TWI814970B - Curable resin compositions, dry films, hardened materials and electronic parts - Google Patents

Abstract

The present invention provides a curable resin composition capable of obtaining a cured product having excellent embedding properties with high resolution and high-density wiring patterns, a dry film having a resin layer obtained from the composition, the composition or the dry film. The hardened material of the resin layer and the electronic parts having the hardened material. A curable resin composition, which contains: (A) photocurable resin, (B) photopolymerization initiator, and (C) silicon dioxide; characterized in that: the aforementioned (A) photocurable resin is 25 The refractive index of the D line measured at 25°C is 1.50 to 1.65, and the (C) silica is covered with an organoalkoxysilane having a refractive index of 1.50 to 1.65 for the D line measured at 25°C.

Description

Curable resin compositions, dry films, hardened materials and electronic parts

The present invention relates to a curable resin composition, dry film, cured product and electronic parts.

Curable resin compositions used in solder resists for semiconductor packages have increasingly higher requirements for fine pitch resolution. On the other hand, since it is also necessary to have resistance to thermal stress, the industry controls the thermal expansion coefficient by adding highly heat-resistant resin or inorganic materials. The inorganic material used has always been silicon dioxide in terms of physical properties such as low CTE or crack resistance, as well as ease of use such as cost and specific gravity. For example, Patent Document 1 discloses a photosensitive resin composition that combines two types of inorganic fillers with specific refractive index and organic fillers with specific particle sizes to provide high resolution and low linear expansion coefficient. Prior technical literature patent documents

Patent Document 1: Japanese Patent No. 6210060

Invent the problem to be solved

However, even with the photosensitive resin composition described in Patent Document 1, it is difficult to obtain sufficient high resolution in response to the high resolution requirements associated with micronization. In addition, since blending silicon dioxide will increase the viscosity of the composition, the embedding accuracy of high-density wiring patterns will deteriorate, and the insulation reliability will also deteriorate. Therefore, an object of the present invention is to provide a curable resin composition capable of obtaining a cured product having excellent embedding properties with high resolution and high-density wiring patterns, a dry film having a resin layer obtained from the composition, the composition or The cured product of the resin layer of the dry film and the electronic component having the cured product. means of solving problems

In order to achieve the above object, the inventors of the present invention focused on surface treatment of silicon dioxide and devoted themselves to research. As a result, the inventors of the present invention found that by blending an organic alkoxy with a refractive index of D line (25° C.) of 1.50 to 1.65 to a photocurable resin having a refractive index of 1.50 to 1.65 for D line (25° C.) Silica coated with silane can solve the above problems, and finally the present invention is completed.

That is, the curable resin composition of the present invention contains: (A) photocurable resin, (B) photopolymerization initiator, and (C) silica; and is characterized by: the aforementioned (A) photocurable The resin has a D-line refractive index of 1.50 to 1.65 measured at 25°C, and the (C) silica mentioned above is covered with an organoalkoxysilane having a D-line refractive index of 1.50 to 1.65 measured at 25°C.

In the curable resin composition of the present invention, it is preferred that the organoalkoxysilane has a Cardo structure.

In the curable resin composition of the present invention, the (C) silica is coated with at least two kinds of the above-mentioned organoalkoxysilane, or is coated with the above-mentioned organoalkoxysilane and an organic alkoxy other than the above-mentioned organoalkoxysilane. It is better to be coated with silane.

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

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

The electronic component of the present invention is characterized by having the aforementioned hardened material. Effect of invention

According to the present invention, it is possible to provide a curable resin composition capable of obtaining a cured product having excellent embedding properties with high resolution and high-density wiring patterns, a dry film having a resin layer obtained from the composition, the composition, or the The hardened material of the resin layer of the dry film and the electronic parts having the hardened material.

Form of carrying out the invention

The curable resin composition of the present invention contains: (A) photocurable resin, (B) photopolymerization initiator, and (C) silicon dioxide; it is characterized in that: the aforementioned (A) photocurable resin is The refractive index of the D line measured at 25°C is 1.50 to 1.65. The aforementioned (C) silica is covered with an organoalkoxysilane having a refractive index of the D line measured at 25°C of 1.50 to 1.65. Traditionally, the refractive index of silicon dioxide's D line (25°C) is 1.42. The higher the filling degree, the greater the scattered light at the interface, making it difficult to obtain small diameter openings. On the other hand, in the present invention, a photocurable resin having a refractive index of 1.50 to 1.65 for transmitting D line (25°C) and an organoalkoxysilane having a refractive index of 1.50 to 1.65 for D line (25°C) are used in combination. The coated silicon dioxide also has excellent resolution and embedding properties for high-density wiring patterns. That is, in the present invention, since the refractive index difference between (A) the photocurable resin having the above-mentioned refractive index and the silica surface coated with the specific organoalkoxysilane having the above-mentioned refractive index is relatively close, it is possible to Prevent the scattering of active energy rays (Rayleigh scattering and Mie scattering). In this way, the penetration rate of active energy rays can theoretically be maximized, and good deep hardening properties can be obtained in the present invention. Therefore, even when silica is highly filled, a hardened product with excellent resolution can be obtained.

In the present invention, the difference between the refractive index of (A) the photocurable resin and the refractive index of the organoalkoxysilane coating (B) silica is preferably 0.10 or less, more preferably 0.08 or less, still more preferably 0.06 Below, the best value is below 0.03. Here, when there are multiple types of (A) photocurable resin and (C) silica-coated organoalkoxysilane each, the refractive index of any one (A) photocurable resin and the coated (B) silica The difference in refractive index of the organoalkoxysilane only needs to be 0.10 or less. However, when there are multiple types of (A) photo-curable resins, in terms of mass %, the refractive index of (A) photo-curable resin and the organic coating (C) silica contained in the (A) photo-curable resin are the largest. The difference in refractive index of alkoxysilane is preferably 0.10 or less.

Furthermore, in the present invention, the organoalkoxysilane preferably has a Cardo structure such as a fluorine skeleton. By blending silica coated with an organoalkoxysilane having a cardo structure, a hardened product with better heat resistance can be obtained; moreover, it can be compared with a non-roughened substrate or a silicon substrate (that is, a smaller anchoring effect). The adhesion to the substrate is also excellent.

In the present invention, a photocurable resin or a photocurable copolymer resin having a maleimide structure that is passed through and used as a starting material is a phenol resin described below as (A) the photocurable resin, and (C) are specified. Silica coated with organoalkoxysilane can be confirmed to not only improve resolution and further improve fluidity, but also improve heat resistance and thermal stability.

The curable resin composition of the present invention is exposed to ultraviolet rays (about 400 nm), and the refractive index is controlled by using the refractive index of D line, which is generally widely stated. The curable resin composition of the present invention is composed of (A) photocurable resin having a refractive index of D line of 1.50 to 1.65 and (C) coated with an organic alkoxysilane having a refractive index of D line of 1.50 to 1.65. ) silicon dioxide, since excellent resolution can be obtained, it is found that the object of the present invention can be fully achieved by a combination of adjusting the refractive index of the D line.

Each component of the curable resin composition of the present invention will be described below.

