KR102457069B1 - Curable resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

The present invention relates to a curable resin composition that is difficult to discolor silver plating and produces a cured product with little decrease in reflectance due to ultraviolet irradiation, a dry film having a resin layer obtained from the composition, and a printed wiring board having the cured product and the cured product to provide. Curable resin composition containing (A) curable resin and (B) titanium oxide WHEREIN: They are curable resin composition etc. whose sulfur concentration of the said curable resin composition is 100 ppm or less. Moreover, curable resin composition containing (A) curable resin and (B) titanium oxide WHEREIN: It is curable resin composition etc. whose sulfur concentration of solid content of the said curable resin composition is 130 ppm or less.

Description

Curable resin composition, dry film, hardened|cured material, and a printed wiring board {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, and more specifically, a curable resin composition obtained from a cured product that is difficult to discolor silver plating and has little decrease in reflectance due to ultraviolet irradiation, and a resin layer obtained from the composition It is related with the dry film which has, its hardened|cured material, and the printed wiring board which has this hardened|cured material.

By apply|coating curable resin composition to base materials, such as a printed wiring board, and hardening it, using as insulating layers, such as a soldering resist, is performed widely (for example, patent document 1). When the curable resin composition is used as an insulating layer of a printed wiring board on which a light emitting element such as a light emitting diode (LED) or an electroluminescence (EL) is mounted, a curable resin composition such as white having high reflectivity so that light can be used effectively It is often composed as

Moreover, in order to improve the reflectance of visible light, and the connection reliability of an electrode, it is performed silver plating process to the surface of the conductive circuit of the mounting part of such a printed wiring board (for example, patent document 2). Since silver plating corrodes and discolors black just by leaving it in the air, in order to prevent deterioration of brightness, reliability, and adhesion to mounting parts due to discoloration, the surface of the silver plating is treated with a discoloration inhibitor. have.

Japanese Patent Application Laid-Open No. 2005-311233 Japanese Patent Application Laid-Open No. 2007-189006

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

Moreover, the insulating layer containing the hardened|cured material of curable resin composition of high reflectance also had the problem that a reflectance gradually falls by exposure to ultraviolet-ray at the time of practical use.

Accordingly, an object of the present invention is a curable resin composition that is difficult to discolor silver plating and provides a cured product with little decrease in reflectance due to ultraviolet irradiation, a dry film having a resin layer obtained from the composition, a cured product and the cured product To provide a printed wiring board having

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject was solvable by making the sulfur concentration in curable resin composition 100 ppm or less, as a result of earnestly examining in view of the above, and came to complete this invention.

Moreover, as a result of earnest examination in view of the above, these inventors discovered that the said subject could be solved by making the sulfur concentration of solid content of curable resin composition 130 ppm or less, and came to complete this invention.

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

Further, in another curable resin composition of the present invention, in the curable resin composition comprising (A) a curable resin and (B) titanium oxide, the sulfur concentration of the solid content of the curable resin composition is 130 ppm or less.

It is preferable that curable resin composition of this invention contains (C) a photoinitiator further.

It is preferable to apply|coat and use the curable resin composition of this invention on copper.

The dry film of this invention has a resin layer obtained by apply|coating and drying the said curable resin composition to a film, It is characterized by the above-mentioned.

The hardened|cured material of this invention is obtained by hardening|curing the said curable resin composition or the resin layer of the said dry film by at least any one of light irradiation and heating, It is characterized by the above-mentioned.

The printed wiring board of this invention has the said hardened|cured material, It is characterized by the above-mentioned.

As for the printed wiring board of this invention, it is preferable that a part of a conductive circuit is silver-plated.

ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition from which it is hard to discolor silver plating, and the hardened|cured material with little fall of the reflectance by ultraviolet irradiation is obtained, the dry film which has a resin layer obtained from this composition, the hardened|cured material, and the print which has this hardened|cured material A wiring board can be provided.

The curable resin composition according to the first embodiment of the present invention is a curable resin composition comprising (A) a curable resin and (B) titanium oxide, wherein the curable resin composition has a sulfur concentration of 100 ppm or less. The curable resin composition according to the second embodiment of the present invention is a curable resin composition comprising (A) a curable resin and (B) titanium oxide, wherein the sulfur concentration of the solid content of the curable resin composition is 130 ppm or less, characterized in that will be. Although the detailed mechanism is not clear, the hardened|cured material obtained from curable resin composition of this invention can not only reduce the discoloration of the silver plating provided on a printed wiring board, but can suppress the fall of the reflectance by ultraviolet irradiation of hardened|cured material.

The hardened|cured material in this invention refers to what was hardened using the energy of light or a heat|fever for curable resin composition. In addition, in the hardened|cured material, liquids, such as a dilution solvent and water, shall be 0.1 mass % or less. Hardening by light does not have designation of a light source, and what is necessary is just to generate|occur|produce a radical reaction of curable resin composition, Especially, a metal halide lamp and a high pressure mercury lamp are preferable. As an energy amount of light, 5-4000 mJ/cm<2> is preferable and 20-2000 mJ/cm<2> is more preferable. As for curing by heat, what is necessary is just to thermoset curable resin composition using a hot-air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, etc. As for hardening temperature, 50-250 degreeC is preferable, More preferably, 70-200 degreeC is preferable. 5-180 minutes are preferable and, as for hardening time, 15-120 minutes are more preferable.

As a conventional suppression method of the decrease of the reflectance by ultraviolet irradiation of hardened|cured material, although using resin of specific structures, such as resin which does not contain an aromatic ring, is mentioned, Although developability and the heat resistance fall were caused in some cases. ADVANTAGE OF THE INVENTION According to curable resin composition of this invention, even if it does not use resin of a specific structure, there can be obtained hardened|cured material with little fall of a reflectance.

In addition, in the conventional alkali developing type curable resin composition, when titanium oxide is highly charged in order to increase reflectance, titanium oxide has a heavy specific gravity, so there is also a problem that development is difficult. When it is set as the curable resin composition of , it is excellent also in developability.

In this invention, the sulfur concentration of the solid content of curable resin composition means the sulfur concentration of the state in which the solvent volatilized from curable resin composition, In the case of a non-solvent, the sulfur concentration of that state is said.

70 ppm or less is preferable and, as for the sulfur concentration of curable resin composition which concerns on 1st Embodiment of this invention, 50 ppm or less is more preferable. Moreover, 100 ppm or less is preferable and, as for the sulfur concentration of solid content of curable resin composition which concerns on 2nd Embodiment of this invention, 80 ppm or less is more preferable. In the present invention, the sulfur concentration can be measured according to the standard "BS EN 14582:2007". As the pretreatment, a quartz tube combustion method may be used, and the ion chromatography method may be used for the measurement of the content.

The sulfur concentration of the curable resin composition according to the first embodiment of the present invention and the sulfur concentration of the solid content of the curable resin composition according to the second embodiment of the present invention are 100 ppm or less and 130 ppm or less, respectively, by blending many components with a low sulfur content. Can be adjusted. In particular, in a white or gray curable resin composition containing titanium oxide as a white coloring agent, in order to fill titanium oxide highly, it is essential to use titanium oxide with a low sulfur concentration. For example, titanium oxide in which sulfuric acid is used in the manufacturing process, particularly during neutralization of surface treatment, tends to have a high sulfur content.

Next, each component of the curable resin composition of this invention is demonstrated. In addition, in this specification, (meth)acrylate is a general term for an acrylate, a methacrylate, and mixtures thereof, and the same applies to other similar expressions.

