JP2017125101A - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition which makes it possible to obtain a cured product having excellent crack resistance after high-temperature treatment such as solder reflow, a dry film having a resin layer obtained from the composition, a cured product thereof, and a printed wiring board having the cured product.SOLUTION: The present invention provides a curable resin composition and the like. The curable resin composition comprises (A) curable resin and (B) inorganic filler. In the (B) inorganic filler, the concentration of sulfur that does not constitute the inorganic filler is 10 ppm or less.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition, a cured product, and a printed wiring board, and more specifically, a curable resin composition from which a cured product excellent in crack resistance after high-temperature treatment such as solder reflow is obtained, and a resin obtained from the composition The present invention relates to a dry film having a layer, a cured product thereof, and a printed wiring board having the cured product.

  The curable resin composition is widely used as an insulating layer such as a solder resist by being applied to a substrate such as a printed wiring board and cured (for example, Patent Document 1). In particular, in a solder resist, an inorganic filler is blended in order to improve crack resistance (for example, Patent Document 2).

JP 2005-31233 A JP 2000-181058 A

  However, when solder reflow or the like is performed on this solder resist at a high temperature of 200 ° C. or higher, there is a problem that sufficient crack resistance cannot be obtained even if an inorganic filler is blended.

  Accordingly, an object of the present invention is to provide a curable resin composition capable of obtaining a cured product excellent in crack resistance after high-temperature treatment such as solder reflow, a dry film having a resin layer obtained from the composition, the cured product, and the cured product. It is providing the printed wiring board which has this.

  As a result of intensive studies in view of the above, the present inventors focused on the impurity concentration of the inorganic filler, and in particular, the crack resistance after high-temperature treatment such as solder reflow affects the concentration of sulfur that does not constitute the inorganic filler. As a result, the present invention has been completed.

  The curable resin composition of the present invention is a curable resin composition containing (A) a curable resin and (B) an inorganic filler, and sulfur that does not constitute the inorganic filler in the (B) inorganic filler. The concentration of is 10 ppm or less.

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

  The cured product of the present invention is obtained by curing the curable resin composition or the resin layer of the dry film.

  The printed wiring board of the present invention comprises the cured product.

  The printed wiring board of the present invention preferably has a conductive member containing at least silver.

According to the present invention, a curable resin composition from which a cured product excellent in crack resistance after high-temperature treatment such as solder reflow is obtained, a dry film having a resin layer obtained from the composition, the cured product, and the cured product. The printed wiring board which has can be provided.
Further, according to the present invention, since the concentration of sulfur not constituting the inorganic filler is reduced, when applied to a printed wiring board having a conductive member containing silver, it is possible to effectively prevent black change due to silver corrosion. Can do.
Further, according to the present invention, in the case of a white curable resin composition for a reflector, in addition to crack resistance after high-temperature treatment such as solder reflow, it is possible to effectively prevent a decrease in reflectance due to light or heat. .

The curable resin composition of the present invention is a curable resin composition containing (A) a curable resin and (B) an inorganic filler, and sulfur that does not constitute the inorganic filler in the (B) inorganic filler. The concentration of is 10 ppm or less.
Although the detailed mechanism is not clear, surprisingly, the cured product obtained from the curable resin composition of the present invention reduces cracks after high-temperature treatment such as solder reflow by reducing the concentration of sulfur that does not constitute the inorganic filler. Resistance can be improved.

  The curable resin composition of the present invention preferably has a sulfur concentration of 100 ppm or less, more preferably 70 ppm or less, and even more preferably 50 ppm or less. Here, the concentration of sulfur in the curable resin composition refers to the concentration of sulfur that does not constitute each component intentionally blended in the curable resin composition.

  In the curable resin composition of the present invention, the concentration of sulfur that does not constitute each component intentionally blended in the solid content of the composition is preferably 130 ppm or less, more preferably 100 ppm or less, and even more preferably 80 ppm or less. Here, the concentration of sulfur in the solid content of the curable resin composition is the amount of sulfur that does not constitute each component that is intentionally blended in the curable resin composition in a state where the solvent is volatilized from the curable resin composition. The concentration refers to the concentration of sulfur that does not constitute each component that is intentionally blended in the curable resin composition in that state in the absence of a solvent.

  The concentration of sulfur in the curable resin composition of the present invention and the concentration of sulfur in the solid content of the composition are reduced to the above range by blending many components with low sulfur content including (B) inorganic filler. can do. For example, in a white or gray curable resin composition containing titanium oxide, it is preferable to use titanium oxide having a low sulfur concentration in order to highly fill titanium oxide. For example, titanium oxide in which sulfuric acid is used during the production process, particularly during neutralization of the surface treatment, tends to have a high sulfur content.

  In the present invention, the concentration of sulfur may be a quartz tube combustion method as a pretreatment, and an ion chromatography method may be used for content measurement. For example, it can be measured according to the standard “BS EN 14582: 2007”.

  The curable resin composition of the present invention is preferably white from the viewpoint of reflectance.

  Next, each component of the curable resin composition of this invention is demonstrated. In addition, in this specification, (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture 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. Moreover, (A) curable resin may or may not have an aromatic ring in the structure.

  (A) It is preferable that curable resin does not contain a sulfur atom in the raw material (for example, starting material etc.) of resin synthesis.

((A-1) Thermosetting resin)
(A-1) As a thermosetting resin, what is necessary is just a resin which is hardened | cured by heating and shows electrical insulation, for example, an epoxy compound, an oxetane compound, a melamine resin etc. are mentioned. In particular, in the present invention, an epoxy compound and an oxetane compound can be suitably used, and these may be used in combination.

