JP6987011B2 - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Description

The present invention relates to curable resin compositions, dry films, cured products and printed wiring boards.

Conventionally, as a material for forming a permanent film such as a solder resist, an interlayer insulating layer, and a coverlay of a printed wiring board, Patent Document 1 describes a carboxyl group-containing polyurethane and a polyfunctional material having a total chlorine content of less than 0.7% by mass. A thermosetting resin composition containing an aliphatic glycidyl ether compound is disclosed.

In recent years, due to the rapid progress of semiconductor parts, electronic devices tend to be lighter, thinner, shorter, smaller, have higher performance, and have more functions. Following this tendency, miniaturization and multi-pinning of semiconductor packages have been put into practical use.
Specifically, instead of IC packages called QFP (quad flat pack package), SOP (small outline package), etc., BGA (ball grid array), CSP (chip scale package), etc. An IC package called is used. In recent years, FC-BGA (flip chip ball grid array) has also been put into practical use as an IC package with a higher density.
In a printed wiring board (also referred to as a package substrate) used for such an IC package, the SRO (Solder Rest Opening) pitch is narrow and formed close to each other, so that short circuits and crosstalk noise occur between the SROs. There is a high risk of crosstalk. Further, the solder resist formed between the SROs is thin and thin, so that cracks are likely to occur. Therefore, a permanent coating such as a solder resist used for a package substrate is required to have high reliability over a long period of time, specifically, high insulation reliability. In particular, as the density of package substrates increases in the future, the demand for reliability is expected to increase further.

Japanese Patent No. 5167113 Japanese Unexamined Patent Publication No. 2010-54912

However, regarding this reliability, the thermosetting resin composition described in Patent Document 1 described above has become insufficient in recent years.
Further, in recent years, as the number of pins of ICs has increased, the wiring distance has increased rapidly, so that the wiring tends not to be roughened as much as possible in order to improve the dielectric characteristics. For such low-roughened or unroughened wiring, higher adhesion than before is required.
Regarding this adhesion, the thermosetting resin composition described in Patent Document 1 described above has become insufficient in recent years.

Further, some colored photosensitive resin compositions contain a compound represented by a predetermined chemical formula, which is excellent in heat resistance and solvent resistance (Patent Document 2). However, the photosensitive resin composition described in Patent Document 2 is a photosensitive resin composition for a color filter, and has a characteristic of being able to sufficiently maintain adhesion under severe high temperature and humidification conditions when used for a printed wiring board. Not obtained.

Therefore, an object of the present invention is a curable resin composition having excellent reliability and adhesion, which is suitable for use in a printed wiring board or the like, a dry film having a resin layer obtained from the composition, the composition or the present invention. It is an object of the present invention to provide a cured product of a resin layer of a dry film and a printed wiring board having the cured product.

As a result of intensive research and development on a curable resin composition having excellent adhesion and reliability, the present inventors have obtained adhesiveness and reliability by using a specific epoxy resin and a specific inorganic filler in combination. We have found that a highly cured product can be obtained, and have completed the present invention.

（Ｄ−１）光反応性の表面処理をされた無機フィラーと、を含有することを特徴とするものである。 The curable resin composition of the present invention comprises (A) a carboxyl group-containing resin, (B-1) a photopolymerization initiator, and (C) an epoxy resin having the following structural formula.

(D-1) It is characterized by containing an inorganic filler which has been subjected to a photoreactive surface treatment.

（Ｄ−２）熱反応性の表面処理をされた無機フィラーと、を含有することを特徴とするものである。 Further, the curable resin composition of the present invention comprises (A) a carboxyl group-containing resin, (B-2) a photobase generator, and (C) an epoxy resin having the following structural formula.

(D-2) It is characterized by containing an inorganic filler which has been subjected to a heat-reactive surface treatment.

In the curable resin composition of the present invention, the average particle size of the surface-treated inorganic filler in (D-1) or (D-2) is 1.0 μm or less, and the maximum particle size is 4. It is preferably 0 μm or less, and the blending ratio of the above-mentioned (D) inorganic filler is preferably 25 to 80% by mass.

The dry film of the present invention is characterized by having a resin layer obtained by applying the curable resin composition to the film and drying the film.
Further, the cured product of the present invention is characterized in that it is obtained by curing the resin layer of the curable resin composition or the dry film.
Further, the printed wiring board of the present invention is characterized by having the above-mentioned cured product.

According to the present invention, a cured product having excellent adhesion and reliability can be obtained.

を含むとともに、（Ｂ−１）光重合開始剤及び（Ｂ−２）光塩基発生剤のうちの少なくとも一方を含み、かつ、無機フィラーとして、当該（Ｂ−１）光重合開始剤を含むときは光反応性の表面処理をされた無機フィラーを、当該（Ｂ−２）光塩基発生材を含むときは、熱光反応性の表面処理をされた無機フィラーを、それぞれ含有するものである。 The curable resin composition of the present invention comprises (A) a carboxyl group-containing resin, (C) an epoxy resin having the following structural formula, and the like.

When containing at least one of (B-1) photopolymerization initiator and (B-2) photobase generator, and containing the (B-1) photopolymerization initiator as an inorganic filler. Contains a photoreactive surface-treated inorganic filler, and when the (B-2) photobase generator is contained, each contains a thermophotoreactive surface-treated inorganic filler.

The curable resin composition of the present invention contains an epoxy resin having the above-mentioned specific structural formula. Since this epoxy resin has a low Gardner hue, that is, a high light transmittance, light reaches the deep part of the coating film coated with the curable resin composition. Therefore, in the case of a composition containing a photoreactive surface-treated inorganic filler, it can react with the surface treatment agent of the photoreactive surface-treated inorganic filler present in the deep part of the coating film. Further, in the case of a composition containing a heat-reactive surface-treated inorganic filler, the photobase generator present in the deep part thereof may react with the surface-treating agent of the heat-reactive surface-treated inorganic filler. can. Therefore, the cured product can be sufficiently cured even in a deep part, the moisture resistance is improved, and the cured product having excellent reliability and adhesion can be obtained.
Further, since the epoxy resin having the above-mentioned specific structural formula has a hydrophobic and heat-resistant skeleton, it is possible to obtain a cured product having excellent moisture resistance, reliability and adhesion.
Further, since the epoxy resin having the above-mentioned specific structural formula has a hydrophobic and heat-resistant skeleton, it has a high glass transition temperature (Tg), and also contains an inorganic filler. Combined with the low coefficient of linear expansion, it has excellent crack resistance and low warpage.
Further, since the epoxy resin having the above-mentioned specific structural formula has a low Gardner hue, it does not inhibit the photoreactivity, so that the resin composition of the present invention has high resolution.
Based on such characteristics, it is considered that the curable resin composition of the present invention has high adhesion, adhesion and reliability.

