TW201940615A - Curable resin composition, dry film, cured product and printed circuit board - Google Patents

Abstract

The present invention relates to a curable resin composition, a dry film, a cured product and a printed circuit board. According to the technical scheme of the invention, based on the curable resin composition, a silver coating hardly discolors and the reflectance reduction of a cured product under the UV irradiation is relieved. Meanwhile, the dry film is prepared by the above curable resin composition and the printed circuit board is prepared based on the cured product. The curable resin composition comprises (A) curable resin and (B) titanium oxide. The sulfur concentration of the curable resin composition is 100 ppm or less. In addition, the curable resin composition might comprise (a) curable resin and (B) titanium oxide. The sulfur concentration of the solid component of the curable resin composition is 130 ppm or less.

Description

   Curable resin composition, dry film, cured product, and printed wiring board   

The present invention relates to a curable resin composition, a cured product, and a printed wiring board. Specifically, the present invention relates to a curable resin composition capable of obtaining a cured product that is not easily discolored by silver plating and has a small reduction in reflectance due to ultraviolet irradiation. A dry film of a resin layer obtained from the composition, a cured product thereof, and a printed wiring board having the cured product.

An insulating layer such as a resist has been widely used by applying a curable resin composition to a substrate such as a printed wiring board and curing it (for example, Patent Document 1). When the curable resin composition is used as an insulating layer of a printed wiring board for mounting light emitting elements such as light emitting diodes (LEDs) and electroluminescence (EL), most of them are highly reflective in a manner that can efficiently use light. It is composed of a curable resin composition such as white.

In addition, in order to improve the reflectance of visible light or the reliability of connection of electrodes, the surface of the conductive circuit of the mounting portion of these printed wiring boards is subjected to silver plating (for example, Patent Document 2). When silver plating is placed in the air in advance, it will be corroded and discolored to black. Therefore, in order to prevent the decrease in brightness, reliability, adhesion to the mounting part, etc. due to discoloration, silver plating is treated with a discoloration preventive agent. surface.

    [Previous Technical Literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2005-311233

[Patent Document 2] Japanese Patent Laid-Open No. 2007-189006

Since the corrosion of silver cannot be completely prevented by the discoloration inhibitor alone, there is room for further improvement in preventing the discoloration of silver plating.

In addition, an insulating layer made of a hardened product of a hardening resin composition having a high reflectance has a problem that the reflectance is gradually decreased due to exposure to ultraviolet rays in practical use.

It is therefore an object of the present invention to provide a hardenable resin composition capable of obtaining a hardened material that is hardly discolored by silver plating and has a low reflectance reduction due to ultraviolet irradiation, a dry film having a resin layer obtained from the composition, a hardened material thereof, and This hardened printed wiring board.

In view of the results of the above-mentioned positive review, the inventors have found that the above-mentioned problems can be solved by setting the sulfur concentration in the curable resin composition to 100 ppm or less, and have completed the present invention.

In addition, in view of the results of the above-mentioned positive review, the present inventors have found that the above-mentioned problems can be solved by reducing the sulfur concentration of the solid content of the curable resin composition to 130 ppm or less, and thus completed the present invention.

That is, the curable resin composition of the present invention is a curable resin composition containing (A) a curable resin and (B) titanium oxide, and the sulfur concentration of the curable resin composition is 100 ppm or less.

In addition, another curable resin composition of the present invention is a curable resin composition containing (A) a curable resin and (B) titanium oxide, wherein the sulfur concentration of the solid content of the curable resin composition is between 130ppm or less.

The curable resin composition of the present invention preferably further contains (C) a photopolymerization initiator.

The curable resin composition of the present invention is preferably used for coating on copper.

The dry film of the present invention is characterized by having a resin layer which is obtained by applying the aforementioned curable resin composition to a film and drying it.

The cured product of the present invention is obtained by curing the resin layer of the curable resin composition or the dry film by at least one of light irradiation and heating.

The printed wiring board of the present invention is characterized by having the aforementioned hardened material.

A part of the conductive circuit of the printed wiring board of the present invention is preferably subjected to silver plating.

According to the present invention, it is possible to provide a hardenable resin composition capable of obtaining a hardened material that is hardly discolored by silver plating and has a small reduction in reflectance due to ultraviolet irradiation, a dry film having a resin layer obtained from the composition, a hardened product thereof, and the like. Hardened printed wiring board.

The curable resin composition according to the first embodiment of the present invention is a curable resin composition containing (A) a curable resin and (B) titanium oxide, wherein the sulfur concentration of the curable resin composition is 100 ppm. the following. The curable resin composition according to the second aspect of the present invention is a curable resin composition containing (A) a curable resin and (B) titanium oxide, and is characterized by sulfur of the solid content of the curable resin composition. The concentration is below 130 ppm. Although the detailed mechanism is not clear, the cured product obtained from the curable resin composition of the present invention can not only reduce the discoloration of the silver plating provided on the printed wiring board, but also suppress the decrease of the reflectance of the cured product due to ultraviolet irradiation.

The hardened material in the present invention means hardened using a light or heat energy to a hardenable resin composition. In addition, in the cured product, a liquid such as a diluent solvent or water is 0.1% by mass or less. No light source is specified by the curing of light, as long as it can cause a radical reaction of the curable resin composition, a metal halide lamp or a high-pressure mercury lamp is desired among them. The energy of light is preferably 5 to 4000 mJ / cm ² , and more preferably 20 to 2000 mJ / cm ² . The hardening by heat may be performed by using a hot-air circulation drying furnace, an IR furnace, a hot plate, a forced oven, or the like to heat-harden the curable resin composition. The hardening temperature is preferably 50 to 250 ° C, and more preferably 70 to 200 ° C. The hardening time is preferably 5 to 180 minutes, more preferably 15 to 120 minutes.

As a conventional method for suppressing a decrease in the reflectance of a cured product due to ultraviolet irradiation, a resin having a specific structure such as a resin containing no aromatic ring is used. However, it also reduces the developability or heat resistance. According to the curable resin composition of the present invention, a cured product with a small reflectance can be obtained without using a resin having a specific structure.

In addition, in the conventional alkali-imaging type curable resin composition, if titanium oxide is highly filled in order to improve the reflectance, the specific gravity of titanium oxide is relatively heavy, so there is also a problem that it is difficult to develop the same. When a flexible resin composition is used as an alkali developing type curable resin composition, it is also excellent in developability.

In the present invention, the sulfur concentration of the solid content of the curable resin composition means the sulfur concentration in a state where the solvent is volatilized from the curable resin composition, and the sulfur concentration in the state when there is no solvent.

The sulfur concentration of the curable resin composition according to the first embodiment of the present invention is preferably 70 ppm or less, and more preferably 50 ppm or less. The sulfur concentration of the solid content of the curable resin composition according to the second embodiment of the present invention is preferably 100 ppm or less, and more preferably 80 ppm or less. In the present invention, the sulfur concentration can be measured in accordance with the specification "BS EN 14582: 2007". As the pretreatment, a quartz tube combustion method may be used, and the content may be measured using an ion chromatography method.

The sulfur concentration of the curable resin composition of the first embodiment of the present invention and the sulfur concentration of the solid content of the curable resin composition of the second embodiment of the present invention can be prepared by mixing more components with less sulfur content. And adjusted to below 100ppm and below 130ppm. In particular, in a white or gray curable resin composition containing titanium oxide as a white colorant, it is important to use titanium oxide having a low sulfur concentration in order to highly fill the titanium oxide. For example, titanium oxide using sulfuric acid during manufacturing, especially during surface treatment, tends to have a high sulfur content.

Next, each component of the curable resin composition of the present invention will be described. In addition, in this specification, the term "(meth) acrylate" refers to a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

    [(A) Curable resin]    

The curable resin composition of the present invention contains (A) a curable resin. The (A) curable resin used in the present invention is (A-1) a thermosetting resin or (A-2) a photocurable resin, and may be a mixture thereof. The (A) curable resin may or may not have an aromatic ring in the structure.

(A) It is preferable that the curable resin does not contain a sulfur atom in a raw material (for example, a starting material) for resin synthesis. (A) The sulfur concentration of the curable resin is preferably 200 ppm or less, and more preferably 90 ppm or less.

