WO2016015398A1 - Light-cured thermosetting resin composition, dry film, cured material, and printed circuit board - Google Patents

Abstract

A light-cured thermosetting resin composition, a dry film, a cured material, and a printed circuit board. The light-cured thermosetting resin composition comprises: (A) a carboxyl-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, (D) a thermosetting component, and (E) titanium oxide. The (A) carboxyl-containing resin comprises (A-1) a bisphenol-type carboxyl-containing resin and (A-2) a novolac-type carboxyl-containing resin, wherein the mass ratio of the (A-1) bisphenol-type carboxyl-containing resin to the (A-2) novolac-type carboxyl-containing resin (the (A-1) bisphenol-type carboxyl-containing resin:the (A-2) novolac-type carboxyl-containing resin) is in the range of 20:80-60:40.

Description

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

The present invention relates to a photocurable thermosetting resin composition which is soluble in an aqueous alkali solution, a dry film and a cured product thereof, and a printed circuit board having a cured product formed using the same. More specifically, the present invention relates to a resin composition capable of forming a cured product having light reflectivity and applied to a substrate to form a printed wiring board, a dry film thereof, and a cured product obtained by curing the cured product, and A printed circuit board that functions as a reflector such as an LED or an EL having the cured product.

Background technique

In recent years, in backlights of liquid crystal displays such as lighting devices, mobile terminals, personal computers, and televisions, light-emitting diodes (LEDs) and electroluminescence (EL) have been used as light sources. Further, in order to effectively utilize the light emitted from these light sources, a reflector having light reflectivity is used. The reflector is a reflector that is light-reflective on the substrate itself, and a resin composition having light reflectivity is applied onto the substrate, and is cured by light or the like to form a cured product. (Piece, etc.), thus made a reflector (see Japanese Patent Laid-Open 2011-017010).

The resin composition used in such use usually uses titanium oxide as an inorganic filler. Further, in order to increase the reflectance, a method of making the content of titanium oxide as large as possible is employed. However, when the content of titanium oxide is increased as described above, there is a problem that the toughness of the cured coating film obtained from the resin composition is lowered and cracks are generated. On the other hand, for example, the curable resin composition for a solder resist needs to satisfy the solder heat resistance.

Summary of the invention

Problems to be solved by the invention

Accordingly, it is an object of the present invention to provide a case where the content of titanium oxide is large. A photocurable thermosetting resin composition, a dry film and a cured product thereof, and a printed circuit board having a cured product formed using the cured product, which suppress crack generation without lowering solder heat resistance.

Solution to solve the problem

In order to solve the above problems, the inventors conducted intensive studies. First, in order to eliminate cracks, it is considered to use a carboxyl group-containing resin having a bisphenol skeleton as a soft skeleton. However, since the bisphenol type carboxyl group-containing resin is not high in heat resistance, the solder heat resistance of the cured coating film is lowered. On the other hand, the novolac type carboxyl group-containing resin has high solder heat resistance, but lacks flexibility, and cannot suppress crack generation.

Thus, the present inventors have found that by uniformly compounding a bisphenol type carboxyl group-containing resin and a novolak type carboxyl group-containing resin, it is possible to suppress crack generation without lowering solder heat resistance even when the content of titanium oxide is large. Cured product.

That is, the present invention is a photocurable thermosetting resin composition comprising: (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) a photosensitive monomer, and (D) heat. The curable component, (E) titanium oxide, the (A) carboxyl group-containing resin comprises (A-1) a bisphenol type carboxyl group-containing resin and (A-2) a novolak type carboxyl group-containing resin, and the (A-1) bisphenol The mass ratio of the carboxyl group-containing resin to the (A-2) novolac type carboxyl group-containing resin, that is, the (A-1) bisphenol type carboxyl group-containing resin/the (A-2) novolac type carboxyl group-containing resin is 20/ Range of 80 to 60/40.

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

Further, the present invention is a cured product obtained by photocuring and thermally curing the photocurable thermosetting resin composition or the dry film.