Hereinafter, each component of the curable resin composition of the present invention will be described. In addition, in this specification, (meth) acrylate is a generic term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

[(A) Carboxyl group-containing resin]
As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule can be used. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof. When only a carboxyl group-containing resin having no ethylenically unsaturated double bond is used, in order to make the composition photocurable, a compound having a plurality of ethylenically unsaturated groups in the molecule described later, that is, light It is necessary to use a reactive monomer together.
Specific examples of the carboxyl group-containing resin include the following compounds (either oligomer or polymer).

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

(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-based polyols and polyether-based compounds. A carboxyl group-containing urethane resin obtained by a double addition 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.

(3) 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 ( Meta) A carboxyl group-containing photosensitive urethane resin obtained by a double addition reaction of an acrylate or a modified partial acid anhydride thereof, a carboxyl group-containing dialcohol compound and a diol compound.

(4) During the synthesis of the resin according to (2) or (3), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added to the terminal (4). Meta) Acryloylated carboxyl group-containing photosensitive urethane resin.

(5) During the synthesis of the resin according to (2) or (3), one isocyanate group and one or more (meth) acryloyl groups are formed in the molecule, such as an isophorone diisocyanate and a pentaerythritol triacrylate homomolar reaction product. Carboxyl group-containing photosensitive urethane resin that is terminal (meth) acrylicized by adding the compound to be possessed.

(6) A carboxyl group-containing photosensitive resin obtained by reacting a bifunctional or higher polyfunctional (solid) epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride to a hydroxyl group existing in a side chain.

(7) Carboxyl in which a (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the generated hydroxyl group. Group-containing photosensitive resin.

(8) A dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid is reacted with a bifunctional oxetane resin, and the generated primary hydroxyl group is subjected to two bases such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. Carboxyl group-containing polyester resin to which acid anhydride is added.

(9) 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, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine with respect to the alcoholic hydroxyl group of the obtained reaction product. A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as an acid.

(10) A 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 substance with a polybasic acid anhydride.

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

(12) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and one or more (meth) acryloyl groups in one molecule to the resins (1) to (11).
In addition, in this specification, (meth) acrylate is a generic term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

The acid value of the (A) carboxyl group-containing resin is preferably 20 to 200 mgKOH / g. (A) When the acid value of the carboxyl group-containing resin is 20 to 200 mgKOH / g, it becomes easy to form a pattern of the cured product. More preferably, it is 50 to 130 mgKOH / g.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the development resistance of the film of the exposed portion is improved, and the resolution is excellent. On the other hand, when the weight average molecular weight is 150,000 or less, the solubility of the unexposed portion is good, the resolution is excellent, and the storage stability may be improved. The weight average molecular weight can be measured by gel permeation chromatography.

The blending amount of the (A) carboxyl group-containing resin is, for example, 10 to 60% by mass, preferably 20 to 60% by mass, based on the total amount of the curable resin composition excluding the solvent. The strength of the coating film can be improved by setting the content to 10% by mass or more, preferably 20% by mass or more. Further, when the content is 60% by mass or less, the viscosity becomes appropriate and the workability is improved.
These carboxyl group-containing resins can be used without being limited to those listed above, and one type may be used alone or a plurality of types may be mixed and used. Among them, the carboxyl group-containing resin synthesized by using the phenol compound such as the carboxyl group-containing resins (10) and (11) as a starting material is suitable for HAST test under high voltage, that is, B-HAST resistance and PCT resistance. Since it is excellent, it can be suitably used.

[(B-1) Photopolymerization Initiator or (B-2) Photobase Generator]
As the photopolymerization initiator, any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator can be used.

Examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphinoxide, and bis- (2,). 6-Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphinoxide, bis- (2,6-dimethoxybenzoyl) phenylphosphin oxide, bis- (2,6-dimethoxybenzoyl) 2,6-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphinoxide, bis- (2,4,6- Bisacylphosphinoxides such as trimethylbenzoyl) -phenylphosphine oxide (IGM Resins Omnirad 819); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (IGM Resins) Monoacylphosphinoxides such as Omnirad TPO); 1-hydroxy-cyclohexylphenylketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane. -1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2- Hydroxyacetophenones such as methyl-1-phenylpropane-1-one; benzoyls such as benzoin, benzyl, benzoinmethyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ether Kind: Benzoyls such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, etc. Ethyl; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-4-) Methylphenyl) Methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and other acetophenones; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4 -Thioxanthons such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1 -Anthraquinones such as chloroanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate, p-dimethyl Ethyl benzoates such as ethyl benzoates; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and other oxime esters; bis (η5-2,4-cyclopentadiene-1-yl) -bis (2, 6-Difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pill-1-yl) ethyl) ) Phenyl] Titanosen such as titanium; phenyldisulfide 2-nitrofluorene, butyloin, anisoinethyl ether, azobisisobutyronitrile, tetramethylthium disulfide and the like can be mentioned. As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination. Of these, monoacylphosphine oxides and oxime esters are preferable, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3. -Il]-, 1- (O-acetyloxime) is more preferable.

The blending amount of the photopolymerization initiator is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. When it is 0.5 parts by mass or more, the surface curability is good, and when it is 20 parts by mass or less, halation is less likely to occur and good resolution can be obtained.

The photobase generator produces one or more basic substances that can function as a catalyst for a thermal curing reaction by changing the molecular structure by irradiation with light such as ultraviolet rays or visible light or by cleaving the molecules. It is a compound. Examples of the basic substance include secondary amines and tertiary amines.

Examples of the photobase generator include α-aminoacetophenone compound, oxime ester compound, N-formylated aromatic amino compound, N-acylated aromatic amino compound, nitrobenzyl carbamate compound, alcooxybenzyl carbamate compound and the like. .. Of these, an oxime ester compound and an α-aminoacetophenone compound are preferable, and an oxime ester compound is more preferable. Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) is more preferable. As the α-aminoacetophenone compound, a compound having two or more nitrogen atoms is particularly preferable. One type of photobase generator may be used alone, or two or more types may be used in combination.

In addition, examples of the photobase generator include quaternary ammonium salts.

Other photobase generators include WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate) and WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl) -2-). Propionic] piperidine), WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinone-2-yl) ethylylate, etc. can also be used.

Further, some substances of the above-mentioned photopolymerization initiator also function as a photobase generator. As the photopolymerization initiator that also functions as a photobase generator, an oxime ester-based photopolymerization initiator and an α-aminoacetophenone-based photopolymerization initiator are preferable.

The blending amount of the photobase generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. When it is 0.1 part by mass or more, the surface curability is good, and when it is 20 parts by mass or less, halation is less likely to occur and good resolution can be obtained.