[(A) Photocurable resin] (A) The photocurable resin is a photocurable resin having a refractive index of D line (25° C.) of 1.50 to 1.65. It is preferable to use a compound having one or more ethylenically unsaturated groups in the molecule. As the compound having an ethylenically unsaturated group, any well-known and commonly used compound may be used. Polymers such as alkali-soluble resins having an ethylenically unsaturated group, photopolymerizable oligomers, photosensitive monomers, etc. may be used. The polymerizable vinyl monomer, etc. may be a radically polymerizable monomer or a cationically polymerizable monomer. Examples of ethylenically unsaturated groups include vinyl groups and (meth)acrylyl groups. In this specification, (meth)acrylyl refers to the term collectively referring to acrylyl, methacrylyl and mixtures thereof, and the same applies to other similar expressions.

When the composition of the present invention is an alkali-developing type, (A) the photocurable resin is preferably an alkali-soluble resin. (A) If the photocurable resin is an alkali-soluble resin, a cured product with particularly excellent resolution can be obtained. The alkali-soluble resin may be any resin having an alkali-soluble group, and the alkali-soluble group may be, for example, any one of a phenolic hydroxyl group, a thiol group, and a carboxyl group. Examples of the alkali-soluble resin include compounds having two or more phenolic hydroxyl groups, carboxyl group-containing resins, compounds having phenolic hydroxyl groups and carboxyl groups, and compounds having two or more thiol groups. Among them, compounds having excellent developability are preferred. Carboxyl-containing resin. Preferred among the carboxyl group-containing resins are photocurable resins using phenol resins as starting materials, photocurable copolymer resins having a maleimide structure, and photocurable resins having an acrylic epoxy ester structure. (A) Photocurable resin can be used individually by 1 type or in combination of 2 or more types.

Specific examples of (A) the photocurable resin include, but are not limited to, the following compounds (which may be either oligomers or polymers).

(1) Addition of (meth)acrylic acid to carboxyl-containing resins obtained by copolymerization of unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene and α-methylstyrene Carboxyl group-containing photosensitivity with a copolymer structure formed from compounds with one epoxy group and one or more (meth)acrylyl groups in the molecule, such as glyceryl ester and α-methylglycidyl (meth)acrylate. resin.

(2) Having an amine group obtained by reacting a diisocyanate such as an aromatic diisocyanate, a carboxyl-containing diol compound, a diol compound, and a compound having one isocyanate group and one or more (meth)acrylyl groups in the molecule Carboxyl-containing photosensitive resin with formate structure.

(3-1) A urethane structure based on the addition polymerization reaction of diisocyanate, (meth)acrylate of bifunctional epoxy resin or its partial acid anhydride modified product, carboxyl-containing diol compound and diol compound Carboxyl-containing photosensitive resin. (3-2) The carboxyl group-containing photosensitive resin of (3-1) is further added with a compound having one epoxy group and one or more (meth)acrylyl groups in the molecule to form a carboxyl group-containing photosensitive resin with urethane Carboxyl-containing photosensitive resin with ester structure. (3-3) Mix diisocyanate, (meth)acrylate of bifunctional epoxy resin or its partial acid anhydride modified product, carboxyl group-containing diol compound, diol compound and a molecule having 1 hydroxyl group and 1 or more ( A carboxyl-containing photosensitive resin with a urethane structure is obtained by reacting a meth)acrylyl compound. (3-4) Use diisocyanate, (meth)acrylate of bifunctional epoxy resin or its partial acid anhydride modified product, carboxyl group-containing diol compound, diol compound and a compound having one or more isocyanate groups in the molecule A carboxyl-containing photosensitive resin with a urethane structure is obtained by reacting a (meth)acrylyl compound.

(4) Polyfunctional epoxy resin is reacted with unsaturated monocarboxylic acids such as (meth)acrylic acid, and dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are reacted A carboxyl group-containing photosensitive resin added to the hydroxyl group present in the side chain.

(5) A polyfunctional epoxy resin in which the hydroxyl group of a bifunctional epoxy resin is further epoxidized with epichlorohydrin reacts with a monocarboxylic acid containing an unsaturated group, and a dibasic acid anhydride is added to the resulting carboxyl group-containing photosensitivity of the hydroxyl group. resin.

(6) An epoxy compound having multiple epoxy groups in one molecule, and a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenylethyl alcohol, is reacted with an unsaturated monocarboxylic acid And the carboxyl group-containing photosensitive resin is obtained by reacting the alcoholic hydroxyl group of the reaction product with polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic anhydride.

(7) The reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with a monocarboxylic acid containing an unsaturated group, and the resulting reaction is Carboxyl-containing photosensitive resin obtained by reacting the product with polybasic acid anhydride.

(8) The reaction product obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethyl carbonate or propyl carbonate is reacted with a monocarboxylic acid containing an unsaturated group to obtain Carboxyl group-containing photosensitive resin obtained by reacting the reaction product with polybasic acid anhydride.

(9) For unsaturated carboxylic acids such as N-phenylmaleimine, N-phenylmaleimine and other maleimines or maleimine derivatives, (meth)acrylic acid and other , hydroxyalkyl (meth)acrylate and other unsaturated group-containing compounds with hydroxyl groups, and styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene and other unsaturated group-containing compounds with aromatic rings. The compound is a monomer carboxyl-containing copolymerized resin added with glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, epoxycyclohexylmethyl (meth)acrylate, etc. The molecule has 1 It is a carboxyl group-containing photosensitive resin with a copolymer structure composed of an epoxy group and one or more (meth)acrylyl groups.

(10) Add glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, and epoxy (meth)acrylate to the above-mentioned carboxyl group-containing photosensitive resins (2) to (8) It is a carboxyl group-containing photosensitive resin made from compounds having one epoxy group and one or more (meth)acrylyl groups in the molecule such as hexyl methyl ester.

When (A) the photocurable resin is an alkali-soluble resin, its acid value is preferably in the range of 40 to 200 mgKOH/g, and more preferably in the range of 45 to 120 mgKOH/g. (A) If the acid value of the photocurable resin is 40 mgKOH/g or more, alkali development is easy. On the other hand, if it is 200 mgKOH/g or less, it is preferable because it is easy to draw a normal cured product pattern.

Examples of the photopolymerizable oligomer include phenol novolak (meth)acrylic epoxy ester, cresol novolak (meth)epoxy acrylate, and bisphenol type (meth)acrylic epoxy ester. ) Epoxy acrylate; epoxy urethane (meth)acrylate, polyester (meth)acrylate, etc.

Examples of the photopolymerizable vinyl monomer include well-known and commonly used ones, such as styrene derivatives such as styrene, chlorostyrene, α-methylstyrene, triallyl isocyanate, and phthalic acid. Allyl compounds such as diallyl ester and diallyl isophthalate; esters of (meth)acrylic acid such as phenyl (meth)acrylate and phenoxyethyl (meth)acrylate; see Isocyanurate type poly(meth)acrylates such as [(meth)acryloxyethyl]isocyanurate and the like.

