride, and then dried over anhydrous magnesium sulfate. After concentration, purification was carried out by silica gel column chromatography (developing solvent hexane/ethyl acetate 2/1 (volume ratio)).

Next, 15 mL of a 1 N aqueous sodium hydroxide solution was added and stirred overnight. After the reaction is completed, the precipitate is removed by filtration, and concentrated hydrochloric acid is added dropwise to make The reaction solution was acidic, then extracted with chloroform and concentrated to give 520 mg of cinnamic acid derivative D.

Next, 0.49 g (2.80 mmol) of cinnamic acid derivative D was dissolved in 10 mL of dehydrated tetrahydrofuran under a nitrogen atmosphere in a 100 mL three-necked flask, and 1-ethyl-3-(3-dimethylamino group was added thereto in an ice bath. Propyl)carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.64 g (3.4 mmol, 1.2 eq). After 30 minutes, 0.33 ml (3.4 mmol, 1.2 eq) of acridine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, followed by stirring overnight. After the reaction was completed, the reaction solution was concentrated and dissolved in water. After extracting with chloroform, the mixture was washed with a sodium hydrogencarbonate aqueous solution, 1N hydrochloric acid and brine, and dried over sodium sulfate, and then purified by column chromatography (developing solvent: chloroform/methanol 100/1 to 50/1) 152 mg of the thermal base generator E-1 represented by the following chemical formula (E-1) was obtained.

Synthesis Example 5 (thermal base generator E-2, formula (5))

2.00 g of potassium carbonate was added to 15 mL of methanol in a 100 mL flask. Ethoxycarbonylmethyl(triphenyl)phosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.67 g (6.2 mmol) and 2-hydroxy-1-naphthaldehyde formaldehyde 1.07 g (6.2 mmol) in a 50 mL flask (Tokyo) The product was dissolved in 10 mL of methanol, and a sufficiently stirred potassium carbonate solution was slowly added dropwise. Stir 3 small After confirming the completion of the reaction by TLC, the potassium carbonate was removed by filtration and concentrated under reduced pressure. After concentration, 50 mL of a 1 N aqueous sodium hydroxide solution was added, and the mixture was stirred for 1 hour. After completion of the reaction, the triphenylphosphine oxide was removed by filtration, and concentrated hydrochloric acid was added dropwise to make the reaction solution acidic. The precipitate was collected by filtration and washed with a small amount of chloroform to give 1.20 g of 3-(2-hydroxy-1-naphthalenyl)-acrylic acid. Next, 1.00 g (4.67 mmol) of 3-(2-hydroxy-1-naphthyl)-acrylic acid was dissolved in 20 mL of dehydrated tetrahydrofuran in a 100 mL three-necked flask, and 1-ethyl-3-(3-dimethylamino group was added. Propyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.07 g (5.60 mmol). After 30 minutes, 0.65 ml (5.60 mmol) of acridine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, and the mixture was stirred at room temperature overnight. The reaction liquid was concentrated, extracted with chloroform, washed with diluted hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution and brine, and filtered to give 480 mg of the hot base generator E-2 represented by the following formula (E-2).

Synthesis Example 6 (Hot alkaline generator E-3)

Into a flask equipped with a stirrer, 3.5 g of stearylamine, 1.3 g of triethylamine, and 50 ml of chloroform were placed, and a solution of 4.4 g of 9-fluorenylmethylammonium imide carbonate dissolved in 20 ml of chloroform was added dropwise thereto under ice cooling. . After removing the ice bath and stirring for 18 hours, the reaction liquid was diluted with chloroform, washed with water, and dehydrated, and then chloroform was distilled off under reduced pressure. The obtained colorless powder from chloroform and The mixed solvent of n-hexane was recrystallized to obtain a hot base generator E-3 4.0 g.

Synthesis Example 7 (thermal base generator E-4)

1.6 g of 2-hydroxyindole, 1.2 g of stearyl isocyanate, 1.0 g of triethylamine, and 20 ml of ether were placed in a flask equipped with a stirrer, and the mixture was further stirred at room temperature for 18 hours, and then the crystal formed was collected under reduced pressure. , obtained a hot base generator E-4 2.0g.

Synthesis Example 8 (alkali agent E-5)

408 g of 4-phenylsulfonylbenzenesulfonyl acetic acid was heated and dissolved in 4 L of methanol. In this solution, 132 g of 1,3-dioxylpropane carbonate was added in small portions at 50 °C. The obtained solution was cooled, and the precipitated crystals were collected by filtration to obtain 478 g of an alkali generating agent E-5 represented by the following chemical formula (E-5).