[(C) Epoxy resin having a specific structural formula]
The curable resin composition of the present invention contains an epoxy resin having the following structural formula.
By containing the above epoxy resin having a low Gardner hue, light can reach the deep part of the coating film, and a cured product having excellent adhesion and reliability can be obtained. Therefore, the curable resin composition of the present invention is used for printed wiring boards that are required to be reliable in high temperature and high humidity environments, especially for gauge insulating materials and laminates used in semiconductor devices. It is suitable for use and suitable for semiconductor packages and in-vehicle use.
The curable resin composition contains the above-mentioned epoxy compound and a specific surface-treated inorganic filler described later as essential components, whereby crack resistance and excellent adhesion in a high-temperature and high-humidity environment are achieved. Has sex, etc.

The curable resin composition of the present invention contains an epoxy resin having the specific structural formula (C) and an epoxy resin other than the epoxy resin having the specific structural formula (C) as long as the effects peculiar to the present invention are not impaired. , Can be included. Epoxy resins other than the epoxy resin having the specific structural formula (C) are epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; novolak type. Epoxy resin; biphenol novolak type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; bixirenol Mold or biphenol type epoxy resin or a mixture thereof; bisphenol S type epoxy resin; bisphenol A novolak type epoxy resin; tetraphenylol ethane type epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl xylenoyl ethane resin Naphthalene group-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymerized epoxy resin; cyclohexyl maleimide and glycidyl methacrylate copolymerized epoxy resin; epoxy-modified polybutadiene rubber derivative; CTBN-modified epoxy resin, etc. However, it is not limited to these.

The blending amount of the epoxy resin having the specific structural formula (C) is, for example, 1 to 100 parts by mass, preferably 10 to 80 parts by mass, and 20 to 60 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. The unit is more preferable. (C) When the blending amount of the epoxy resin having the specific structural formula is 10 parts by mass or more, the crack resistance and the insulation reliability are further improved, and when it is 100 parts by mass or less, the storage stability is improved.

[(D-1) Photoreactive surface-treated inorganic filler or (D-2) Heat-reactive surface-treated inorganic filler]
The curable resin composition of the present invention contains (D-1) a photoreactive surface-treated inorganic filler or (D-2) a heat-reactive surface-treated inorganic filler. By including the inorganic filler, the crack resistance of the cured product is further improved.
Here, the surface-treated inorganic filler can improve the compatibility with (A) a carboxyl group-containing resin or (C) an epoxy resin.
Further, in the curable resin composition of the present invention containing (D-1) a photoreactive surface-treated inorganic filler, the (B-1) photopolymerization initiator is cleaved by the transmitted light and photoreacts. Since it reacts with an inorganic filler that has been subjected to a sexual surface treatment, it is possible to improve the curability of the deep part of the coating film.
Further, in the curable resin composition of the present invention containing the (D-2) heat-reactive surface-treated inorganic filler, the (B-2) photobase generator generates a base by the transmitted light. Since it reacts with the heat-reactive surface-treated inorganic filler, the curability of the deep part of the coating film can be improved.
Therefore, the curable resin composition of the present invention contains (B-1) a photopolymerization initiator when it contains (D-1) a photoreactive surface-treated inorganic filler, and (D-2) a thermal reaction. When the inorganic filler having a sex surface treatment is contained, the (B-2) photobase generator is contained. Since some substances of the photopolymerization initiator also function as a photobase generator as described above, the photopolymerization initiator and the photobase generator are not distinguished from each other.

The surface-treated inorganic filler is not particularly limited, and known and commonly used fillers such as silica, crystalline silica, Neuburg silica soil, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, and natural materials are used. Inorganic fillers such as mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, and zinc flower can be used. Of these, silica is preferable, and spherical silica is more preferable because it has a small surface area and stress is less likely to be the starting point of cracks because it is dispersed throughout.

Here, the surface-treated inorganic filler has a photocurable reactive group as a curable reactive group that reacts with the (B-1) photopolymerization initiator in the inorganic filler of (D-1) on the surface of the inorganic filler. In the inorganic filler of (D-2), the thermosetting reactive group is inorganic as the curable reactant that reacts with the (B-2) photoinitiator. The surface of the filler is surface-treated so that it can be introduced.
(D-1) Examples of the photocurable reactive group of the photoreactive surface-treated inorganic filler include a vinyl group, a styryl group, a methacrylic group, an acrylic group and the like. Among them, as the photocurable reactive group, a methacrylic group, an acrylic group and a vinyl group are preferable.
(D-2) The heat-curable reactive groups of the heat-reactive surface-treated inorganic filler include hydroxyl groups, carboxyl groups, isocyanate groups, amino groups, imino groups, epoxy groups, oxetanyl groups, mercapto groups, and methoxymethyl. Examples thereof include a group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, an oxazoline group and the like. Of these, amino groups and epoxy groups are preferable.
Further, the inorganic filler of (D-1) or the inorganic filler of (D-2) may have two or more kinds of curable reactive groups. As the inorganic filler (D), surface-treated silica is preferable. By including the surface-treated silica, the CTE can be lowered and the glass transition temperature can be raised.

(D) The method for introducing the curable reactive group onto the surface of the inorganic filler is not particularly limited, and it may be introduced by using a known and commonly used method, and a surface treatment agent having a curable reactive group, for example, a curable reactive group may be introduced. The surface of the inorganic filler may be treated with a coupling agent or the like.

(D) As the surface treatment of the inorganic filler, surface treatment with a coupling agent is preferable. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like can be used. Of these, a silane coupling agent is preferable.

As the silane coupling agent, a silane coupling agent capable of introducing a curing reactive group into the (D) inorganic filler is preferable. Examples of the silane coupling agent into which a thermosetting reactive group can be introduced include a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, and a silane coupling agent having an isocyanate group. Agents are mentioned, and among them, a silane coupling agent having an epoxy group is more preferable. Examples of the silane coupling agent into which a photocurable reactive group can be introduced include a silane coupling agent having a vinyl group, a silane coupling agent having a styryl group, a silane coupling agent having a methacrylic group, and a silane coupling agent having an acrylic group. Agents are preferred, with silane coupling agents having a methacryl group being more preferred.

The inorganic filler (D-1) or (D-2) may be blended in the curable resin composition of the present invention in a surface-treated state, and the surface-untreated inorganic filler and the surface treatment agent may be mixed. The inorganic filler may be surface-treated in the composition by blending separately, but it is preferable to blend the inorganic filler which has been surface-treated in advance. By blending the inorganic fillers that have been surface-treated in advance, it is possible to prevent deterioration of crack resistance and the like due to the surface treatment agent that may remain in the surface treatment when they are blended separately. In the case of surface treatment in advance, it is preferable to mix a pre-dispersion liquid in which (D) an inorganic filler is pre-dispersed in a solvent or a resin component, and the surface-treated inorganic filler is pre-dispersed in a solvent, and the pre-dispersion liquid is used as a composition. It is more preferable to add the pre-dispersion liquid to the composition after sufficient surface treatment when pre-dispersing the surface-untreated inorganic filler in the solvent.