Further, the present invention is a printed circuit board having the aforementioned cured product.

Effect of the invention

According to the present invention, even when the content of the titanium oxide is large, a cured product capable of suppressing generation of cracks without lowering the heat resistance to soldering can be obtained. The printed circuit board with cured product of the invention can also Used as a reflector.

detailed description

The present invention is characterized in that it contains photocuring of (A) carboxyl group-containing resin, (B) photopolymerization initiator, (C) photosensitive monomer, (D) thermosetting component, and (E) titanium oxide. In the thermosetting resin composition, the (A) carboxyl group-containing resin comprises (A-1) a bisphenol type carboxyl group-containing resin and (A-2) a novolac type carboxyl group-containing resin, and the (A-1) bisphenol type is contained. The mass ratio of the carboxyl resin to the (A-2) novolak type carboxyl group-containing resin (the (A-1) bisphenol type carboxyl group-containing resin / the (A-2) novolak type carboxyl group-containing resin) is 20/80 to The range of 60/40.

In the present invention, since the mass ratio of the (A-1) bisphenol type carboxyl group-containing resin to the (A-2) novolak type carboxyl group-containing resin is set to a specific range, even if the content of (E) titanium oxide is large In the case of the crack, the generation of cracks can be suppressed, and the welding heat resistance is excellent. Further, since the photocurable thermosetting resin composition of the present invention can have a large content of (E) titanium oxide, a white cured coating film having high reflectance can be obtained. Here, the reflectance of the cured coating film is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more.

In the photocurable thermosetting resin composition of the present invention, the (A-1) bisphenol type carboxyl group-containing resin and the (A-2) novolak type carboxyl group-containing resin can be used in the molecule for imparting alkali developability. A well-known resin of a carboxyl group. 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. Specific examples are shown below.

Examples of the (A-1) bisphenol type carboxyl group-containing resin include:

(A-1-1) 2-functional epoxy resin such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and (methyl) a carboxyl group-containing photosensitive resin obtained by reacting acrylic acid and adding a polybasic acid anhydride to the produced hydroxyl group;

(A-1-2) The hydroxy group of the above-mentioned bifunctional epoxy resin is further epoxidized with epichlorohydrin a carboxyl group-containing photosensitive resin obtained by reacting a functional epoxy resin with (meth)acrylic acid and adding a polybasic acid anhydride to the produced hydroxyl group;

(A-1-3) Further adding the resin of the above (A-1-1) or (A-1-2) to glycidyl (meth)acrylate or α-methylglycidyl (meth)acrylate A carboxyl group-containing photosensitive resin obtained by a compound having one epoxy group and one or more (meth)acryloyl groups in the molecule.

Examples of the (A-2) novolac type carboxyl group-containing resin include:

(A-2-1) A phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A cresol novolak type epoxy resin, a dicyclopentadiene cresol novolac type epoxy resin, etc. The polyfunctional epoxy resin reacts with (meth)acrylic acid to add a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the hydroxyl group present in the side chain. Carboxyl group-containing photosensitive resin;

(A-2-2) A polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of the above polyfunctional epoxy resin with epichlorohydrin is reacted with (meth)acrylic acid to form a polyhydroxy acid anhydride to form a hydroxyl group. And the obtained carboxyl group-containing photosensitive resin;

(A-2-3) 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 resin, and the obtained hydroxyl group is a partial ester of (meth)acrylate. a carboxyl group-containing photosensitive resin obtained by reacting a remaining hydroxyl group with a polybasic acid anhydride;

(A-2-4) Further adding (meth)acrylic acid glycidyl ester or (meth)acrylic acid α-methyl shrinkage to any of the above resins (A-2-1) to (A-2-3) A carboxyl group-containing photosensitive resin obtained by a compound having one epoxy group and one or more (meth)acryloyl groups in a molecule such as a glyceride.

Here, the cresol novolac type carboxyl group-containing resin is preferable because it is superior in solder heat resistance to the phenol novolac type carboxyl group-containing resin.