    ((A-1) thermosetting resin)    

The (A-1) thermosetting resin may be any resin that is hardened by heating and exhibits electrical insulation, and examples thereof include epoxy compounds, oxetane compounds, and melamine resins. In particular, in the present invention, an epoxy compound and an oxetane compound can be preferably used, or these can be used in combination.

As the epoxy compound, a conventionally-used compound having one or more epoxy groups can be used, and among them, a compound having two or more epoxy groups is preferred. For example, monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl (meth) acrylate, etc., bisphenol A epoxy resin, bisphenol S epoxy resin, Bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, alicyclic epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-di Glycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, ginseng ( A compound having two or more epoxy groups in one molecule such as 2,3-epoxypropyl) isocyanurate, triglycidyl (2-hydroxyethyl) isocyanurate, and the like. These can be used alone or in combination of two or more depending on the required characteristics.

Specific examples of the compound having two or more epoxy groups include jER828, jER834, jER1001, jER1004 made by Mitsubishi Chemical Corporation, Epiclon 840, Epiclon 850, Epiclon 1050, and Epiclon 2055 made by DIC. EPOTOT YD-011, YD-013, YD-127, YD-128 made by Nippon Steel & Sumitomo Chemical Co., Ltd., DER317, DER331, DER661, DER664 made by Nihon Chemical Co., Ltd., and Sumitomo Chemical ( Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, and AER330, AER331, AER661, AER664, etc. (all product names) made by Asahi Kasei Corporation Phenol A type epoxy resin; jERYL 903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152 and Epiclon 165 manufactured by DIC Corporation, EPOTOT YDB-400 and YDB-500 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Japan DER542 manufactured by Chemical Co., Ltd., Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and brominated rings such as AER711 and AER714 manufactured by Asahi Kasei Corporation (both trade names). Oxygen resin; jER 152, jER 154 made by Mitsubishi Chemical Corporation, DEN431, DEN438 made by Japan Chemical Corporation, Epiclon N-730, Epiclon N-770 made by DIC , Epiclon N-865, EPOTOT YDCN-701, YDCN-704 made by Nippon Steel & Sumitomo Chemical Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE made by Nippon Kayakusho -306, NC-3000, Sumi-epoxy ESCN-195X, ESCN-220 made by Sumitomo Chemical Co., Ltd., ARECEN-235, ECN-299 made by Asahi Kasei Industrial Co., Ltd., and Nippon Steel & Sumitomo Chemical Co., Ltd. YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A, Epiclon N-680 made by DIC (shares), N-690, N-695 (both trade names) novolac epoxy resins; Epiclon 830 made by DIC (stock), jER 807 made by Mitsubishi Chemical (stock), and Nippon Steel & Sumikin Chemical (stock) EPOTOT YDF-170, YDF-175, YDF-2004, etc. (all are trade names) bisphenol F-type epoxy resins; EPOTOT ST-2004, ST-2007, ST-3000 made by Nippon Steel & Sumikin Chemical Co., Ltd. (Brand name) hydrogenated bisphenol A epoxy resin; jER 604 manufactured by Mitsubishi Chemical Corporation, EPOTOT YH-434 manufactured by Nippon Steel & Sumitomo Chemical Corporation; Sumi-epoxy manufactured by Sumitomo Chemical Corporation Glycidylamine type epoxy resin such as ELM-120, etc. (both trade names); Hydantoin type epoxy resin; Dicel ), Alicyclic epoxy resin made of Celloxide 2021, etc. (both trade names); YL-933 made by Mitsubishi Chemical Corporation, TEN, EPPN-501, EPPN-502, etc. (made by Nihon Chemical Co., Ltd.) (Both trade names) trihydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, YL-6121 (all trade names), etc. manufactured by Mitsubishi Chemical Corporation Type epoxy resin or a mixture of these; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Co., Ltd., EXA-1514 (trade name) manufactured by DIC Co., Ltd., etc. Epoxy resin; bisphenol A novolac epoxy resin such as jER 157S (trade name) manufactured by Mitsubishi Chemical Corporation; tetrahydroxybenzene (jeryl-931 (all trade names) manufactured by Mitsubishi Chemical Corporation) Hexane type epoxy resin; TEPIC, etc. (both trade names) and other heterocyclic epoxy resins made by Nissan Chemical Industry Co., Ltd .; Glycidylbenzene diphenyl, etc. Formate resins; tetraglycidyl xylylene ethane resins such as ZX-1063 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; ESN-190, ESN-360, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., DIC (shares) system HP-4032, EXA-4750, EXA-4700, etc. Naphthyl-containing epoxy resins; HP-7200, HP-7200H, etc., made of DIC (shares), epoxy resins with a dicyclopentadiene skeleton; CP-50S, CP-50M, made by Nippon Oil (stocks) And other glycidyl methacrylate copolymers are epoxy resins; further, there are copolymerized epoxy resins of cyclohexyl maleimide and glycidyl methacrylate; CTBN modified epoxy resins (for example, Nippon Steel & Sumikin Chemical Co., Ltd.'s YR-102, YR-450, etc.), but not limited to them. Among these, a bisphenol A epoxy resin, a heterocyclic epoxy resin, or a mixture thereof is particularly preferred because of its excellent discoloration resistance.

These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

Next, an oxetane compound will be described. Contains the following general formula (I):

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) A specific example of the oxetane compound represented by the oxetane ring is exemplified by 3-ethyl-3-hydroxymethyl. Oxetane (manufactured by Toa Synthetic Co., Ltd., trade name OXT-101), 3-ethyl-3- (phenoxymethyl) oxetane (manufactured by Toa Synthetic Co., Ltd., trade name OXT) -211), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (manufactured by Toa Kosei Co., Ltd., trade name OXT-212), 1,4-bis {[(( 3-ethyl-3-oxetanyl) methoxy] methyl} benzene (manufactured by Tohsei Corporation, trade name OXT-121), bis (3-ethyl-3-oxetanylmethyl) ) Ether (manufactured by Toa Kosei Co., Ltd., trade name OXT-221) and the like. Furthermore, phenol novolak type oxetane compounds and the like are also exemplified. These oxetane compounds may be used in combination with the above-mentioned epoxy compound, or may be used alone.

    ((A-2) photocurable resin)    

Next, as the (A-2) photocurable resin, any resin that is hardened by irradiation with active energy rays and exhibits electrical insulation properties may be used. In particular, in the present invention, it is preferred to use one or more vinyls in the molecule Unsaturated compounds.

As the compound having an ethylenically unsaturated bond, conventionally used photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like can be used. Examples of such photopolymerizable oligomers include unsaturated polyester-based oligomers, (meth) acrylate-based oligomers, and the like. Examples of the (meth) acrylate-based oligomer include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, and bisphenol epoxy (meth) acrylate Epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether ( (Meth) acrylates, (meth) acrylates modified by polybutadiene, and the like.

As the photopolymerizable vinyl monomer is a conventional one, examples of which are styrene derivatives such as styrene, chlorostyrene, α-methylstyrene, etc .; vinyl acetate, vinyl butyrate, or vinyl benzoate, etc. Vinyl esters; vinyl isobutyl ether, vinyl n-butyl ether, vinyl third butyl ether, vinyl n-pentyl ether, vinyl isoamyl ether, vinyl n-octadecane Vinyl ethers such as vinyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, and triethylene glycol monomethyl vinyl ether; acrylamide, methacrylamide, N-hydroxymethyl Acrylamide, N-hydroxymethylmethacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, N-butoxymethacrylamide, etc. ( (Meth) acrylamidines; triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, and other allyl compounds; 2-ethyl (meth) acrylate Hexyl ester, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate (Meth) acrylic acid esters; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, etc .; Alkoxyalkanediol mono (meth) acrylates, such as methoxyethyl methacrylate, ethoxyethyl (meth) acrylate; ethylene glycol di (meth) acrylate, succinic acid Alcohol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Polyalkylene poly (meth) acrylates such as pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylic acid, ethoxylated trimethylolpropane triacrylate, polyoxyalkylene glycol poly (meth) acrylates such as trimethylolpropane triacrylate; neopentyl hydroxypivalate Poly (meth) acrylates such as alcohol ester di (meth) acrylates; see [(Meth) acryloxyethyl] isocyanurate and other poly (meth) acrylates ) Acid esters and the like. These can be used individually or in combination of two or more depending on the requirements.