Synthesis Example 9 (base generator E-6)

In a 500 mL eggplant-shaped flask, 10.0 g (72.4 mmol) of sesame phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and hexamethylenetetramine (manufactured by Tokyo Chemical Industry Co., Ltd.) (15.2 g (109 mmol, 1.5 eq)) were dissolved in trifluoroethylene. 100 ml of acetic acid (manufactured by Kanto Chemical Co., Ltd.) was reacted at 95 ° C for 10 hours. After completion of the reaction, 200 ml of 1N hydrochloric acid was added to an ice bath, and the mixture was stirred for 15 minutes. After the completion of the stirring, the mixture was extracted with chloroform and washed with hydrochloric acid/saturated brine to give 2. <RTI ID=0.0></RTI> </ RTI> </ RTI> 6- hydroxy-3,4-methylenedioxybenzaldehyde (14.3 mmol).

Next, 2.00 g of potassium carbonate was added to 20 mL of methanol in a 200 mL flask. Ethoxycarbonylmethyl(triphenyl)phosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.15 g (14.3 mmol), 6-hydroxy-3,4-methylenedioxybenzaldehyde 2.38 was placed in a 100 mL flask. g (14.3 mmol) was dissolved in 25 mL of methanol, and a well-stirred potassium carbonate solution was slowly added dropwise. After stirring for 3 hours, it was confirmed by thin layer chromatography that after completion of the reaction, the potassium carbonate was removed by filtration and concentrated under reduced pressure. After concentration, 30 mL of a 1N aqueous sodium hydroxide solution was added and stirred overnight. After completion of the reaction, the precipitate was removed by filtration, and concentrated hydrochloric acid was added dropwise to make the reaction liquid acidic. The precipitate was collected by filtration, and washed with a small amount of chloroform to give 2.90 g (13.9 mmol) of 2-hydroxy-4,5-methylenedioxycinnamic acid.

Next, 2.90 g (13.9 mmol) of 2-hydroxy-4,5-methylenedioxycinnamic acid was dissolved in 40 mL of dehydrated tetrahydrofuran under a nitrogen atmosphere in a 100 mL three-necked flask, and 1-ethyl- 3-(3-dimethylaminopropyl)carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.20 g (16.7 mmol, 1.2 eq). After 30 minutes, 1.65 ml (16.7 mmol, 1.2 eq) of acridine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, followed by stirring overnight. After the reaction was completed, the reaction solution was concentrated and dissolved in water. After extracting with chloroform, it was washed with a sodium hydrogencarbonate aqueous solution, 1N hydrochloric acid, and brine, and dried over sodium sulfate. Purification by silica gel column chromatography (developing solvent: chloroform/methanol 100/1 to 50/1) to obtain 485 mg (1.76 mmol) of the thermal base generator (E-6) represented by the following chemical formula (E-6). ).

According to the various components shown in Tables 1 and 2 below, and the ratios (mass parts) shown in Tables 1 and 2, compounded by a mixer, and then kneaded by a 3-roll mill to prepare photocurable heat. A curable resin composition.

A-1: carboxyl group-containing resin, cresol novolak type, solid content 65%, acid value 80 mgKOH/g, equivalent to (7) carboxyl group-containing resin

A-2: carboxyl group-containing resin, ZFR-1401H, bisphenol F type manufactured by Nippon Kayaku Co., Ltd., solid content 60%, acid value 100 mgKOH/g, equivalent to (8) carboxyl group-containing resin

A-3: carboxyl group-containing resin, CYCLOMER P (ACA) Z250, acrylic copolymer type manufactured by Daicel-Cytec Co., Ltd., solid content 45%, acid value 70 mgKOH/g, equivalent to (1) and (10) Carboxyl containing resin

A-4: carboxyl group-containing polyurethane resin, solid content 50%, acid value 47 mgKOH/g, equivalent to (2) and (5) carboxyl group-containing resin

A-5: a carboxyl group-containing resin starting from a phenol compound, having a solid content of 71% and an acid value of 88 mgKOH/g, which corresponds to (9) a carboxyl group-containing resin

B-1: Photopolymerization initiator, IRGACURE 907, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one manufactured by BASF Corporation

B-2: Photopolymerization initiator, IRGACURE 369, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, manufactured by BASF Corporation

C-1: Photosensitive monomer, NK Ester A-DPH, dipentaerythritol hexaacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.

C-2: Photosensitive monomer, NKEster A-TMPT, Trimethylolpropane triacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.