[(A) curable resin]

Curable resin composition of this invention contains (A) curable resin. (A) curable resin used in this invention is (A-1) thermosetting resin or (A-2) photocurable resin, These mixtures may be sufficient. In addition, (A) curable resin may have an aromatic ring in structure, and does not need to have it.

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

((A-1) thermosetting resin)

(A-1) As a thermosetting resin, what is necessary is just resin which hardens|cures by heating and shows electrical insulation, For example, an epoxy compound, an oxetane compound, a melamine resin, etc. are mentioned. In particular, in this invention, an epoxy compound and an oxetane compound can be used suitably, These may be used together.

As said epoxy compound, the well-known and usual compound which has one or more epoxy groups can be used, Especially, the compound which has two or more epoxy groups is preferable. For example, monoepoxy compounds such as monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether and glycidyl (meth) acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type Epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4' -diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanu The compound which has 2 or more epoxy groups in 1 molecule, such as a rate and a triglycidyl tris (2-hydroxyethyl) isocyanurate, is mentioned. These can be used individually or in combination of 2 or more types according to a required characteristic.

Specifically, as a compound having two or more epoxy groups, jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Co., Ltd., Epiclone 840, Epiclone 850, Epiclone 1050, and Epiclone 2055 manufactured by DIC Corporation. , Epotote YD-011, YD-013, YD-127, YD-128 manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., D.E.R. 317, D.E.R. 331, D.E.R. 661, D.E.R. 664, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, A.E.R. 330, A.E.R. 331, A.E.R. 661, A.E.R. bisphenol A epoxy resins such as 664 (all are brand names); Mitsubishi Chemical Co., Ltd. jERYL903, DIC Co., Ltd. Epiclone 152, Epiclone 165, Shin-Nitetsu Sumikin Chemical Co., Ltd. Epottot YDB-400, YDB-500, Dow Chemical Nihon ( D.E.R. 542, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESB-400, ESB-700, Asahi Kasei Materials Co., Ltd. A.E.R. 711, A.E.R. Brominated epoxy resins, such as 714 (all are brand names); Mitsubishi Chemical Co., Ltd. jER152, jER154, Dow Chemical Nippon Co., Ltd. D.E.N. 431, D.E.N. 438, DIC Co., Ltd. Epiclon N-730, Epiclon N-770, Epiclon N-865, Shin-Nittetsu Sumikin Chemical Co., Ltd. Epotote YDCN-701, YDCN-704, Nippon Gaya EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESCN-195X, ESCN-220, Asahi A.E.R. by Kasei Materials Co., Ltd. ECN-235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd. -704, YDCN-704A, DIC Corporation Epiclon N-680, N-690, N-695 (all are brand names), such as novolak-type epoxy resins; Epiclon 830 manufactured by DIC Co., Ltd., jER807 manufactured by Mitsubishi Chemical Co., Ltd., EPOTOT YDF-170, YDF-175, YDF-2004 manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd. (all brand names) of bisphenol F-type epoxy resin; Hydrogenated bisphenol-A epoxy resins, such as EPOTOT ST-2004, ST-2007, and ST-3000 (brand name) by the Shin-Nittetsu Sumikin Chemical Co., Ltd. product; jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epottot YH-434 manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd.; Glycidylamine type epoxy resins, such as Sumitomo Chemical Co., Ltd. product Sumi-epoxy ELM-120 (all are brand names); hydantoin-type epoxy resin; alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Co., Ltd. (all are brand names); Trihydroxyphenylmethane type epoxy resins, such as YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501, EPPN-502 manufactured by Dow Chemical Corporation (all are brand names); Bixylenol type or biphenol type epoxy resins, such as Mitsubishi Chemical Co., Ltd. product YL-6056, YX-4000, YL-6121 (all are brand names), or mixtures thereof; bisphenol S-type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Corporation, and EXA-1514 (trade name) manufactured by DIC Corporation; Bisphenol A novolak-type epoxy resins, such as the Mitsubishi Chemical Corporation jER157S (brand name); tetraphenylolethane type epoxy resins such as jERYL-931 manufactured by Mitsubishi Chemical Co., Ltd. (all are brand names); Heterocyclic epoxy resins, such as TEPIC (all are brand names) made from Nissan Chemical Industry Co., Ltd.; Diglycidyl phthalate resins, such as Nichiyu Co., Ltd. product Blemmer DGT; Tetraglycidyl xylenoyl ethane resins, such as ZX-1063 by the Shin-Nittetsu Sumikin Chemical Co., Ltd. product; Naphthalene group-containing epoxy resins such as ESN-190, ESN-360 manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., HP-4032 manufactured by DIC Corporation, EXA-4750, and EXA-4700; Epoxy resins having dicyclopentadiene skeletons such as HP-7200 and HP-7200H manufactured by DIC Corporation; glycidyl methacrylate copolymerization type epoxy resins such as CP-50S and CP-50M manufactured by Nichiyu Co., Ltd.; Furthermore, copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Although CTBN-modified epoxy resins (For example, YR-102, YR-450, etc. made by Shin-Nittetsu Sumikin Chemical Co., Ltd.) etc. are mentioned, It is not limited to these. Among these, a bisphenol A epoxy resin, a heterocyclic epoxy resin, or a mixture thereof is preferable at the point which is especially excellent in 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 is demonstrated. The general formula (I):

Specific examples of the oxetane compound containing an oxetane ring represented by (wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) include 3-ethyl-3-hydroxymethyloxetane (Toagose ( Co., Ltd. product, trade name OXT-101), 3-ethyl-3-(phenoxymethyl) oxetane (Toagosei Co., Ltd. product, trade name OXT-211), 3-ethyl-3-(2-ethylhexyloxymethyl) ) oxetane (manufactured by Toagosei Co., Ltd., trade name OXT-212), 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (manufactured by Toagose Co., Ltd., trade name) OXT-121), bis(3-ethyl-3-oxetanylmethyl)ether (Toagosei Co., Ltd. product, brand name OXT-221) etc. are mentioned. Moreover, the oxetane compound of a phenol novolak type, etc. are mentioned. These oxetane compounds may be used together with the said epoxy compound, and may be used independently.

((A-2) photocurable resin)

Next, as the photocurable resin (A-2), any resin that is cured by active energy ray irradiation and exhibits electrical insulation properties is sufficient, and in particular, in the present invention, a compound having one or more ethylenically unsaturated bonds in the molecule is preferable. is used sparingly

As a compound which has an ethylenically unsaturated bond, a well-known and usual photopolymerizable oligomer, a photopolymerizable vinyl monomer, etc. are used. Among these, as a photopolymerizable oligomer, an unsaturated polyester type oligomer, a (meth)acrylate type oligomer, etc. are mentioned. Examples of the (meth)acrylate oligomer include epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and bisphenol epoxy (meth)acrylate, urethane (meth) Acrylate, epoxyurethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene modified (meth)acrylate, etc. are mentioned.

As a photopolymerizable vinyl monomer, A well-known and usual thing, For example, Styrene derivatives, such as styrene, chlorostyrene, (alpha)-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate, or vinyl benzoate; Vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; (such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide meth)acrylamides; allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isoboronyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) ) esters of (meth)acrylic acid such as acrylates; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate; Alkoxyalkylene glycol mono(meth)acrylates, such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate alkylene polyol poly(meth)acrylates such as , pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate; Polyoxyalkylene glycol poly(es) such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane tri(meth)acrylate meth) acrylates; poly(meth)acrylates such as hydroxypivalate neopentyl glycol ester di(meth)acrylate; Isocyanurate-type poly(meth)acrylates, such as tris[(meth)acryloxyethyl] isocyanurate, etc. are mentioned. These can be used individually or in combination of 2 or more types according to a required characteristic.