In the curable resin composition of the present invention, the inorganic filler of (D-1) or the inorganic filler of (D-2) preferably has an average particle size of 1 μm or less because it is excellent in crack resistance. More preferably, it is 0.8 μm or less. In the present specification, the average particle size refers to the value of D50, which is a value measured using, for example, a Microtrack particle size analyzer manufactured by Nikkiso Co., Ltd.

Further, the inorganic filler of (D-1) or the inorganic filler of (D-2) preferably has a maximum particle size of 4.0 μm or less because it reacts efficiently and is excellent in crack resistance and adhesion. .. It is more preferably 3.0 μm or less. In the present specification, the maximum particle size refers to the value of D100, which is a value measured using, for example, a Microtrack particle size analyzer manufactured by Nikkiso Co., Ltd.

The blending amount of the inorganic filler is preferably 25 to 85% by mass, more preferably 30 to 75% by mass, and preferably 35 to 70% by mass based on the total solid content of the curable resin composition. More preferred.

Examples of the photopolymerizable oligomer include unsaturated polyester-based oligomers and (meth) acrylate-based oligomers. Examples of the (meth) acrylate-based oligomer include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, and bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, and epoxy urethane (meth). ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate and the like.

As the photopolymerizable vinyl monomer, known and commonly used ones, 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, (Meta) acrylamides such as methacrylicamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylicamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide; triallyl isocyanurate, diallyl phthalate, Allyl compounds such as diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydroflufreel (meth) acrylate, isoboronyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. (Meta) acrylic acid esters; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates, pentaerythritol tri (meth) acrylates; methoxyethyl (meth) acrylates, ethoxyethyl Alkoxyalkylene glycol mono (meth) acrylates such as (meth) acrylates; ethylene glycol di (meth) acrylates, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylates, 1,6-hexanediol di ( Alkylene polyol poly (meth) acrylates such as meth) acrylates, trimethylol propanetri (meth) acrylates, pentaerythritol tetra (meth) acrylates, dipentaerythritol hexa (meth) acrylates; diethylene glycol di (meth) acrylates, triethylene glycol di. Polyoxyalkylene glycol poly (meth) acrylates, ethoxylated trimethylol propane triacrylates, propoxylated trimethylol propanetri (meth) acrylates, etc. T) Acrylate; Poly (meth) acrylate such as neopentyl glycol ester di (meth) acrylate of hydroxypivalate; Isocyanulate type poly (meth) acrylate such as tris [(meth) acryloxyethyl] isocyanurate. Can be mentioned. These can be used alone or in combination of two or more according to the required characteristics.

The blending amount of the compound having an ethylenically unsaturated bond is preferably 3 to 40 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. When it is 3 parts by mass or more, the surface curability is improved, and when it is 40 parts by mass or less, halation is suppressed. More preferably, it is 5 to 30 parts by mass.

(Thermosetting catalyst)
The curable resin composition of the present invention preferably contains a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. , 1- (2-Cyanoethyl) -2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N Examples thereof include amine compounds such as -dimethylbenzylamine, 4-methyl-N and N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine-isosianulic acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isosianulic acid adduct can also be used, preferably as these adhesion-imparting agents. A compound that also functions is used in combination with a thermosetting catalyst.

The blending amount of the thermosetting catalyst is preferably 0.05 to 40 parts by mass, and more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the (C) epoxy resin.

(Hardener)
The curable resin composition of the present invention can contain a curing agent. Examples of the curing agent include phenol resins, polycarboxylic acids and their acid anhydrides, cyanate ester resins, active ester resins, maleimide compounds, alicyclic olefin polymers and the like. The curing agent may be used alone or in combination of two or more.

The curing agent has a ratio of (C) a functional group capable of a thermosetting reaction such as an epoxy group of a thermosetting resin such as an epoxy resin and a functional group in the curing agent that reacts with the functional group of the curing agent. It is preferable to blend in a ratio such that the functional group / the functional group capable of the thermosetting reaction (equivalent ratio) = 0.2 to 3. Within the above range, the balance between storage stability and curability is excellent.

(Colorant)
The curable resin composition of the present invention may contain a colorant. As the colorant, known colorants such as red, blue, green, yellow, black, and white can be used, and any of pigments, dyes, and pigments may be used. However, it is preferable not to contain halogen from the viewpoint of reducing the environmental load and affecting the human body.

The amount of the colorant added is not particularly limited, but is preferably 10 parts by mass or less, and particularly preferably 0.1 to 7 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.

(Organic solvent)
The curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition, adjusting the viscosity when applied to a substrate or a carrier film, and the like. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethyl benzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol and propylene glycol monomethyl ether. , Dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether and other glycol ethers; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbi Esters such as tall acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha are known. Conventional organic solvents can be used. These organic solvents can be used alone or in combination of two or more.

(Other optional ingredients)
Further, the curable resin composition of the present invention may contain other additives known and commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, antistatic agents, antibacterial / antifungal agents, antifoaming agents, leveling agents, and thickening agents. Agents, adhesion-imparting agents, thixo-imparting agents, photo-initiating aids, sensitizers, thermoplastic resins, organic fillers, mold release agents, surface treatment agents, dispersants, dispersion aids, surface modifiers, stabilizers , Fluorescent material and the like.

The curable resin composition of the present invention may contain a thermosetting resin other than the (C) epoxy resin as long as the effects of the present invention are not impaired. The thermosetting resin may be any resin that is cured by heating and exhibits electrical insulating properties, and examples thereof include epoxy compounds other than (C) epoxy resin, oxetane compounds, melamine resins, and silicone resins. These may be used together.

The curable resin composition of the present invention may be used as a dry film or may be used as a liquid. When used as a liquid, it may be one-component or two-component or more.

Next, the dry film of the present invention has a resin layer obtained by applying and drying the curable resin composition of the present 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 the viscosity to an appropriate level, and then a comma coater, a blade coater, a lip coater, a rod coater, and a squeeze coater. , Reverse coater, transfer coater, gravure coater, spray coater, etc., and apply to a uniform thickness on the carrier film. Then, the applied composition is usually dried at a temperature of 40 to 130 ° C. for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, but is generally selected as appropriate in the range of 3 to 150 μm, preferably 5 to 60 μm after drying.