D-1: Thermosetting component, EPICLON N-660 manufactured by DIC Corporation, cresol novolac type epoxy resin, epoxy equivalent 202-212 g/eq

D-2: thermosetting component, jER828 manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A epoxy resin, epoxy equivalent 184-194 g/eq

E-1: hot alkali generator, alkali production starting temperature 110 ° C

E-2: hot alkali generator, alkali production starting temperature 150 ° C

E-3: hot alkali generator, alkali production starting temperature 135 ° C

E-4: hot alkali generator, alkali production starting temperature 145 ° C

E-5: hot alkali generator, alkali production starting temperature 124 ° C

E-6: hot alkali generator, alkali production starting temperature 160 ° C

Melamine: heat curing catalyst

F-1: filler, LMP-100 manufactured by Fuji Talc Industry Co., Ltd., talc

F-2: Filler, BARIACE B-30 manufactured by Suga Chemical Industry Co., Ltd., barium sulfate

G-1: antioxidant, IRGANOX 1010 manufactured by BASF Corporation, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]

X-1: Colorant, C.I. Pigment Blue 15:3

X-2: coloring agent, C.I. Pigment Yellow147

X-3: Defoamer, FLOWLEN AC-902 manufactured by Kyoeisha Chemical Co., Ltd., organic antimony defoamer

X-4: solvent, dipropylene glycol monomethyl ether

<storage stability>

The photocurable thermosetting resin composition of the above-mentioned Examples and Comparative Examples was stored in a thermostat bath at 50° C. for 24 hours, and the viscosity increase rate was calculated by the following formula (A) from the change in viscosity before and after storage, and the storage stability was evaluated. .

Viscosity increase rate (%) = {(viscosity after storage - viscosity before storage) / Paul Viscosity before storage}×100..式(A)

○: viscosity increase rate is less than 50%

△: viscosity increase rate is 50% or more and less than 100%

×: The viscosity increase rate is 100% or more

<developing life>

The photocurable thermosetting resin composition of the above examples and comparative examples was applied to the copper foil substrate on which the pattern was formed by screen printing, and dried at 80 ° C for from 50 minutes to 80 minutes. The substrate was taken out every 10 minutes and naturally cooled to room temperature. The substrate was developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C under a pressure of 0.2 MPa for 60 seconds, and the presence or absence of the residue was evaluated. The judgment criteria are as follows.

○: No residue at all

△: slightly residue

×: There are a lot of residues.

<Method for producing substrate for evaluation of soldering resistance, acid resistance and alkali resistance>

The photocurable thermosetting resin composition of the above examples and comparative examples was applied to the copper foil substrate on which the pattern was formed by screen printing, and dried at 80 ° C for 30 minutes, and naturally cooled to room temperature. The substrate was exposed to light using an exposure apparatus equipped with a high-pressure mercury lamp and a negative film, and developed with a 1 wt% sodium carbonate aqueous solution at 30 ° C under a pressure of 0.2 MPa for 60 seconds to obtain a resist pattern. The substrate was heated at 130 ° C for 60 minutes to be cured to prepare a substrate for evaluation.

<heat resistance to soldering>

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

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

△: slightly exfoliated when repeated for 3 times or more for 10 seconds.

×: The resist layer is bulged and exfoliated when it is immersed for 10 seconds within 3 times.

<acid resistance>

The evaluation substrate was immersed in a 10 vol% H ₂ SO ₄ aqueous solution at room temperature for 20 minutes, and the impregnation and the elution of the coating film were visually confirmed, and the peeling due to peeling of the tape was confirmed.

○: No changes were observed

△: only slightly changed

×: The coating film is bulged or swollen

<Alkaline resistance>

The evaluation substrate was immersed in a 10 vol% aqueous NaOH solution at room temperature for 20 minutes, and the impregnation and the elution of the coating film were visually confirmed, and the peeling due to peeling of the tape was confirmed.

○: No changes were observed

△: only slightly changed

×: The coating film is bulged or swollen

<Solvent resistance>

The evaluation substrate was immersed in propylene glycol monomethyl ether at room temperature for 20 minutes, and the impregnation and the elution of the coating film were visually confirmed, and the peeling due to peeling of the tape was confirmed.

○: No changes were observed

△: only slightly changed

×: The coating film is bulged or swollen

As is apparent from Tables 3 and 4, the photocurable thermosetting resin composition of the present invention can be suitably used as a resin for solder resist which has excellent characteristics even in a heat curing reaction at a low temperature without shortening the drying management range. combination.

Claims (8)

A photocurable thermosetting resin composition comprising: (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, (D) a thermosetting component, and (E) heat Alkali-producing agent. The photocurable thermosetting resin composition according to claim 1, wherein the (E) thermal alkali generator has a base initiation temperature of 40 ° C or higher. The photocurable thermosetting resin composition according to claim 1, wherein the (E) thermal alkali generator has a base alkalinity starting temperature of 90 ° C or more and 150 ° C or less. The photocurable thermosetting resin composition according to claim 1, wherein the (E) thermal base generator is compounded in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the (A) carboxyl group-containing resin. . The photocurable thermosetting resin composition according to any one of claims 1 to 4, which is used for forming a solder resist. A photocurable thermosetting dry film obtained by applying the photocurable thermosetting resin composition according to any one of claims 1 to 5 to a carrier film and drying it. A cured product obtained by photocuring a photocurable thermosetting resin composition according to any one of claims 1 to 5 or a dry film of claim 5 and thermally curing the film. A printed circuit board having the cured product of claim 7.