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 is utilized because it has a large amount of free carboxyl groups in the side chain of the main chain polymer. Development of an 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 coating 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 fine. Above the necessary level, the drawing of the 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 moisture resistance of the coating film after the exposure is good, 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.

(A-1) Mass ratio of bisphenol type carboxyl group-containing resin to (A-2) novolak type carboxyl group-containing resin ((A-1) bisphenol type carboxyl group-containing resin / (A-2) novolak type carboxyl group-containing resin ) is in the range of 20/80 to 60/40.

When the compounding ratio of the bisphenol-type carboxyl group-containing resin is less than 20% by mass, the crack resistance is lowered, which is not preferable. On the other hand, when it exceeds 60% by mass, the solder heat resistance is lowered, which is not preferable.

The mass ratio of the (A-1) bisphenol type carboxyl group-containing resin to the (A-2) novolak type carboxyl group-containing resin is preferably 30/70 to 60/40, particularly preferably 30/70 to 50/50.

When the total amount of the (A) carboxyl group-containing resin is 100 parts by mass, the total amount of the (A-1) bisphenol type carboxyl group-containing resin and the (A-2) novolak type carboxyl group-containing resin is 40 to 100 parts by mass, more preferably 50 to 100 parts by mass. When the total amount of the bisphenol-type carboxyl group-containing resin and the (A-2) novolac type carboxyl group-containing resin is 40 parts by mass or more, the solder heat resistance and the crack resistance are good. In addition, the content rate of the (A) carboxyl group-containing resin in the photocurable resin composition is not particularly limited.

In addition, the (A) carboxyl group-containing resin may contain a (A-1) bisphenol type carboxyl group-containing resin and (A-2) novolak type carboxyl group-containing resin in a range that does not inhibit the curing of the present invention. Resin. For example, the (A) carboxyl group-containing resin may further contain a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid and an unsaturated group-containing compound, a carboxyl group-containing urethane resin obtained by reacting a diisocyanate with a diol compound, or the like.

(B) which can be suitably used in the photocurable thermosetting resin composition of the present invention As the photopolymerization initiator, an oxime ester-based photopolymerization initiator having an oxime ester group, an alkylphenone-based photopolymerization initiator, and an α-aminoacetophenone-based photopolymerization initiator can be suitably used. One or more kinds of photopolymerization initiators in the group consisting of an acylphosphine oxide-based photopolymerization initiator and a titanocene-based 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-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.

The amount of the photopolymerization initiator to be added 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 0.1 to 25 parts by mass, photocurability and resolution are excellent, and adhesion and PCT resistance are also improved, and electroless gold plating resistance is further obtained. 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 (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, for example, Ethylene Alcohol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, butanediol diacrylate, pentanediol Diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tetramethylolethane triacrylate, tetramethylol methane tetraacrylate And glycerin diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc., 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-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, preferably 10 to 90 parts by mass, more preferably 15 parts by mass to 85 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin. of. When it is set as the said compounding amount, the photocurability improves, pattern formation becomes easy, and the intensity|strength of a cured coating film also improves.

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 many types, and various types can be imparted depending on the structure. Sex.