(A) The refractive index of the D line (25° C.) of the photocurable resin is preferably 1.52 or more, more preferably 1.54 or more.

(A) The blending amount of the photocurable resin is, for example, 10 to 50% by mass relative to the total solid content of the curable resin composition. In addition, the curable resin composition of the present invention may contain a photocurable compound whose refractive index at D line (25° C.) is less than 1.50. For example, the blending amount of a photocurable compound with a refractive index of less than 1.50, relative to the total amount of the photocurable compound with a refractive index of less than 1.50 and the photocurable resin with a refractive index of 1.50 to 1.65, can be reduced as long as it does not reach 50 mass % is enough. Examples of the photocurable compound having a refractive index of less than 1.50 include hydroxyalkyl (meth)acrylate such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate. Class; alkoxyalkylene glycol mono(meth)acrylates such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, etc.; ethylene glycol di(meth)acrylate , butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate Alkylene polyol poly(meth)acrylate such as acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.; diethylene glycol di(meth)acrylate, triethylene glycol Polyoxyalkylene glycol poly(methyl)glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate, etc. ) Acrylic esters; poly(meth)acrylates such as hydroxytrimethylacetate neopentyl glycol ester di(meth)acrylate, etc.

[(B) Photopolymerization initiator] (B) The photopolymerization initiator may be any photopolymerization initiator that is known as a photopolymerization initiator or a photoradical generator.

(B) Photopolymerization initiator includes, for example, bis-(2,6-dichlorobenzyl)phenylphosphine oxide and bis-(2,6-dichlorobenzyl)-2,5 -Dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzyl)- 1-Naphthylphosphine oxide, bis-(2,6-dimethoxybenzyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzyl)-2,4 ,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6 -Trimethylbenzyl)-phenylphosphine oxide and other bisylphosphine oxides; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichloro Benzyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine oxide, trimethylethyl Monocarboxyl phosphine oxides such as isopropyl phenyl phosphinate, 2,4,6-trimethylbenzyl diphenylphosphine oxide); 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-propanyl)-phenylmethyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. Hydroxyacetophenones; benzoin, diphenylethylenedione, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzene Benzoins such as azoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michlerone, methylbenzophenone, 4, 4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone and other benzophenones; acetophenone, 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinyl-1-propanone, 2-phenylmethyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(Dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N- Acetophenones such as dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4 -Thioxanthones such as diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylthioxanthone Anthraquinones such as anthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2-aminoanthraquinone; acetophenone dimethyl ketal, benzyl Ketals such as dimethyl ketal; benzene such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, p-dimethylethylbenzoate, etc. Formic acid esters; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethanone, 1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime) and other oxime esters; bis(eta ⁵ -2,4-cyclopentadienyl) En-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro- 3-(2-(1-pyrrol-1-yl)ethyl)phenyl]titanium and other titanocenes; phenyl disulfide 2-nitrofluoride, butyoin, anisoin ethyl ether , azobisisobutyronitrile, tetramethylthiuram disulfide, etc. The photopolymerization initiator can be used individually by 1 type or in combination of 2 or more types.

(B) The blending amount of the photopolymerization initiator is, for example, 0.1 to 30% by mass relative to the total solid content of the curable resin composition.

[(C)Silicon dioxide] In the present invention, (C) silica is coated with an organoalkoxysilane having a refractive index of D line (25° C.) of 1.50 to 1.65. Examples of silica include fused silica, spherical silica, amorphous silica, crystalline silica, sol silica, and the like, and spherical silica is preferred.

The organoalkoxysilane having a refractive index of D line (25° C.) of 1.50 to 1.65 is not particularly limited, as long as a well-known and commonly used organoalkoxysilane can be used. Examples include (the following refractive index measured at D line (25° C., also called sodium D line)), KBM-202SS (dimethoxydiphenylsilane: refractive index 1.54) manufactured by Shin-Etsu Chemical Industry Co., Ltd. , X-12-1156 (organosilane containing methoxy and mercapto groups: refractive index: 1.52), Oxygen and vinyl siloxane: refractive index 1.51), 3-Aminopropyltrimethoxysilane: refractive index 1.50), KBM-1403 (styryltrimethoxysilane: refractive index 1.50), Osaka Gas Chemicals SC-001 (fluorine-containing silane: refractive index 1.56) , SC-003 (containing silane: refractive index 1.53), etc. Among them, an alkoxysilane having an aromatic ring is preferred, and an organic alkoxysilane having a Cardo structure is particularly preferred. Furthermore, as mentioned above, from the viewpoint of heat resistance, organoalkoxysilanes having a fluorine skeleton such as SC-001 and SC-003 are preferred, and organoalkoxysilane having a quintilium skeleton having a Cardo structure is more preferred. The alkoxy group of the aforementioned organoalkoxysilane is, for example, an alkoxy group having 1 to 5 carbon atoms. The aforementioned organoalkoxysilane may be used alone or in combination of two or more types according to the refractive index of (A) the photocurable resin.

Examples of the above-mentioned organoalkoxysilanes having a fluorine skeleton having a Cardo structure include organoalkoxysilanes represented by the following formulas (1-1) and formula (1-2). (In the formula, n and m each independently represent an integer from 1 to 6).

Examples of commercially available products of the organoalkoxysilane represented by the formula (1-1) include OGSOL SC-001 manufactured by Osaka Gas Chemicals Co., Ltd. In addition, commercially available products of the organoalkoxysilane represented by the aforementioned formula (1-2) include, for example, OGSOL SC-003 manufactured by Osaka Gas Chemicals Co., Ltd.

The aforementioned organoalkoxysilane may have a hardening reactive group. The curing reactive group is not particularly limited as long as it is a group that can undergo a curing reaction with a component blended in the curable resin composition (for example, a photocurable resin or a thermosetting resin). Hardening reactive group.

The coating method is not particularly limited, and it may be carried out by a known and commonly used method such as a method of treating silica using the above-mentioned organoalkoxysilane as a silane coupling agent.

The coating of organoalkoxysilane having a refractive index of D line (25° C.) of 1.50 to 1.65 is, for example, 1 to 50 parts by mass relative to 100 parts by mass of silica.

(C) Silica is preferably coated with at least two types of the above-mentioned organoalkoxysilanes, or with the above-mentioned organoalkoxysilanes and an organic alkoxysilanes other than the above-mentioned organoalkoxysilanes. By blending silica coated in this way, a hardened product with low CTE and excellent cold and heat resistance can be obtained. This coating treatment can be before, after or at the same time as the coating treatment using the aforementioned organoalkoxysilane.

The organoalkoxysilane with a refractive index of D line (25° C.) of 1.50 to 1.65 may or may not have a hardening reactive group. When the organoalkoxysilane with a refractive index of D line (25°C) of 1.50 to 1.65 does not have a hardening reactive group, it is preferably used in combination with an organoalkoxysilane having a hardening reactive group. By using it in combination, heat resistance, thermal stability, and crack resistance during hot and cold cycles can be improved.