Moreover, when making the composition of this invention into the photosensitive resin composition of an alkali developing type, it is preferable to use carboxyl group-containing resin as (A) curable resin. Carboxyl group-containing photosensitive resin which has an ethylenically unsaturated group may be sufficient as carboxyl group-containing resin, and it is not necessary to 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 listed below (any of oligomers and polymers may be used).

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate or isobutylene. When this carboxyl group-containing resin has an aromatic ring, at least 1 sort(s) of an unsaturated carboxylic acid and an unsaturated group containing compound should just have an aromatic ring.

(2) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyols and polyethers Carboxyl groups by polyaddition reaction of diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups Containing urethane resin. When this carboxyl group-containing urethane resin has an aromatic ring, at least 1 sort(s) of diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound should just have an aromatic ring.

(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol , Bisphenol A alkylene oxide adduct diol, a terminal carboxyl group-containing urethane obtained by reacting an acid anhydride with the terminal of a urethane resin by polyaddition reaction of a diol compound such as a diol having a phenolic hydroxyl group and an alcoholic hydroxyl group Suzy. When this carboxyl group-containing urethane resin has an aromatic ring, at least 1 sort(s) of a diisocyanate compound, a diol compound, and an acid anhydride should just have an aromatic ring.

(4) Diisocyanate and bifunctional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin A photosensitive carboxyl group-containing urethane resin by polyaddition reaction of a (meth)acrylate or a partial acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, at least one of diisocyanate, (meth)acrylate of a bifunctional epoxy resin or a partial acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound has an aromatic ring do.

(5) During the synthesis of the resin of (2) or (4) above, a compound having one hydroxyl group and one or more (meth)acryloyl group is added to a molecule such as hydroxyalkyl (meth)acrylate, and the terminal ( Meth) acrylated carboxyl group-containing urethane resin. When this photosensitive carboxyl group containing urethane resin has an aromatic ring, the compound which has one hydroxyl group and one or more (meth)acryloyl group may have an aromatic ring in a molecule|numerator.

(6) During the synthesis of the resin of (2) or (4), an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, having one isocyanate group and one or more (meth)acryloyl groups in the molecule A carboxyl group-containing urethane resin obtained by adding a compound to (meth)acrylated terminal. When this photosensitive carboxyl group containing urethane resin has an aromatic ring, the compound which has one isocyanate group and one or more (meth)acryloyl groups in a molecule|numerator may have an aromatic ring.

(7) A polyfunctional epoxy resin is reacted with (meth)acrylic acid, and a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is added to the hydroxyl group present in the side chain. A photosensitive carboxyl group-containing resin. When this photosensitive carboxyl group-containing resin has an aromatic ring, at least 1 sort(s) of a polyfunctional epoxy resin and a dibasic acid anhydride should just have an aromatic ring.

(8) A photosensitive carboxyl group-containing resin in which (meth)acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of the bifunctional epoxy resin with epichlorohydrin, and dibasic acid anhydride is added to the generated hydroxyl group. When this photosensitive carboxyl group-containing resin has an aromatic ring, at least 1 sort(s) of a bifunctional epoxy resin and a dibasic acid anhydride should just have an aromatic ring.

(9) A polyester resin containing a carboxyl group in which a dicarboxylic acid is reacted with a polyfunctional oxetane resin, and a dibasic acid anhydride is added to the primary hydroxyl group generated. When this photosensitive carboxyl group containing polyester resin has an aromatic ring, at least 1 sort(s) of polyfunctional oxetane resin, dicarboxylic acid, and dibasic acid anhydride should just have 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 or propylene oxide is reacted with an unsaturated group-containing monocarboxylic acid, and the resulting reaction product is polybasic acid A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.

(11) 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 or propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

(12) In an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and (meth)acrylic acid An unsaturated group-containing monocarboxylic acid is reacted, and polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid are reacted with the alcoholic hydroxyl group of the obtained reaction product. The carboxyl group-containing photosensitive resin obtained. When this photosensitive carboxyl group-containing polyester resin has an aromatic ring, at least one of an epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, an unsaturated group-containing monocarboxylic acid, and a polybasic acid anhydride You need to have an directional ring.

(13) In the resin of any one of (1) to (12) above, one epoxy group and one or more (meth) ) Photosensitive carboxyl group-containing resin formed by further adding a compound having an acryloyl group. When this photosensitive carboxyl group containing urethane resin has an aromatic ring, the compound which has one epoxy group and one or more (meth)acryloyl groups in a molecule|numerator may have an aromatic ring.

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

(15) An unsaturated monocarboxylic acid is reacted with a copolymer of a compound each having one epoxy group and an unsaturated double bond in one molecule and a compound having an unsaturated double bond, and the resulting secondary hydroxyl group is saturated or unsaturated A photosensitive carboxyl group-containing resin obtained by reacting a polybasic acid anhydride.

(16) A photosensitive hydroxyl group and carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride, and then reacting the resulting carboxylic acid with a compound each having one epoxy group and an unsaturated double bond in one molecule .

Since the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone/polymer, development by a diluted aqueous alkali solution is possible.

Moreover, among the above, since the composition excellent in dry to touch property and discoloration is obtained when (A) carboxyl group-containing resin which does not have an aromatic ring in Examples (14) - (16) and Example (1) is obtained, it is preferable.

The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH/g, more preferably in the range of 40 to 180 mgKOH/g. If it is in the range of 20 to 200 mgKOH/g, adhesion of the coating film is obtained, alkali development is facilitated, dissolution of the exposed part by the developer is suppressed, lines are not thinner than necessary, and normal resist pattern drawing is easy. It is preferable because it

In addition, although the weight average molecular weight of carboxyl group-containing resin used by this invention changes with resin frame|skeleton, the range of 2,000-150,000 is preferable. If it is this range, the adhesion-free performance is favorable, the coating-film moisture resistance after exposure is favorable, and it is hard to generate|occur|produce a film|membrane decrease at the time of image development. Moreover, if it is the range of the said weight average molecular weight, a resolution will improve, developability will become favorable, and storage stability will become favorable. More preferably, it is 5,000-100,000. A weight average molecular weight can be measured by gel permeation chromatography.

In addition, (A) when an epoxy resin and a carboxyl group-containing resin are used together as the curable resin, the equivalent of the epoxy group contained in the epoxy resin is preferably 2.0 or less with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin, more preferably is 1.5 or less. This is because developability tends to improve when the equivalence ratio becomes small.

[(B) titanium oxide]

Curable resin composition of this invention contains (B) titanium oxide. (B) A sulfur concentration of 100 ppm or less is preferable and, as for titanium oxide, it is more preferable that it is 50 ppm or less. In addition, a commercially available titanium oxide having a sulfur concentration of 100 ppm or less may be used, and a commercially available titanium oxide having a sulfur concentration of more than 100 ppm may be subjected to heat treatment or chemical treatment, or purification treatment such as washing or calcination to reduce the sulfur concentration. It may be lowered and combined. Here, the sulfur contained in (B) titanium oxide refers to all the sulfur detected by analysis, (B) sulfur adsorbed to titanium oxide, and (B) sulfur contained as an impurity in titanium oxide.

(B) The method for producing titanium oxide may be any of a sulfuric acid method and a chlorine method, and the chlorine method is preferable. In addition, it is preferable not to use sulfuric acid in the manufacturing process. Further, the surface treatment of (B) titanium oxide is not particularly limited, but titanium oxide treated with an acid other than sulfuric acid such as hydrochloric acid, nitric acid, phosphoric acid or acetic acid when neutralizing the surface treatment is preferable.

