WO2015196702A1 - Photocurable thermosetting resin composition for manufacturing printed circuit board, dry film, cured product, and printed circuit board - Google Patents

Abstract

A photocurable thermosetting resin composition for manufacturing a printed circuit board, a dry film, a cured product, and a printed circuit board. The photocurable thermosetting resin composition for manufacturing a printed circuit board contains: (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, (D) a thermosetting component, and (E) a hollow filler.

Description

Photocurable thermosetting resin composition for producing a printed circuit board, dry film, cured product, and printed circuit board Technical field

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

Background technique

At present, a photocurable thermosetting resin composition for a solder resist for a part of a consumer printed circuit board and a large-sized industrial printed circuit board is imaged by development after ultraviolet irradiation from the viewpoint of high precision and high density. A photocurable thermosetting resin composition for a liquid development type solder resist which is subjected to final curing (complete curing) by heat and/or light irradiation. Among them, the photocurable thermosetting resin composition for an alkali-developable photo-resistance solder using a dilute aqueous solution as a developing solution has become a mainstream in the production of an actual printed circuit board. It is used in large quantities (see JP-A 2013-539072).

Summary of the invention

Problems to be solved by the invention

One of the purposes of using a solder resist is to protect the printed circuit board as an insulating material. However, in recent years, high-density mounting and high current of printed circuit boards have caused problems in that solder resists act like capacitors. When the solder resist acts as a capacitor, the current that should not flow may circulate, causing malfunction or malfunction of the electronic device. In order to solve this problem, a low dielectric constant of a solder resist is required.

An object of the present invention is to provide a photocurable thermosetting resin composition for producing a printed wiring board, a dry film, a cured product thereof, and an ink having the cured product, which are capable of exhibiting excellent low dielectric constant. Brush the board.

Solution to solve the problem

The inventors of the present invention have conducted intensive studies to successfully lower the dielectric constant of the photocurable thermosetting resin composition for producing a printed wiring board, and have completed the present invention.

That is, according to the present invention, there is provided a photocurable thermosetting resin composition for producing a printed circuit board, comprising: (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) A photosensitive monomer, (D) a thermosetting component, and (E) a hollow filler. Here, in the present invention, the average particle diameter d50 of the (E) hollow filler is preferably in the range of 1 μm to 100 μm. Further, in the invention, the (E) hollow filler is preferably hollow glass or hollow silica.

According to the present invention, there is provided a dry film for producing a printed circuit board obtained by applying the photocurable thermosetting resin composition for producing a printed wiring board to a carrier film and drying the film.

According to the present invention, there is provided a cured product which is photocurable and thermally cured by the above-mentioned photocurable thermosetting resin composition for producing a printed circuit board or the above-mentioned dry film for manufacturing a printed circuit board. owned.

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

Effect of the invention

According to the present invention, it is possible to provide a photocurable thermosetting resin composition for producing a printed wiring board and a dry film for producing a printed circuit board, which are excellent in low dielectric constant by containing a hollow filler.

Further, according to the present invention, it is possible to provide a cured product having a low dielectric constant and a printed circuit board having the cured product.

detailed description

The present invention is a photocurable thermosetting resin composition for producing a printed circuit board The photocurable thermosetting resin composition (hereinafter referred to as a photocurable thermosetting resin composition) contains (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, and (D) a thermosetting component. And (E) a hollow filler. Since the photocurable thermosetting resin composition of the present invention contains the above components (A) to (E), it is possible to obtain a cured product having high sensitivity, low dielectric constant, and excellent solder heat resistance. In the case of high sensitivity, the exposure time at the time of obtaining a cured product can be shortened, so that the tact time is shortened.

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, it is more preferred that the unsaturated double bond is derived from acrylic acid or methacrylic acid or a derivative thereof.