  As said epoxy compound, the well-known and usual compound which has a 1 or more epoxy group can be used, The compound which has a 2 or more epoxy group is especially preferable. For example, monoepoxy compounds such as monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl (meth) acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, Cresol novolac 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) isocyanurate, tri Rishijirutorisu (2-hydroxyethyl) compound having two or more epoxy groups in one molecule, such as a isocyanurate. These can be used alone or in combination of two or more according to the required properties.

Specific examples of the compound having two or more epoxy groups include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, and Epicron 2055, manufactured by DIC Corporation. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., D. Chemicals manufactured by Dow Chemical Japan Co., Ltd. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Chemical Co., Ltd., Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664phenol (all trade names) bisphenol A type epoxy resin; jERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152, Epicron 165 manufactured by DIC Corporation, Epototo YDB-400, YDB manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. -500, manufactured by Dow Chemical Japan Co., Ltd. E. R. 542, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESB-400, ESB-700, Asahi Kasei E-Materials Co., Ltd. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152, jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC Corporation, Epototo YDCN-701, YDCN-704 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., EPPN- manufactured by Nippon Kayaku Co., Ltd. 201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, A made by Asahi Kasei E-Materials Co., Ltd. . E. R. ECN-235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704 YDCN manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. -704A, novolak type epoxy resin such as Epicron N-680, N-690, N-695 (all trade names) manufactured by DIC Corporation; Epicron 830 manufactured by DIC Corporation; jER807 manufactured by Mitsubishi Chemical Corporation Bisphenol F type epoxy resins such as Epototo YDF-170, YDF-175, YDF-2004, etc. (all trade names) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; Epototo ST-2004 and ST- manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as 2007 and ST-3000 (trade name); jER6 manufactured by Mitsubishi Chemical Corporation 04, Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YH-434; Sumitomo Chemical Co., Ltd. Sumi-epoxy ELM-120 etc. (all trade names) Glycidylamine type epoxy resin; Hydantoin type epoxy resin; Daicel Celoxide 2021, etc. (all trade names); cycloaliphatic epoxy resins; YL-933 manufactured by Mitsubishi Chemical Co., Ltd., T.C. manufactured by Dow Chemical Japan Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) such as trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names), etc. Bisylenol type or biphenol type epoxy resins or mixtures thereof; bisphenol S such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd. Type epoxy resin; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; tetraphenylolethane type epoxy resin such as jERYL-931 (all trade names) manufactured by Mitsubishi Chemical Corporation A heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); NOF Corporation Diglycidyl phthalate resin such as Blemmer DGT; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., HP manufactured by DIC Corporation Naphthalene group-containing epoxy resins such as -4032, EXA-4750, and EXA-4700; epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; CP-50S manufactured by NOF Corporation CP-50M and other glycidyl methacrylate copolymer epoxy resins; cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resins; CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) ) Etc., but are limited to these Not. Among these, bisphenol A type epoxy resin, heterocyclic epoxy resin or a mixture thereof is particularly preferable because of excellent discoloration resistance.
These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

（式中、Ｒ^１は、水素原子または炭素数１〜６のアルキル基を示す）により表されるオキセタン環を含有するオキセタン化合物の具体例としては、３−エチル−３−ヒドロキシメチルオキセタン（東亞合成（株）製、商品名ＯＸＴ−１０１）、３−エチル−３−（フェノキシメチル）オキセタン（東亞合成（株）製、商品名ＯＸＴ−２１１）、３−エチル−３−（２−エチルヘキシロキシメチル）オキセタン（東亞合成（株）製、商品名ＯＸＴ−２１２）、１，４−ビス｛［（３−エチル−３−オキセタニル）メトキシ］メチル｝ベンゼン（東亞合成（株）製、商品名ＯＸＴ−１２１）、ビス（３−エチル−３−オキセタニルメチル）エーテル（東亞合成（株）製、商品名ＯＸＴ−２２１）などが挙げられる。さらに、フェノールノボラックタイプのオキセタン化合物なども挙げられる。これらオキセタン化合物は、上記エポキシ化合物と併用してもよく、また、単独で使用してもよい。 Next, the oxetane compound will be described. The following general formula (I),

Specific examples of oxetane compounds 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 (Toagoi). Synthetic Co., Ltd., trade name OXT-101), 3-ethyl-3- (phenoxymethyl) oxetane (Toagosei Co., Ltd., trade name OXT-211), 3-ethyl-3- (2-ethylhex) Siloxymethyl) oxetane (made by Toagosei Co., Ltd., trade name OXT-212), 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene (made by Toagosei Co., Ltd., trade name) OXT-121), bis (3-ethyl-3-oxetanylmethyl) ether (manufactured by Toagosei Co., Ltd., trade name OXT-221), and the like. Furthermore, phenol novolac type oxetane compounds and the like can also be mentioned. These oxetane compounds may be used in combination with the above epoxy compounds, or may be used alone.

((A-2) Photocurable resin)
Next, (A-2) the photo-curable resin may be any resin that is cured by irradiation with active energy rays and exhibits electrical insulation. In particular, in the present invention, one or more ethylenic resins are present in the molecule. A compound having an unsaturated bond is preferably used.

  As the compound having an ethylenically unsaturated bond, known and commonly used photopolymerizable oligomers, photopolymerizable vinyl monomers, and the like are used. Among these, examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.

  As the photopolymerizable vinyl monomer, known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as 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 ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylate (Meth) acrylamides such as luamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl Esters of (meth) acrylic acid such as (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol Hydroxyalkyl (meth) acrylates such as tri (meth) acrylate; alcohols such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Xylalkylene glycol mono (meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol Alkylene polyol poly (meth) acrylates such as propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxy Polyoxyalkylene glycol poly (methyl) such as trimethylolpropane triacrylate and propoxylated trimethylolpropane tri (meth) acrylate ) Acrylates; poly (meth) acrylates such as hydroxypivalic acid neopentyl glycol ester di (meth) acrylate; isocyanurate-type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate It is done. These can be used alone or in combination of two or more according to the required properties.