As titanium oxide, the titanium oxide of any structure among a rutile type, an anatase type, and a Ramsdelite type may be sufficient, and may be used individually by 1 type, and may be used in combination of 2 or more type. Among them, Ramsdelite-type titanium oxide is Ramsdelite-type Li _{0 .} It can obtain by performing _the lithium desorption process by chemical oxidation to ₅ TiO2.

Among the above, use of rutile-type titanium oxide is preferable because heat resistance can be further improved, discoloration due to light irradiation becomes difficult to occur, and quality can be difficult to deteriorate even in a severe use environment. In particular, heat resistance can be further improved by using a rutile-type titanium oxide surface-treated with aluminum oxide such as alumina. The content of rutile-type titanium oxide surface-treated with aluminum oxide in the total titanium oxide is preferably 10 mass % or more, more preferably 30 mass % or more, and the upper limit is 100 mass % or less, that is, the amount of titanium oxide. The total amount may be rutile-type titanium oxide surface-treated with the aluminum oxide. Moreover, since anatase-type titanium oxide has a lower hardness than that of a rutile-type, when anatase-type titanium oxide is used, the point of the moldability of a composition becomes more favorable.

Examples of commercially available titanium oxide having a sulfur concentration of 100 ppm or less include R-931 manufactured by Dupont, Tiona 595 manufactured by CRISTAL, SX3103 manufactured by Sakai Chemical Co., Ltd., and the like.

Such a compounding amount of titanium oxide (B) with respect to the solid content in the curable resin composition (components excluding the organic solvent when the curable resin composition contains an organic solvent) is preferably in the range of 5 to 80% by mass, more preferably Preferably, it is the range of 10-70 mass %. (B) When two or more types of titanium oxide are used as titanium oxide, since reflectance becomes high, it is preferable. In this case, it is preferable that the sulfur concentration of each titanium oxide is 100 ppm or less, respectively, and it is more preferable that the sum of the sulfur concentrations of each titanium oxide is 100 ppm or less.

The curable resin composition of this invention may contain other white coloring agents other than a titanium oxide. As another white colorant, zinc oxide, potassium titanate, zirconium oxide, antimony oxide, lead white, zinc sulfide, lead titanate, etc. are mentioned.

The curable resin composition of the present invention may contain titanium oxide with a sulfur concentration exceeding 100 ppm within a range not impairing the effects of the present invention and a sulfur concentration of the curable resin composition not exceeding 100 ppm. As titanium oxide with a sulfur concentration exceeding 100 ppm, Ishihara Sangyo Co., Ltd. product CR-58, CR-90, R-630, Sakai Chemical Co., Ltd. product R-21 etc. are mentioned.

[(C) Photoinitiator]

Curable resin composition of this invention WHEREIN: When using (A-2) photocurable resin, it is preferable to further add (C) a photoinitiator. (C) As a photoinitiator, if it is a well-known photoinitiator as a photoinitiator and a photoradical generator, any can also be used.

(C) Examples of the photopolymerization initiator include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2). , 6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, Bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2 bisacylphosphine oxides such as, 4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF Japan, IRGACURE 819); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine oxide, P monoacylphosphine oxides such as valoylphenylphosphinate isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan, DAROCUR TPO); 1-Hydroxy-cyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 -{4-[4-(2-Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropane- hydroxyacetophenones such as 1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2- acetophenones such as (dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-di thioxanthone such as isopropyl thioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbox oxime esters such as bazol-3-yl]-,1-(O-acetyloxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)- titanocenes such as bis[2,6-difluoro-3-(2-(1-phyll-1-yl)ethyl)phenyl]titanium; Phenyldisulfide 2-nitrofluorene, butyroin, anisoinethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. are mentioned. All the above photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

Among the above, acylphosphine oxide-type photoinitiators, such as bisacylphosphine oxides and monoacylphosphine oxides, are preferable because there is little adhesion and is excellent in the discoloration inhibitory effect. Especially, it is preferable to use bisacylphosphine oxides at the point which can improve a sensitivity and non-tackiness more.

(C) The compounding quantity of a photoinitiator is 0.1-50 mass parts with respect to 100 mass parts of (A) curable resin in conversion of solid content. (C) By mix|blending a photoinitiator in this range, the photocurability on copper becomes sufficient, sclerosis|hardenability of a coating film becomes favorable, coating-film characteristics, such as chemical-resistance, improve, and deep-part sclerosis|hardenability also improves. More preferably, it is 1-40 mass parts with respect to 100 mass parts of (A) curable resin.

(C) It is preferable to use the thing which does not contain a sulfur atom in a structure as a photoinitiator.

[(D-1) curing agent and (D-2) curing catalyst]

Curable resin composition of this invention WHEREIN: When using (A-1) thermosetting resin, at least any 1 sort(s) of (D-1) hardening|curing agent and (D-2) curing catalyst can further be added.

(D-1) Examples of the curing agent include polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof, aliphatic or aromatic primary or secondary amines, polyamide resins, isocyanate compounds, polymercapto compounds, and the like. Among these, a polyfunctional phenol compound, a polycarboxylic acid, and its acid anhydride are used preferably from the point of workability|operativity and insulation.

As a polyfunctional phenol compound, what is necessary is just a compound which has two or more phenolic hydroxyl groups in 1 molecule, and a well-known and usual thing can be used. Specific examples include phenol novolac resins, cresol novolac resins, bisphenol A, allylated bisphenol A, bisphenol F, bisphenol A novolac resins, vinylphenol copolymer resins, etc., which have high reactivity and have an effect of increasing heat resistance. Since it is high, especially bisphenol A is preferable. Such a polyfunctional phenol compound is also subjected to an addition reaction with at least any one of an epoxy compound and an oxetane compound in the presence of an appropriate curing catalyst.

The polycarboxylic acid and its acid anhydride include a compound having two or more carboxyl groups in one molecule and an acid anhydride thereof, for example, a copolymer of (meth)acrylic acid, a copolymer of maleic anhydride, a condensate of a dibasic acid, etc. can be heard As a commercial item, John Creel (brand name) by BASF Corporation, SMA resin (brand name) by Satoma Corporation, polyazelaic anhydride by Rika Corporation, New Nippon, etc. are mentioned.

As for the compounding ratio of these (D-1) hardening|curing agent, the quantitative ratio normally used is sufficient, with respect to 100 mass parts of (A-1) thermosetting resin, 1-200 mass parts suitably, More preferably, 10-100 mass is wealth

Further, (D-2) the curing catalyst is a compound that can serve as a curing catalyst in the reaction of a thermosetting resin such as an epoxy compound and an oxetane compound, and (D-1) a curing agent, or polymerization when no curing agent is used It is a catalyst compound. Specific examples of the curing catalyst include tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphines, crown ether complexes, and phosphonium ylide, among which arbitrarily, independently Or it can be used in combination of 2 or more types.

Especially, imidazoles, such as brand names 2E4MZ, C11Z, C17Z, 2PZ, azine compounds of imidazoles, such as brand names 2MZ-A and 2E4MZ-A, isocyanur of imidazoles, such as brand names 2MZ-OK and 2PZ-OK Imidazole hydroxymethyl compounds such as acid salts, trade names 2PHZ and 2P4MHZ (all trade names are manufactured by Shikoku Kasei Kogyo Co., Ltd.), dicyandiamide and its derivatives, melamine and its derivatives, diaminomaleonitrile and its derivatives, diethylene amines such as triamine, triethylenetetramine, tetraethylenepentamine, bis(hexamethylene)triamine, triethanolamine, diaminodiphenylmethane, organic acid dihydrazide, 1,8-diazabicyclo[5,4, 0] undecene-7 (trade name DBU, manufactured by San-Apro Co., Ltd.), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane ( Organic phosphine compounds, such as a brand name ATU, Ajinomoto Co., Ltd. product), or a triphenylphosphine, a tricyclohexyl phosphine, a tributyl phosphine, and a methyldiphenyl phosphine, etc. are mentioned suitably.