As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamide-imide film, a polypropylene film, a polystyrene film and the like can be used. The thickness of the carrier film is not particularly limited, but is generally selected as appropriate in the range of 10 to 150 μm. More preferably, it is in the range of 15 to 130 μm.

After forming the resin layer made of the curable resin composition of the present invention on the carrier film, a peelable cover is further applied to the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. It is preferable to stack the films. 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. The cover film may be one having a force smaller than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

In the present invention, the curable resin composition of the present invention may be applied onto the cover film and dried to form a resin layer, and a carrier film may be laminated on the surface thereof. That is, as the film to which the curable resin composition of the present invention is applied when producing the dry film in the present invention, either a carrier film or a cover film may be used.

The printed wiring board of the present invention has a cured product obtained from the curable resin composition of the present invention or the resin layer of a dry film. As a method for producing a printed wiring board of the present invention, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using the above organic solvent, and a dip coating method is applied on the substrate. After coating by a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100 ° C. This forms a tack-free resin layer. Further, in the case of a dry film, a resin layer is formed on the base material by laminating the resin layer on the base material with a laminator or the like so as to be in contact with the base material and then peeling off the carrier film.

The base material includes a printed wiring board and a flexible printed wiring board whose circuit is formed of copper or the like in advance, as well as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, and glass cloth / paper epoxy. , Synthetic fiber epoxy, fluororesin / polyethylene / polyimideene ether, polyphenylene oxide / cyanate, etc. are used for high frequency circuit copper-clad laminates, etc., and all grades (FR-4, etc.) of copper-clad laminates are used. 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, a wafer plate, and the like.

The volatile drying performed after applying the curable resin composition of the present invention is carried out in a hot air circulation type drying oven, an IR furnace, a hot plate, a convection oven, etc. It can be performed by using a method of bringing hot air into countercurrent contact and a method of blowing hot air onto a support from a nozzle).

After forming a resin layer on the printed wiring board, it is selectively exposed to active energy rays through a photomask having a predetermined pattern, and the unexposed portion is exposed to a dilute alkaline aqueous solution (for example, 0.3 to 3 mass% sodium carbonate aqueous solution). ) To form a pattern of the cured product. Further, the cured product is adhered by irradiating the cured product with active energy rays and then heat-curing (for example, 100 to 220 ° C.), or by irradiating the cured product with active energy rays after heat curing, or by performing final finish curing (main curing) only by heat curing. It forms a cured film with excellent properties such as properties and hardness.
When the curable resin composition of the present invention contains a photobase generator, it is preferable to heat it after exposure and before development, and the heating conditions after exposure and before development are, for example, 1 to 1 at 60 to 150 ° C. It is preferable to heat for 60 minutes.

The exposure machine used for the above-mentioned active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm. Further, a direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser based on CAD data from a computer) can also be used. The lamp light source or the laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 450 nm. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 10 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .

The development method can be a dipping method, a shower method, a spray method, a brush method, or the like, and the developers include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, and the like. An alkaline aqueous solution such as ammonia or amines can be used.

The curable resin composition of the present invention is suitably used for forming a cured film on a printed wiring board, more preferably used for forming a permanent film, and more preferably a solder resist. Used to form an interlayer insulating layer and a coverlay. Further, according to the curable resin composition of the present invention, a cured product having excellent crack resistance and insulation reliability can be obtained. Therefore, a printed wiring board having a fine pitch wiring pattern that requires high reliability. For example, it can be suitably used for forming a permanent coating (particularly a solder resist) for a package substrate, particularly FC-BGA.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the following, "part" and "%" are all based on mass unless otherwise specified.
The curable resins of Examples 1 to 20 and Comparative Examples 1 to 5 are blended in the ratios shown in Tables 1 to 3 and premixed with a stirrer and then kneaded with a three-roll mill. The composition was prepared. Various properties of the obtained curable composition were evaluated, and the results are also shown in Tables 1 to 3.

The alkaline developable resins in Tables 1 to 3 were prepared as follows.
[(A-1) Synthesis of alkaline developable resin]
In an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device, 119.4 parts of a novolak type cresol resin (Shonol CRG951, OH equivalent: 119.4 manufactured by Showa Denko Co., Ltd.), potassium hydroxide 1. 19 parts and 119.4 parts of toluene were introduced, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide was gradually added dropwise, and the mixture was reacted at ^{125-132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours.} Then, the mixture was cooled to room temperature, 1.56 parts of 89% phosphoric acid was added to and mixed with this reaction solution to neutralize potassium hydroxide, the non-volatile content was 62.1%, and the hydroxyl value was 182.2 mgKOH / g (307. A propylene oxide reaction solution of novolak-type cresol resin at 9 g / eq.) Was obtained. This had an average of 1.08 mol of propylene oxide added per equivalent amount of phenolic hydroxyl group.
293.0 parts of propylene oxide reaction solution of the obtained novolak type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer and temperature. It was introduced into a reactor equipped with a meter and an air blow tube, and air was blown at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours with stirring. As for the water produced by the reaction, 12.6 parts of water was distilled off as an azeotropic mixture with toluene. Then, the mixture was cooled to room temperature, the obtained reaction solution was neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Then, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak type acrylate resin solution. Next, 332.5 parts of the obtained novolak type acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blow tube, and air was introduced at a rate of 10 ml / min. With stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled, and then taken out. In this way, a solution of the photosensitive carboxyl group-containing resin A-1 having a solid content of 65% and an acid value of 87.7 mgKOH / g as a solid content was obtained. Hereinafter, this solution of the carboxyl group-containing photosensitive resin is referred to as a resin solution A-1.

[(A-2) Synthesis of alkaline developable resin]
Diethylene glycol monoethyl ether acetate 600 g and orthocresol novolac type epoxy resin (EPICLON N-695 manufactured by DIC, softening point 95 ° C., epoxy equivalent 214, average number of functional groups 7.6) 1070 g (number of glycidyl groups (total number of aromatic rings): 5. 0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved.
Then, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. for 2 hours, then heated to 120 ° C. and further reacted for 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Solbesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were charged, reacted at 110 ° C. for 4 hours, cooled, and subjected to photosensitive carboxyl. A group-containing resin solution was obtained. The solid content of the resin solution thus obtained was 65%, and the acid value of the solid content was 89 mgKOH / g. Hereinafter, this solution of the carboxyl group-containing photosensitive resin is referred to as a resin solution A-2.