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. The compound of the group, 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, jER1001, and jER1004 manufactured by Nippon Epoxy Resin Co., Ltd., and EPICLON 840, EPICLON 850, EPICLON 1050, and EPICLON 2055 manufactured by Dainippon Ink and Chemicals, Inc. EPOTOHTO YD-011, YD-013, YD-127, YD-128, manufactured by Dow Chemical Co., Ltd., DER317, DER331, DER661, DER664, manufactured by The Dow Chemical Company, Araldite 6071, Araldite 6084 from Ciba Specialty Chemicals Inc. , Aral 330, AER331, AER661, AER664 manufactured by Asahi Kasei Kogyo Co., Ltd., Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., manufactured by Araldite DY250, Araldite DY260, Sumitomo Chemical Co., Ltd. (e.g., the product name) bisphenol A type epoxy resin; jERYL903 manufactured by Nippon Epoxy Resin Co., Ltd., EPICLON 152, EPICLON 165 manufactured by Dainippon Ink and Chemicals Co., Ltd., and ETOPOHTO YDB-400 manufactured by Tosho Kasei Co., Ltd. YDB-500, DER542 manufactured by The Dow Chemical Company, Araldite 8011 manufactured by Ciba Specialty Chemicals Inc., Sumitomo Sumi-epoxy ESB-400, ESB-700, manufactured by Asahi Kasei Co., Ltd., AER711, AER714, etc. (both trade names) brominated epoxy resin manufactured by Asahi Kasei Kogyo Co., Ltd.; jER152 manufactured by Nippon 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., and EPOTOHTO YDCN-701 and YDCN-704 manufactured by Tosho Kasei Co., Ltd. , Araldite by Ciba Specialty Chemicals Inc. ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN manufactured by Sumitomo Chemical Industries, Ltd. 195X, ESCN-220, AERECN-235, ECN-299, etc. (both trade names) manufactured by Asahi Kasei Kogyo Co., Ltd., and a novolac type epoxy resin; EPICLON 830, Japan Epoxy Resin Co., Ltd. JER807 manufactured by the company, 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, and ST-3000 (trade name) manufactured by Toei Chemical Co., Ltd.; jER604 manufactured by Japan Epoxy Resin Co., Ltd., and EPOOTOTO manufactured by Toshiro Kasei Co., Ltd. YH-434, Araldite MY720 manufactured by Ciba Specialty Chemicals Inc., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all are trade names) glycidylamine type ring Resin; a 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 manufactured by Ciba Specialty Chemicals Inc., etc. All are alicyclic epoxy resins; YL-933 manufactured by Nippon Epoxy Co., Ltd., TEN manufactured by Dow Chemical Co., Ltd., EPPN-501, EPPN-502, etc. (all are trade names) Trihydroxyphenyl Methane type epoxy resin; xylenol type or biphenol type epoxy resin such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Nippon Epoxy Co., Ltd. or a mixture thereof; Japan EBPS-200 manufactured by Kasei Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by Dainippon Ink and Chemicals Co., Ltd.; A bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by the company, jERYL-931 manufactured by Japan Epoxy Resin Co., Ltd., Araldite 163 manufactured by Ciba Specialty Chemicals Inc., etc. (all are trade names) Ethane type epoxy resins; Araldite PT810 Ciba Specialty Chemicals Inc. manufactured by Nissan Chemical Industries, Ltd. of TEPIC (all trade names) heterocyclic epoxy Fatty acid; 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.; Ethylene-based epoxy resin such as HP-4032, EXA-4750, EXA-4700, manufactured by Nippon Steel Chemical Co., Ltd., ESN-190, ESN-360, and Nippon Ink Chemical Industry Co., Ltd.; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 or HP-7200H; a glycidyl methacrylate copolymer epoxy resin such as CP-50S or CP-50M manufactured by Nippon Oil & Fats Co., Ltd.; Copolymerized epoxy resin of maleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Co., Ltd.), CTBN modified ring Oxygen resin (for example, YR-102, YR-450, etc. manufactured by Tosho 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) 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, their oligomers or copolymers, etc. Functional oxetane, and oxetane with novolac resin, poly(p-hydroxystyrene), Cardo type bisphenol, calixarene, resorcinol calixarene, or sesquisilane An etherified product of a resin having a hydroxyl group such as oxyalkylene. 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. are used as the episulfide resin (D-3) having two or more cyclic thioether groups in the molecule. Manufactured YSLV-120TE and the like. In addition, it is also possible to use a similar synthetic method to remove the novolac The epoxy resin in which the oxygen atom of the epoxy group of the epoxy resin is replaced with a sulfur atom or the like.

The amount of the (D) thermosetting component to be added is 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 2.5 equivalents per equivalent of the carboxyl group of the carboxyl group-containing resin (A). More preferably, it is the range of 0.8-2.0 equivalent. When the compounding amount of the thermosetting component is in the above range, the heat resistance and the strength of the cured coating film are good.