  When the composition of the present invention is an alkali development type photosensitive resin composition, a carboxyl group-containing resin is preferably used as the (A) curable resin. The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group, and may or 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 following compounds (any of oligomers and polymers).

  (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene. When this carboxyl group-containing resin has an aromatic ring, it is sufficient that at least one of the unsaturated carboxylic acid and the unsaturated group-containing compound has an aromatic ring.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group. When this carboxyl group-containing urethane resin has an aromatic ring, it is sufficient that at least one of diisocyanate, a carboxyl group-containing dialcohol compound and a diol compound has an aromatic ring.

  (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group. When this carboxyl group-containing urethane resin has an aromatic ring, it is sufficient that at least one of a diisocyanate compound, a diol compound, and an acid anhydride has an aromatic ring.

  (4) Diisocyanate and bifunctional epoxy resin 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, biphenol type epoxy resin ( Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, at least one of diisocyanate, bifunctional epoxy resin (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound is aromatic. It only needs to have a ring.

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

  (6) During the synthesis of the resin of the above (2) or (4), one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule may have an aromatic ring.

  (7) Photosensitivity obtained by reacting polyfunctional epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride to the hydroxyl group present in the side chain Carboxyl group-containing resin. When this photosensitive carboxyl group-containing resin has an aromatic ring, it is sufficient that at least one of the polyfunctional epoxy resin and the dibasic acid anhydride has an aromatic ring.

  (8) A photosensitive carboxyl group obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the resulting hydroxyl group Containing resin. When this photosensitive carboxyl group-containing resin has an aromatic ring, it is sufficient that at least one of a bifunctional epoxy resin and a dibasic acid anhydride has an aromatic ring.

  (9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group. When this photosensitive carboxyl group-containing polyester resin has an aromatic ring, it is sufficient that at least one of a polyfunctional oxetane resin, dicarboxylic acid and dibasic acid anhydride has an aromatic ring.

  (10) Reaction product obtained by reacting 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, with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.

  (11) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate 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) 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) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid. When this photosensitive carboxyl group-containing polyester resin has an aromatic ring, an epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in a molecule, an unsaturated group-containing monocarboxylic acid and a polybasic It suffices that at least one of the acid anhydrides has an aromatic ring.

  (13) One epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate and the like in any one of the resins (1) to (12) above A photosensitive carboxyl group-containing resin obtained by adding a compound having a group. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, a compound having one epoxy group and one or more (meth) acryloyl 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 a compound having an oxirane ring and an ethylenically unsaturated group in one molecule.

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

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

  Since the carboxyl group-containing resin as described above has many carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.

  Moreover, among the above, when the carboxyl group-containing resin having no aromatic ring in the examples (14) to (16) and the example (1) is used, a composition excellent in dryness to touch and discoloration is obtained. Therefore, it is preferable.

  The acid value of the carboxyl group-containing resin is desirably in the range of 20 to 200 mgKOH / g, and more preferably in the range of 40 to 180 mgKOH / g. When it is in the range of 20 to 200 mg KOH / g, adhesion of the coating film is obtained, alkali development is facilitated, dissolution of the exposed portion by the developer is suppressed, and the line does not fade more than necessary, and normal This is preferable because the resist pattern can be easily drawn.

  Moreover, although the weight average molecular weight of carboxyl group-containing resin used by this invention changes with resin frame | skeletons, the range of 2,000-150,000 is preferable. Within this range, tack-free performance is good, the moisture resistance of the coated film after exposure is good, and film loss is less likely to occur during development. Further, when the weight average molecular weight is within the above range, the resolution is improved, the developability is good, and the storage stability is improved. More preferably, it is 5,000-100,000. The weight average molecular weight can be measured by gel permeation chromatography.

  In addition, when using together an epoxy resin and carboxyl group-containing resin as (A) curable resin, the equivalent of the epoxy group contained in an epoxy resin is 2 with respect to 1 equivalent of the carboxyl group contained in carboxyl group-containing resin. 0.0 or less is preferable, and 1.5 or less is more preferable. This is because developability tends to improve as the equivalent ratio decreases.

[(B) Inorganic filler]
The curable resin composition of this invention contains the inorganic filler whose concentration of sulfur which does not comprise the inorganic filler in an inorganic filler is 10 ppm or less as (B) inorganic filler. (B) A commercially available inorganic filler having a sulfur concentration of 10 ppm or less that does not constitute an inorganic filler in the inorganic filler may be used as the inorganic filler, and a commercially available inorganic filler having a sulfur concentration exceeding 10 ppm. The agent may be blended at a reduced sulfur concentration by heat treatment or chemical treatment, or by performing purification treatment such as washing or firing. Here, (B) sulfur which does not constitute the inorganic filler in the inorganic filler does not mean sulfur (for example, a sulfur atom contained in the molecule of barium sulfate) contained in the inorganic filler itself (B), (B) Sulfur adsorbed on the inorganic filler or (B) sulfur contained as an impurity in the inorganic filler. (B) Such sulfur contained in the inorganic filler can be detected by analysis. (B) One or more inorganic fillers may be combined, but when two or more inorganic fillers are combined, the sulfur concentration of each inorganic filler may be 10 ppm or less.

  The kind of inorganic filler is not particularly limited. Examples of inorganic fillers include silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, calcium carbonate, magnesium carbonate, natural mica, synthetic mica, barium sulfate, barium titanate, iron oxide Non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, zinc white and the like can be used. The inorganic filler may be used alone or in combination of two or more. Of the inorganic fillers, barium sulfate is preferred. Moreover, in the case of the resin composition for reflectors, it is preferable to make a resin composition white at the point which can prevent the fall of the reflectance by light or a heat | fever effectively. Examples of the inorganic filler used in this case include titanium oxide, aluminum hydroxide, zinc oxide, potassium titanate, zirconium oxide, antimony oxide, lead white, zinc sulfide, lead titanate and the like, and titanium oxide is particularly preferable.