[(A-3) Synthesis of alkaline developable resin]
In a flask equipped with a thermometer, agitator, a dropping funnel, and a reflux cooler, 325.0 parts of dipropylene glycol monomethyl ether as a solvent was heated to 110 ° C., 174.0 parts of methacrylic acid, ε-caprolactone-modified methacrylic acid. (Average molecular weight 314) 174.0 parts, 77.0 parts of methyl methacrylate, 222.0 parts of dipropylene glycol monomethyl ether, and t-butylperoxy2-ethylhexanoate as a polymerization catalyst (Perbutyl O manufactured by Nichiyu Co., Ltd.) ) 12.0 parts of the mixture was added dropwise over 3 hours, and the mixture was further stirred at 110 ° C. for 3 hours to inactivate the polymerization catalyst to obtain a resin solution.
After cooling this resin solution, 289.0 parts of Cyclomer A200 manufactured by Daicel Chemical Industry Co., Ltd., 3.0 parts of triphenylphosphine and 1.3 parts of hydroquinone monomethyl ether are added, the temperature is raised to 100 ° C., and the mixture is stirred. A ring-opening addition reaction of an epoxy group was carried out to obtain a photosensitive carboxyl group-containing resin solution.
The resin solution thus obtained had a weight average molecular weight (Mw) of 15,000, a solid content of 57%, and an acid value of the solid material of 79.8 mgKOH / g. Hereinafter, this solution of the carboxyl group-containing photosensitive resin is referred to as a resin solution A-3.

In Tables 1 to 3, the photopolymerization initiators are as follows.
(B-1.1): Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide) manufactured by IGM Resins.
(B-1, B-2.1): Omnirad 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one) manufactured by IGM Resins.
(B-1, B-2.1): Irgacure OXE02 (Etanon, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (o) manufactured by BASF Japan Ltd. -Acetyl oxime)
(B-2.1): WPBG-082 (guanidium 2- (3-benzoylphenyl) propionate) manufactured by Wako Pure Chemical Industries, Ltd.

（Ｃ−２）：上記の骨格を有するエポキシ樹脂（エポキシ当量２３２） In Tables 1 to 3, the special epoxy resin which is the epoxy resin having the specific structural formula (C) of the present invention is as follows.
(C-1): Epoxy resin having the following skeleton (epoxy equivalent 210)

(C-2): Epoxy resin having the above skeleton (epoxy equivalent 232)

（Ｃ−４）ダウケミカル社製ＤＥＮ４３１（フェノールノボラックエポキシ樹脂）
（Ｃ−５）ＤＩＣ社製Ｎ−８７０ ７５ＥＡ（ビスフェノールＡノボラック型エポキシ樹脂）
（Ｃ−６）ＤＩＣ社製ＨＰ−７２４１（トリスフェノールメタン型エポキシ樹脂） Further, the cured resin compositions in Tables 1 to 3 may contain the following epoxy resins (C-3) to (C-6) as epoxy resins other than the epoxy resin containing the above-mentioned specific structural formula (C).
(C-3) Alicyclic epoxy resin having the following skeleton (epoxy equivalent 96)

(C-4) DEN431 (phenol novolac epoxy resin) manufactured by Dow Chemical Co., Ltd.
(C-5) N-870 75EA manufactured by DIC (bisphenol A novolak type epoxy resin)
(C-6) HP-7241 (trisphenol methane type epoxy resin) manufactured by DIC Corporation.

[(D-1.1) Inorganic treatment → Preparation of methacrylic acid treated silica slurry]
After raising the temperature of a water slurry of 50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle size: 500 nm) to 70 ° C., 1% of a 10% sodium silicate aqueous solution is added to the silica particles in terms of silica particles. did. Hydrochloric acid was added to this slurry to adjust the pH to 4, and the mixture was aged for 30 minutes. Further, while maintaining the pH at 7 ± 1 with hydrochloric acid, a 20% _{aqueous solution of sodium aluminate (NaAlO 2} ) was added to the silica particles with alumina (alumina (NaAlO 2). Al ₂ O ₃ ) 5% was added in terms of conversion. After that, a 20% sodium hydroxide water bath was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Then, the slurry was filtered and washed with water using a filter press and vacuum dried to obtain solid silica particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. 50 g of silica particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly mixed. A dispersed silica solvent-dispersed product was obtained.

[(D-1.2) Inorganic treatment → Preparation of barium sulfate slurry treated with methacrylic silane]
A water slurry of 50 g of barium sulfate particles (precipitating barium 100 manufactured by Sakai Chemical Industry Co., Ltd.) was heated to 70 ° C., and then a 10% sodium silicate aqueous solution was added to the silica particles in an amount of 1% in terms of silica particles. Hydrochloric acid was added to this slurry to adjust the pH to 4, and the mixture was aged for 30 minutes. Further, while maintaining the pH at 7 ± 1 with hydrochloric acid, a 20% _{aqueous solution of sodium aluminate (NaAlO 2} ) was added to the silica particles with alumina (alumina (NaAlO 2). Al ₂ O ₃ ) 5% was added in terms of conversion. After that, a 20% sodium hydroxide water bath was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Then, the slurry was filtered and washed with water using a filter press and vacuum dried to obtain a solid substance of barium sulfate particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. 50 g of barium sulfate particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) were added. A uniformly dispersed silica solvent-dispersed product was obtained.

[(D-1.3) Preparation of methacrylic silane treated silica slurry]
50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle size: 500 nm), 48 g of PMA as a solvent, and 2 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly dispersed. A silica solvent-dispersed product was obtained.

[(D-1.4) Preparation of Acrylic Silane Treated Silica Slurry]
50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle size: 500 nm), 48 g of PMA as a solvent, and 2 g of a silane coupling agent having an acrylic group (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly dispersed. A silica solvent-dispersed product was obtained.

[(D-1.5) Preparation of Vinylsilane Treated Silica Slurry]
50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle size: 500 nm), 48 g of PMA as a solvent, and 2 g of a silane coupling agent having a vinyl group (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly dispersed. A silica solvent-dispersed product was obtained.

[(D-1.6) Inorganic treatment → Preparation of methacrylic acid treated silica slurry]
A water slurry of 50 g of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 400 nm) was heated to 70 ° C., and then 1% of a 10% sodium silicate aqueous solution was added to the silica particles in terms of silica particles. .. Hydrochloric acid was added to this slurry to adjust the pH to 4, and the mixture was aged for 30 minutes. Further, while maintaining the pH at 7 ± 1 with hydrochloric acid, a 20% _{aqueous solution of sodium aluminate (NaAlO 2} ) was added to the silica particles with alumina (alumina (NaAlO 2). Al ₂ O ₃ ) 5% was added in terms of conversion. After that, a 20% sodium hydroxide water bath was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Then, the slurry was filtered and washed with water using a filter press and vacuum dried to obtain solid silica particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. 50 g of silica particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly mixed. A dispersed silica solvent-dispersed product was obtained.