Examples of organosilanes other than the aforementioned organoalkoxysilane include KBM-502 (refractive index: 1.43), KBM-503 (refractive index: 1.43), KBE-502 (refractive index: 1.43), and KBE-503 (refractive index: 1.43), KBM-5803 (refractive index: 1.44), KR-503 (refractive index: 1.45) and other methacrylic silane, KBM-5103 (refractive index: 1.43), X-12-1048 (refractive index: 1.45), Silanes with refractive index less than 1.50 such as X-12-1050 (refractive index: 1.48), KR-513 (refractive index: 1.45), KBM-1003 (refractive index: 1.39), etc. The organosilane other than the above-mentioned organoalkoxysilane is preferably a silane having a reactive group with the component (A). Among them, silane methacrylate is preferred from the viewpoint of physical properties such as tensile strength. In addition, in order to control the refractive index, epoxy silane such as KBM-403 (refractive index: 1.43) may be mixed and added.

When it is further coated with an organosilane other than the above-mentioned organoalkoxysilane, the coating amount of the organosilane other than the above-mentioned organoalkoxysilane is 1 to 50 parts by mass relative to 100 parts by mass of silica.

In addition, (C) silicon dioxide may be further coated with an inorganic substance. The inorganic substance is not particularly limited, and examples thereof include hydrous oxides of silicon, hydrous oxides of aluminum, hydrous oxides of zirconium, hydrous oxides of zinc, and hydrous oxides of titanium.

When it is further covered with an inorganic substance, the coating with the inorganic substance is, for example, 1 to 40 parts by mass relative to 100 parts by mass of silica.

(C) The average particle size of silica is, for example, 0.01 to 0.8 μm. Here, in this specification, the average particle diameter of (C) silica is the average particle diameter (D50) including not only the particle diameter of primary particles but also the particle diameter of secondary particles (aggregates), and is based on D50 value measured by laser diffraction method. An example of a measuring device based on the laser diffraction method is Microtrac MT3300EXII manufactured by MicrotracBEL Corporation.

The average particle size of (C) silica can also be adjusted, and it is preferably pre-dispersed by, for example, a bead mill or a jet mill. In addition, the inorganic filler is preferably blended in a slurry state; by blending in a slurry state, it is easily highly dispersed, can prevent aggregation, and is easy to handle.

(C) Silica can be used individually by 1 type or in combination of 2 or more types. The blending amount of (C) silica may be, for example, 10 mass % or more, further 20 mass % or more, or even 30 mass % or more relative to the total solid content of the curable resin composition. The upper limit of the blending amount of silica is, for example, 80% by mass or less.

The curable resin composition of the present invention may contain well-known and commonly used inorganic fillers other than (C) silica within a range that does not impair the effects of the present invention. Examples of such inorganic fillers include silica other than silica coated with an organoalkoxysilane having a refractive index of D line (25° C.) of 1.50 to 1.65, Neuburg silica, aluminum hydroxide, and glass powder. , Talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, slag wool, aluminum silicate, calcium silicate, Zinc and other inorganic fillers.

(thermosetting resin) The curable resin composition of the present invention may contain a thermosetting resin. The thermosetting resin can improve the heat resistance of the cured product and improve the adhesion to the substrate. Thermosetting resins include isocyanate compounds, blocked isocyanate compounds, amine resins, benzoxazine resins, carbodiimide resins, cyclic carbonate compounds, epoxy compounds, multifunctional oxetane compounds, and cyclodiimide resins. A well-known and commonly used thermosetting resin such as sulfur resin. Among these, epoxy compounds, polyfunctional oxetane compounds, and compounds having two or more thioether groups in the molecule, that is, episulfide resins, are particularly preferred; epoxy compounds are more preferred. Thermosetting resin can be used individually by 1 type or in combination of 2 or more types.

The above-mentioned epoxy compound is a compound having an epoxy group, and any conventionally known compound can be used. Examples thereof include polyfunctional epoxy compounds having a plurality of epoxy groups in the molecule. Furthermore, it may also be a hydrogenated epoxy compound.

Examples of polyfunctional epoxy compounds include epoxidized vegetable oil; bisphenol A-type epoxy resin; hydroquinone-type epoxy resin; bisphenol-type epoxy resin; thioether-type epoxy resin; brominated epoxy resin; and novolac-type epoxy resin. Epoxy resin; biphenol novolak type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidyl amine type epoxy resin; hydantoin type epoxy resin; alicyclic type Epoxy resin; trihydroxyphenylmethane type epoxy resin; dixylenol type or biphenol type epoxy resin or mixtures thereof; bisphenol S type epoxy resin; bisphenol A novolak type epoxy resin; Tetrahydroxyphenyl ethane type epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl xylenyl ethane resin; naphthyl-containing epoxy resin; having two Epoxy resin with cyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resin; epoxy modified Polybutadiene rubber derivatives; CTBN modified epoxy resin, etc., but not limited to these. These epoxy resins can be used individually by 1 type or in combination of 2 or more types. Among them, novolak type epoxy resin, bisphenol type epoxy resin, dixylenol type epoxy resin, biphenol type epoxy resin, biphenol novolak type epoxy resin, naphthalene type epoxy resin Or a mixture of these is preferred.

Examples of polyfunctional oxetane compounds include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetane) Butylmethoxy)methyl] ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3- Ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxaacrylate cyclobutyl)methyl ester, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or Examples of such polyfunctional oxetanes such as oligomers and copolymers include oxetanol and novolac resin, poly(p-hydroxystyrene), cardo-type bisphenols, Calixarenes, resorcinol calixarenes, or etherates of resins with hydroxyl groups such as sesquioxane, etc. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate.

Examples of compounds having multiple cyclic thioether groups in the molecule include bisphenol A type episulfide resin. In addition, an episulfide resin in which the oxygen atoms of the epoxy groups of the novolak-type epoxy resin are replaced with sulfur atoms using the same synthesis method can also be used.

Examples of amino-based resins such as melamine derivatives and benzoguanamine derivatives include methylolmelamine compounds, hydroxymethylbenzoguanamine compounds, hydroxymethylglycoluril compounds, and hydroxymethylurea compounds.

A polyisocyanate compound may be blended as the isocyanate compound. Examples of the polyisocyanate compound include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, Aromatic polyisocyanates such as m-xylylene diisocyanate and 2,4-toluene isocyanate dimer; tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, and trimethylhexamethylene Aliphatic polyisocyanates such as diisocyanate, 4,4-methylene bis(cyclohexyl isocyanate) and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; and the isocyanate compounds listed previously Adducts, biurets and isocyanurates, etc.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound that can react with the isocyanate blocking agent include the above-mentioned polyisocyanate compounds. Examples of isocyanate blocking agents include phenol-based blocking agents; lactam-based blocking agents; active methylene-based blocking agents; alcohol-based blocking agents; oxime-based blocking agents; and thiol-based blocking agents; Acid amide-based blocking agents; acyl-imine-based blocking agents; amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents, etc.

The blending amount of the thermosetting resin is, for example, 1 to 50% by mass based on the total solid content of the composition.