As the (A) carboxyl group-containing resin, a carboxyl group-containing resin starting from an epoxy resin, a carboxyl group-containing polyurethane resin having a urethane skeleton, a carboxyl group-containing copolymer resin having a copolymerization structure of an unsaturated carboxylic acid, and a phenol are preferable. The compound is a carboxyl group-containing resin as a starting material.

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

(1) A carboxyl group-containing resin obtained by copolymerizing 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 isobutylene. .

(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 urethane resin obtained by addition polymerization of a diol compound such as an alcoholic hydroxyl group compound.

(3) A diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, or a polycarbonate polyol, a polyether polyol, or a polyester polyol. Polyaddition reaction of a diol compound such as a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group A urethane resin, a terminal carboxyl group-containing urethane resin obtained by reacting a terminal of the urethane 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)acryloyl groups in a molecule such as a hydroxyalkyl (meth)acrylate is added to the synthesis of the resin of the above (2) or (4), and the terminal is terminated. (Meth)acryloyl carboxylated polyurethane resin.

(6) Adding an isocyanate group and one or more (meth) groups in a molecule such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate in the synthesis of the resin of the above (2) or (4) A carboxyl group-containing urethane resin which is terminally (meth)acrylylated by a compound of an acryl 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 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 A carboxyl group-containing photosensitive resin obtained by adding a hydroxyl group to a dibasic acid anhydride. Here, the 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 resins (1) to (9), a molecule such as glycidyl (meth)acrylate or α-methylglycidyl (meth)acrylate has one epoxy group and one molecule. A carboxyl group-containing photosensitive resin obtained from the above (meth)acryloyl 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.

The acid value of the (A) 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, 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 It is finer than necessary, and the drawing of a normal resist pattern becomes easy. More preferably, it is 45-120 mgKOH/g.

The weight average molecular weight of the (A) 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. Further, in the range of the above weight average molecular weight, the resolution is improved, the developability is good, and the storage stability is improved. 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 is 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 alkyl phenyl ketone ( The alkylphenone is one or more types of photopolymerization initiators in the group consisting of a photopolymerization initiator, an α-aminoacetophenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and a titanocene 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, it is also possible to suitably use two oxime ester groups in the molecule. Photopolymerization initiator. The oxime ester photopolymerization initiator is preferably an oxime ester compound having a carbazole structure.

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-methylphenyl)- 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 acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl). - phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-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.

(B) 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 (A) carboxyl group-containing resin. When the compounding amount is from 0.1 to 25 parts by mass, a cured film having excellent photocurability and resolution, improved adhesion and PCT resistance, and excellent chemical resistance such as electroless gold plating resistance can be obtained. 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 cured film can be suppressed to be severe, and the deep curability can be lowered.

The photocurable thermosetting resin composition may be a photoinitiator or a sensitizer in addition to the photopolymerization initiator. The photopolymerization initiator, the photoinitiation aid, and the sensitizer which can be suitably used in the photocurable thermosetting resin composition are benzoin compounds and acetophenone. A compound, an anthraquinone compound, a thioxanthone 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 (A) 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 Polyacrylates such as acrylates, bisphenol A diacrylates, and ethylene oxide adducts or propylene oxide adducts of these phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, three a polyacrylate of glycidyl ether such as methylolpropane triglycidyl ether or triglycidyl isocyanurate; and 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 Acrylate, etc., and/or each of the above-mentioned acrylates Acrylates and the like.

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-acryloyloxydiethoxyphenyl)propane, 2,2-bis-(4-acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-acryloyloxyl 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.

(C) The compounding amount of the photosensitive monomer 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 (A) carboxyl group-containing resin. It is preferred. When it is set as the said compounding quantity, the photocurability improves, pattern formation becomes easy, and the intensity|strength of a cured film can also improve.

As the (D) thermosetting component, a blocked isocyanate compound, an amino 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 well-known thermosetting resin such as a functional 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 having two or more 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 oxetane in the molecule. a compound of the group, that is, a polyfunctional oxetane compound (D-2); a compound having two or more thioether groups in the molecule, that is, an episulfide resin (D-3) Wait.