(B) The method of reducing the concentration of sulfur that does not constitute the inorganic filler in the inorganic filler to 10 ppm is not particularly limited. For example, adjustment of the inorganic filler manufacturing process (cleaning process, neutralization method, etc.), specific Specifically, the use of a sulfuric acid reagent in the production process of the inorganic filler, reduction of the amount used, deletion of the remainder, and the like can be mentioned. Moreover, it is also possible to treat with an acid other than sulfuric acid such as hydrochloric acid, nitric acid, phosphoric acid and acetic acid at the time of neutralization of the surface treatment.
Here, when the inorganic filler is barium sulfate, for example, barite is reduced and roasted with coke to be leached with hot water to obtain a barium sulfide aqueous solution, and then this barium sulfide aqueous solution and hydrochloric acid are reacted to convert barium chloride. After the preparation, there is a method of reacting a bow nitrate (sodium sulfate) solution deiron-purified with potassium permanganate, and filtering, washing and drying the resulting barium sulfate precipitate. Also, a water-soluble zinc salt is added to the barium sulfate slurry to deposit a zinc compound on the surface of the barium sulfate, and the resulting slurry is filtered, washed with water, dried, and then pulverized with a pulverizer as necessary. And a method of obtaining composite particles.

The titanium oxide may be a rutile type, anatase type, or ramsdellite type titanium oxide, and may be used alone or in combination of two or more. Of these, ramsdellite-type titanium oxide can be obtained by subjecting ramsdellite-type Li _0.5 TiO ₂ to a lithium desorption treatment by chemical oxidation. In addition, although the manufacturing method of a titanium oxide may be any of a sulfuric acid method and a chlorine method, the chlorine method is preferable.

  Among the above, when using rutile type titanium oxide, heat resistance can be further improved, discoloration caused by light irradiation is less likely to occur, and quality can be hardly deteriorated even under severe use environment. preferable. In particular, heat resistance can be further improved by using rutile titanium oxide surface-treated with aluminum oxide such as alumina. The content of rutile titanium oxide surface-treated from aluminum oxide in the total titanium oxide 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, the total amount of titanium oxide may be rutile type titanium oxide surface-treated with the aluminum oxide. In addition, since anatase type titanium oxide has lower hardness than that of rutile type, when anatase type titanium oxide is used, it is better in terms of moldability of the composition.

  Examples of commercially available titanium oxide having a sulfur concentration of 10 ppm or less include Tiona595 manufactured by CRISTAL.

  The (B) inorganic filler preferably has a mass reduction ratio of 1% by mass or less when the inorganic filler is heated from 200 ° C. to 800 ° C. at a rate of 10 ° C./min.

  (B) It is preferable that a value in the Lab value of a Munsell color system is -1.0-1.0, and, as for (B) inorganic filler, it is more preferable that it is -1.0-0.5.

  (B) The inorganic filler preferably has a pH of 4.0 to 9.0, more preferably 5.0 to 9.0, and particularly preferably 7.5 to 9.0. .

  (B) The average primary particle diameter of the inorganic filler is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm, and still more preferably 0.1 to 1 μm.

  (B) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. (B) As for the compounding quantity of an inorganic filler, 0.1-300 mass parts is preferable with respect to 100 mass parts of (A) curable resin in conversion of solid content, and 1-200 mass parts is more preferable.

((C) Photopolymerization initiator)
In the curable resin composition of the present invention, when (A-2) a photocurable resin is used, it is preferable to further add (C) a photopolymerization initiator. (C) Any photopolymerization initiator may be used as long as it is a known photopolymerization initiator as a photopolymerization initiator or a photoradical generator.

  (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- (2,4 , 6-Trimethylbenzoyl) -phenylphosphine oxy Bisacylphosphine oxides such as Id (BASF Japan Co., Ltd., IRGACURE819); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl Phenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF Japan Ltd., DAROCUR TPO), etc. Monoacylphosphine oxides; 1-hydroxy-cyclohexyl phenyl ketone, 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, Hydroxyacetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc. Benzoins; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone; acetophenone, , 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl)- Acetophenones such as 1- [4- (4-morpholinyl) phenyl] -1-butanone and N, N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxa Thioxanthones such as Ton, 2,4-Diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, etc. Anthraquinones; 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; -Octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole Oxime esters such as 3-yl]-, 1- (0-acetyloxime); bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) Titanocenes such as -1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium; phenyl Examples include disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. Any of the above photopolymerization initiators may be used alone or in combination of two or more.

  Among the above, acyl phosphine oxide photopolymerization initiators such as bisacyl phosphine oxides and monoacyl phosphine oxides are preferable because they have less tack and are excellent in color change suppressing effect. Among these, it is preferable to use bisacylphosphine oxides from the viewpoint that sensitivity and tack-free property can be further improved.

  (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 blending the photopolymerization initiator in this range, the photocurability on copper becomes sufficient, the curability of the coating film is improved, the coating properties such as chemical resistance are improved, Deep part curability is also improved. More preferably, it is 1-40 mass parts with respect to 100 mass parts of (A) curable resin.

  (C) It is preferable to use a photopolymerization initiator that does not contain a sulfur atom in the structure.

((D-1) Curing Agent and (D-2) Curing Catalyst)
In the curable resin composition of the present invention, when (A-1) a thermosetting resin is used, at least one of (D-1) a curing agent and (D-2) a curing catalyst is further added. can do.

  (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, polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof are preferably used from the viewpoints of workability and insulation.