When the composition of the present invention is used as an alkali-dominant photosensitive resin composition, as the (A) curable resin, a carboxyl group-containing resin is preferably used. The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group, and may not have an aromatic ring.

Specific examples of the carboxyl group-containing resin that can be used in the composition of the present invention include the compounds (either oligomers or polymers) listed below.

(1) Carboxyl group obtained by copolymerization of unsaturated carboxylic acids such as (meth) acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, isobutylene, etc. Resin. When the carboxyl group-containing resin has an aromatic ring, at least one of an unsaturated carboxylic acid and an unsaturated group-containing compound may have an aromatic ring.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and carboxyl-containing glycol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid And polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct glycols, phenolic hydroxyl groups and alcohols A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diol compound such as a hydroxy compound or the like. When the carboxyl group-containing urethane resin has an aromatic ring, at least one of a diisocyanate, a carboxyl group-containing diol compound, and a diol compound may have an aromatic ring.

(3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, poly Polyamino acid obtained by the polyaddition reaction of olefinic polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, diol compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups, and the like An urethane resin containing a terminal carboxyl group formed by reacting an end of an ester resin with an acid anhydride. When the carboxyl group-containing urethane resin has an aromatic ring, at least one of a diisocyanate compound, a diol compound, and an acid anhydride may have an aromatic ring.

(4) Diisocyanate and bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bixylenol epoxy resin, biphenol (Meth) acrylic acid esters of bifunctional epoxy resins such as type epoxy resins or modified anhydrides thereof, carboxyl-containing diol compounds, and photosensitive amine-containing amine groups obtained by polyaddition reaction of diol compounds Formate resin. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, as long as it is a diisocyanate, a (meth) acrylate of a bifunctional epoxy resin or a partial anhydride modification thereof, a carboxyl group-containing diol compound, and a diol At least one of the compounds may have an aromatic ring.

(5) In the resin synthesis of the above (2) or (4), the terminal of the compound having one hydroxyl group and one or more (meth) acrylfluorenyl groups in the molecule such as hydroxyalkyl (meth) acrylate is added (a ) Acrylated carboxyl group-containing urethane resin. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one hydroxyl group and one or more (meth) acrylfluorenyl groups in a molecule may have an aromatic ring.

(6) In the resin synthesis of the above (2) or (4), a molecule containing a mole reactant such as isophorone diisocyanate and pentaerythritol acrylate has one isocyanate group and one or more (methyl) groups (Meth) acrylated carboxyl group-containing urethane resins of acryl-based compounds. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one isocyanate group and one or more (meth) acrylfluorenyl groups in the molecule may have an aromatic ring.

(7) Addition of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. on the side chain to the reaction of the polyfunctional epoxy resin with (meth) acrylic acid A photosensitive carboxyl group-containing resin of an acid anhydride. When the photosensitive carboxyl group-containing resin contains an aromatic ring, at least one of the polyfunctional epoxy resin and the dibasic acid anhydride may contain an aromatic ring.

(8) A photosensitive carboxyl group-containing resin which further epoxidizes the hydroxyl group of a bifunctional epoxy resin with (meth) acrylic acid with epichlorohydrin and adds a dibasic acid anhydride to the generated hydroxyl group. When the photosensitive carboxyl group-containing resin contains an aromatic ring, at least one of the difunctional epoxy resin and the dibasic acid anhydride may contain an aromatic ring.

(9) A polyfunctional oxetane resin is reacted with a dicarboxylic acid to add a carboxylic acid-containing polyester resin having a dibasic acid anhydride to the generated primary hydroxyl group. When the photosensitive carboxyl-containing polyester resin contains an aromatic ring, at least one of a polyfunctional oxetane resin, a dicarboxylic acid, and a dibasic acid anhydride may contain an aromatic ring.

(10) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide, propylene oxide, and the like and reacting a monocarboxylic acid containing an unsaturated group to make the obtained A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

(11) reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate, propyl carbonate, etc., with a monocarboxylic acid containing an unsaturated group, A carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride.

(12) A compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group, and (meth) acrylic acid, etc. Reaction of unsaturated monocarboxylic acids, polyhydric polyhydric alcohols and maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic acid, etc. A carboxyl group-containing photosensitive resin obtained by an acid anhydride reaction. When the photosensitive carboxyl-containing polyester resin has an aromatic ring, as long as the epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, an unsaturated monocarboxylic acid and a polybasic acid anhydride At least one of them may have an aromatic ring.

(13) A molecule having any of epoxy resins (1) to (12) above and further including glycidyl (meth) acrylate, α-methyl glycidyl (meth) acrylate, and the like has one epoxy group and A photosensitive carboxyl group-containing resin composed of one or more (meth) acrylfluorenyl compounds. When the photosensitive carboxyl group-containing polyurethane resin has an aromatic ring, a compound having one epoxy group and one or more (meth) acrylfluorenyl groups in the molecule may have an aromatic ring.

(14) A photosensitive carboxyl group-containing resin obtained by reacting a carboxyl group-containing (meth) acrylic copolymer resin with one molecule having an ethylene oxide ring and an ethylenically unsaturated group.

(15) The copolymer of a compound each having an epoxy group and an unsaturated double bond and a compound having an unsaturated double bond in one molecule is reacted with an unsaturated monocarboxylic acid, and the resulting secondary hydroxyl group is saturated or not reacted. A photosensitive carboxyl group-containing resin obtained by saturated polybasic acid anhydride.

(16) After reacting a hydroxyl-containing polymer with a saturated or unsaturated polybasic acid anhydride, reacting a generated carboxylic acid with a compound each having one epoxy group and an unsaturated double bond in one molecule, and a photosensitive hydroxyl-containing group And carboxyl resin.

As described above, the carboxyl group-containing resin has a large number of carboxyl groups in the main chain / polymer side chain, so it can be developed with a dilute alkaline aqueous solution.

Furthermore, if (A) a carboxyl group-containing resin which does not have an aromatic ring in the examples (14) to (16) or (1) is used, a composition having excellent touch-drying property and discoloration can be obtained. Better.

The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH / g, and more preferably in the range of 40 to 180 mgKOH / g. If it is in the range of 20 to 200 mgKOH / g, the adhesiveness of the coating film can be obtained, alkali development becomes easy, and the dissolution of the exposed portion due to the developing solution is suppressed, and the line is not thinned more than necessary, and normal. The drawing of the resist pattern becomes easier, so it is preferable.

The weight average molecular weight of the carboxyl group-containing resin used in the present invention varies depending on the resin skeleton, but it is preferably in the range of 2,000 to 150,000. If it is in this range, the non-tackiness is good, the moisture resistance of the coating film after exposure is good, and film reduction is unlikely to occur during development. In addition, if the weight average molecular weight is within the above range, resolution can be improved, developability is good, and storage stability is good. More preferably 5,000 ~ 100,000. The weight average molecular weight can be measured by a gel permeation chromatography.

When an epoxy resin and a carboxyl group-containing resin are used as the (A) curable resin, it is preferable that the epoxy group equivalent of the carboxyl group contained in the carboxyl group-containing resin is 2.0 or less. It is more preferably 1.5 or less. This is because a smaller equivalent ratio tends to improve the developability.

    [(B) Titanium oxide]    

The curable resin composition of the present invention contains (B) titanium oxide. (B) The titanium oxide preferably has a sulfur concentration of 100 ppm or less, and more preferably 50 ppm or less. In addition, commercially available titanium oxide having a sulfur concentration of 100 ppm or less can be used. Commercially available titanium oxide having a sulfur concentration of more than 100 ppm can be subjected to heat treatment or chemical treatment, and purification treatment such as washing and firing can be used to make sulfur. Blend after concentration reduction. Here, the sulfur contained in (B) titanium oxide refers to all sulfur detected by analysis, and includes sulfur adsorbed on (B) titanium oxide and sulfur contained in (B) titanium oxide as an impurity.