(hardening accelerator) The curable resin composition of the present invention may contain a curing accelerator. Examples of the hardening accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanoethyl -Imidazole derivatives such as 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamine, benzyldimethylamine, 4-(dimethylamine) Methylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, 4 -Amine compounds such as dimethylaminopyridine; hydrazine compounds such as adipic acid dihydrazine and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, etc. Furthermore, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, and 2-vinyl-2 can also be used. ,4-Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methyl S-triazine derivatives such as acryloxyethyl-S-triazine/isocyanuric acid adduct. The hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

The blending amount of the hardening accelerator is, for example, 0.01 to 30% by mass based on the total solid content of the composition.

(colorant) The curable resin composition of the present invention may also contain a colorant. As the coloring agent, well-known coloring agents such as red, blue, green, yellow, black, and white can be used, and they can be any of pigments, dyes, and pigments. However, from the viewpoint of reducing environmental burden and impact on the human body, it is best not to contain halogen. The colorant can be used individually by 1 type or in combination of 2 or more types.

The blending amount of the colorant is, for example, 0.01 to 10% by mass based on the total solid content of the composition.

(organic solvent) The curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when coating on a substrate or film. Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellulose, methylcellulose, butylcellulose, and carbitol. Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether Glycol ethers such as base ethers; ethyl acetate, butyl acetate, butyl lactate, cellulose acetate, butyl cellulose acetate, carbitol acetate, butyl carbitol ethyl Acid esters, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc.; aliphatic hydrocarbons such as octane, decane, etc.; petroleum ether, naphtha, solvents Well-known and commonly used organic solvents such as petroleum solvents such as naphtha are used. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

(other optional ingredients) Furthermore, the curable resin composition of the present invention may be blended with other additives that are well-known and commonly used in the field of electronic materials. Examples of other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antioxidants, antibacterial/antifungal agents, defoaming agents, and leveling agents. , Tackifier, adhesion imparting agent, thixotropy imparting agent, photoinitiating agent, sensitizer, organic filler, elastomer, thermoplastic resin, release agent, surface treatment agent, dispersant, dispersing aid, Surface modifier, stabilizer, phosphor, etc.

Furthermore, the curable resin composition of the present invention may contain an alkali-soluble resin or a solvent-soluble resin other than the photocurable resin (A) within a range that does not impair the effects of the present invention.

The curable resin composition of the present invention is not particularly limited, and may be, for example, a photocurable thermosetting resin composition or a non-thermosetting photocurable resin composition. Alternatively, it may be an alkali development type or a solvent development type. That is, when the composition of the present invention is an alkali developing type containing an alkali-soluble resin, a negative pattern cured film can be obtained by active energy ray irradiation and an alkali developing solution; when it does not contain an alkali-soluble resin, then A negative pattern cured film can be obtained by irradiating active energy rays and a developer composed of an organic solvent.

Any component contained in the curable resin composition of the present invention may be selected from known and commonly used components in accordance with the curability or use.

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

The dry film of the present invention has a resin layer obtained by coating the curable resin composition of the present invention on a carrier film and drying it. When forming a dry film, first dilute the curable resin composition of the present invention with the above-mentioned organic solvent and adjust it to an appropriate viscosity, and then use a notch wheel coater, a blade coater, a lip coater, or a rod coater to form a dry film. , extrusion coater, reverse roll coater, transfer roll coater, gravure coater, spray coater, etc. to coat the carrier film to a uniform thickness. Thereafter, a resin layer can be formed by drying the coated composition at a temperature of 40 to 130°C for 1 to 30 minutes. The coating film thickness is not particularly limited. Generally speaking, the film thickness after drying is within the range of 3 to 150 μm, preferably 5 to 60 μm.

As the carrier film, a plastic film can be used, for example, a polyester film such as polyethylene terephthalate (PET), a polyamide film, a polyamide film, a polypropylene film, or a polystyrene film can be used. Film, etc. The thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 μm. More preferably, it is in the range of 15~130μm.

After the resin layer composed of the curable resin composition of the present invention is formed on the carrier film, it is preferable to further laminate a peelable cover film on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. The peelable covering film can be, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. As the cover film, any one that has smaller adhesion force between the resin layer and the carrier film when the cover film is peeled off can be used.

Furthermore, 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, in the present invention, the film to which the curable resin composition of the present invention is applied when producing a dry film can be used as both a carrier film and a cover film.

The manufacturing method of the printed wiring board using the curable resin composition of the present invention may be any conventionally known method. Taking an alkali-developable photocurable thermosetting resin composition as an example, the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using the above-mentioned organic solvent, and the curable resin composition is prepared by a dip coating method. , flow coating method, roller coating method, rod coating method, screen printing method, curtain coating method, etc. After coating on the substrate, the organic solvent contained in the composition is volatilized and dried at a temperature of 60~100℃ ( Temporarily dry) to form a non-sticky resin layer. In the case of a dry film, the resin layer is bonded to the substrate by a laminator or the like so that the resin layer is in contact with the substrate, and then the carrier film is peeled off to form the resin layer on the substrate.

Examples of the substrate include a printed wiring board or a flexible printed wiring board with a circuit formed in advance using copper or the like. Examples of the substrate include those using paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimide, Copper cladding for high-frequency circuits such as glass cloth/non-fiber epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluororesin/polyethylene/polyphenylene ether, polyphenylene ether/cyanate ester, etc. The material of laminates, etc., shall be copper-clad laminates of all grades (FR-4, etc.). Others include metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, Glass substrate, ceramic substrate, wafer board, etc. Pre-processing can also be performed on the circuit. For example, GliCAP manufactured by Shikoku Kasei Co., Ltd., New Organic AP (Adhesion promoter) manufactured by MEC Co., Ltd., Nova Bond manufactured by Atotech Japan Co., Ltd. can be used for pre-processing to improve the solder resist and hardening. The adhesion of the film, etc., or pre-treatment with rust inhibitors.

The volatilization drying after coating the curable resin composition of the present invention can be carried out using a hot air circulation drying oven, an IR oven, a heating plate, a convection oven, etc. (using a heat source equipped with an air heating method such as steam, the inside of the dryer can be The hot air counter-current contact method and the method of blowing the support from the nozzle) are carried out.

After the resin layer is formed on the printed wiring board, it is selectively exposed to active energy rays through a mask formed with a specific pattern, and the unexposed parts are developed with a dilute alkali aqueous solution (such as 0.3~3 mass% sodium carbonate aqueous solution). Form a pattern of hardened matter. Then, the hardened material is irradiated with active energy rays and then heated and hardened (for example, 100~220°C), or heated and hardened and then irradiated with active energy rays, or only heated and hardened for final trim hardening (formal hardening) to form adhesion, hardness, etc. Cured film with excellent properties.

The exposure machine used for the above-mentioned active energy ray irradiation can be equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and can irradiate active energy rays in the range of 350~450nm. A projection exposure machine using a projection lens or 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 be used for maskless exposure without contact with the substrate. The light source or laser light source of the direct drawing machine can have a maximum wavelength in the range of 350~450nm. The exposure amount used to form an image varies with the film thickness, etc. Generally speaking, it can be 10~1000mJ/ ^cm2 , preferably in the range of 20~800mJ/ ^cm2 .