Examples of the polyfunctional epoxy compound (D-1) include jER828, jER834, jER1001, and jER1004 manufactured by Nippon Epoxy Resin Co., Ltd., EPICLON840, EPICLON850, EPICLON1050, and EPICLON2055 manufactured by Dainippon Ink and Chemicals, Inc. EPOTOHTO YD-011, YD-013, YD-127, YD-128 manufactured by Tohto Kasei Co., Ltd., DER317, DER331, DER661, DER664 manufactured by The Dow Chemical Company, and Araldite 6071 of Ciba Specialty Chemicals Inc. Aricite6084, Araldite DY250, Araldite DY260, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., AER330, AER331, AER661, AER manufactured by Asahi Kasei Kogyo Co., Ltd. 664 (all are brand names) bisphenol A type epoxy resin; jERYL903 manufactured by Japan Epoxy Resin Co., Ltd., EPICLON 152, EPICLON 165 manufactured by Dainippon Ink and Chemicals Co., Ltd., and ETOPOHTO YDB-400 manufactured by Toshiro Kasei Co., Ltd. , YDB-500, DER542 manufactured by The Dow Chemical Company, Araldite 8011 manufactured by Ciba Specialty Chemicals Inc. Sumi-epoxy ESB-400, ESB-700 manufactured by Chemical Industry Co., Ltd., AER711 and AER714 manufactured by Asahi Kasei Kogyo Co., Ltd. (both trade names) brominated epoxy resin; jER152 manufactured by Japan Epoxy Resin Co., Ltd. , jER154, DEN431, DEN438 manufactured by The Dow Chemical Co., Ltd., EPICLONN-730, EPICLONN-770, EPICLONN-865 manufactured by Dainippon Ink and Chemicals Co., Ltd., EPOOTOTO YDCN-701, YDCN- manufactured by Tosho Kasei Co., Ltd. 704, Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307 manufactured by Ciba Specialty Chemicals Inc., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. 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., and EPOOTOY YDF-170 manufactured by Toshiro Kasei Co., Ltd. YDF-175, YDF-2004, Araldite XPY306 (all are trade names) bisphenol F type epoxy resin manufactured by Ciba Specialty Chemicals Inc.; EPOTOHTO ST-2004, ST-2007, ST- manufactured by Tohto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as 3000 (trade name); 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., Sumitomo Chemical Industry Co., Ltd. Sumi-epoxy ELM-120 (all trade name) Glycidylamine type epoxy resin manufactured by Nippon Co., Ltd.; and hydantoin type epoxy resin such as Araldite CY-350 (trade name) manufactured by Ciba Specialty Chemicals Inc.; CELLOXIDE 2021 manufactured by Daicel Chemical Industry Co., Ltd., Araldite CY175, CY179 (all are trade names) alicyclic epoxy resin manufactured by Ciba Specialty Chemicals Inc.; YL-933 manufactured by Japan Epoxy Resin Co., Ltd., Dow Chemical TEN, EPPN-501, EPPN-502, etc. (all trade names) manufactured by the company, trishydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, YL-6121 manufactured by Japan Epoxy Resin Co., Ltd. Ethyl xylenol type or biphenol type epoxy resin (all of which are trade names) or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., Dainippon Ink Chemistry Bisphenol S type epoxy resin such as EXA-1514 (trade name) manufactured by Industrial Co., Ltd.; bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Nippon Epoxy Resin Co., Ltd.; JERYL-931 manufactured by the company, Araldite 163 manufactured by Ciba Specialty Chemicals Inc. (all are trade names), tetrahydroxyphenylethane type epoxy resin; Araldite PT810 manufactured by Ciba Specialty Chemicals Inc., manufactured by Nissan Chemical Industries Co., Ltd. a heterocyclic epoxy resin such as TEPIC (trade name); a diglycidyl phthalate resin such as BLEMMER DDT manufactured by Nippon Oil & Fats Co., Ltd.; and a tetraglycidyl group such as ZX-1063 manufactured by Toshiro Kasei Co., Ltd. Tetraglycidyl xylenoyl ethane resin; ESN-190, ESN-360, manufactured by Dainippon Ink Chemical Co., Ltd., manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene-based epoxy resin such as HP-4032, EXA-4750, and EXA-4700; epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink and Chemicals Co., Ltd.; Made by the club CP-50S, CP-50M and other glycidyl methacrylate copolymer epoxy resin; further copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy modified polybutadiene A rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), a CTBN-modified epoxy resin (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd., etc.), and the like, 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) may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether or 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)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate , (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, oligomers or copolymers thereof, etc. Polyfunctional oxetane, and oxetane with novolac resin, poly(p-hydroxystyrene), Cardo type bisphenol, calixarene, resorcinol calixarene, or half An etherified product of a resin having a hydroxyl group such as siloxane. Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate may, for example, be mentioned.