The compounding quantity of these (D-2) curing catalysts is sufficient in a normal ratio, It is 0.05-10 mass parts suitably with respect to 100 mass parts of (A) curable resin, More preferably, it is 0.1-6 mass parts.

[(E) antioxidant]

It is preferable that curable resin composition of this invention contains (E) antioxidant further. (E) By containing an antioxidant, the effect of preventing oxidative deterioration of curable resin, etc. and suppressing discoloration is acquired, while heat resistance improves, the effect that resolution (linewidth reproducibility) becomes favorable can also be acquired . That is, when (B) titanium oxide is used, resolution may deteriorate by reflecting light, but favorable resolution will be acquired by containing (E) antioxidant.

(E) Antioxidants include radical scavengers that invalidate generated radicals and peroxide decomposers that decompose generated peroxides into harmless substances to prevent new radicals from being generated. You may use combining the above.

Specifically, as the (E) antioxidant acting as a radical scavenger, for example, hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t- Butyl-p-cresol, 2,2-methylene-bis(4-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) Butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3',5'- phenol-based compounds such as di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, quinone-based compounds such as metaquinone and benzoquinone; and amine compounds such as bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate and phenothiazine. As a commercial item, IRGANOX 1010 (above, BASF Japan Co., Ltd. product, brand name) etc. can be used, for example.

Moreover, as (E) antioxidant which acts as a peroxide decomposing agent, phosphorus compounds, such as triphenylphosphite, etc. are mentioned, for example.

Among the above, it is preferable to use a phenolic antioxidant from the point from which the inhibitory effect of discoloration, the improvement of heat resistance, and favorable resolution are further acquired.

(E) 0.01 mass parts - 10 mass parts are preferable with respect to 100 mass parts of (A) curable resin, and, as for the compounding quantity in the case of using antioxidant, 0.01-5 mass parts are more preferable. (E) By making the compounding quantity of antioxidant into 0.01 mass part or more, the effect by addition of the antioxidant mentioned above can be acquired reliably, On the other hand, by setting it as 10 mass parts or less, photoreaction is not inhibited, and favorable alkali development properties can be obtained, and good properties such as dry to touch properties and coating film properties can also be ensured.

In addition, since (E) antioxidant, especially phenolic antioxidant, may exhibit an additional effect by using together with a heat-resistant stabilizer, you may mix|blend a heat-resistant stabilizer with the resin composition of this invention.

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

0.01 mass parts - 10 mass parts are preferable with respect to 100 mass parts of (A) curable resin, and, as for the compounding quantity in the case of using a heat-resistant stabilizer, 0.01-5 mass parts are more preferable.

The curable resin composition of this invention may contain a filler. A filler is used in order to raise the physical strength etc. of the hardened|cured material obtained. The filler is not particularly limited, and known and usual fillers, for example, silica, crystalline silica, Neuburg 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, inorganic pigments such as zinc oxide and the like can be used, but the filler preferably does not contain sulfur.

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

The curable resin composition of the present invention may contain a reactive diluent solvent. The reactive diluent solvent is used to adjust the viscosity of the composition to improve workability, and to increase crosslinking density or to improve adhesion and the like, and a photocurable monomer may be used. As a photocurable monomer, the said photopolymerizable vinyl monomer etc. can be used. It is preferable that the reactive diluent solvent does not contain a sulfur atom in raw materials (starting raw materials, etc.) for resin synthesis.

Preferably the compounding ratio of such a reactive dilution solvent is 1-100 mass parts with respect to 100 mass parts of (A) curable resin, More preferably, it is a ratio of 1-70 mass parts. By setting it as the range of the said compounding ratio, photocurability improves, pattern formation becomes easy, and the intensity|strength of a cured film can also be improved.

Moreover, curable resin composition of this invention can be made to contain an organic solvent for the objective of manufacture of a composition, viscosity adjustment at the time of apply|coating to a board|substrate or a carrier film, etc. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether glycol ethers such as acetate and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; A well-known and usual organic solvent, such as petroleum solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. These organic solvents can be used individually or in combination of 2 or more types.

Moreover, you may mix|blend with the curable resin composition of this invention other well-known and usual additives in the field|area of an electronic material. Examples of the other additives include a thermal polymerization inhibitor, an ultraviolet absorber, a silane coupling agent, a plasticizer, a flame retardant, an antistatic agent, an anti-aging agent, an antibacterial/mildew inhibitor, an antifoaming agent, a leveling agent, a thickener, an adhesion imparting agent, a thixotropic imparting agent, and other colorants. , a photoinitiation auxiliary agent, a sensitizer, a curing accelerator, a mold release agent, a surface treatment agent, a dispersing agent, a dispersing auxiliary agent, a surface modifier, a stabilizer, a phosphor, and the like.

The curable resin composition of this invention may be used as a dry film, and may be used as a liquid phase. When using as a liquid phase, one-component type may be sufficient, and two or more components may be sufficient as it. In particular, (A) curable resin and (B) when two or more liquids are included including components other than titanium oxide, (A) curable resin and (B) titanium oxide may be blended in the same formulation or may be blended in different formulations. none.

Next, the dry film of this invention has a resin layer obtained by apply|coating and drying the curable resin composition of this invention on a carrier film. When forming a dry film, first, the curable resin composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater , a gravure coater, a spray coater, or the like, is applied to a uniform thickness on the carrier film. Then, a resin layer can be formed by drying the apply|coated composition at the temperature of 50-130 degreeC for 1 to 30 minutes normally. Although there is no restriction|limiting in particular about the coating film thickness, Generally, it is 10-150 micrometers as a film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

As a carrier film, a plastic film is used, For example, polyester films, such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, etc. can be used. Although there is no restriction|limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

After forming a resin layer containing the curable resin composition of the present invention on a carrier film, it is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. do. As a peelable cover film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, the surface-treated paper etc. can be used, for example. As a cover film, when peeling a cover film, what is necessary is just to be smaller than the adhesive force of a resin layer and a carrier film.

Moreover, in this invention, a resin layer is formed by apply|coating and drying the curable resin composition of this invention on the said protective film, and you may laminate|stack a carrier film on the surface. That is, when manufacturing a dry film in this invention, you may use any of a carrier film and a protective film as a film which apply|coats curable resin composition of this invention.

In addition, when using the curable resin composition of this invention as a photocurable thermosetting composition, by performing exposure (light irradiation) with respect to the resin layer obtained after apply|coating the composition and volatilizing the solvent, an exposure part (light irradiation) part) is hardened. Specifically, by a contact or non-contact method, through a photomask on which a pattern is formed, selectively exposed to an active energy ray, or directly pattern-exposed by a laser direct exposure machine, and the unexposed portion is exposed to a diluted alkali aqueous solution (for example, , 0.3-3 mass % sodium carbonate aqueous solution), a resist pattern is formed. In addition, by heating to a temperature of about 100 to 180 ° C. and thermosetting (post-cure), a cured film (cured product) excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties can be formed. .

When the curable resin composition of the present invention is used as a thermosetting composition, the composition is applied and the solvent is volatilized and dried, for example, by heating to a temperature of about 100 to 180 ° C. It is possible to form a cured film (cured product) excellent in various properties such as hygroscopicity, adhesion, and electrical properties.