As the (E) titanium oxide, titanium oxide by a sulfuric acid method, a chlorine method, a rutile type or an anatase type titanium oxide, and surface treatment using a surface treatment of a hydrated metal oxide or surface treatment with an organic compound can be used. Wait. Among these titanium oxides, rutile-type titanium oxide is more preferable. Anatase type titanium oxide is often used because it has a high whiteness compared to the rutile type. However, since anatase-type titanium oxide has photocatalytic activity, it sometimes causes discoloration of the resin in the photocurable resin composition. On the other hand, although the rutile-type titanium oxide is slightly inferior in whiteness to the anatase type, it has almost no photoactivity, and thus a stable coating film can be obtained.

As the rutile-type titanium oxide, a known rutile-type titanium oxide can be used. Specifically, TR-600, TR-700, TR-750, TR-840 manufactured by FUJI TITANIUM INDUSTRY CO, LTD., R-550, R-580, R-630 manufactured by Ishihara Sangyo Co., Ltd., R-820, CR-50, CR-60, CR-90, CR-97, KR-270, KR-310, KR-380, etc. manufactured by Titan Kogyo, Ltd. Among these rutile-type titanium oxides, titanium oxide treated with surface hydrated alumina or aluminum hydroxide is particularly preferable from the viewpoint of dispersibility, storage stability, and flame retardancy.

The compounding amount of the (E) titanium oxide is preferably 50 to 300 parts by mass, more preferably 150 to 300 parts by mass, even more preferably 200 to 300 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin. When the compounding amount is 50 parts by mass or more, a good reflectance can be obtained. On the other hand, in the case of 300 parts by mass or less, the toughness of the cured coating film is good.

As the (F) heat curing catalyst, an imidazole having a primary average particle diameter of 15 μm or less is preferable. For example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, An imidazole derivative such as 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole. In addition, as a commercial item, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (product name of all imidazole type compounds) manufactured by Shikoku Chemicals Co., Ltd., etc. are mentioned, for example. More preferably, the imidazole having a reaction initiation temperature of 100 ° C or more is used. Further, it may be used alone or in combination of two or more.

The ratio of the amount of the (F) heat-curing 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, per 100 parts by mass of the (A) carboxyl group-containing resin.

In the photocurable thermosetting resin composition of the present invention, a (G) filler other than titanium oxide may be blended as needed in order to increase the physical strength of the coating film and the like. As such a (G) filler, a commonly known inorganic or organic filler can be used, and barium sulfate, spherical silica, and talc are particularly preferably used. Further, in order to obtain flame retardancy, a metal hydroxide such as a metal oxide or aluminum hydroxide may be used as the extender pigment filler. The compounding amount of these (G) fillers is preferably 150 parts by mass or less, more preferably 5 to 100 parts by mass, particularly preferably 10 to 70 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin. When the amount of the filler (G) is 150 parts by mass or less, the viscosity of the composition does not become too high, the printability is good, and the occurrence of deterioration in toughness of the cured product or the like can be suppressed.

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-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 part or all of the epoxy groups of the epoxy resin having various skeletons to be modified with the two-terminal carboxylic acid-modified butadiene-acrylonitrile rubber. A resin or the like. 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 adjustment of viscosity to coat a substrate or a 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 (H-1) or/and (2) which can deactivate the generated radicals, which can decompose the generated peroxide into a harmless substance and a peroxide decomposition which does not generate new radicals. Antioxidant (H) such as agent (H-2).

Examples of the specific antioxidant of the antioxidant (H-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-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1, 3,5- Phenolic, p-methoxyphenol (methoquinone) such as tris(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 (H-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 (H) 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 (I).