The above-mentioned developing method can be carried out by dipping method, rinsing method, spray method, brush method, etc. The developing liquid can use potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia , alkali aqueous solutions of amines, etc.

The curable resin composition of the present invention is suitable for forming cured films on electronic parts, especially for forming cured films on printed wiring boards. It is more suitable for forming permanent coatings, and is more suitable for forming solder resists and interlayer insulating layers. , cladding, sealing materials. In addition, it is suitable for forming permanent coatings (especially solder resists) for printed wiring boards that require high reliability, such as packaging substrates, especially FC-BGA. In addition, the curable resin composition of the present invention can be suitably used for printed wiring boards that have wiring patterns even if the roughness of the circuit surface is small, such as printed wiring boards for high frequencies. For example, even if the surface roughness Ra is 0.05 μm or less, particularly 0.03 μm or less, it can be suitably used. In addition, it can also be suitably used when forming a cured film on a low-polarity base material, such as a base material containing an active ester. Furthermore, it is also suitable for forming a cured film on a non-roughened wafer or a glass substrate. Example

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. In addition, the following "parts" and "%" are based on mass unless otherwise specified.

[Synthesis of photocurable resin] (Photocurable resin A-1) Add 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formaldehyde to a flask equipped with a cooling tube and a stirrer, maintain the temperature below 40°C, and add 228 parts of 25% sodium hydroxide aqueous solution. After the addition, react at 50°C for 10 hours. After the reaction was completed, the mixture was cooled to 40°C and neutralized to pH 4 with a 37.5% phosphoric acid aqueous solution while maintaining the temperature below 40°C. Thereafter, it was allowed to stand to separate the water layer. After separation, add 300 parts of methyl isobutyl ketone to dissolve evenly, wash three times with 500 parts of distilled water, and remove water, solvent, etc. under reduced pressure at a temperature below 50°C. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1,230 parts of a methanol solution of the polymethylol compound. A part of the obtained methanol solution of the polymethylol compound was dried at room temperature in a vacuum dryer, and the solid content was found to be 55.2%. 500 parts of the methanol solution of the polymethylol compound and 440 parts of 2,6-xylenol were added to a flask equipped with a cooling tube and a stirrer, and the mixture was uniformly dissolved at 50°C. After uniform dissolution, remove the methanol under reduced pressure at a temperature below 50°C. Thereafter, 8 parts of oxalic acid was added and the reaction was carried out at 100°C for 10 hours. After the reaction, the distillate was removed under reduced pressure of 180° C. and 50 mmHg to obtain 550 parts of novolak resin A. Add 130 parts of novolac resin A, 2.6 parts of 50% sodium hydroxide aqueous solution, and toluene/methyl isobutyl ketone (mass ratio = 2) into an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device. /1) 100 parts, replace the system with nitrogen while stirring, then heat and raise the temperature, slowly introduce 60 parts of propylene oxide at 150°C and 8kg/ ^cm2 to react. The reaction continued for about 4 hours until the gauge pressure reached 0.0kg/ ^cm2 , and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% hydrochloric acid aqueous solution were added and mixed to neutralize sodium hydroxide. The neutralization reaction product was diluted with toluene and washed three times with water, and the solvent was removed with an evaporator to obtain a propylene oxide adduct of novolak resin A with a hydroxyl value of 189 g/eq. This is based on the average addition of 1 mole of propylene oxide per 1 equivalent of phenolic hydroxyl groups. Add 189 parts of the propylene oxide adduct of the novolac resin A, 36 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether, and 140 parts of toluene to a mixing bowl equipped with a mixer, a thermometer, and air. The reactor was blown into a tube, and the temperature was raised to 115° C. while stirring while blowing in air. Water and toluene generated by the reaction were distilled off as an azeotropic mixture, and the reaction was further allowed to react for 4 hours, and then cooled to room temperature. The obtained reaction solution was washed with water using a 5% NaCl aqueous solution, and toluene was removed by distillation under reduced pressure, and then diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution with a solid content of 67%. Next, 322 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were added to a four-necked flask equipped with a stirrer and a reflux cooler, and the mixture was heated to 110°C. , add 60 parts of tetrahydrophthalic anhydride, react for 4 hours, and then take it out after cooling. The photosensitive carboxyl-containing resin solution A-1 thus obtained has a solid content of 70% and an acid value of 81 mgKOH/g. In addition, the numerical values described in Table 1 are parts by mass of solid content excluding solvent.

(Photocurable resin A-2) 81.5 parts of carbitol acetate was added to a separate flask equipped with a cooling tube serving as a reaction tank, and after nitrogen replacement, the temperature was raised to 80°C. In addition, 30 parts of N-phenylmaleimide and 120 parts of carbitol acetate were added to the dripping tank 1, and 29 parts of styrene and 20 parts of carbitol acetate were added to the dripping tank 2. For 2-hydroxyethyl methacrylate, add 21 parts of acrylic acid and 10.6 parts of carbitol acetate into dripping tank 3, and add 10 parts of carbitol acetate as polymerization initiator into dripping tank 4. LUPEROX 11 (trade name; manufactured by ARKEMA Yoshitomi Co., Ltd., hydrocarbon solution containing 70% tert-butyl peroxypivalate) and 21.2 parts of carbitol acetate. While maintaining the reaction temperature at 80° C., dripping was performed from dripping tanks 1, 2, and 4 over 3 hours, and from dripping tank 3 over 2.5 hours. After the completion of the dropwise addition, the reaction was continued at 80° C. for 30 minutes. Thereafter, the reaction temperature was raised to 95° C., and the reaction was continued for 1.5 hours to obtain a polymer solution before radically polymerizable double bond introduction reaction. Next, 9.9 parts of glycidyl methacrylate, 7.4 parts of carbitol acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, and ANTAGE W-400 (Kawaguchi Chemical Co., Ltd.) as a polymerization inhibitor were added to the polymer solution. Industrial Co., Ltd.) 0.2 part, and reacted at 115°C while introducing a mixed gas of nitrogen and oxygen (oxygen concentration: 7%) to obtain a photosensitive carboxyl group-containing radical polymerizable polymer solution A-2. This photosensitive carboxyl-containing copolymer resin has a solid content of 32% and an acid value of 120 mgKOH/g. In addition, the numerical values described in Table 1 are parts by mass of solid content excluding solvent.

(Photocurable resin A-3) To 700 g of diethylene glycol monoethyl ether acetate, add 1070 g of o-cresol novolac type epoxy resin [manufactured by DIC Co., Ltd., EPICLONN-695, softening point 95°C, epoxy equivalent 214, average number of functional groups 7.6] (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 are heated to 100°C and stirred to uniformly dissolve. Next, 4.3 g of triphenylphosphine was added, and the reaction was heated to 110° C. for 2 hours. Then, 1.6 g of triphenyl phosphine was further added, and the temperature was raised to 120° C. and the reaction was further carried out for 12 hours. 562 g of aromatic hydrocarbon (SOLVESSO 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were added to the obtained reaction liquid, and the reaction was carried out at 110° C. for 4 hours. Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylate was added to the obtained reaction liquid, and the reaction was carried out at 115° C. for 4 hours to obtain a carboxyl group-containing resin solution. The solid content of the photosensitive carboxyl-containing resin solution A-3 thus obtained was 65%, and the acid value of the solid content was 87 mgKOH/g. In addition, the numerical values described in Table 1 are parts by mass of solid content excluding solvent.