In addition, when the curable resin composition of the present invention is used as a photocurable composition, the composition is applied, the solvent is volatilized to dryness, and exposure (light irradiation) is performed, whereby the exposed portion (light irradiated portion) is cured. , a cured film (cured product) can be formed.

Further, the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, the organic solvent, and is applied to a substrate by a dip coating method, a flow coating method, a roll coating method, a bar coating method, and screen printing. After coating by a method such as a method or a curtain coat method, 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-stick resin layer. In addition, in the case of a dry film in which the composition is applied on a carrier film or a protective film, dried and wound as a film, the composition layer of the present invention is bonded to the substrate by a laminator or the like so that the substrate is in contact with the substrate, and then the carrier film is peeled off. Thereby, a resin layer can be formed.

Examples of the base material include printed wiring boards and flexible printed wiring boards in which a circuit is previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin. ㆍCopper-clad laminate of all grades (FR-4, etc.), other metal substrates, polyimide, etc. A film, a PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, etc. are mentioned.

The volatilization drying or thermal curing is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. (a method of countercurrent contact with hot air in the dryer using a heat source of an air heating method by steam, and a support from a nozzle spraying method) can be used.

As the exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc. are mounted, and any device that irradiates ultraviolet rays in the range of 350 to 450 nm is sufficient, and furthermore, direct drawing A device (eg, a laser direct imaging device that draws an image with a laser directly by CAD data from a computer) can also be used. As a lamp light source or a laser light source of a straight drawing machine, what exists in the range of 350-410 nm of maximum wavelength may be sufficient. The exposure amount for image formation varies depending on the film thickness and the like, but can be generally within the range of 20 to 1000 mJ/cm 2 , preferably 20 to 800 mJ/cm 2 .

The developing method may be a dipping method, a shower method, a spray method, a brush method, or the like. As the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines is used. Can be used.

The curable resin composition of the present invention is suitably used for forming a cured film on a printed wiring board, that is, for a printed wiring board, more suitably used for forming a permanent film, and still more suitably used for forming a solder resist or coverlay. used to do Particularly suitably, it is used for forming a solder resist, ie as a solder resist composition. In addition, in order to form a solder dam, you may use curable resin composition of this invention. In addition, when the curable resin composition of the present invention is white, it emits light from a light emitting diode (LED) or electroluminescence (EL) used as the light source in backlights of liquid crystal displays such as lighting equipment, portable terminals, personal computers, and televisions. It is suitably used for the reflecting plate which reflects the falling light. Moreover, curable resin composition of this invention can be used suitably for formation of the printed wiring board which has a silver-plated conductive circuit. Also when a silver plating process is given to a reflecting plate in order to raise a reflectance, curable resin composition of this invention can be used suitably.

As for the printed wiring board of this invention, it is preferable that a part of a conductive circuit is silver-plated. When the curable resin composition of this invention is a photocurable resin composition, after exposure and image development, in the case of a thermosetting resin composition, what is necessary is just to silver-plate a part of exposed conductive circuit after pattern printing. A silver plating process is not specifically limited, What is necessary is just to use a conventionally well-known method.

[Example]

Hereinafter, this invention is demonstrated in more detail using an Example.

(Synthesis Example 1 of Curable Resin (Photosensitive Copolymer A))

In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 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, ε-caprolactone-modified methacrylic acid (average molecular weight) 314) 174.0 parts by mass, 77.0 parts by mass of methyl methacrylate, 222.0 parts by mass of dipropylene glycol monomethyl ether, and t-butylperoxy2-ethylhexanoate as a polymerization catalyst (manufactured by Nichiyu Co., Ltd., perbutyl O) The mixture of 12.0 mass parts was dripped over 3 hours, it stirred at 110 degreeC for 3 hours, the polymerization catalyst was deactivated, and the resin solution was obtained. After cooling this resin solution, 289.0 parts by mass, 3.0 parts by mass of triphenylphosphine, and 1.3 parts by mass of hydroquinone monomethyl ether were added to Cychroma M100 manufactured by Daicel Co., Ltd. after cooling, and the temperature was raised to 100° C. and stirred for a ring-opening addition reaction of the epoxy group. was performed to obtain photosensitive copolymer resin A (varnish).

Thus, the obtained photosensitive copolymer resin A (varnish) had a solid content concentration of 45.5 mass %, and the acid value of the solid material was 79.8 mgKOH/g. Moreover, the weight average molecular weight (Mw) of the obtained photosensitive copolymer resin A was 15,000.

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

Deionized water: 200 parts by mass and sodium sulfate: 0.3 parts by mass were charged into a pressure-resistant vessel equipped with a thermometer, a cooling tube, and a stirrer, and dissolution was confirmed.

Then, BPO (benzoyl peroxide): 5 parts by mass as a polymerization initiator and MSD (α-methylstyrene dimer): 5 parts by mass as a chain transfer agent: MMA (methyl methacrylate): 10.4 parts by mass, n-BA (normal -Butyl acrylate): 5 mass parts, MAA (methacrylic acid): 24.6 mass parts, and St (styrene): It added to the monomer mixture containing 60 mass parts, and it melt|dissolved sufficiently.

Thereafter, the dispersing agent was added so that the concentration became 300 ppm, and the mixture was sufficiently stirred, and after replacing the inside of the furnace with nitrogen, the temperature was raised to perform suspension polymerization. After completion of polymerization, the resulting suspension was filtered through a mesh having a scale of 30 µm and dried with warm air at 40°C to obtain a granular resin. Thus obtained granular resin (copolymer resin) was fully melt|dissolved using the organic solvent DPM (dipropylene glycol methyl ether), and the non-photosensitive copolymer resin B (varnish) was obtained.

Thus, the obtained non-photosensitive copolymer resin B (varnish) had a solid content concentration of 50 mass %, and the acid value of the solid material was 160 mgKOH/g. In addition, 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 photosensitive resin C))

To 600 g of diethylene glycol monoethyl ether acetate, 1070 g (glycidyl) of orthocresol novolak type epoxy resin (DIC Corporation, EPICLONN-695, softening point 95°C, epoxy equivalent 214, average number of functional groups 7.6) Radix number (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were added thereto, and the mixture was heated and stirred at 100° C. for uniform dissolution. Then, 4.3 g of triphenylphosphine was added, and after heating at 110 degreeC and reaction for 2 hours, the temperature was raised to 120 degreeC, and reaction was performed for 12 hours further. To the obtained reaction solution, 415 g of aromatic hydrocarbons (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added, reacted at 110° C. for 4 hours, cooled, and cresol novolac photosensitive resin C (varnish). ) was obtained.

Thus, the solid content concentration of the cresol novolak-type photosensitive resin C (varnish) obtained was 65 mass %, and the acid value of solid content was 89 mgKOH/g. Moreover, the weight average molecular weight (Mw) of the obtained cresol novolak-type photosensitive resin C was 9,000.

In addition, the weight average molecular weight of the obtained resin is pump LC-6AD manufactured by Shimatsu Seisakusho Co., Ltd., and Column Shodex (registered trademark) KF-804, KF-803, KF manufactured by Showa Denko Co., Ltd. -802 was determined by high performance liquid chromatography in triplicate.

(Analysis method of sulfur concentration)

About each component shown in the following table|surface, the sulfur concentration was measured by the following method. 0.25 g of each component was measured, respectively, and this was used as a measurement sample. As a pretreatment, using a Mitsubishi Chemical Co., Ltd. sample combustion apparatus: QF-02 type, the combustion process was performed to each measurement sample by the quartz tube combustion method according to the following conditions.