Examples of the ultraviolet absorber (I) 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 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. Hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone. Specific as a benzoate derivative Examples thereof include 2-ethylhexyl salicylate, phenyl salicylate, p-tert-butylphenyl salicylate, and 2,4-di-tert-butylphenyl-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 (I) 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 (I) 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 (H). 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 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 compound can be used without particular limitation, and for example, it can be used. Aliphatic thiols such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercapto diethyl ether, dimercapto diethyl sulfide, phthalic thiol, 4, 4 Aromatic thiols such as '-dimercaptodiphenyl sulfide and 1,4-benzenedithiol; ethylene glycol bis(mercaptoacetate), polyethylene glycol bis(mercaptoacetate), propylene glycol double (mercaptoacetate), glycerol tris(mercaptoacetate), trimethylolethane tris(mercaptoacetate), trimethylolpropane tris(mercaptoacetate), pentaerythritol tetrakis(mercaptoacetate) Poly(mercaptoacetate) of polyhydric alcohol such as 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-mercaptopropionate) a poly(3-mercaptopropionate) of a polyol such as pentaerythritol tetrakis(3-mercaptopropionate) or dipentaerythritol hexa(3-mercaptopropionate); 1,4-bis(3-mercaptobutyryl) Oxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol Four (3-巯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-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 (manufactured by Sankyo Chemical Co., Ltd.: trade name ZISNET F), 2 -Dibutylamino-4,6-dimercapto-s-triazine (III Manufactured by Kasei 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.

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, a thiazole-based or a triazole-based compound, or a rust preventive agent may be blended. Further, there are known conventional additives such as a bisphenol-based or triazine-thiol-based anti-copper agent.

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, and phenothiazine, sub a nitro compound, a chelate compound of a nitroso compound and Al, and the like.

(Manufacturing method of printed circuit board)

The printed wiring board of the present invention has a cured product obtained from the photocurable thermosetting resin composition of the present invention on a substrate.

In the method for producing a printed wiring board of the present invention, for example, the photocurable thermosetting resin composition is adjusted to a viscosity suitable for the coating method using the organic solvent, and the photocurable thermosetting resin composition is dip coated. Method, flow coating method, roll coating method, bar coating method, screen printing method, curtain coating method, etc. are applied to a substrate, and the organic solvent contained in the composition is volatilized at a temperature of about 60 to 100 ° C. Dry (temporary drying) to form a non-stick 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. Then, it is heated to a temperature of, for example, about 140 to 180 ° C to be thermally cured, thereby reacting the (A) carboxyl group-containing resin with the (D) thermosetting component to obtain heat resistance, chemical resistance, and moisture absorption resistance. A printed circuit board of a cured coating film having excellent 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.

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.

(dry film)

The photocurable thermosetting resin composition of the present invention may be used in the form of a dry film in addition to a method of directly applying a liquid to a substrate, the dry film having a polyethylene terephthalate in advance. A resin layer formed by applying a photocurable thermosetting resin composition to a film such as a glycol ester and drying it. The case where the photocurable thermosetting resin composition of the present invention is used as a dry film is shown below.

The dry film has a structure in which a 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 a photocurable thermosetting resin composition 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 coating 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 coating 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 suitably used for forming a cured coating film on a printed circuit board. The cured coating film is preferably a permanent insulating coating film, and particularly preferably a solder resist layer or a coating layer. Further, the photocurable thermosetting resin composition of the present invention can also be used as an interlayer insulating material, a buried via filler, and a solder dam forming material.

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 was taken as (A) carboxyl group-containing resin *3.

Synthesis Example 2

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 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 with 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 *5.

Synthesis Example 3

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 *7.

According to the various components shown in Tables 1 and 2 below and the ratios (parts by mass) shown in Tables 1 and 2, compounded by a mixer, and then kneaded by a three-roll mill to prepare photocuring. A thermosetting resin composition. In addition, the compounding ratio (parts by mass) of the carboxyl group-containing resin is expressed in terms of solid content.