  As the polyfunctional phenol compound, any compound having two or more phenolic hydroxyl groups in one molecule may be used, and known ones 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, and the like, which have high reactivity and increase heat resistance. Bisphenol A is particularly preferred because of its high effect. Such a polyfunctional phenol compound undergoes an addition reaction with at least one of an epoxy compound and an oxetane compound in the presence of a suitable curing catalyst.

  Polycarboxylic acids and acid anhydrides thereof are compounds having two or more carboxyl groups in one molecule and acid anhydrides thereof, such as (meth) acrylic acid copolymer and maleic anhydride copolymer. And condensates of dibasic acids. Examples of commercially available products include Jonkrill (product group name) manufactured by BASF, SMA resin (product group name) manufactured by Sartomer, and polyazeline acid anhydride manufactured by Shin Nippon Chemical Co., Ltd.

  The blending ratio of these (D-1) curing agents is sufficient in the usually used quantitative ratio, and (A-1) is preferably 1 to 200 parts by mass, and more preferably 100 parts by mass of the thermosetting resin. Is 10 to 100 parts by mass.

  In addition, (D-2) a curing catalyst is a compound that can be a curing catalyst in the reaction between a thermosetting resin such as an epoxy compound and an oxetane compound and (D-1) a curing agent, or when a curing agent is not used. It is a compound that becomes a polymerization catalyst. Specific examples of the curing catalyst include tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphine, crown ether complexes, and phosphonium ylides. It can be used alone or in combination of two or more.

  In particular, imidazoles such as trade names 2E4MZ, C11Z, C17Z, and 2PZ, AZINE compounds such as trade names 2MZ-A and 2E4MZ-A, and isocyanurates of imidazoles such as trade names 2MZ-OK and 2PZ-OK. Imidazole hydroxymethyl compounds such as trade names 2PHZ and 2P4MHZ (both trade names are manufactured by Shikoku Chemicals Co., Ltd.), dicyandiamide and derivatives thereof, melamine and derivatives thereof, diaminomaleonitrile and derivatives thereof, diethylenetriamine, triethylenetetramine, Amines such as tetraethylenepentamine, bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, organic acid dihydrazide, 1,8-diazabicyclo [5,4,0] undecene-7 (trade name DB , Manufactured by San Apro Co., Ltd.), 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (trade name ATU, manufactured by Ajinomoto Co., Inc.), or Suitable examples include organic phosphine compounds such as triphenylphosphine, tricyclohexylphosphine, tributylphosphine, and methyldiphenylphosphine.

  The blending amount of these (D-2) curing catalysts is sufficient in a normal ratio, and is preferably 0.05 to 10 parts by mass, more preferably 0.0 to 100 parts by mass of (A) curable resin. 1 to 6 parts by mass.

((E) Antioxidant)
The curable resin composition of the present invention preferably further contains (E) an antioxidant. (E) By containing an antioxidant, it is possible to prevent the oxidative deterioration of the curable resin and the like and to suppress discoloration. In addition, the heat resistance is improved and the resolution (line width) is improved. The effect that the reproducibility is improved can also be obtained. That is, when (B) titanium oxide is used, the resolution may be deteriorated by reflecting light, but (E) by containing an antioxidant, good resolution can be obtained. It will be possible.

  (E) Antioxidants include radical scavengers that invalidate the generated radicals, and peroxide decomposers that decompose the generated peroxides into innocuous substances and prevent the generation of new radicals. 1 type may be used independently and may be used in combination of 2 or more type.

  Specifically, examples of the (E) antioxidant acting as a radical scavenger include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, and 2,6-di-t-butyl. -P-cresol, 2,2-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, , 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′-di-t- Phenolic compounds such as butyl-4-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2 6,6-tetramethyl-4-piperidyl) - sebacate, and the like amine compounds such as phenothiazine. As a commercial item, IRGANOX1010 (above, BASF Japan Ltd. make, brand name) etc. can be used, for example.

  Examples of the (E) antioxidant that functions as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite.

  Among the above, it is preferable to use a phenol-based antioxidant from the viewpoint of further obtaining an effect of suppressing discoloration, an improvement in heat resistance and a good resolution.

  (E) As for the compounding quantity in the case of using antioxidant, 0.01-10 mass parts is preferable with respect to 100 mass parts of (A) curable resin, and 0.01-5 mass parts is more preferable. (E) By making the compounding quantity of antioxidant 0.01 mass part or more, the effect by addition of the above-mentioned antioxidant can be acquired reliably, on the other hand, by being 10 mass parts or less, Good alkali developability can be obtained without inhibiting the photoreaction, and good touch drying properties and coating film properties can be ensured.

  In addition, (E) antioxidants, particularly phenolic antioxidants, may exhibit further effects when used in combination with a heat stabilizer, and therefore the resin composition of the present invention has a heat resistant stability. An agent may be blended.

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

  The amount of the heat stabilizer used is preferably 0.01 to 10 parts by mass and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of (A) curable resin.

  The curable resin composition of the present invention may contain a reactive diluent solvent. The reactive dilution solvent is used to improve workability by adjusting the viscosity of the composition, to increase the crosslink density, to improve adhesion, and the like, and a photocurable monomer or the like can be used. As the photocurable monomer, the above-mentioned photopolymerizable vinyl monomer or the like can be used. It is preferable that the reactive dilution solvent does not contain a sulfur atom in the raw material for resin synthesis (starting material and the like).

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

  The curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier film. Examples of organic solvents 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 , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarby Tall acetate, propylene glycol monomethyl ether acetate, dip Propylene glycol monomethyl ether acetate, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha, organic solvents conventionally known can be used. These organic solvents can be used alone or in combination of two or more.