[(D-2.1) Inorganic treatment → Preparation of epoxy silane treated silica slurry]
After raising the temperature of a water slurry of 50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle size: 500 nm) to 70 ° C., 1% of a 10% sodium silicate aqueous solution is added to the silica particles in terms of silica particles. did. Hydrochloric acid was added to this slurry to adjust the pH to 4, and the mixture was aged for 30 minutes. Further, while maintaining the pH at 7 ± 1 with hydrochloric acid, a 20% _{aqueous solution of sodium aluminate (NaAlO 2} ) was added to the silica particles with alumina (alumina (NaAlO 2). Al ₂ O ₃ ) 5% was added in terms of conversion. After that, a 20% sodium hydroxide water bath was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Then, the slurry was filtered and washed with water using a filter press and vacuum dried to obtain solid silica particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. 50 g of silica particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a silane coupling agent having an epoxy group (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly mixed. A dispersed silica solvent-dispersed product was obtained.

[(D-2.2) Inorganic treatment → Preparation of barium sulfate slurry treated with epoxy silane]
A water slurry of 50 g of barium sulfate particles (precipitating barium 100 manufactured by Sakai Chemical Industry Co., Ltd.) was heated to 70 ° C., and then a 10% sodium silicate aqueous solution was added to the silica particles in an amount of 1% in terms of silica particles. Hydrochloric acid was added to this slurry to adjust the pH to 4, and the mixture was aged for 30 minutes. Further, while maintaining the pH at 7 ± 1 with hydrochloric acid, a 20% _{aqueous solution of sodium aluminate (NaAlO 2} ) was added to the silica particles with alumina (alumina (NaAlO 2). Al ₂ O ₃ ) 5% was added in terms of conversion. After that, a 20% sodium hydroxide water bath was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Then, the slurry was filtered and washed with water using a filter press and vacuum dried to obtain a solid substance of barium sulfate particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. 50 g of barium sulfate particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a silane coupling agent having an epoxy group (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) were added. A uniformly dispersed silica solvent-dispersed product was obtained.

[(D-2.3) Preparation of Epoxy Silane Treated Silica Slurry]
50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle size: 500 nm), 48 g of PMA as a solvent, and 2 g of a silane coupling agent having an epoxy group (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly dispersed. A silica solvent-dispersed product was obtained.

[(D-2.4) Preparation of amino-treated silica slurry]
50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle size: 500 nm), 48 g of PMA as a solvent, and 2 g of a silane coupling agent having an acrylic group (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly dispersed. A silica solvent-dispersed product was obtained.

[(D-3) Preparation of silica slurry]
A silica solvent-dispersed product was obtained in which 50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle size: 500 nm), 48 g of PMA as a solvent, and 2 g of a dispersant (BYK-111) were uniformly dispersed.

[(D-4) Preparation of Inorganic Treated Barium Sulfate Slurry]
A water slurry of 50 g of barium sulfate particles (precipitating barium 100 manufactured by Sakai Chemical Industry Co., Ltd.) was heated to 70 ° C., and then a 10% sodium silicate aqueous solution was added to the silica particles in an amount of 1% in terms of silica particles. Hydrochloric acid was added to this slurry to adjust the pH to 4, and the mixture was aged for 30 minutes. Further, while maintaining the pH at 7 ± 1 with hydrochloric acid, a 20% _{aqueous solution of sodium aluminate (NaAlO 2} ) was added to the silica particles with alumina (alumina (NaAlO 2). Al ₂ O ₃ ) 5% was added in terms of conversion. After that, a 20% sodium hydroxide water bath was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Then, the slurry was filtered and washed with water using a filter press and vacuum dried to obtain a solid substance of barium sulfate particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. A silica solvent-dispersed product obtained by uniformly dispersing 50 g of barium sulfate particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a dispersant (BYK-111) was obtained. ..

[(D-5) Preparation of barium sulfate slurry]
A barium sulfate solvent-dispersed product was obtained in which 50 g of barium sulfate particles (precipitating barium 100 manufactured by Sakai Chemical Industry Co., Ltd.), 48 g of PMA as a solvent, and 2 g of a dispersant (BYK-111) were uniformly dispersed.

Further, the cured resin compositions shown in Tables 1 to 3 may contain the following components.
・ DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.
・ CZ-601D (blue colorant) manufactured by Nikko Bics Co., Ltd.
・ CZ-309D (yellow colorant) manufactured by Nikko Bics Co., Ltd.
・ DICY (dicyandiamide)

(Making a dry film)
The curable resin compositions of Examples and Comparative Examples shown in Tables 1 to 3 are such that the curable resin composition of each Example and Comparative Example is placed on PET at 10 m / min using a die coater from 60 to 60. A dry film was obtained by passing it through a drying oven at 120 ° C. and volatilizing the solvent.

(Preparation of standard evaluation board)
The dry film obtained by the above method was laminated on a test substrate using a vacuum laminator CVP-300 (manufactured by Nikko Materials Co., Ltd.) to obtain a laminate of a photosensitive resin composition. A DXP-3580 (Ultra High Pressure Mercury Lamp DI Exposure Machine manufactured by ORC) was used on this laminate, and pattern exposure was performed according to the evaluation items so that the number of curing stages was 10 with a Stoffer 41-stage step tablet. Ten minutes after the exposure, the PET film was peeled off, and development was carried out with a 1% by mass sodium carbonate aqueous solution at 30 ° C. for a development time twice the breakpoint (shortest development time). Then, an evaluation substrate was obtained by exposing with a UV conveyor (made by ORC, metal halide lamp) at an integrated exposure amount of 2000 mJ / cm ² and curing at 170 ° C. for 60 minutes in a heat circulation type Box furnace.

<Glass transition temperature Tg>
Each curable resin composition was formed on a copper foil substrate so as to have a film thickness of about 40 μm, and was exposed in a strip-shaped pattern of 50 mm × 3 mm. Then, development and curing were carried out under the same conditions as those for producing the standard evaluation substrate.
The cured film of the evaluation substrate obtained as described above was peeled off from the copper foil, and evaluation was carried out. The measurement was performed using a TMA measuring device (model name: TMA6000 manufactured by Shimadzu Corporation), and Tg was evaluated. The evaluation criteria are as follows.
◎… 180 ℃ or more ○… 170 ℃ or more and less than 180 △ …… 160 ℃ or more and less than 170 × …… less than 160 ℃

<Evaluation of toughness (manufacturing of copper foil substrate with resin layer)>
A curable resin composition was formed on a copper foil substrate so as to have a film thickness of about 40 μm, and was exposed in a strip-shaped pattern of 80 mm × 10 mm. Then, development and curing were carried out under the same conditions as those for producing the standard evaluation substrate.
The cured film of the evaluation substrate obtained as described above was peeled off from the copper foil, and evaluation was carried out. The measurement was performed using a tensile tester (model name: AGS-G 100N manufactured by Shimadzu Corporation), and the maximum point stress or the elongation at break was evaluated. The evaluation criteria are as follows.
◎… Maximum point stress 80 MPa or more, or breaking point elongation 6% or more ○… Maximum point stress 70 MPa or more and less than 80 MPa, or breaking point elongation 4% or more and less than 6% Δ… Maximum point stress 50 MPa or more and less than 70 MPa, breaking point elongation Rate 2% or more and less than 4% ×… Maximum point stress less than 50 MPa or breaking point elongation rate less than 2%