Table 1

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7	Example 8	Example 9	Example 10	Example 11
												(A-1) Carboxyl group-containing resin*1	40.0	40.0	40.0	20.0	60.0		20.0	40.0	20.0	20.0	20.0
(A-1) Carboxyl group-containing resin*2						40.0	20.0
												(A-2) Carboxyl group-containing resin*3	60.0			80.0	40.0	60.0	60.0	30.0	30.0	30.0	20.0
(A-2) Carboxyl group-containing resin *4		60.0						30.0
												(A-2) Carboxyl group-containing resin*5			60.0
(A-3) Carboxyl group-containing resin *6									50.0		60.0
												(A-3) Carboxyl group-containing resin*7										50.0
Photopolymerization initiator*8	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
												Photopolymerization initiator*9	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
Photosensitive monomer *10	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
												Photosensitive monomer*11	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
Thermosetting component*12	28.0	28.0	28.0	28.0	28.0	28.0	28.0	28.0	28.0	28.0	28.0
												Thermosetting component*13	25.0	25.0	25.0	25.0	25.0	25.0	25.0	25.0	25.0	25.0	25.0
Titanium oxide*14	250.0	250.0	250.0	250.0	250.0	250.0	250.0	250.0	250.0	250.0	250.0
												Titanium oxide*15
Filler*16	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
												Filler*17	30.0	30.0	30.0	30.0	30.0	30.0	30.0	30.0	30.0	30.0	30.0
Antioxidant*18	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0
												Defoamer*19	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
Dispersant*20	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
												Organic solvent*21	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
∑	501.0	501.0	501.0	501.0	501..0	501.0	501.0	501.0	501.0	501.0	501.0

Table 2

	Example 12	Example 13	Example 14	Example 15	Example 16	Example 17	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
											(A-1) Carboxyl group-containing resin*1	40.0	40.0	30.0	40.0	40.0	40.0	10.0	70.0	40.0	40.0
(A-1) Carboxyl group-containing resin*2
											(A-2) Carboxyl group-containing resin*3	30.0		70.0	60.0	60.0	60.0	90.0	30.0	60.0
(A-2) Carboxyl group-containing resin *4		30.0
											(A-2) Carboxyl group-containing resin*5	30.0	30.0
(A-3) Carboxyl group-containing resin *6										60
											(A-3) Carboxyl group-containing resin*7
Photopolymerization initiator*8	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
											Photopolymerization initiator*9	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
Photosensitive monomer *10	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
											Photosensitive monomer*11	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
Thermosetting component*12	28.0	28.0	28.0	28.0	28.0	28.0	28.0	28.0	28.0	28.0
											Thermosetting component*13	25.0	25.0	25.0	25.0	25.0	25.0	25.0	25.0	25.0	25.0
Titanium oxide*14	250.0	250.0	250.0	130.0	300.0	50.0	250.0	250.0		250.0
											Titanium oxide*15				120.0
Filler*16	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
											Filler*17	30.0	30.0	30.0	30.0	30.0	30.0	30.0	30.0	30.0	30.0
Antioxidant*18	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0	3.0
											Defoamer*19	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
Dispersant*20	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0
											Organic solvent*21	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
∑	501.0	501.0	501.0	501.0	551.0	301.0	501.0	501.0	251.0	501.0

*1: (A-1) bisphenol type carboxyl group-containing resin, ZFR-1401H, double made by Nippon Kayaku Co., Ltd. Phenol F type, solid content 60%, acid value 100mgKOH/g

*2: (A-1) bisphenol type carboxyl group-containing resin, ZAR-1035, bisphenol A type manufactured by Nippon Kayaku Co., Ltd., solid content 65%, acid value 100 mgKOH/g

*3: (A-2) cresol novolac type carboxyl group-containing resin, solid content 65%, acid value 80 mgKOH/g, see Synthesis Example 1

*4: (A-2) cresol novolak type carboxyl group-containing resin, PCR-1169H, phenol novolac type manufactured by Nippon Kayaku Co., Ltd., solid content 65%, acid value 100 mgKOH/g

*5: (A-2) cresol novolac type carboxyl group-containing resin, carboxyl group-containing resin starting from phenol compound, solid content 71%, acid value 88 mgKOH/g, see Synthesis Example 2

*6: (A-3) Acrylic copolymer type other than (A-1) and (A-2), CYCLOMER P (ACA) Z250, acrylic copolymer type manufactured by Daicel-Cytec Co., Ltd., solid content 45%, acid value 70mgKOH/g

*7: (A-3) a carboxyl group-containing resin other than (A-1) and (A-2), a carboxyl group-containing urethane resin, a solid content of 50%, and an acid value of 47 mgKOH/g, see Synthesis Example 3.