(B) The manufacturing method of titanium oxide may be either a sulfuric acid method or a chlorination method, and a chlorination method is preferable. Furthermore, it is preferable not to use sulfuric acid in a manufacturing process. The surface treatment of (B) titanium oxide is not particularly limited, but when the surface treatment is neutralized, titanium oxide treated with an acid other than sulfuric acid such as hydrochloric acid, nitric acid, phosphoric acid, and acetic acid is preferred.

The titanium oxide may be any one of rutile type, anatase type, and ramsdellite type, and may be used alone or in combination of two or more types. These medium orthorite-type titanium oxides are obtained by chemically oxidizing orthorhomite-type Li _0.5 TiO _{2 and} performing a lithium release treatment.

Among the above, if rutile-type titanium oxide is used, heat resistance can be further improved, discoloration due to light irradiation is hardly caused, and quality is not easily reduced even under strict use environment, so it is preferable. In particular, by using a rutile-type titanium oxide surface-treated with an aluminum oxide such as alumina, heat resistance can be further improved. The content of rutile titanium oxide surface-treated with aluminum oxide in all titanium oxides is preferably 10% by mass or more, more preferably 30% by mass or more, and the upper limit is 100% by mass or less, that is, titanium oxide may also be used. The entire amount is rutile-type titanium oxide surface-treated with the above-mentioned aluminum oxide. In addition, since the anatase-type titanium oxide has a lower hardness than the rutile type, when the anatase-type titanium oxide is used, the shape of the composition becomes better.

Examples of commercially available titanium oxides having a sulfur concentration of 100 ppm or less are R-931 manufactured by Dupont, Tiona595 manufactured by Cristal, and SX3103 manufactured by Sakai Chemical Industry Co., Ltd., and the like.

The blending amount of such (B) titanium oxide is preferably in the range of 5 to 80% by mass with respect to the solid content in the curable resin composition (when the curable resin composition contains an organic solvent, components other than organic solvents). , More preferably in the range of 10 to 70% by mass. As the titanium oxide (B), when two or more kinds of titanium oxides are used, it is preferable because the reflectance becomes high. In this case, the sulfur concentration of each titanium oxide is preferably 100 ppm or less, and more preferably, the sum of the sulfur concentration of each titanium oxide is 100 ppm or less.

The curable resin composition of the present invention may contain a white colorant other than titanium oxide. Examples of other white colorants include zinc oxide, potassium titanate, zirconia, antimony oxide, lead white, zinc sulfide, lead titanate, and the like.

The curable resin composition of the present invention may contain titanium oxide having a sulfur concentration of more than 100 ppm as long as the sulfur concentration of the curable resin composition does not exceed 100 ppm. Examples of titanium oxide having a sulfur concentration of more than 100 ppm are CR-58, CR-90, and R-630 manufactured by Ishihara Industry Co., Ltd., and R-21 manufactured by Sakai Chemical Industry Co., Ltd., and the like.

    [(C) Photopolymerization initiator]    

When the photocurable resin (A-2) is used in the curable resin composition of the present invention, (C) a photopolymerization initiator is preferably further added. As the (C) photopolymerization initiator, any one can be used as long as it is a photopolymerization initiator known as a photopolymerization initiator or a photoradical generator.

Examples of the (C) photopolymerization initiator include bis- (2,6-dichlorobenzyl) phenylphosphine oxide, and bis- (2,6-dichlorobenzyl) -2,5- Dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzylidene) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzylidene) -1-naphthalene Phenylphenylphosphine oxide, bis- (2,6-dimethoxybenzyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzyl) -2,4,4- Trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzylidene) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzene Dimethylphosphine) phenylphosphine oxide (made by Japan BASF (Stock), IRGACURE819) and other bisfluorenylphosphine oxides; 2,6-dimethoxybenzyldiphenylphosphine oxide, 2,6-di Chlorobenzyldiphenylphosphine oxide, methyl 2,4,6-trimethylbenzylphenylphosphinate, 2-methylbenzyldiphenylphosphine oxide, pentamidine Monofluorenylphosphine oxides, such as isopropyl phenylphosphinate, 2,4,6-trimethylbenzylidene diphenylphosphine oxide (Darocur TPO, manufactured by BASF, Japan); 1-hydroxyl -Cyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanyl) benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1 -Hydroxyacetophenones such as ketones; benzoin, biphenylhydrazone, benzoin methyl ether, benzoin ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc. Benzoin; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Mieketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenones and other benzophenones; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholine-1-acetone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2- (dimethylamino) -2-[(4 -Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, and the like; Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, Thioxanthones such as 2,4-diisopropylthioxanthone; anthracene Quinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2-aminoanthraquinone, etc. Anthraquinones; acetals such as acetophenone dimethyl acetal and benzyl dimethyl acetal; 4-dimethylamino ethyl benzoate, 2- (dimethylamino) ethyl benzoate, Parabens such as ethyl p-dimethylbenzoate; 1,2-octanediol, 1- [4- (phenylthio)-, 2- (O-benzyl oxime)], ethyl Ketones, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime) and other oxime esters; Bis (η5-2,4-Hexadiene-1-yl) -bis (2,6-difluoro-3- (1H-prop-1-yl) phenyl) titanium, bis (dicyclopentadiene ) -Bis (2,6-difluoro-3- (2- (1- -1-yl) ethyl) phenyl] titanium and other titanocene; phenyl disulfide 2-nitropyrene, butyroin, anisoin ethyl ether, azobisiso Butyronitrile, tetramethylthiuram disulfide, etc. The above photopolymerization initiators may be used singly or in combination of two or more kinds.

Among the above, fluorenylphosphine oxide-based photopolymerization initiators such as bisfluorenylphosphine oxides and monofluorenylphosphine oxides are preferred because they have low tackiness and excellent discoloration suppression effects. Among them, when bisfluorenyl phosphine oxides are used, it is more preferable in terms of improving sensitivity and non-tackiness.

The amount of the (C) photopolymerization initiator is 0.1 to 50 parts by mass based on 100 parts by mass of the curable resin (A) in terms of solid content. By blending the (C) photopolymerization initiator within this range, the photohardenability on copper becomes sufficient, the hardenability of the coating film becomes better, the coating film properties such as chemical resistance are improved, and the deep hardenability is also improved. More preferably, it is 1 to 40 parts by mass based on 100 parts by mass of the curable resin (A).

(C) The photopolymerization initiator is preferably one which does not contain sulfur atoms in the structure.

    [(D-1) Hardener and (D-2) Hardening Catalyst]    

When the (A-1) thermosetting resin is used in the curable resin composition of the present invention, either (D-1) a curing agent or (D-2) a curing catalyst may be further added.

Examples of the (D-1) hardener include polyfunctional phenol compounds, polycarboxylic acids and their anhydrides, aliphatic or aromatic primary or secondary amines, polyamine resins, isocyanate compounds, and polythiol compounds. Among these, a polyfunctional phenol compound, a polycarboxylic acid, and its anhydride are preferably used from the viewpoint of workability and insulation properties.

As the polyfunctional phenol compound, any compound having two or more phenolic hydroxyl groups in one molecule may be used, and a conventional one can be used. Specific examples include phenol novolac resin, cresol novolac resin, bisphenol A, acrylic bisphenol A, bisphenol F, novolac resin of bisphenol A, vinyl phenol copolymer resin, etc., based on high reactivity improvement The effect of heat resistance is high, and bisphenol A is particularly preferred. Such a polyfunctional phenol compound is subjected to an addition reaction with at least one of an epoxy compound and an oxetane compound in the presence of a suitable curing catalyst.

Examples of the polycarboxylic acid and its anhydride-based compound having two or more carboxyl groups in one molecule and its anhydride include, for example, a copolymer of (meth) acrylic acid, a copolymer of maleic anhydride, and a condensate of a dibasic acid. Examples of commercially available products include JONCRYL (trade name) manufactured by BASF, SMA resin (trade name) manufactured by SARTOMER, and pimelic anhydride manufactured by Nippon Physicochemical Corporation.

The mixing ratio of these (D-1) hardeners is sufficient in the proportion of the amount usually used, and it is preferably 1 to 200 parts by mass, and more preferably 100 parts by mass of (A-1) thermosetting resin. 10 to 100 parts by mass.