Examples of the cyclosulfide resin (D-3) having two or more cyclic thioether groups in the above-mentioned molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Nippon Epoxy Resin Co., Ltd., and Dongdu Chemical Co., Ltd. YSLV-120TE manufactured by the club. 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.

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 preferably from 0.6 to 1 equivalent per 1 equivalent of the carboxyl group of the carboxyl group-containing resin. 2.5 equivalents, more preferably in the range of 0.8 to 2.0 equivalents. When the compounding amount of the thermosetting component is within the above range, The heat resistance, alkali resistance, electrical insulation properties, strength of the cured film, and the like are good.

(E) Hollow filler means a filler which is internally hollow. The average particle diameter d50 of the hollow filler is preferably from 1 μm to 110 μm, and more preferably from 10 μm to 100 μm.

The hollow filler may be any as long as it has a cavity inside, and is preferably hollow glass or hollow silica.

Specific examples of the hollow glass include Glass Bubbles K1, K15, K20, S22, K25, K37, S38, VS5500, S42XHS, K46, iM16K, S60J, S60HS, iM30K, and Potters-Ballotini Co. manufactured by Sumitomo 3M Limited. Sphericel 110P8, 60P18, 34P30, 25P45, Q-CEL 5020, 5020FPS, 7014, 7040S, Ceramic Multi Cellular CMC-20, CMC-15L, Extendospheres SG, etc. manufactured by Ltd., Ltd. Specific examples of the hollow silica include Treatrear 1110 manufactured by JGC C&C.

The hollow filler may be used alone or in combination of two or more.

The amount of the hollow filler (E) is preferably 200 parts by mass or less, more preferably 20 to 150 parts by mass, even more preferably 30 to 130 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin. (E) When the compounding amount of the hollow filler is 200 parts by mass or less, a cured product having good printability and high strength can be obtained.

Further, the photocurable thermosetting resin composition of the present invention can be used (F) as a binder polymer in order to improve the dryness of the touch, improve the handleability, and the like. For example, a polyester-based polymer, a urethane-based polymer, a polyester urethane-based polymer, a polyamide-based polymer, a polyester amide-based polymer, an acrylic polymer, a cellulose-based polymer, or a polylactic acid can be used. A polymer, a phenoxy polymer, or the like. 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 elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyester amide elastomer, an acrylic elastomer, or an olefin elastomer can be used. In addition, it is also possible to use a skeleton having various skeletons. A resin obtained by modifying a part or all of the epoxy group of the epoxy resin with a carboxylic acid-modified butadiene-acrylonitrile rubber having two terminals. Further, an epoxy group-containing polybutadiene-based elastomer, an acryl-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 for the purpose of (A) synthesis of a carboxyl group-containing resin, preparation of a composition, or application of a viscosity to adjust a coating on 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). a radical scavenger (G-1) or/and (2) which can deactivate the generated radicals, which can decompose the generated peroxide into a harmless substance and a peroxide which does not generate new radicals. Antioxidant (G) such as agent (G-2).