*8: Photopolymerization initiator, diethyl thioxanthone

*9: Photopolymerization initiator, LUCIRIN TPO manufactured by BASF, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide

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

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

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

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

*14: Titanium oxide, CR-97 manufactured by Ishihara Sangyo Co., Ltd., rutile type

*15: Titanium oxide, CR-Super70 manufactured by Ishihara Sangyo Co., Ltd., rutile type

*16: Filler, LMP-100, talc manufactured by Fuji Talc Industry Co., Ltd.

*17: Filler, BARIACE B-30 manufactured by 堺Chemical Industries, Ltd., barium sulfate

*18: Antioxidant, IRGANOX1010 manufactured by BASF, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]

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

*20: Dispersant, BYK-110 manufactured by BYK Chemical Co., Ltd., dispersant for titanium oxide

*21: Solvent, dipropylene glycol monomethyl ether

<Method for Producing Substrate for Evaluation of Resistance to Welding Thermal Resistance and Crack 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 for 90 seconds under a pressure of 0.2 MPa to obtain a resist pattern. The substrate was heated at 150 ° 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 swelling and peeling of the cured coating film 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 a bulging and peeling of the cured coating film when immersed for 10 seconds within 2 times.

<Crack resistance>

According to JIS K 5600-5-6, the cured coating film was cross-cut in a checkerboard pattern, and the presence or absence of cracks in the cured coating film was observed with an optical microscope.

○: Curing film without crack

△: The cured coating film is slightly cracked

×: The cured coating film has a large number of cracks

<reflectance>

The photocurable thermosetting resin composition of the above examples and comparative examples was applied to a glass plate of 150 mm × 75 mm by screen printing so as to have a film thickness of 20 μm. Then, it was dried to form a coating film, and the reflectance of the coating film at 420 nm was measured using an integrating sphere apparatus (V-670 ILN-725 type manufactured by JASCO Co., Ltd.).

◎: The reflectance is 90% or more

○: The reflectance is 80% or more and less than 90%

△: The reflectance is 70% or more and less than 80%

×: reflectance is lower than 70%

table 3

Table 4

As is apparent from Tables 3 and 4, the photocurable thermosetting resin composition of the present invention can be suitably used as an excellent resistance to cracking resistance even when the content of titanium oxide is large, and the resistance to soldering heat resistance is not lowered. A resin composition for flux. In addition, it is understood that a white coating film having a high reflectance can be obtained by using the photocurable thermosetting resin composition of the present invention.

Claims (4)

1. A photocurable thermosetting resin composition comprising:

   (A) a carboxyl group-containing resin,

   (B) photopolymerization initiator,

   (C) photosensitive monomer,

   (D) a thermosetting component, and

   (E) titanium oxide,

   The (A) carboxyl group-containing resin comprises (A-1) a bisphenol type carboxyl group-containing resin and (A-2) a novolak type carboxyl group-containing resin,

   a mass ratio of the (A-1) bisphenol type carboxyl group-containing resin to the (A-2) novolak type carboxyl group-containing resin, that is, the (A-1) bisphenol type carboxyl group-containing resin / (A) -2) The novolac type carboxyl group-containing resin is in the range of 20/80 to 60/40.
2. A photocurable thermosetting dry film obtained by applying the photocurable thermosetting resin composition according to claim 1 to a film and drying it.
3. A cured product obtained by photocuring and thermally curing the photocurable thermosetting resin composition according to claim 1 or the dry film according to claim 2.
4. A printed circuit board having the cured product of claim 3.