In addition, the (D-2) curing catalyst is a compound that can become a curing catalyst in the reaction between a thermosetting resin such as an epoxy compound and an oxetane compound and a (D-1) curing agent or does not use curing. It can be used as a polymerization catalyst. Specific examples of the hardening catalyst include tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphines, and phosphonium ions, which are crown ether complexes. Any of these can be used alone or in combination of two or more.

Among them, imidazoles with trade names such as 2E4MZ, C11Z, C17Z, 2PZ, etc., or imidazine compounds with trade names such as 2MZ-A, 2E4MZ-A, etc., and imidazoles with trade names such as 2MZ-OK, 2PZ-OK, etc. Isocyanurates, imidazole hydroxymethyl bodies such as 2PHZ, 2P4MHZ (trade names are manufactured by Shikoku Chemical Industries, Ltd.), dicyandiamide and its derivatives, melamine and its derivatives, two Aminomalononitrile and its derivatives, diethylene glycol triamine, triethylene glycol tetraamine, tetraethylene ethylene pentaamine, bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, organic Amines such as acid dihydrazine, 1,8-diazabicyclo [5,4.0] undecene-7 (trade name DBU, manufactured by SAN APRO (stock)), 3,9-bis (3-amine Propyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (trade name ATU, manufactured by Ajinomoto (stock)) or triphenylphosphine, tricyclohexylphosphine, tris Organic phosphine compounds such as butylphosphine and methyldiphenylphosphine.

The compounding amount of the (D-2) hardening catalyst is sufficient in a normal ratio, and is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 6 parts by mass, with respect to 100 parts by mass of the (A) hardening resin.

    [(E) Antioxidant]    

The curable resin composition of the present invention preferably further contains (E) an antioxidant.

By containing the (E) antioxidant, in addition to the effects of preventing oxidative degradation of the curable resin and the like and suppressing discoloration, it is possible to improve the heat resistance and also to obtain the effect of good resolution (line width reproducibility). That is, when (B) titanium oxide is used, the resolvability may be deteriorated due to reflected light, but by containing (E) an antioxidant, it becomes a person who can obtain good resolvability.

(E) Antioxidants include radical scavengers that neutralize the generated free radicals, or peroxide decomposers that decompose the generated peroxides into harmless substances and do not generate new free radicals. They can be used alone. One type may be used in combination of two or more types.

Specifically, examples of the (E) antioxidant functioning as a radical scavenger include hydroquinone, 4-tert-butylcatechol, 2-tert-butylhydroquinone, hydroquinone monomethyl ether, 2, 6-Di-tert-butyl-p-cresol, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-ginseno (2-methyl- 4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-para- (3,5-di-tert-butyl-4-hydroxybenzyl) ) Benzene, 1,3,5-ginseng (3 ', 5'-di-third-butyl-4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) Phenolic compounds such as ketones, quinone compounds such as hydroquinone monomethyl ether, benzoquinone, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, phenothiazine, etc. Amine compounds and the like. As a commercially available product, for example, IRGANOX 1010 (the above is a Japanese BASF (stock) system, trade name) and the like can be used.

Examples of the (E) antioxidant that functions as a peroxide decomposition agent include phosphorus-based compounds such as triphenyl phosphate.

Among the above, when a phenol-based antioxidant is used, it is preferable in terms of further obtaining a discoloration suppressing effect, improving heat resistance, and good resolution.

The blending amount when (E) the antioxidant is used is preferably 0.01 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of the (A) curable resin. The effect of adding the above-mentioned antioxidant can be surely obtained by setting the compounding amount of the (E) antioxidant to 0.01 parts by mass or more. On the other hand, by setting the amount to 10 parts by mass or less, a good alkali can be obtained without hindering the light reaction The developability is also good to ensure the touch dryness or coating film physical properties.

Further, (E) an antioxidant, especially a phenol-based antioxidant and a heat-resistant stabilizer may be used in combination to achieve further effects. Therefore, a heat-resistant stabilizer may be blended in the resin composition of the present invention.

Examples of the heat-resistant stabilizer include phosphorus-based and hydroxylamine-based heat-resistant stabilizers. These heat-resistant stabilizers may be used individually by 1 type, and may use 2 or more types together.

When the heat-resistant stabilizer is used, its blending amount is preferably 0.01 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of the (A) curable resin.

The curable resin composition of the present invention may contain a filler. The filler is used in order to increase the physical strength of the obtained cured product. The filler is not particularly limited, and conventionally used fillers such as silica, crystalline silica, Neuenburg, silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, Synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, zinc white and other inorganic pigments, but the filler is preferably free of sulfur.

When using a filler, the compounding quantity is 0.1-300 mass parts with respect to 100 mass parts of (A) curable resin.

The curable resin composition of the present invention may contain a reactive diluent. The reactive diluting solvent is used for adjusting the viscosity of the composition and improving workability, while increasing the crosslinking density, improving adhesion, and the like. Photocurable monomers and the like can be used. As the photocurable monomer, the aforementioned photopolymerizable vinyl monomer and the like can be used. It is preferred that the reactive dilution solvent does not contain a sulfur atom in the resin synthesis raw material (starting raw material).

The mixing ratio of these reactive diluent solvents is preferably 1 to 100 parts by mass, more preferably 1 to 70 parts by mass, with respect to 100 parts by mass of the (A) curable resin. By setting it as the range of the said compounding ratio, photohardenability can be improved, pattern formation can be made easy, and the cured film strength can be improved.

In addition, the curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition or adjusting viscosity when applied to a substrate or a carrier film. As the organic solvent, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; plasmin, methyl lysin, butyl lysin, and carbiten Glycol ethers of alcohols, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, and the like Class; ethyl acetate, butyl acetate, butyl lactate, lysinoacetate, butyl lysone acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate Esters, dipropylene glycol monomethyl ether acetate, esters of propylene carbonate, etc .; aliphatic hydrocarbons such as octane, decane, etc .; petroleum-based solvents such as petroleum ether, petroleum spirit, solvent petroleum spirit, etc. Commonly used organic solvents. These organic solvents may be used alone or in combination of two or more.

In addition, the curable resin composition of the present invention may be formulated with other additives conventionally used in the field of electronic materials. Examples of other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial / mildew proof agents, defoamers, leveling agents, and thickeners Agents, adhesion-imparting agents, rheology-imparting agents, other colorants, photopolymerization aids, sensitizers, hardening accelerators, mold release agents, surface treatment agents, dispersants, dispersion aids, surface modifiers, Stabilizers, phosphors, etc.

The curable resin composition of the present invention can be used as a dry film or as a liquid. When it is used as a liquid, it may be one liquid or two liquid or more. In particular, when two or more components containing (A) curable resin and (B) titanium oxide are prepared, the (A) curable resin and (B) titanium oxide can be formulated in the same formulation or in different formulations.

Next, the dry film of the present invention has a resin layer obtained by applying and curing the curable resin composition of the present invention on a carrier film. When forming a dry film, first, dilute the curable resin composition of the present invention with the above-mentioned organic solvent to adjust the viscosity to a suitable viscosity, and then apply the cut-off wheel coater, doctor blade coater, lip mold coater, rod coater, and extrusion coating Applicator, reverse roll coater, transfer roll coater, gravure coater, spray coater, etc., apply uniform thickness on the carrier film. Subsequently, the coated composition is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a resin layer. The thickness of the coating film is not particularly limited, but the thickness of the film after drying is generally selected from a range of 10 to 150 μm, preferably 20 to 60 μm.

As the carrier film, a plastic film is used. For example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyimide film, a polypropylene film, or a polystyrene film can be used. Wait. The thickness of the carrier film is not particularly limited, and is generally appropriately selected in a range of 10 to 150 μm.

After a resin layer made of the curable resin composition of the present invention is formed on a carrier film, in order to prevent dust and the like from adhering to the surface of the film, it is preferable to further laminate a film on the surface of the film to peel off. As a peelable top cover film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used, for example. The upper cover film may be any one having a lower adhesion force than the resin layer and the carrier film when the upper cover film is peeled off.

In addition, in the present invention, it is only necessary to form a resin layer by coating and curing the curable resin composition of the present invention on the protective film, and laminating a carrier film on the surface. That is, any of a carrier film and a protective film may be used as the film for coating the curable resin composition of the present invention when a dry film is produced in the present invention.