1. Combustion conditions

(1) Conditions for temperature increase (temperature increase section)

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

(2) Combustion conditions (combustion section)

Inlet (inlet): 850℃, Outlet (outlet): 900℃

(3) Combustion time 40min (total)

2. Gas conditions (all values indicated by the flow meter of the device body)

(1) Oxygen SUB 100ml/min

(2) Oxygen MAIN 200ml/min

(3) Argon/Oxygen 100ml/min (conversion at 700℃)

(4) Total flow rate 400ml/min

3. Gas conditions for combustion

(1) Up to 700°C of temperature rising part: argon, after 700°C: oxygen

(2) Combustion section up to 900°C: Oxygen

4. Absorption liquid 0.3% hydrogen peroxide 15ml (after combustion treatment, volume up to 25ml)

The ion content of the absorbed liquid after the mass-up obtained above was measured by an ion chromatography method under the following conditions, and the sulfur concentration of each component was calculated|required.

Ion Chromatograph: ICS-1500 (Thermo Fisher Scientific)

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

Column: IonPac AS12A (manufactured by Thermo Fisher Scientific)

Flow: 1ml/min

Suppressor: ASRS300

Injection volume: 25 μl

The determination criteria of the sulfur concentration of each component in Tables 1-4 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 formulation shown in Tables 1 to 4 below, each component was blended and premixed with a stirrer, then dispersed with a triaxial roll mill and kneaded to prepare a composition, respectively. In addition, the compounding quantity in a table|surface shows a mass part.

*1) Photosensitive copolymer resin A synthesized above

*2) Non-photosensitive copolymer resin B synthesized above

*3) Cresol novolac-type resin C synthesized above

*4) jER828, manufactured by Mitsubishi Chemical Co., Ltd.

*5) Epicoat 157S-70 (solvent 30% by mass diluted product), manufactured by Mitsubishi Chemical Co., Ltd.

*6) TEPIC-HP, manufactured by Nissan Chemical High School Co., Ltd.

*7) Titanium oxide produced by chlorine method (no use of sulfuric acid in the production process), surface treatment: Al ₂ O ₃ , ZrO ₂ , TiO ₂ concentration: 91%, manufactured by Crystal Corporation

*8) Titanium oxide produced by chlorine method (no use of sulfuric acid in the production process), surface treatment: Si/Al, TiO ₂ concentration: 80%, manufactured by DuPont

*9) Titanium oxide produced by chlorine method (no use of sulfuric acid in the production process), surface treatment: Si/Al, TiO ₂ concentration: 91%, manufactured by Sakai Chemical Co., Ltd.

*10) Titanium oxide produced by the sulfuric acid method (there is use of sulfuric acid in the production process), surface treatment: Si/Al, TiO ₂ concentration: 91%, manufactured by Sakai Chemical Co., Ltd.

*11) Titanium oxide produced by chlorine method (there is use of sulfuric acid in the production process), surface treatment: Al/Zr, TiO ₂ concentration: 93%, manufactured by Ishihara Sangyo Co., Ltd.

*12) Silica, manufactured by Tatsumori Co., Ltd.

*13) Barium sulfate

*14) Bisacylphosphine oxide-based photopolymerization initiator, manufactured by BASF Japan

*15) Monoacylphosphine oxide-based photopolymerization initiator, manufactured by BASF Japan Co., Ltd.

*16) α-aminoacetophenone-based photopolymerization initiator, manufactured by BASF Japan

*17) Dipentaerythritol hexaacrylate

*21) dicyandiamide

*22) Melamine, manufactured by Nissan Chemical Industries, Ltd.

*23) Shin-Etsu Chemical High School Co., Ltd.

*24) BASF Japan Co., Ltd.

About the curable resin composition of each obtained Example and a comparative example, evaluation was performed according to the following. The result is shown in the following table|surface.

The manufacturing conditions of an evaluation board|substrate are shown below.

Application: Screen printing, film thickness of 30 µm at the time of application, film thickness of 20 µm after drying

Drying: 80℃ 30 minutes, using a hot air circulation drying furnace

Exposure: 600mJ/cm2, exposure machine of metal halide lamp light source

Development: 1 wt% sodium carbonate, liquid temperature 30°C, development time 60 seconds, pressure 0.2 MPa

Post Cure: 150℃ for 60 minutes, using a hot air circulation drying furnace

(1) Measurement of sulfur concentration of curable resin composition

For each composition of Examples and Comparative Examples, the sulfur concentration was measured by the method described in the method for analyzing the sulfur concentration.

(2) silver plating discoloration

Each of the compositions of Examples and Comparative Examples was applied, dried, exposed, developed, and post-cured to a FR-4 material under the above-described substrate production conditions, and cured, and silver plating was performed on the copper portion of the circuit-forming substrate obtained. The substrate was placed in a sealable glass container, sealed, and placed in an oven at 80°C. Each board|substrate was taken out after 24 hours and 48 hours after injection|throwing-in, and the change of a silver plating part was evaluated. The judgment criteria are as follows.

(circle): There is no discoloration of a silver plating part after 48 hours.

(triangle|delta): There is no discoloration of the silver plating part after 24 hours, but the silver plating part after 48 hours is discolored.

x: The silver plating part is discolored after 24 hours.

(3) Breakpoint (developability)

Each of the developable compositions of Examples and Comparative Examples was applied to FR-4 material under the above substrate preparation conditions and dried, and 30° C., 1 wt% sodium carbonate solution was blown into a dry coating film obtained by drying at a pressure of 0.2 MPa, so that the dried coating film was completely The time until dissolution was measured. The judgment criteria are as follows.

○: 30 seconds or less

△: more than 30 seconds and less than 40 seconds

×: 40 seconds or longer

(4) UV resistance

Each composition of Examples and Comparative Examples was cured by applying, drying, exposing, developing, and post-curing each composition to the FR-4 material under the above-mentioned conditions for preparing the substrate. investigated. The reflectance in wavelength 555 nm before and behind UV irradiation was measured with the spectrophotometer (CM-2600d, Konica Minolta Sensing Co., Ltd. product). The judgment criteria are as follows.

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

△: The difference in reflectance before and after irradiation is more than 1 and less than 2

x: the difference in reflectance before and after irradiation is 2 or more

(5) reflectance

The coating film surface of the substrate obtained by applying, drying, exposing, developing, and post-cure each composition of Examples and Comparative Examples to FR-4 material under the above substrate manufacturing conditions and curing it was measured with a spectrophotometer (CM-2600d, Konica Minolta Sensing). Co., Ltd. product, and the reflectance in wavelength 555 nm was measured. The judgment criteria are as follows.

(double-circle): reflectance 88% or more

○: reflectance of 85% or more and less than 88%

(triangle|delta): reflectance 80% or more and less than 85%

x: the reflectance is less than 80%

(6) discoloration resistance

Each composition of Examples and Comparative Examples was cured by applying, drying, exposing, developing, and post-curing each composition to FR-4 material under the above-mentioned substrate manufacturing conditions, and repeating 5 times in a reflow furnace (up to 285°C) processed. Using a colorimeter, the rate of change ΔE of the substrate before and after the treatment was determined. The judgment criteria are as follows.

◎: ΔE is 2 or less

○: ΔE is greater than 2 and less than or equal to 3

Δ: ΔE is more than 3 and less than 4

×: ΔE is 4 or more

According to the formulations shown in Tables 9 to 12 below, each component was blended and premixed with a stirrer, then dispersed with a triaxial roll mill and kneaded to prepare a composition, respectively. 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 9-12 are as follows.

A: 0ppm or more and less than 60ppm

B: 60ppm or more and less than 130ppm

C: 130ppm or more and less than 180ppm

D: 180ppm or more

*18) Epoxy acrylate MA-2000, manufactured by Mitsubishi Chemical Co., Ltd.