Examples of the specific antioxidant of the antioxidant (G-1) which functions as a radical scavenger include hydroquinone, 4-tert-butylcatechol, 2-tert-butylhydroquinone, hydroquinone monomethyl ether, and 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-uncle Butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-three Phenolic, p-methoxyphenol (methoquinone) such as (3',5'-di-tert-butyl-4-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione An anthraquinone compound such as benzoquinone, an amine compound such as bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate or phenothiazine, or the like.

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), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 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), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), and Sumilizer TPS. (manufactured by Sumitomo Chemical Co., Ltd., trade name).

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.

Examples of the ultraviolet absorber include a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, and anthranilic acid. An acid ester derivative, a dibenzoylmethane derivative or the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-di. Hydroxyl Base 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 hydroxyphenyltriazine and bis-ethylhexyloxyphenol methoxyphenyltriazine.

The ultraviolet absorber 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, TINUVIN 405, and TINUVIN 460. TINUVIN 479 (above, manufactured by Ciba Specialty Chemicals Inc., trade name) and the like.

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

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 mercaptothiazole can be used as the chain transfer agent. Wait. Specific examples of the chain transfer agent include chain transfer agents having a carboxyl group such as mercapto succinic acid, thioglycolic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, a chain transfer agent having a hydroxyl group such as mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxythiophenol, and derivatives thereof; 1-butyl mercaptan, butyl 3-mercaptopropionate, 3- Methyl mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethanethiol, 4-methylthiophenol, dodecyl mercaptan, propanethiol, butyl mercaptan, pentane Mercaptan, 1-octyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, thioglycerol, 4,4-thiobisthiophenol, and the like.

Further, a polyfunctional thiol-based compound can be used, and it is not particularly limited, and for example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercapto diethyl ether, and dimercaptodiethyl can be used. Aromatic thiols such as aliphatic thiols such as thioethers, xylylenethiol, 4,4'-dimercaptodiphenyl sulfide, and 1,4-benzenedithiol; ethylene glycol bis(indenyl) Acetate), polyethylene glycol bis(mercaptoacetate), propylene glycol bis(mercaptoacetate), glycerol tris(mercaptoacetate), trimethylolethane tris(mercaptoacetate), three Poly(mercaptoacetate) of polyhydric alcohols such as methylolpropane tris(mercaptoacetate), pentaerythritol tetrakis(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 Polyhydric alcohols such as mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), etc. - mercaptopropionate; 1,4-bis(3-mercaptobutyryloxy)butane, 1,3 ,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptobutyrate) And more (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-butyrolactam, N-methoxy- 2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-indenyl- 4-butyrolactam, N-(2-methoxy)ethyl-2-indolyl-4-butyrolactam, N-(2-ethoxy)ethyl-2-indolyl-4-butyrolactam, 2-mercapto-5-valerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N-(2-methoxy)ethyl-2-mercapto-5-valerolactam, N-(2-ethoxy)ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole , 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-caprolactam, 2,4,6-trimethyl-s-triazine (tri- co-formation Manufactured by the company: 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 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, aminobenzotriazole-containing, silane coupling agent, and the like.

In the photocurable thermosetting resin composition of the present invention, when a thermosetting component having two or more cyclic (thio)ether groups in the above molecule is used, it is preferred to contain a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1- Imidazole derivatives such as cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine An amine compound such as an adipic compound, adipic acid dihydrazide or azelaic acid dihydrazide; a phosphorus compound such as triphenylphosphine or the like. In addition, as a commercial item, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (trade name of all imidazole type compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U manufactured by San-Apro Ltd. -CAT (registered trademark) 3503N, U-CAT3502T (both trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic guanidine compounds and their salts) and the like. In particular, it is not limited thereto, and may be a thermosetting catalyst of an epoxy resin or an oxetane compound or a substance which promotes a reaction between an epoxy group and/or an oxetanyl group and a carboxyl group, and may be used alone. Use or mix two or more types. In addition, guanamine, methyl decylamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, 2-vinyl-2,4 can also be used. -diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl- A s-triazine derivative such as a s-triazine-isocyanuric acid addition product, and a compound which functions as an adhesion-imparting agent is preferably used in combination with the above-mentioned thermosetting catalyst.