When the curable resin composition of the present invention is used as a photocurable thermosetting composition, the resin layer obtained by coating the composition and evaporating and drying the solvent is exposed (light irradiation) to expose the exposed portion ( The light-irradiated part) hardens. Specifically, the contact or non-contact method is used to selectively use active energy ray exposure through a patterned mask or direct pattern exposure using a laser direct exposure machine, using a dilute aqueous alkali solution (for example, 0.3 to 3% by mass). Aqueous sodium carbonate solution) develops an unexposed portion to form a resist pattern. Further, it is heated to a temperature of about 100 to 180 ° C to be thermally cured (post-cured) to form a hardened film (cured material) having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.

When the curable resin composition of the present invention is used as a thermosetting composition, the composition is coated, the solvent is volatilized and dried, and then heated to a temperature of about 100 to 180 ° C to be thermally cured to form heat resistance and chemical resistance. A hardened film (hardened material) having excellent properties such as resistance, moisture absorption resistance, adhesion, and electrical properties.

In addition, when the curable resin composition of the present invention is used as a photocurable composition, the exposed portion (light irradiated portion) is hardened by applying the composition, volatilizing and drying the solvent, and then exposing (light irradiating). Thereby, a hardened film (hardened material) can be formed.

In addition, the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method by using the above-mentioned organic solvent, and the substrate is subjected to a dip coating method, a flow coating method, a roll coating method, a rod coating method, After coating by screen printing method, curtain flow coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of about 60 to 100 ° C to form a non-sticky resin layer. In addition, when the above composition is coated on a carrier film or a protective film, dried to form a film, and rolled into a dry film, the lamination machine or the like is used to attach the layer of the composition of the present invention to a substrate in contact with the substrate. After the substrate is removed, the carrier film is peeled off to form a resin layer.

As the substrate, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance by copper, etc., examples include the use of paper phenol, paper epoxy resin, glass cloth epoxy resin, and glass polyimide. , Glass cloth / non-woven epoxy resin, glass cloth / paper epoxy resin, synthetic fiber epoxy resin, fluororesin / polyethylene / polyphenylene oxide, polyphenylene oxide / isocyanate, etc. Materials, and examples are copper clad laminates of all grades (FR-4, etc.), and other examples are metal substrates, polyimide films, PER films, polyethylene naphthalate (PEN) films, glass substrates, Ceramic substrate, wafer board, etc.

The above-mentioned volatilization drying or thermal hardening can use a hot-air circulation type drying furnace, IR furnace, heating plate, convection oven, etc. To the support).

As the exposure machine used for the above-mentioned active energy ray irradiation, if it is a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, and the like, it can irradiate ultraviolet rays in the range of 350 to 450 nm, and direct drawing Device (such as a laser direct imaging device that draws an image from a computer's CAD data with a direct laser). The light source or laser light source of the direct drawing machine, as long as the maximum wavelength falls in the range of 350 ~ 410nm. The amount of exposure used for image formation varies with film thickness, etc., but can generally be in the range of 20 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .

As the above-mentioned development method, a dipping method, a rinsing method, a spray method, a brushing method, or the like can be used, and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Aqueous alkali solution of ammonia, amine, etc.

The curable resin composition of the present invention is used to form a hardened film on a printed wiring board, that is, it is better used as a printed wiring board, more preferably it is used to form a permanent film, and even better. It is used to form a resist or an upper film. It is particularly preferably used for forming a resist, that is, as a resist composition. The curable resin composition of the present invention can also be used for forming a solder stopper. In addition, the hardening resin composition of the present invention can be used in a backlight of a liquid crystal display of a lighting device, a mobile terminal, a personal computer, a television, or the like, by making it white, so that it emits light as a light source. A reflective plate that reflects light from a diode (LED) or electroluminescence (EL). In addition, the curable resin composition of the present invention can be preferably used for forming a printed wiring board having a conductive circuit subjected to silver plating treatment. When the reflective plate is subjected to a silver plating treatment in order to increase the reflectance, the curable resin composition of the present invention can be preferably used.

The printed wiring board of the present invention is preferably a part of the conductive circuit that is subjected to silver plating. The curable resin composition of the present invention is after exposure / development when the photocurable resin composition is used, and after pattern printing when the thermosetting resin composition is used, a part of the exposed conductive circuit is silvered. Just electroplating. The silver plating treatment is not particularly limited as long as a conventionally known method is used.

    [Example]    

Hereinafter, the present invention will be described in more detail using examples.

    (Synthesis example 1 of curable resin (photosensitive copolymer resin A))    

In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux cooler, 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent was heated to 110 ° C, and 174.0 parts by mass of methacrylic acid and ε-caprolactone were modified. 174.0 parts by mass of methacrylic acid (average molecular weight 314), 77.0 parts by mass of methyl methacrylate, 222.0 parts by mass of dipropylene glycol monomethyl ether, and third butylperoxy 2-ethylhexanoate as a polymerization catalyst ( 12.0 parts by mass of PERBUTYL O) manufactured by Nippon Oil Co., Ltd. was added dropwise over 3 hours, and further stirred at 110 ° C. for 3 hours to deactivate the polymerization catalyst to obtain a resin solution. After cooling the resin solution, 289.0 parts by mass of CYCLOMER M100 manufactured by DAICEL (stock), 3.0 parts by mass of triphenylphosphine, and 1.3 parts by mass of hydroquinone monomethyl ether were added, and the mixture was heated to 100 ° C. with stirring to perform an epoxy group. A ring-opening addition reaction to obtain a photosensitive copolymer resin A (varnish).

The solid content concentration of the photosensitive copolymer resin A (varnish) thus obtained was 45.5% by mass, and the acid value of the solid matter was 79.8 mgKOH / g. The weight average molecular weight (Mw) of the obtained photosensitive copolymerized resin A was 15,000.

    (Synthesis example 2 of curable resin (non-photosensitive copolymer resin B))    

Into a pressure-resistant container equipped with a thermometer, a cooling pipe, and a stirrer, feed deionized water: 200 parts by mass, and sodium sulfate: 0.3 parts by mass, and confirm dissolution.

Subsequently, 5 parts by mass of BPO (benzylidene peroxide) as a polymerization initiator and MSD (α-methylstyrene dimer) as a chain transfer agent were added to 5 parts by mass of MMA (methyl Methyl acrylate): 10.4 parts by mass, n-BA (n-butyl acrylate): 5 parts by mass, MAA (methacrylic acid): 24.6 parts by mass, and St (styrene): 60 parts by mass of the monomer mixture Fully dissolved.

Subsequently, a dispersant was added to a concentration of 300 ppm, and the mixture was sufficiently stirred. The interior of the kettle was replaced with nitrogen, and the temperature was raised to perform suspension polymerization. After the polymerization was completed, the obtained suspension was filtered through a mesh sieve having a mesh opening of 30 μm, and dried with warm air at 40 ° C. to obtain a granular resin. The granular resin (copolymerized resin) thus obtained was sufficiently dissolved using an organic solvent DPM (dipropylene glycol methyl ether) to obtain a non-photosensitive copolymerized resin B (varnish).

The solid content concentration of the non-photosensitive copolymer resin B (varnish) thus obtained was 50% by mass, and the acid value of the solid matter was 160 mgKOH / g. The weight-average molecular weight (Mw) of the obtained non-photosensitive copolymer resin B was 10,000.

    (Synthesis example 3 of curable resin (cresol novolac-type photosensitive resin C))    

To 600 g of diethylene glycol monoethyl ether acetate, 1070 g of o-cresol novolac epoxy resin (EPICLONN-695, softening point: 95 ° C, epoxy equivalent: 214, average number of functional groups: 7.6) manufactured by DIC (stock) is fed. (Number of glycidyl groups (total number of aromatic rings): 5.0 moles), 360 g of acrylic acid (5.0 moles), and 1.5 g of hydroquinone were heated and stirred at 100 ° C. to be uniformly dissolved. Next, 4.3 g of triphenylphosphine was fed, and the reaction was heated at 110 ° C. for 2 hours, and then the temperature was raised to 120 ° C. and the reaction was further performed for 12 hours. 415 g of aromatic hydrocarbon (SOLVESSO 150) and 456.0 g of tetrahydrophthalic anhydride (3.0 mol) were fed into the obtained reaction solution, and the reaction was carried out at 110 ° C for 4 hours, followed by cooling to obtain a cresol novolac type photosensitivity. Resin C (varnish).