*19) Phosphorus-containing methacrylate Kayama PM2 manufactured by Nippon Kayaku Co., Ltd.

*20) acrylate monomer light ester HO manufactured by Kyoesha Chemical Co., Ltd.

*25) Idemitsu Kosan Co., Ltd. product

About the curable resin composition of each obtained Example and a comparative example, evaluation was performed according to the following. The result is shown in the following table|surface.

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

Application: Screen printing, film thickness of 30 µm at the time of application, film thickness of 20 µm after drying

Drying: 80℃ 30 minutes, using a hot air circulation drying furnace

Exposure: 600mJ/cm2, exposure machine of metal halide lamp light source

Development: 1 wt% sodium carbonate, liquid temperature 30°C, development time 60 seconds, pressure 0.2 MPa

Post cure (curing): 150℃ 60 minutes, using a hot air circulation drying furnace

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

The manufacturing conditions of the evaluation board|substrates in Examples 2-16 - 2-18 and Comparative Example 2-3 are shown below.

Application: Screen printing, film thickness of 30 µm at the time of application, film thickness of 20 µm after drying

Drying: 80℃ 30 minutes, using a hot air circulation drying furnace

Post cure (curing): 150℃ 60 minutes, using a hot air circulation drying furnace

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

The manufacturing conditions of the evaluation board|substrate in Example 2-19 and Comparative Example 2-4 are shown below.

Materials: FR-4 material

Application: Screen printing, film thickness of 30 µm at the time of application, film thickness of 20 µm after drying

UV: 1000mJ/cm2 metal halide lamp

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

(1) Measurement of sulfur concentration of curable resin composition

The solid content samples of each curable resin composition of Examples and Comparative Examples formed a coating film in a state in which the solvent was volatilized by the above method on copper foil, and 0.25 g of the formed coating film peeled from the copper foil was weighed to obtain a measurement sample. . In Examples 2-1 to 2-18 and Comparative Examples 2-1 to 2-3, a coating film after drying was used, and in Examples 2-19 and Comparative Example 2-4, a coating film after UV curing was used.

In addition, 0.25 g of each composition was measured for the sample of a composition, and this was used as a measurement sample.

The sulfur concentration was measured by the method described in the method for analyzing the sulfur concentration above.

(2) silver plating discoloration

The silver plating process was given to the copper part of the circuit formation board|substrate obtained by hardening each composition of an Example and a comparative example with the said manufacturing method. The substrate was placed in a sealable glass container, sealed, and placed in an oven at 80°C. After injection|throwing-in, each board|substrate was taken out after 24 hours and 48 hours, and the change of a silver plating part was evaluated. The judgment criteria are as follows.

(circle): There is no discoloration of a silver plating part after 48 hours.

(triangle|delta): There is no discoloration of the silver plating part after 24 hours, but the silver plating part after 48 hours is discolored.

x: The silver plating part is discolored after 24 hours.

(3) Breakpoint (developability)

Each of the developable compositions of Examples and Comparative Examples was applied to FR-4 material under the above substrate preparation conditions and dried, and 30° C., 1 wt% sodium carbonate solution was blown into a dry coating film obtained by drying at a pressure of 0.2 MPa, and the dried coating film was completely The time until dissolution was measured. The judgment criteria are as follows.

○: 30 seconds or less

△: more than 30 seconds and less than 40 seconds

×: 40 seconds or longer

(4) UV resistance

100J of UV light using a metal halide lamp as a light source was irradiated to the surface of the coating film of the board|substrate obtained by making each composition of an Example and a comparative example harden|cure FR-4 material by the said manufacturing method. The reflectance in wavelength 555 nm before and behind UV irradiation was measured with the spectrophotometer (CM-2600d, Konica Minolta Sensing Co., Ltd. product). The judgment criteria are as follows.

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

△: The difference in reflectance before and after irradiation is more than 1 and less than 2

x: the difference in reflectance before and after irradiation is 2 or more

(5) reflectance

The coating film surface of the substrate obtained by curing each composition of Examples and Comparative Examples by the above production method on FR-4 material was measured with a spectrophotometer (CM-2600d, manufactured by Konica Minolta Sensing Co., Ltd.) at a wavelength of 555 nm. The reflectance was measured. The judgment criteria are as follows.

(double-circle): reflectance 88% or more

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

(triangle|delta): reflectance 80% or more and less than 85%

x: the reflectance is less than 80%

(6) discoloration resistance

The substrate obtained by curing each composition of Examples and Comparative Examples on FR-4 material by the above production method was repeatedly treated 5 times in a reflow furnace (up to 285°C). Using a colorimeter, the rate of change ΔE of the substrate before and after the treatment was determined. The judgment criteria are as follows.

◎: ΔE is 2 or less

○: ΔE is greater than 2 and less than or equal to 3

Δ: ΔE is more than 3 and less than 4

×: ΔE is 4 or more

As shown in the said table, in the composition whose sulfur concentration of curable resin composition is 100 ppm or less, it turns out that it is hard to discolor silver plating in all, and hardened|cured material with little fall of the reflectance by ultraviolet irradiation is obtained. Moreover, in the case of a developable type, it turns out that it is excellent also in developability.

In addition, as shown in the table above, in the composition in which the sulfur concentration of the solid content of the curable resin composition is 130 ppm or less, it is difficult to discolor the silver plating, and it can be seen that a cured product with little decrease in reflectance due to ultraviolet irradiation is obtained. . Moreover, in the case of a developable type, it turns out that it is excellent also in developability.

Claims (11)

(A) a curable resin and (B) a curable resin composition comprising titanium oxide, wherein the curable resin composition has a sulfur concentration of 100 ppm or less, and (B) titanium oxide does not use sulfuric acid in the manufacturing process. and (B) titanium oxide containing two or more kinds of titanium oxide, and as the two or more kinds of titanium oxide, a titanium oxide having a sulfur concentration of 0 ppm or more and less than 50 ppm, and an oxidation having a sulfur concentration of 50 ppm or more and less than 100 ppm Curable resin composition for printed wiring boards containing titanium. (A) a curable resin and (B) a curable resin composition comprising titanium oxide, wherein the sulfur concentration of the solid content of the curable resin composition is 130 ppm or less, and the (B) titanium oxide does not use sulfuric acid in the manufacturing process. It is titanium oxide, and the (B) titanium oxide includes two or more kinds of titanium oxide, and as the two or more kinds of titanium oxide, a titanium oxide having a sulfur concentration of 0 ppm or more and less than 60 ppm, and a sulfur concentration of 60 ppm or more and 130 ppm Curable resin composition for printed wiring boards containing less titanium oxide. The curable resin composition for a printed wiring board according to claim 1 or 2, further comprising (C) a photoinitiator. The curable resin composition for a printed wiring board according to claim 1 or 2, wherein the composition is applied on copper and used. It has a resin layer obtained by apply|coating and drying the curable resin composition for printed wiring boards of Claim 1 or 2 to a film, Curable dry film characterized by the above-mentioned. Hardened|cured material obtained by hardening|curing the curable resin composition for printed wiring boards of Claim 1 or 2 by at least any one of light irradiation and a heating, The hardened|cured material characterized by the above-mentioned. A cured product obtained by curing the resin layer of the dry film according to claim 5 by at least any one of light irradiation and heating. It has the hardened|cured material of Claim 6, The printed wiring board characterized by the above-mentioned. It has the hardened|cured material of Claim 7, The printed wiring board characterized by the above-mentioned. The printed wiring board according to claim 8, wherein a part of the conductive circuit is plated with silver. The printed wiring board according to claim 9, wherein a part of the conductive circuit is plated with silver.