  Furthermore, you may mix | blend the other well-known and usual additive in the field | area of an electronic material with the curable resin composition of this invention. Other additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial / antifungal agents, antifoaming agents, leveling agents, thickening agents Agent, adhesion imparting agent, thixotropic property imparting agent, other colorant, photoinitiator aid, sensitizer, curing accelerator, mold release agent, surface treatment agent, dispersant, dispersion aid, surface modifier, Examples thereof include stabilizers and phosphors.

  The curable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more. Particularly when (A) curable resin and (B) components other than inorganic filler are used to make two or more liquids, (A) curable resin and (B) inorganic filler are different even if blended into the same preparation. You may mix | blend with a formulation.

  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 above organic solvent to adjust to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, and a squeeze coater. Apply a uniform thickness on the carrier film using a reverse coater, transfer roll coater, gravure coater, spray coater or the like. Then, the resin layer can be formed by drying the applied composition at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

  As the carrier film, a plastic film is used. For example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like 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 the resin layer made of the curable resin composition of the present invention is formed on the carrier film, a peelable cover film is further formed on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. It is preferable to laminate. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As a cover film, what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.

  In the present invention, a resin layer may be formed by applying and drying the curable resin composition of the present invention on the protective film, and a carrier film may be laminated on the surface. That is, as a film to which the curable resin composition of the present invention is applied when producing a dry film in the present invention, either a carrier film or a protective film may be used.

  Further, when the curable resin composition of the present invention is used as a photocurable thermosetting composition, the resin layer obtained after applying the composition and evaporating and drying the solvent is exposed to light (light By performing (irradiation), the exposed portion (the portion irradiated with light) is cured. Specifically, exposure is selectively performed with an active energy ray through a photomask having a pattern formed by a contact method or a non-contact method, or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution ( For example, a resist pattern is formed by developing with a 0.3 to 3 mass% sodium carbonate aqueous solution. Furthermore, 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 characteristics ) Can be formed.

  When the curable resin composition of the present invention is used as a thermosetting composition, the composition is applied, the solvent is evaporated and dried, and then heated to a temperature of, for example, about 100 to 180 ° C. Thus, a cured film (cured product) excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics can be formed.

  Moreover, when using the curable resin composition of this invention as a photocurable composition, the composition is apply | coated, a solvent is volatilized and dried, exposure (light irradiation) is performed, and an exposure part (light A cured film (cured product) can be formed by curing the irradiated portion).

  In addition, the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using, for example, the organic solvent, and the dip coating method, the flow coating method, the roll coating method, the bar coater on the substrate. After coating by a method such as a printing method, a screen printing method, or a curtain coating method, a tack-free resin layer is formed by volatile drying (temporary drying) of an organic solvent contained in the composition at a temperature of about 60 to 100 ° C. Can be formed. In the case of a dry film obtained by applying the above composition on a carrier film or a protective film and drying and winding up as a film, the layer of the composition of the present invention is brought into contact with the substrate by a laminator or the like. After bonding together, the resin layer can be formed by peeling off the carrier film.

  Examples of the base material include printed wiring boards and flexible printed wiring boards that have been previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy. It is made of materials such as copper-clad laminates for high-frequency circuits using synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., and copper-clad laminates of all grades (FR-4 etc.) Examples thereof include a plate, a metal substrate, a polyimide film, a PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, and a wafer plate.

  The volatile drying or thermal curing is performed by a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, or the like (a method and nozzle in which hot air in a dryer is brought into countercurrent contact with a steam source having a heat source of an air heating method) And a method of spraying on a support.

As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, and the like may be used as long as the apparatus irradiates ultraviolet rays in a range of 350 to 450 nm. Furthermore, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. The lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 410 nm. The exposure amount for image formation varies depending on the film thickness and the like, but is generally 20 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .

  The developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  The curable resin composition of the present invention is preferably used for forming a cured film on a printed wiring board, that is, for a printed wiring board, more preferably used for forming a permanent film, Preferably, it is used to form a solder resist or coverlay. Particularly preferably, it is used for forming a solder resist, that is, as a solder resist composition. In addition, you may use the curable resin composition of this invention in order to form a solder dam. In addition, the curable resin composition of the present invention is white so that it can be used as a light source in a backlight of a liquid crystal display such as a lighting fixture, a portable terminal, a personal computer, and a television. It is suitably used for a reflector that reflects light emitted from luminescence (EL). Moreover, the curable resin composition of this invention can be used suitably for formation of the printed wiring board which has a conductive circuit by which silver plating process was carried out. The curable resin composition of the present invention can also be suitably used when silver plating is applied to the reflector in order to increase the reflectance.

  The printed wiring board of the present invention preferably has a conductive member containing silver. In order to form a conductive member containing silver, a publicly known and commonly used method is used. For example, the conductive member is subjected to silver plating treatment or a silver paste is applied, and at least one of drying and curing is performed. Can be mentioned. In the case of silver plating, when the curable resin composition of the present invention is a photocurable resin composition, after exposure and development, and in the case of a thermosetting resin composition, after the pattern printing, the exposed conductive circuit A part may be silver-plated.

Hereinafter, the present invention will be described in more detail with reference to examples.
(Synthesis example 1 of photocurable resin)
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., 174.0 parts by mass of methacrylic acid, and ε-caprolactone modified Methacrylic acid (average molecular weight 314) 174.0 parts by mass, methyl methacrylate 77.0 parts by mass, dipropylene glycol monomethyl ether 222.0 parts by mass, and t-butylperoxy 2-ethylhexanoate as a polymerization catalyst A mixture of 12.0 parts by mass (manufactured by NOF Corporation, Perbutyl O) was added dropwise over 3 hours, and the mixture was further stirred at 110 ° C. for 3 hours to deactivate the polymerization catalyst to obtain a resin solution. After cooling this resin solution, 289.0 parts by mass of Daicel Cyclomer M100, 3.0 parts by mass of triphenylphosphine and 1.3 parts by mass of hydroquinone monomethyl ether were added, and the temperature was raised to 100 ° C. By stirring, a ring-opening addition reaction of an epoxy group was performed to obtain a photosensitive copolymer resin A (varnish).