The ratio of the amount of the thermosetting catalyst to the usual amount is sufficient. For example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, based on the (A) carboxyl group-containing resin.

In the photocurable thermosetting resin composition of the present invention, a filler other than hollow silica can be blended in a range that does not adversely affect the properties. As such a filler, a conventionally known inorganic or organic filler can be used, and barium sulfate, spherical silica, 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 photocurable thermosetting resin composition of the present invention may further contain a thixotropic agent such as fine powder silica, 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 silicone-based, a fluorine-based or a polymer-based polymer, and/or a leveling agent, a silane coupling agent such as an imidazole-based compound, a thiazole-based or a triazole-based compound, and a coloring agent 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 '- Methylene bis(4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, reaction product of copper and organic chelating agent, water yang a methyl ester, 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 the coating method by using the organic solvent, for example, by a dip coating method, a flow coating method, a roll coating method, a bar coating method, or a screen printing method. A method such as a curtain coating method is applied to a substrate, and the organic solvent contained in the composition is volatilized (temporarily dried) at a temperature of about 60 to 100 ° C to form a non-stick dry coating film. 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 by ~3% aqueous sodium carbonate solution to form a resist pattern. Further, the thermosetting component is heated to a temperature of, for example, about 130 to 180 ° C to be thermally cured, whereby (A) the carboxyl group-containing resin reacts with the thermosetting component to form heat resistance, chemical resistance, and moisture absorption resistance. A cured 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 on 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-polyimide, glass cloth/non-woven fabric, epoxy resin, glass cloth/paper-ring A copper-clad laminate of all grades (FR-4, etc.) of a composite material such as an oxygen resin, a synthetic fiber-epoxy resin, a fluororesin, a polyethylene, a PPO, or a cyanate.

The volatilization drying which is carried out after applying the photocurable thermosetting resin composition of the present invention can be carried out by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a device having a heat source using an air heating method using steam). The hot air convection contact method in the dryer 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). Exposure of the film (by active energy ray The irradiated portion is cured.

As the exposure machine used for the active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device that directly draws an image by laser based on CAD data from a computer) or an exposure machine equipped with a metal halide lamp can be used ( An ultra-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 silicate, or ammonia can be used. An aqueous alkali solution such as an amine.

The photocurable thermosetting resin composition of the present invention may have a photocurable heat on a film having a polyethylene terephthalate or the like in addition to a method of directly applying a liquid to a substrate. The curable resin composition is applied in the form of a dry film of a resin layer formed by drying and 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 and drying the photocurable thermosetting resin composition of the present invention on a carrier film or a cover film. 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, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm can be used.

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 lower adhesive force to the resin layer than the carrier film and the resin layer can be used.

A cured film is formed on a printed circuit board 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 the circuit is formed. A resin layer. When the formed resin layer is exposed, developed, and cured in the same manner as described above, a cured film can be formed. The carrier film may be peeled off before or after exposure.

The photocurable thermosetting resin composition of the present invention is used to form a cured film on a printed circuit board. As the cured film, a development type permanent insulating film is preferable, and a development type solder resist layer or a cover layer is particularly preferable. In addition, the photocurable thermosetting resin composition of the present invention can also be used as an interlayer insulating material, a hole-filling filler, and a material for forming a solder dam.

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

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 number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone, 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, and after cooling. 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 called a carboxyl group-containing resin *1.

Synthesis Example 2

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 *4.