The solid content concentration of the cresol novolac photosensitive resin C (varnish) thus obtained was 65% by mass, and the acid value of the solid matter was 89 mgKOH / g. The weight average molecular weight (Mw) of the obtained cresol novolac photosensitive resin C was 9,000.

The weight-average molecular weight of the obtained resin was obtained by connecting the pump LC-6AD made by Shimadzu Corporation with three Shodex (registered trademark) KF-804, KF-803, and KF-802 manufactured by Showa Denko Corporation. High-speed liquid chromatography.

    (Analytical method of sulfur concentration)    

For each component shown in the following table, the sulfur concentration was measured by the following method. 0.25 g of each component was measured and used as a measurement sample. As a pretreatment, a sample combustion device manufactured by Mitsubishi Chemical Corporation (QF-02) was used: QF-02, and each measurement sample was subjected to a combustion treatment by a quartz tube combustion method according to the following conditions.

Combustion conditions

(1) Heating conditions (heating part)

Room temperature → (5 ℃ / min) → 200 ℃ → (10 ℃ / min) → 500 ℃ → (5 ℃ / min) → 900 ℃ for 5 minutes

(2) Combustion conditions (combustion section)

Note inlet (inlet): 850 ° C, outlet (outlet): 900 ° C

(3) Burning time 40 minutes (total)

2. Gas conditions (indicated by the flowmeters of all device bodies)

(1) Oxygen (pair) 100ml / min

(2) oxygen (main) 200ml / min

(3) 100ml / min of argon / oxygen (switch at 700 ℃)

(4) Total flow 400ml / min

3. Gas conditions during combustion

(1) Before 700 ° C: argon, after 700 ° C: oxygen

(2) Combustion part: before 900 ℃: oxygen

4. Absorption liquid 15% 0.3% hydrogen peroxide aqueous solution (after burning treatment, make up to 25ml)

The absorbing solution after the above-mentioned fixed volume was measured for ion content by ion chromatography according to the following conditions, and the sulfur concentration of each component was determined.

Ion chromatograph: ICS-1500 (manufactured by Thermo Fisher Scientific)

Eluent: 2.7mM Na ₂ CO ₃ /0.3mM NaHCO ₃

Column: IonPac AS12A (manufactured by Thermo Fisher Scientific)

Flow: 1ml / min

Sampler: ASRS300

Injection volume: 25μl

The determination criteria of the sulfur concentration of each component in Tables 1 to 4 are as follows.

A: 0ppm or more and less than 50ppm

B: 50ppm or more and less than 100ppm

C: 100ppm or more and less than 150ppm

D: 150ppm or more

According to the formulas in Tables 1 to 4, the ingredients are prepared, and after pre-mixing with a blender, they are dispersed and kneaded with a 3-roll kneader to prepare each composition. In addition, the compounding quantity in a table | surface shows a mass part.

* 9) Titanium oxide produced by the chlorination method (sulfuric acid is not used in the production process), surface treatment: Si / Al, TiO ₂ concentration: 91%, manufactured by Sakai Chemical Industry Co., Ltd. * 10) Oxidation produced by the sulfuric acid method Titanium (sulfuric acid used in the manufacturing process), surface treatment: Si / Al, TiO ₂ concentration: 91%, titanium chemical industry (stock) * 11) Titanium oxide manufactured by the chlorination method (sulfuric acid used in the manufacturing process), surface Treatment: Al / Zr, TiO ₂ concentration: 93%, Ishihara Industry Co., Ltd. * 12) silicon oxide, Longsen Co., Ltd. * 13) barium sulfate * 14) bisfluorenyl phosphine oxide-based photopolymerization initiator * 15) Monofluorinated phosphine oxide based photopolymerization initiator from Japan BASF (stock), * 16) Alpha-aminoacetophenone based photopolymerization initiator from Japan BASF (stock), Japan BASF (stock) Manufacturing * 17) Dipentaerythritol hexaacrylate * 21) Dicyanodimethamine * 22) Melamine, manufactured by Nissan Chemical Industry Co., Ltd. * 24) manufactured by BASF Japan

The curable resin compositions obtained in the respective Examples and Comparative Examples were evaluated based on the following. The results are shown in the following table.

The production conditions of the evaluation substrate are shown below.

Coating: screen printing, film thickness is 30μm when coating, film thickness is 20μm after drying

Drying: 80 ° C for 30 minutes, using hot air circulation drying oven

Exposure: 600mJ / cm ² , exposure machine for metal halide light source

Imaging: 1wt% sodium carbonate, liquid temperature 30 ℃, imaging time 60 seconds, pressure 0.2MPa

Post-curing: 150 ° C for 60 minutes, using hot air circulation drying oven

    (1) Measurement of sulfur concentration of curable resin composition    

The sulfur concentration of each composition in Examples and Comparative Examples was measured by the method described in the above-mentioned method for analyzing sulfur concentration.

    (2) Discoloration of silver plating    

Each composition of the examples and comparative examples was coated on the FR-4 material under the substrate manufacturing conditions described above, and the copper portion of the circuit-forming substrate obtained by drying, exposing, developing, and post-curing was cured with silver plating. The substrate is placed in a sealable glass container, sealed, and placed in an 80 ° C oven. After the addition, each substrate was taken out 24 hours and 48 hours later, and the change in the silver plating portion was evaluated. The judgment criteria are as follows.

○: After 48 hours, the silver plating part did not change color

△: After 24 hours, the silver plating part did not change color, but after 48 hours, the silver plating part changed color

×: Discoloration of silver plating part after 24 hours

    (3) Rupture point (imageability)    

The dry coating film obtained by coating and drying each composition of the imaging type of the examples and comparative examples on the FR-4 material under the above substrate manufacturing conditions was blown at 30 ° C and 1% by weight of carbonic acid at a pressure of 0.2 MPa. Sodium solution was measured until the dry coating film was completely dissolved. The judgment criteria are as follows.

○: 30 seconds or less

△: More than 30 seconds and less than 40 seconds

×: 40 seconds or more

    (4) UV resistance    

Each composition of the examples and comparative examples was coated on the FR-4 material under the substrate manufacturing conditions described above, and the surface of the coating film of the substrate obtained by drying, exposing, developing, and post curing was irradiated with UV using a metal halide lamp as a light source. Light 100J. With a spectrophotometer (CM-2600d, manufactured by KONICA MINOLTA SENSING), the reflectance at a wavelength of 555 nm before and after UV irradiation was measured. The judgment criteria are as follows.

○: The reflectance difference before and after irradiation is 1 or less

△: The reflectance difference before and after irradiation exceeds 1 and does not reach 2

×: The reflectance difference before and after irradiation is 2 or more

    (5) Reflectivity    

Each composition of the examples and comparative examples was coated on the FR-4 material under the substrate manufacturing conditions described above, and the surface of the coating film of the substrate obtained by drying, exposure, development, and post-curing was cured with a spectrophotometer (CM-2600d , Manufactured by KONICA MINOLTA SENSING (KK), and the reflectance at a wavelength of 555 nm was measured. The judgment criteria are as follows.

◎: The reflectance is 88% or more

○: The reflectance is 85% or more and less than 88%

△: The reflectance is 80% or more and less than 85%

×: The reflectance is less than 80%

    (6) Discoloration resistance    

Each of the compositions of the examples and comparative examples was coated on the FR-4 material under the substrate manufacturing conditions described above, and the substrates obtained by drying, exposure, development, and post-curing and hardening were repeatedly processed 5 times in a reflow oven (up to 285 ° C). . Using a color difference meter, the substrate change rate ΔE before and after processing was obtained. The judgment criteria are as follows.

◎: △ E is 2 or less

○: △ E exceeds 2 and 3 or less

△: △ E is more than 3 and less than 4

×: △ E is 4 or more

According to the formulas in Tables 9 to 12 below, each component is prepared, and after pre-mixing with a mixer, it is dispersed and kneaded with a 3-roll kneader to prepare each composition. In addition, the compounding quantity in a table | surface shows a mass part. The determination criteria of the sulfur concentration of each component in Tables 9 to 12 are as follows.