<Warp>
Each curable resin composition was formed on a 35 μm copper foil substrate treated with CZ-8101B under the condition of an etching rate of 1.0 μm / m ² so as to have a film thickness of about 20 μm, and the entire surface was exposed. After that, development and curing were carried out under the predetermined conditions.
The cured film of the evaluation substrate obtained as described above was cut out to a size of 50 mm × 50 mm and placed on a horizontal table with the cured film surface facing down. After standing still, the distance from the horizontal table to the Cu foil was measured and the amount of warpage was measured.
◎… Less than 10 mm ○… 10 mm or more, less than 15 mm △… 15 mm or more, less than 20 mm ×… Less than 20 mm

<Low-Profile Adhesion-Initial Adhesion>
A curable resin composition was formed on a copper foil treated with CZ-8201B under a condition of an etching rate of 0.5 μm / m ² so as to have a film thickness of about 20 μm, and the entire surface was exposed. Then, development and curing were carried out under the same conditions as those for producing the above-mentioned standard evaluation substrate. Then, a thermosetting adhesive Araldite (manufactured by Nichiban Co., Ltd.) was formed on the surface of the curable resin composition, adhered to a FR-4 substrate, and cured at 80 ° C. for 6 hours. Then, the evaluation substrate was cut at intervals of 20 mm, and both sides were peeled off so that the Cu foil width became 10 mm width to prepare an evaluation strip. This evaluation strip was subjected to a 90 ° peel test using a tensile tester (model name: AGS-G 100N manufactured by Shimadzu Corporation) to evaluate the adhesion. The evaluation criteria are as follows.
⊚: 6.0 N / cm or more ○: 5.0 or more and less than 6.0 N / cm Δ: 4.0 or more and less than 5.0 N / cm ×: 4.0 N / cm or less

<Low-Profile Adhesion-Adhesion after HAST50h>
A curable resin composition was formed on a copper foil treated with CZ-8201B under a condition of an etching rate of 0.5 μm / m ² so as to have a film thickness of about 20 μm, and the entire surface was exposed. Then, development and curing were carried out under the same conditions as those for producing the standard evaluation substrate. Then, a thermosetting adhesive Araldite (manufactured by Nichiban Co., Ltd.) was formed on the surface of the curable resin composition, adhered to a FR-4 substrate, and cured at 80 ° C. for 6 hours. Then, the evaluation substrate was cut at intervals of 20 mm, and both sides were peeled off so that the Cu foil width became 10 mm width to prepare an evaluation strip. This evaluation strip was treated at 130 ° C. and 85% for 50 hours, and a 90 ° peel test was performed using a tensile tester (model name: AGS-G 100N manufactured by Shimadzu Corporation) to evaluate the adhesion. The evaluation criteria are as follows.
⊚: 5.0 N / cm or more ○: 4.0 or more and less than 5.0 N / cm Δ: 3.0 or more and less than 4.0 N / cm ×: less than 3.0 N / cm

<Resolution evaluation>
A curable resin composition was formed on a plated copper substrate treated with CZ-8101B under a condition of an etching rate of 1.0 μm / m ² so as to have a film thickness of about 20 μm, and exposure was performed with various aperture patterns. Then, development was carried out under the same conditions as those for producing the standard evaluation substrate, and curing was carried out under the evaluation conditions.
The opening diameter of the evaluation substrate obtained by the above was observed, and it was confirmed that no halation or undercut occurred and the evaluation was performed.
◎… Good opening diameter at 60 μm ○… Good opening diameter at 70 μm △… Good opening diameter at 80 μm ×… Good opening diameter at 80 μm cannot be obtained or development is not possible

<HAST resistance>
A curable resin composition was formed so as to have a film thickness of about 20 μm on a substrate on which a comb-shaped pattern of L / S = 20/20 μm treated with CZ-8101B at an etching rate of 1.0 μm / m ^{2 was formed.} , Full exposure was performed. Then, development and curing were carried out under the same conditions as those for producing the standard evaluation substrate.
After that, the electrodes were connected and the HAST test was conducted under the conditions of 130 ° C, 85%, and 5V.
⊚: 400h pass
◯: 350h pass
Δ: 300h pass
×: NG within 250 hours

<TCT resistance>
A curable resin composition was formed on a package substrate treated with CZ-8101B at an etching rate of 1.0 μm / m ^{2 so} as to have a Cu film thickness of about 18 μm, and SRO 80 μm was exposed on a copper pad. rice field. Then, development and curing were carried out under the same conditions as those for producing the standard evaluation substrate. Then, Au plating treatment, solder bump formation, and Si chip were mounted to obtain an evaluation substrate.
The evaluation substrate obtained as described above was placed in a thermal cycle machine in which a temperature cycle was performed between −65 ° C. and 150 ° C., and TCT (Thermal Cycle Test) was performed. Then, the surface of the cured film at 600 cycles, 800 cycles and 1000 cycles was observed. The judgment criteria are as follows.
⊚: No abnormality in 1000 cycles ○: No abnormality in 800 cycles, cracks in 1000 cycles △: No abnormality in 600 cycles, cracks in 800 cycles ×: Cracks in 600 cycles

From the results shown in Tables 1 to 3, it can be seen that the cured product of the curable resin composition of Examples 1 to 20 of the present invention is excellent in crack resistance, insulation reliability, and adhesion. On the other hand, when the curable resin compositions of Comparative Examples 1 to 5 were used, the adhesiveness was poor and it was difficult to obtain insulation reliability.

Claims (6)

(A) Carboxyl group-containing resin and
(B-1) Photopolymerization initiator and
(C) An epoxy resin having the following structural formula and

(D-1) Photoreactive surface-treated inorganic filler and
A curable resin composition comprising. The average particle diameter of the inorganic filler which has been surface-treated is at 1.0μm or less, and the curable resin composition according to claim 1 Symbol placement maximum particle size is less than 4.0 .mu.m. The curable resin composition according to claim 1 or 2 , wherein the blending ratio of the surface-treated inorganic filler is 25 to 80% by mass. A dry film having a resin layer obtained by applying the curable resin composition according to any one of claims 1 to 3 to a film and drying the film. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 3 or the resin layer of the dry film according to claim 4. A printed wiring board comprising the cured product according to claim 5.