[Preparation of inorganic fillers] C-1: 60 g of spherical silica (SFP-20M manufactured by Denka, average particle diameter: 400 nm), 40 g of MEK (methyl ethyl ketone) as a solvent, and a silane coupling agent having a methoxy group (KBM manufactured by Shin-Etsu Chemical Industry Co., Ltd. -202SS: The refractive index of D line (25° C.): 1.54) 2 g was uniformly dispersed to obtain silica solvent dispersion product C-1.

C-2: 60 g of spherical silica (SFP-20M manufactured by Denka, average particle diameter: 400 nm), 40 g of MEK (methyl ethyl ketone) as a solvent, and silane having a methoxy group and a fluorine skeleton having a Cardo structure were coupled. 2 g of mixture (SC-001 manufactured by Osaka Gas Chemicals: refractive index of D line (25° C.): 1.56) was uniformly dispersed to obtain silica solvent dispersion C-2.

C-3: 60 g of spherical silica (SFP-20M manufactured by Denka, average particle diameter: 400 nm), 40 g of MEK (methyl ethyl ketone) as a solvent, and silane having a methoxy group and a fluorine skeleton having a Cardo structure were coupled. 2 g of the mixture (SC-003 manufactured by Osaka Gas Chemicals: refractive index of D line (25° C.): 1.53) was uniformly dispersed to obtain silica solvent dispersion C-3.

C-4: 60 g of spherical silica (SFP-20M manufactured by Denka, average particle diameter: 400 nm), 40 g of MEK (methyl ethyl ketone) as a solvent, and silane having a methoxy group and a fluorine skeleton having a Cardo structure were coupled. After 2 g of the mixture (SC-001 manufactured by Osaka Gas Chemicals: refractive index of D line (25°C): 1.56) was uniformly dispersed, a silane coupling agent having a methoxy group and a methacryl group (KBM manufactured by Shin-Etsu Chemical Industry Co., Ltd. -503: The refractive index of D line (25°C): 1.43) 1 g was uniformly dispersed to obtain silica solvent dispersion product C-4.

C-5: 60 g of spherical silica (SFP-20M manufactured by Denka, average particle diameter: 400 nm), 40 g of MEK (methyl ethyl ketone) as a solvent, and silane having a methoxy group and a fluorine skeleton having a Cardo structure were coupled. After 2 g of the mixture (SC-001 manufactured by Osaka Gas Chemicals Co., Ltd.: refractive index of D line (25°C): 1.56) was uniformly dispersed, a silane coupling agent having a methoxy group and an amine group (KBM-573 manufactured by Shin-Etsu Chemical Industry Co., Ltd.: The refractive index of D line (25° C.: 1.43) 1 g was uniformly dispersed to obtain silica solvent dispersion product C-5.

R-1: 60 g of spherical silica (SFP-20M manufactured by Denka, average particle diameter: 400 nm), 40 g of MEK (methyl ethyl ketone) as a solvent, and a silane coupling agent (silane coupling agent) having a methoxy group and a methacryl group were KBM-503 manufactured by Shin-Etsu Chemical Industry Co., Ltd.: refractive index of D line (25° C.): 1.43) 2 g was uniformly dispersed to obtain silica solvent dispersion product R-1.

R-2: 60 g of spherical silica (SFP-20M manufactured by Denka, average particle diameter: 400 nm, refractive index of D line (25° C.) 1.42) and 40 g of MEK (methyl ethyl ketone) as a solvent were uniformly dispersed to obtain Silica solvent dispersion R-2.

R-3： 60 g of barium sulfate (B-30NC manufactured by Sakai Chemical Industry Co., Ltd. (untreated surface), average particle diameter: 300 nm, refractive index of D line (25°C): 1.65) and 40 g of MEK (methyl ethyl ketone) as a solvent were mixed The mixture was uniformly dispersed to obtain barium solvent dispersion product R-3. These are blended so that the solid content becomes the numerical value of Examples and Comparative Examples.

＜Refractive index measurement method＞ The refractive index of the photocurable resin, organoalkoxysilane and inorganic filler prepared above was measured using a refractometer ER-7MW manufactured by ERMA Company. Each sample was applied on glass and dried under the conditions of D line and 25°C. Measured below.

[Examples 1 to 6, Comparative Examples 1 and 2] The above-mentioned resin solution (varnish) is blended with various ingredients shown in the table in the indicated proportions (parts by mass), premixed with a stirrer, and then kneaded with a three-roller mill to prepare a curable resin composition.

＜Preparation of dry film＞ The curable resin composition prepared as above was diluted by adding 300 g of methyl ethyl ketone, and stirred with a mixer for 15 minutes to obtain a coating liquid. The coating liquid was applied to a polyethylene terephthalate film with a thickness of 38 μm (carrier film: EmbletPTH-25 manufactured by UNITIKA), and dried at a general temperature of 80° C. for 15 minutes to form a resin layer with a thickness of 20 μm. Next, a biaxially stretched polypropylene film (cover film: OPPFOA manufactured by FUTAMURA Corporation) was bonded to the resin layer to form a dry film.

<Resolution> A vacuum laminator (CVP-600: manufactured by Nikko-Materials Co., Ltd.) was used on the copper of the dry film acid-treated copper-clad laminate of each example and comparative example in the first chamber at 100°C. After laminating under the conditions of vacuum pressure 3hPa and vacuum time 30 seconds, press under the conditions of pressing pressure 0.5MPa and pressing time 30 seconds to obtain the evaluation substrate. Thereafter, a DI exposure machine (light source: mercury short arc lamp) was used to expose 10 layers of exposure in the exposure grid table (41 layers) to form an opening pattern of φ30 μm. The PET film was then peeled off and exposed to 60 layers. Develop (1 mass % Na ₂ CO ₃ , 30°C, 0.2MPa) in seconds to form a pattern of the resin layer. Next, use a UV conveyor belt furnace equipped with a high-pressure mercury lamp to irradiate the resin layer with an exposure dose of 1J/ ^cm2 , and then heat it at 160°C for 60 minutes to completely harden the resin layer to produce an evaluation substrate with a patterned cured film, and conduct Length measurement of photosensitive hardened coating films. ◎: Top 30μm, Bottom opening 95~100% 〇: Top 30μm, Bottom opening 85% or more but less than 95% △: Top or Bottom both 80~90% opening accuracy ×: Halo or undercut occurs

＜Embeddingability and BHAST resistance＞ After acid treatment is performed on a substrate with a circuit pattern having a conductor thickness of 10 μm L/S = 8 μm/8 μm, the dry film is laminated, exposed, developed, and cured in the same manner as the above <Resolution> evaluation, and the embedding properties are confirmed. , conduct BHAST at 130℃, 85%, 3V and evaluate the insulation reliability. ◎: Embedded without gaps, achieving insulation reliability of BHAST 300hrs or more 〇: Embedded without gaps, achieving insulation reliability of BHAST200 or above but less than 300hrs △: A gap of about 1~2μm is confirmed, and the insulation resistance does not reach 200hrs. ×: Looseness of 5 μm or more is confirmed.