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

  In addition, the weight average molecular weight of the obtained resin is the pump LC-6AD manufactured by Shimadzu Corporation and the column Shodex (registered trademark) KF-804, KF-803, KF-802 manufactured by Showa Denko K.K. The measurement was performed by high performance liquid chromatography connected to a triplet.

(Method for producing inorganic filler (barium sulfate A))
First, barite was reduced and roasted with coke and leached with warm water to obtain an aqueous barium sulfide solution. Next, this barium sulfide aqueous solution and hydrochloric acid are reacted to form barium chloride, and then reacted with a boron nitrate (sodium sulfate) solution deiron-purified with potassium permanganate, and the resulting barium sulfate precipitate is filtered, It was washed with water and dried to produce barium sulfate A in which impurities such as unreacted sodium sulfate were reduced.

(Method for producing inorganic filler (barium sulfate B))
A 3% NaOH aqueous solution was added to barium sulfate “Variace B-55” manufactured by Sakai Chemical Industry Co., Ltd. prepared with water to obtain a barium sulfate slurry. A zinc sulfate aqueous solution was dropped into the obtained barium sulfate slurry, and then aged as it was, followed by filtration, washing with water and drying. The dried product was pulverized using a jet mill to obtain composite particles of barium sulfate B.

(Method for analyzing the concentration of sulfur in inorganic fillers that do not constitute inorganic fillers)
About each inorganic filler shown in the following table | surface, the density | concentration of sulfur was measured with the following method. 0.25 g of each inorganic filler was weighed and used as a measurement sample. As pre-treatment, sample combustion equipment manufactured by Mitsubishi Chemical Analytech Co., Ltd .: AQF-2100H type is used, and each measurement sample is subjected to combustion treatment by the quartz tube combustion method according to the following conditions, and the generated gas is absorbed into the absorbent. I let you.
1. Combustion conditions 500 ° C. × 10 min. And oxygen / argon (mixing ratio 4: 3), flow rate 700ml / m
Heating was performed under conditions of in.
2. Absorbing solution 0.01% hydrogen peroxide solution approx. 5ml (after combustion treatment, up to 10ml)

The sulfate solution was measured for the absorption solution according to the following conditions by an ion chromatography method, and the sulfur concentration was calculated from the sulfate ion concentration.
Ion chromatograph: ICS-1100 (manufactured by 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 rate: 1.5ml / min
Suppressor: AERS-500
Injection volume: 100 μl

The criteria for determining the concentration of sulfur that does not constitute the inorganic filler in each inorganic filler are as follows.
A: 0 ppm to 5 ppm B: more than 5 ppm to 10 ppm C: more than 10 ppm to 25 ppm D: more than 25 ppm to 50 ppm E: more than 50 ppm

  In accordance with the composition shown in the following table, each component was blended, premixed with a stirrer, dispersed with a three-roll mill, and kneaded to prepare compositions. In addition, the compounding quantity in a table | surface shows a mass part.

※ 実施例３、および比較例３は白色硬化性樹脂組成物を構成。
＊１）ｊＥＲ８２８、ビスフェノールＡ型樹脂、三菱化学（株）製
＊２）合成例１で得られた感光性共重合樹脂Ａ
＊３）ジペンタエリスリトールヘキサアクリレート
＊４）エポキシアクリレート ＭＡ−２０００、三菱化学（株）製
＊５）リン含有メタクリレート カヤマーＰＭ２ 日本化薬（株）製
＊６）アクリレートモノマー ライトエステルＨＯ 共栄社化学（株）製
＊７）硫酸法で製造した酸化チタン（製造工程における硫酸の使用あり）、表面処理：Ｓｉ／Ａｌ、ＴｉＯ_２濃度：９１％、堺化学工業（株）製
＊８）シリカ、（株）龍森製
＊９）硫酸バリウム、堺化学工業（株）製
＊１０）塩素法で製造した酸化チタン（製造工程における硫酸の使用なし）、表面処理：Ａｌ_２Ｏ_３、ＺｒＯ_２、ＴｉＯ_２濃度：９１％、ＣＲＩＳＴＡＬ社製
＊１１）ビスアシルフォススフィンオキサイド系光重合開始剤、ＢＡＳＦジャパン（株）製
＊１２）ジシアンジアミド
＊１３）メラミン、日産化学工業（株）製
＊１４）信越化学工業（株）製
＊１５）フェノール系酸化防止剤、ＢＡＳＦジャパン（株）製
＊１６）高沸点石油系溶剤、出光興産（株）製

* Example 3 and Comparative Example 3 constitute a white curable resin composition.
* 1) jER828, bisphenol A type resin, manufactured by Mitsubishi Chemical Corporation * 2) Photosensitive copolymer resin A obtained in Synthesis Example 1
* 3) Dipentaerythritol hexaacrylate * 4) Epoxy acrylate MA-2000, manufactured by Mitsubishi Chemical Corporation * 5) Phosphorus-containing methacrylate Kayamer PM2 Nippon Kayaku Co., Ltd. * 6) Acrylate monomer Light ester HO Kyoeisha Chemical Co., Ltd. * 7) Titanium oxide manufactured by the sulfuric acid method (use of sulfuric acid in the manufacturing process), surface treatment: Si / Al, TiO ₂ concentration: 91%, manufactured by Sakai Chemical Industry Co., Ltd. * 8) Silica, ) Made by Tatsumori * 9) Barium sulfate, manufactured by Sakai Chemical Industry Co., Ltd. * 10) Titanium oxide produced by the 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 CRISTAL * 11) Bisacylphosphine oxide photopolymerization initiator, manufactured by BASF Japan Ltd. * 12) Dicyan Diamide * 13) Melamine, Nissan Chemical Industries * 14) Shin-Etsu Chemical * 15) Phenolic antioxidants, BASF Japan * 16) High boiling petroleum solvent, Idemitsu Kosan ( Co., Ltd.