Synthesis Example 3

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, it 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 an epoxy of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. Propane reaction solution. It is a product in which an average of 1.08 moles of alkylene oxide is added per one equivalent of the phenolic hydroxyl group.

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. The water formed by the reaction distilled off 12.6 g of water 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 added. The mixture was placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min. While stirring, 60.8 g of tetrahydrophthalic anhydride was slowly added thereto, and the mixture was allowed to pass at 95 to 101 ° C. Reaction 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 called a carboxyl group-containing resin *5.

According to the various components shown in the following Table 1 and the ratios (mass parts) shown in Tables 1 and 2, the mixture was premixed with a stirrer, and then kneaded by a three-roll mill to prepare photocurable heat. A curable resin composition. In addition, the average particle diameter d50 of the hollow filler is a value measured by the laser diffraction scattering particle size distribution measuring apparatus (MICROTRACK MT3200II manufactured by Nikkiso Co., Ltd.).

Table 1

Table 2

	Example 15	Example 16	Example 17	Example 18	Example 19	Example 20	Example 21	Example 22	Comparative example 1	Comparative example 2
											Carboxyl group containing resin*1	154.0	154.0	154.0	154.0	154.0	154.0	154.0	154.0	154.0	154.0
Carboxyl group containing resin*2
											Carboxyl group containing resin*3
Carboxyl group containing resin*4
											Carboxyl group containing resin*5
Photopolymerization initiator*6	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
											Photopolymerization initiator*7
Photosensitive monomer *8	20.0	20.0	20.0	20.0	20.0	20.0	20.0	20.0	20.0	20.0
											Photosensitive monomer *9
Thermosetting component*10	44.0		22.0	22.0	22.0	22.0	22.0	22.0	22.0	22.0
											Thermosetting component*11		44.0	22.0	22.0	22.0	22.0	22.0	22.0	22.0	22.0
Heat curing catalyst *12	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
											Colorant*13	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3	0.3
Colorant*14	0.7	0.7	0.7	0.7	0.7	0.7	0.7	0.7	0.7	0.7
											Filler*15	70.0	70.0				35.0	35.0	35.0
Filler*16			70.0			35.0
											Filler*17				70.0			35.0
Filler*18					140.0			70.0
											Filler*19									70.0
Filler*20										70.0
											Antioxidant*21	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1	0.1
Defoamer*22	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0
											Organic solvent*23	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
∑	305.1	305.1	305.1	305.1	375.1	305.1	305.1	340.1	305.1	305.1

*1: Carboxyl group-containing resin starting from epoxy resin, cresol novolac type, solid content 65%, acid value 80 mgKOH/g

*2: carboxyl group-containing resin starting from epoxy resin, ZFR-1401H, bisphenol F type manufactured by Nippon Kayaku Co., Ltd., solid content 60%, acid value 100 mgKOH/g

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

*4: Carboxyl group-containing polyurethane resin, solid content 50%, acid value 47 mgKOH/g

*5: Carboxyl group-containing resin starting from a phenol compound, solid content 71%, acid value 88 mgKOH/g

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

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

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

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

*10: Thermosetting component, EPICLON N-660 manufactured by DIC Corporation, cresol novolak type epoxy resin, epoxy equivalent 202-212g/eq

*11: Thermosetting component, jER828 manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A epoxy resin, epoxy equivalent 184-194 g/eq

*12: heat curing catalyst, DCDA, dicyandiamide

*13: Colorant, C.I. Pigment Blue 15:3

*14: Colorant, C.I. Pigment Yellow147

*15: Hollow filler, Glass Bubbles iM30K manufactured by Sumitomo 3M Limited, insulating glass, average particle size 16 μm

*16: Hollow filler, Glass Bubbles K1 manufactured by Sumitomo 3M Limited, insulating glass, average particle size 65 μm