<High Temperature Placement Test> A vacuum laminator (CVP-600: manufactured by Nikko-Materials) was used on the copper of the copper-clad laminate treated with CZ8101 manufactured by MEC Corporation for the dry film of each Example and Comparative Example at 100°C. After lamination in the first chamber under the conditions of vacuum pressure 3hPa and vacuum time 30 seconds, pressing was performed under the conditions of pressing pressure 0.5MPa and pressing time 30 seconds to obtain the evaluation substrate. Thereafter, the DI exposure machine was used to expose 10 layers of exposure in the exposure grid table (41 layers) to form a hollow pattern of φ200 μm. The PET film was peeled off and displayed for 60 seconds. image (1% by mass Na ₂ CO ₃ , 30°C, 0.2MPa) to form a pattern of the resin layer. Next, the resin layer was irradiated with an exposure dose of 1 J/cm ² using a UV conveyor furnace equipped with a high-pressure mercury lamp, and then heated at 160° C. for 60 minutes to completely cure the resin layer, thereby producing an evaluation substrate with a patterned cured film. The substrate was placed in a constant temperature bath in an oxygen environment at 175° C., and it was confirmed that the peeling time of the transparent tape did not occur. ◎: No peeling for more than 2000hrs 〇: Slight peeling occurs for more than 1500hrs and less than 2000hrs △: Peeling occurs for more than 1000hrs but less than 1500hrs ×: Peeling occurs within 1000hrs

＜CTE＞ A cured film was formed on the low-profile copper foil under the same conditions as the above <High Temperature Placement Test>. The obtained cured film was peeled off from the copper foil, a sample was cut out so that a measurement size (3 mm×10 mm size) could be obtained, and CTE was measured using TMA6100 manufactured by Hitachi High-Tech Corporation. The measurement conditions are to use a test load of 5g, heat the sample from room temperature at a heating rate of 10°C/min, and repeat this step twice to obtain a linear expansion coefficient (CTE (α2)) below Tg for the second time. It is found that the smaller the CTE, the better the thermal stability. ◎：30ppm or less 〇: More than 30ppm and less than 40ppm △: More than 40ppm and less than 50ppm ×: 50ppm ultra

＜Cold and heat resistance evaluation＞ Each dry film was laminated on a BT substrate with a 2mm copper wire pattern in the same manner as the above <High Temperature Placement Test> and <Resolution> Evaluation, and exposed, developed, UV and thermally cured. However, the pattern during exposure was changed to a 3mm square cured film pattern, and an evaluation substrate with a 3mm square cured film pattern formed on the copper wire was produced. Place this substrate into a thermal cycler that can perform temperature cycling between -50°C and 150°C, and perform TCT (ThermalCycle Test). Then, the cracks at 1000 cycles are confirmed. ◎: No cracks after 1000 cycles. 〇: Cracks occur in 500~750 cycles. △: Cracks occur after more than 250 cycles but less than 500 cycles. ×: Cracks occurred after less than 250 cycles.

※The difference in the refractive index of the D line (25°C) between the photocurable resin (A) and the organoalkoxysilane in Example 2 is the difference from the photocurable resin in *2

*1: Solution A-1 of the photocurable resin synthesized above (refractive index of D line (25°C): 1.56) *2: Solution A-2 of the photocurable resin synthesized above (refractive index of D line (25°C): 1.55) *3: Solution A-3 of the photocurable resin synthesized above (refractive index of D line (25°C): 1.56) *4: Omnirad TPO (2,4,6-trimethylbenzyl-diphenyl-phosphine oxide) manufactured by IGM Resins *5: Omnirad907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one) manufactured by IGM Resins *6: DPHA (dipentaerythritol hexaacrylate, refractive index of D line (25°C) 1.48) manufactured by Nippon Kayaku Co., Ltd. *7: jER828 (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. *8: Glycidyl of NC-6000 (2-(4-hydroxyphenyl)-2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propane manufactured by Nippon Kayaku Co., Ltd. Ether compounds) ＊9: NC-3000H (biphenol novolak type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. ＊10：Phthalocyanine blue *11: Dicyanodiamide *12: Melamine C-1: Solvent dispersion C-1 of silica prepared above and coated with a silane coupling agent having a methoxy group (refractive index of D line (25°C): 1.54) C-2: Solvent dispersion C-2 of silica prepared above and coated with a silane coupling agent (refractive index of D line (25°C): 1.56) having a methoxy group and a fluorine skeleton having a cardo structure. C-3: Solvent dispersion C-3 of silica prepared above and coated with a silane coupling agent (refractive index of D line (25° C.): 1.53) having a methoxy group and a fluorine skeleton having a Cardo structure. C-4: The above-prepared silane coupling agent (refractive index of D line (25°C) 1.56) having a methoxy group and a fluorine skeleton with a cardo structure, and a silane coupling agent having a methoxy group and a methacrylyl group Solvent dispersion C-4 of silica coated with silane coupling agent (refractive index of D line (25°C): 1.43) C-5: The silane coupling agent prepared above (refractive index of D line (25°C) 1.56) having a methoxy group and a fluorine skeleton with a Cardo structure, and the silane coupling agent having a methoxy group and an amine group (Refractive index of D line (25°C): 1.43) Solvent dispersion of silica coated C-5 R-1: Solvent dispersion R-1 of silica prepared above and coated with a silane coupling agent having a methoxy group and a methacrylyl group (refractive index of D line (25°C): 1.43) R-2: Solvent dispersion R-2 of the silica prepared above (refractive index of D line (25°C): 1.42) R-3: Solvent dispersion R-3 of the barium prepared above (refractive index of D line (25°C): 1.65)

From the results shown in the above table, it can be seen that the curable resin compositions of Examples 1 to 6 of the present invention can obtain cured products excellent in resolution and embedding properties of high-density wiring patterns.

Claims (6)

A curable resin composition, which contains: (A) photocurable resin, (B) photopolymerization initiator, and (C) silicon dioxide; characterized in that: the aforementioned (A) photocurable resin is 25 The refractive index of D line measured at 25℃ is 1.50~1.65. The aforementioned (C) silica is covered with an organoalkoxysilane having a refractive index of D line measured at 25℃ 1.50~1.65. The aforementioned organoalkoxysilane Has a skeleton. The curable resin composition according to claim 1, wherein the organoalkoxysilane has a cardo structure. The curable resin composition of Claim 1 or 2, wherein the (C) silica is covered with at least two of the aforementioned organoalkoxysilane, or is coated with at least two of the aforementioned organoalkoxysilane and the aforementioned organoalkoxysilane. Coated with organoalkoxysilane. A dry film characterized by 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 it. A cured product characterized by being obtained by curing the resin layer of the curable resin composition according to any one of claims 1 to 3 or the dry film according to claim 4. An electronic component characterized by having the following features as claimed in claim 5 of hardened matter.