  The obtained curable resin compositions of Examples and Comparative Examples were evaluated according to the following. The results are shown in the table below.

The conditions for producing the evaluation substrates in Examples 1 to 3 and Comparative Examples 1 to 3 are shown below.
Substrate: FR-4 material Application: Screen printing, 30 μm film thickness at application, 20 μm film thickness after drying
Drying: 80 ° C. for 30 minutes, using a hot-air circulating drying furnace Exposure: 600 mJ / cm ² , exposure device for metal halide lamp light source Development: 1 wt% sodium carbonate, liquid temperature 30 ° C., development time 60 seconds,
Pressure 0.2MPa
Post cure (curing): 150 ° C. for 60 minutes, using a hot-air circulation type drying furnace Under the above production conditions, a cured product was formed on the evaluation substrate.

Base material: FR-4 material The production conditions of the evaluation substrate in Example 4 are shown below.
Application: Screen printing, film thickness at the time of application 30 μm, film thickness after drying 20 μm
Drying: 80 ° C. for 30 minutes, using a hot air circulation drying oven Post cure (curing): 150 ° C. for 60 minutes, using a hot air circulation drying oven Under the above production conditions, a cured product was formed on the evaluation substrate.

The conditions for producing the evaluation substrate in Example 5 are shown below.
Substrate: FR-4 material Application: Screen printing, 30 μm film thickness at application, 20 μm film thickness after drying
UV: 1000 mJ / cm ² metal halide lamp A cured product was formed on the evaluation substrate under the above production conditions.

(1) Sulfur concentration measurement of curable resin composition Samples of solid contents of the curable resin compositions of Examples and Comparative Examples were formed on a copper foil in a state where the solvent was volatilized by the above method. 0.25 g of the formed coating film peeled off from the copper foil was weighed and used as a measurement sample. In addition, Examples 1-3 and Comparative Examples 1-3 used the coating film after drying, Example 4 used the coating film after thermosetting, and Example 5 used the coating film after UV hardening.
On the other hand, the composition sample weighed 0.25 g of each composition and used it as a measurement sample.
The sulfur concentration was measured by the method described in the above sulfur concentration analysis method.
The criteria for determining the sulfur concentration of each composition are as follows.
α: 0 ppm to 130 ppm −: Not evaluated

(2) Discoloration of silver in the silver-plated part The silver part was subjected to silver plating on the copper part of the circuit-formed substrate obtained by curing the compositions of Examples and Comparative Examples under the above-described production conditions. The substrate was placed in a sealable glass container, sealed, and placed in an oven at 80 ° C. After the introduction, each substrate was taken out 48 hours later, and the change of silver in the silver plating portion was evaluated. The judgment criteria are as follows.
○: No silver discoloration in the silver plating part after 48 hours.
X: The silver of the silver plating part has discolored 48 hours afterward.

(3) UV resistance Each of the compositions of Examples and Comparative Examples was irradiated with 100 J of UV light using a metal halide lamp as a light source on the coating film surface of the substrate obtained by curing under the above-described production conditions. The reflectance (Y value of the XYZ color system) before and after UV irradiation was measured with a spectrocolorimeter (CM-2600d, manufactured by Konica Minolta Sensing Co., Ltd.). The judgment criteria are as follows.
○: Reflectance difference before and after irradiation is 1 or less ×: Reflectance difference before and after irradiation is more than 1 −: Not evaluated

(4) Crack resistance after high-temperature treatment A solder resist layer having an opening pattern of 3 mm □ was formed on each of the compositions of Examples and Comparative Examples under the above-described production conditions, and a test substrate was produced. Using this test substrate, after high-temperature treatment under conditions of 260 ° C. × 5 minutes, the presence or absence of cracks in the opening was visually confirmed. The evaluation criteria are as follows.
○: No cracks occurred.
X: Cracks are generated.

  As shown in the above table, in the curable resin composition in which the concentration of sulfur that does not constitute the inorganic filler in the inorganic filler is 10 ppm or less, all are excellent in crack resistance after high-temperature treatment, and the silver plating part It turns out that the hardened | cured material which is hard to discolor silver of this is obtained. In addition, in the case of a white curable resin composition for a reflector, in addition to the above characteristics, a cured product that can effectively prevent a decrease in reflectance due to light or heat is obtained because of excellent UV resistance. I understand.

  Moreover, the reflectance at a wavelength of 555 nm was measured and evaluated for the coating film surface of the substrate obtained by curing the composition of Example 3 by the above-described production method. In addition, the substrate was also evaluated for resistance to discoloration (after processing repeatedly 5 times in a reflow furnace (maximum 285 ° C.), the change rate ΔE of the substrate before and after processing was determined using a color difference meter). As a result, good results were obtained in both reflectance and discoloration resistance.

Claims (5)

  In the curable resin composition containing (A) a curable resin and (B) an inorganic filler, the concentration of sulfur that does not constitute the inorganic filler in the (B) inorganic filler is 10 ppm or less. A curable resin composition.   A dry film comprising a resin layer obtained by applying and drying the curable resin composition according to claim 1 on a film.   A cured product obtained by curing the curable resin composition according to claim 1 or the resin layer of the dry film according to claim 2.   A printed wiring board comprising the cured product according to claim 3. The printed wiring board according to claim 4, further comprising a conductive member containing at least silver.