*17: Hollow filler, Extendospheres TG manufactured by Potters-Ballotini Co., Ltd., hollow glass, average particle size 95 μm

*18: hollow filler, manufactured by JGC C&C. Thorrerear 1110, hollow silica solid content 20 wt% isopropyl alcohol dispersion, hollow silica, average particle size 55 nm

*19: Non-hollow filler, B-30 manufactured by Suga Chemical Co., Ltd., barium sulfate, average particle diameter 0.3 μm

*20: Non-hollow filler, Crystalite 3K, manufactured by Ronson Co., Ltd., silica, average particle size 34.4 μm

*21: Antioxidant, IRGANOX 1010 manufactured by BASF Corporation, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]

*22: Defoamer, FLOWLEN AC-902 manufactured by Kyoeisha Chemical Co., Ltd., silicone defoamer

*23: Solvent, dipropylene glycol monomethyl ether

<sensitivity>

The photocurable thermosetting resin composition for producing a printed circuit board described in Tables 1 and 2 was applied by a screen printing method to a circuit having a copper thickness of 35 μm which was washed and dried after polishing. The pattern substrate was dried in a hot air circulating drying oven at 80 ° C for 30 minutes. Then, ultraviolet light having a wavelength of 365 nm was irradiated with a light amount of 400 mJ/cm ² through a photomask, which was manufactured by ORC MANUFACTURING CO., LTD., as a test piece, and a developing solution (carbonic acid) having a pressure of 2 kg/cm ^{2 was used} . The sodium aqueous solution was developed for 60 seconds, and then the number of stages of the residual coating film was visually determined. The photomask used was a stage exposure meter No. 2 manufactured by Eastman Kodak Company.

<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 swelling and peeling of the resist layer was visually evaluated. The judgment criteria are as follows.

◎: No peeling was observed even if the dipping was repeated 4 times or more for 10 seconds.

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

△: slightly exfoliated when repeated for 10 times and 10 seconds of immersion

×: There is swelling and exfoliation of the cured film when it is immersed for 10 seconds within 2 times.

<Dielectric constant Dk>

The measurement was carried out in accordance with JIS K6911.

○: below 2.5

△: 2.5 or more and less than 3.0

×: 3.0 or more

table 3

Table 4

	Example 15	Example 16	Example 17	Example 18	Example 19	Example 20	Example 21	Example 22	Comparative example 1	Comparative example 2
											Sensitivity	10	10	10	10	10	10	10	10	6	6
Resistance to soldering heat	◎	◎	◎	◎	◎	◎	◎	◎	○	○
											Dielectric constant	○	○	○	○	○	○	○	○	×	×

As is apparent from Tables 3 and 4, the photocurable thermosetting resin composition of the present invention can form a cured product having a low dielectric constant, and has high sensitivity and excellent soldering heat resistance, so that it can be suitably used for formation. A composition of a solder resist is used.

Claims (6)

1. A photocurable thermosetting resin composition for producing a printed circuit board, comprising:

   (A) a carboxyl group-containing resin;

   (B) a photopolymerization initiator;

   (C) a photosensitive monomer;

   (D) a thermosetting component;

   (E) Hollow filler.
2. The photocurable thermosetting resin composition for producing a printed wiring board according to claim 1, wherein the (E) hollow filler has an average particle diameter d50 of from 1 μm to 110 μm.
3. The photocurable thermosetting resin composition for producing a printed circuit board according to claim 1 or 2, wherein the (E) hollow filler is hollow glass or hollow silica.
4. A dry film for producing a printed circuit board, which is obtained by applying the photocurable thermosetting resin composition for producing a printed wiring board according to any one of claims 1 to 3 to a carrier film. Dried out.
5. A cured product of the photocurable thermosetting resin composition for producing a printed circuit board according to any one of claims 1 to 3, or the printed circuit for manufacturing the same according to claim 4. The dry film of the board is obtained by photocuring and heat curing.
6. A printed circuit board having the cured product of claim 5.