A: Above 0ppm and less than 60ppm

B: More than 60ppm and less than 130ppm

C: more than 130ppm and less than 180ppm

D: 180ppm or more

The curable resin compositions obtained in the respective Examples and Comparative Examples were evaluated based on the following. The results are shown in the following table.

The production conditions of the evaluation substrates in Examples 2-1 to 2-15 and Comparative Examples 2-1 and 2-2 are shown below.

Coating: screen printing, film thickness is 30μm when coating, film thickness is 20μm after drying

Drying: 80 ° C for 30 minutes, using hot air circulation drying oven

Exposure: 600mJ / cm ² , exposure machine for metal halide light source

Imaging: 1wt% sodium carbonate, liquid temperature 30 ℃, imaging time 60 seconds, pressure 0.2MPa

Post-curing (hardening): 150 ° C for 60 minutes, using hot air circulation drying oven

A hardened material was formed on the evaluation substrate under the above-mentioned production conditions.

The production conditions of the evaluation substrates in Examples 2-16 to 2-18 and Comparative Examples 2-3 are shown below.

Coating: screen printing, film thickness is 30μm when coating, film thickness is 20μm after drying

Drying: 80 ° C for 30 minutes, using hot air circulation drying oven

Post-curing (hardening): 150 ° C for 60 minutes, using hot air circulation drying oven

Based on the above production conditions, a cured product was formed on the evaluation substrate.

The production conditions of the evaluation substrates in Examples 2-19 and Comparative Examples 2-4 are shown below.

Base material: FR-4

Coating: screen printing, film thickness is 30μm when coating, film thickness is 20μm after drying

UV: 1000mJ / cm ² , metal halide lamp

A hardened material was formed on the evaluation substrate under the above-mentioned production conditions.

    (1) Measurement of sulfur concentration of curable resin composition    

Samples of the solid content of each curable resin composition in Examples and Comparative Examples were formed on the copper foil in a solvent-volatile coating film by the method described above, and 0.25 g of the coating film peeled off from the copper foil was measured as a test sample. In addition, Examples 2-1 to 2-18 and Comparative Examples 2-1 to 2-3 use coating films after drying, and Examples 2-19 and Comparative Examples 2-4 use UV curing coating films.

On the other hand, a sample of the composition was obtained by measuring 0.25 g of each composition as a measurement sample. The sulfur concentration was measured by the method described in the sulfur concentration analysis method described above.

    (2) Discoloration of silver plating    

The copper parts of the circuit-forming substrate obtained by curing each of the compositions of the examples and comparative examples by the above-mentioned manufacturing method were subjected to silver plating treatment. The substrate was placed in a sealable glass container, sealed, and placed in an 80 ° C oven. After the addition, each substrate was taken out 24 hours and 48 hours later, and the change in the silver plating portion was evaluated. The judgment criteria are as follows.

○: After 48 hours, the silver plating part did not change color

△: After 24 hours, the silver plating part did not change color, but after 48 hours, the silver plating part changed color

×: Discoloration of silver plating part after 24 hours

    (3) Rupture point (imageability)    

The dry coating film obtained by coating and drying each composition of the imaging type of the examples and comparative examples on the FR-4 material under the above substrate manufacturing conditions was blown at 30 ° C and 1 wt% of carbonic acid at a pressure of 0.2 MPa Sodium solution was measured until the dry coating film was completely dissolved. The judgment criteria are as follows.

○: 30 seconds or less

△: More than 30 seconds and less than 40 seconds

×: 40 seconds or more

    (4) UV resistance    

Each of the compositions of the examples and comparative examples was irradiated with UV light 100J using a metal halide lamp as a light source on the surface of the coating film of the substrate obtained by curing the FR-4 material by the above-mentioned production method. With a spectrophotometer (CM-2600d, manufactured by KONICA MINOLTA SENSING), the reflectance at a wavelength of 555 nm before and after UV irradiation was measured. The judgment criteria are as follows.

○: The reflectance difference before and after irradiation is 1 or less

△: The reflectance difference before and after irradiation exceeds 1 and does not reach 2

×: The reflectance difference before and after irradiation is 2 or more

    (5) Reflectivity    

Each composition of the examples and comparative examples was cured on the FR-4 material by the above-mentioned production method. The coating film surface of the substrate was measured with a spectrophotometer (CM-2600d, manufactured by KONICA MINOLTA SENSING (stock)), and the measurement wavelength was 555 nm Of reflectance. The judgment criteria are as follows.

◎: The reflectance is 88% or more

○: The reflectance is 85% or more and less than 88%

△: The reflectance is 80% or more and less than 85%

×: The reflectance is less than 80%

    (6) Discoloration resistance    

The substrates obtained by curing the respective compositions of the examples and comparative examples on the FR-4 material according to the above-mentioned manufacturing method were repeatedly processed 5 times in a reflow furnace (up to 285 ° C). Using a color difference meter, the substrate change rate ΔE before and after processing was obtained. The judgment criteria are as follows.

◎: △ E is 2 or less

○: △ E exceeds 2 and 3 or less

△: △ E is more than 3 and less than 4

×: △ E is 4 or more

As shown in the above table, it can be seen that all the compositions having a sulfur concentration of 100 ppm or less of the curable resin composition are hardened products that are not easily discolored by silver plating and have a small reduction in reflectance due to ultraviolet irradiation. In addition, it can be seen that the developability at the time of the image development type is also excellent.

Further, as shown in the above table, it can be seen that all the compositions having a sulfur content of the solid content of the curable resin composition of 130 ppm or less are hardened products that are hardly discolored by silver plating and have a small reduction in reflectance due to ultraviolet irradiation. In addition, it can be seen that the developability at the time of the image development type is also excellent.

Claims (8)

    A curable resin composition comprising (A) a curable resin and (B) a titanium oxide-containing curable resin composition, wherein the (A) curable resin is selected from the group consisting of (A-1) thermosetting At least one of a thermosetting resin and (A-2) a photocurable resin, and the (A-1) thermosetting resin is at least one selected from an epoxy compound and an oxetane compound, and the (A-2) ) The photocurable resin is at least one selected from the group consisting of the following carboxyl-containing resins, (1) a carboxyl-containing resin obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated group-containing compound, and (2) the carboxyl-containing resin of the above (1) In the resin, a photosensitive carboxyl group resin obtained by adding a compound having one epoxy group and one or more (meth) acrylfluorene groups in the molecule, and the sulfur concentration of the (B) titanium oxide is 100 ppm or less. The sulfur concentration of the curable resin composition is 100 ppm or less.         A curable resin composition comprising (A) a curable resin and (B) a titanium oxide-containing curable resin composition, wherein the (A) curable resin is selected from the group consisting of (A-1) thermosetting At least one of a thermosetting resin and (A-2) a photocurable resin, and the (A-1) thermosetting resin is at least one selected from an epoxy compound and an oxetane compound, and the (A-2) ) The photocurable resin is at least one selected from the group consisting of the following carboxyl-containing resins, (1) a carboxyl-containing resin obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated group-containing compound, and (2) the carboxyl-containing resin described in (1) above. In the resin, a photosensitive carboxyl group resin obtained by adding a compound having one epoxy group and one or more (meth) acrylfluorene groups in the molecule, and the sulfur concentration of the (B) titanium oxide is 100 ppm or less. The sulfur content of the solid content of the curable resin composition is 130 ppm or less.         The curable resin composition according to claim 1 or 2, further comprising (C) a photopolymerization initiator.         The curable resin composition according to claim 1 or 2, which is used for coating on copper.         A hardenable dry film, characterized by having a resin layer, which is obtained by applying a hardenable resin composition according to any one of claims 1 to 4 on a film and drying it.         A hardened material characterized by hardening a curable resin composition according to any one of claims 1 to 4 or a resin layer of a dry film according to claim 5 by at least one of light irradiation and heating.         A printed wiring board characterized by having a hardened body as claimed in claim 6.         As in the printed wiring board of claim 7, a part of the conductive circuit is treated with silver plating.