KR20210148177A - Curable resin composition, dry film, cured product and electronic component - Google Patents

Abstract

Curable resin composition to obtain a cured product excellent in resolution and embedding properties of high-density wiring patterns, dry film having a resin layer obtained from the composition, cured product of the resin layer of the composition or the dry film, and electron having the cured product provide parts. A curable resin composition comprising (A) a photocurable resin, (B) a photoinitiator, and (C) silica, wherein the (A) photocurable resin has a refractive index in the D line measured at 25° C. of 1.50 to 1.65 , wherein (C) silica is coated with an organoalkoxysilane having a refractive index in the D-line measured at 25°C of 1.50 to 1.65, a curable resin composition or the like.

Description

Curable resin composition, dry film, cured product and electronic component

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

In curable resin composition used for the soldering resist of a semiconductor package, etc., the request|requirement of the resolution precision accompanying fine pitch formation is increasing. On the other hand, since resistance to thermal stress must also be provided, control of the coefficient of thermal expansion by addition of high heat-resistant resin or inorganic material is performed. As the inorganic material used therein, silica has been conventionally used not only in terms of physical properties such as low CTE and crack resistance, but also in terms of ease of use such as cost and specific gravity.

For example, Patent Document 1 discloses a photosensitive resin composition that provides high resolution and a low coefficient of linear expansion by combining two types of inorganic fillers with specific refractive indices and organic fillers with specific particle sizes.

Japanese Patent No. 6210060 Publication

However, also in the photosensitive resin composition of patent document 1, it was difficult to acquire sufficient high resolution with respect to the high request|requirement of the resolution precision accompanying fine pitch formation.

Moreover, by mix|blending silica, the viscosity of a composition increased, the embedding precision of a high-density wiring pattern was inferior, and there also existed a problem of the fall of insulation reliability.

Therefore, an object of the present invention is a curable resin composition to obtain a cured product excellent in resolution and embedding properties of high-density wiring patterns, a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or the dry film; and to provide an electronic component having the cured product.

The present inventors earnestly studied, paying attention to the surface treatment of silica, toward realization of the said objective. As a result, the present inventors prepared silica coated with an organoalkoxysilane having a refractive index of 1.50 to 1.65 in the D-line (25°C) with respect to a photocurable resin having a refractive index in the D-line (25°C) of 1.50 to 1.65. By mix|blending, it discovered that the said subject could be solved, and came to complete this invention.

That is, the curable resin composition of the present invention is a curable resin composition comprising (A) a photocurable resin, (B) a photoinitiator, and (C) silica, the D measured at 25° C. of the (A) photocurable resin The refractive index in the line is 1.50 to 1.65, and the silica (C) is coated with an organoalkoxysilane having a refractive index in the line D measured at 25°C of 1.50 to 1.65.

As for the curable resin composition of this invention, it is preferable that the said organic alkoxysilane has a cardo structure.

In curable resin composition of this invention, it is preferable that said (C) silica is coat|covered with at least 2 types of said organoalkoxysilane, or coat|covered with said organoalkoxysilane and organoalkoxysilane other than the said organoalkoxysilane. .

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

The hardened|cured material of this invention is obtained by hardening|curing the resin layer of the said curable resin composition or the said dry film, It is characterized by the above-mentioned.

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

According to the present invention, a curable resin composition obtained from a cured product having excellent resolution and embedding properties of a high-density wiring pattern, a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or the dry film, and the same An electronic component having a cured product can be provided.

The curable resin composition of the present invention is a curable resin composition comprising (A) a photocurable resin, (B) a photoinitiator, and (C) silica. The refractive index in the above is 1.50 to 1.65, and the silica (C) is coated with an organoalkoxysilane having a refractive index in the D line measured at 25°C of 1.50 to 1.65.

Conventionally, the refractive index of silica at D-line (25°C) is 1.42, the higher the filling is, the more the scattered light at the interface increases, and it is difficult to obtain a small-diameter aperture.

In contrast, in the present invention, a photocurable resin having a refractive index in the D-line (25°C) of 1.50 to 1.65 and silica coated with an organoalkoxysilane having a refractive index in the D-line (25°C) of 1.50 to 1.65 are used in combination. By doing so, the resolution and embedding of the high-density wiring pattern are also excellent.

That is, in the present invention, (A) the refractive index difference between the photocurable resin having the refractive index and the silica surface coated with the specific organoalkoxysilane having the refractive index is relatively close, so active energy ray scattering (Rayleigh scattering and non-scattering) You can prevent this from happening. Thereby, the transmittance|permeability of an active energy ray becomes the maximum theoretically, and favorable deep-part sclerosis|hardenability can be acquired in this invention. Accordingly, a cured product having excellent resolution can be obtained even when the silica is highly filled.

In the present invention, (A) the difference between the refractive index of the photocurable resin and (C) the refractive index of the organic alkoxysilane coating silica is preferably 0.10 or less, more preferably 0.08 or less, still more preferably 0.06 or less, and still more preferably 0.03 The following are especially preferable. Here, when (A) the photocurable resin and (C) each of a plurality of organic alkoxysilanes covering silica exist, the refractive index of any (A) photocurable resin and (C) the refractive index of the organic alkoxysilane covering silica The difference may be 0.10 or less. However, (A) when there are a plurality of photocurable resins, (A) the refractive index of the photocurable resin contained most in (A) the photocurable resin in terms of mass %, and (C) the organic alkoxysilane covering silica It is preferable that the difference in refractive index is 0.10 or less.

Moreover, in this invention, it is preferable that the said organoalkoxysilane has cardo structures, such as a fluorene skeleton. By mix|blending the silica coated with the organoalkoxysilane which has a cardo structure, the hardened|cured material which is further excellent in heat resistance is obtained, and it is also excellent in adhesiveness with the board|substrate without roughening or a silicon substrate (that is, the board|substrate with little anchor effect).

In the present invention, (A) a photocurable resin starting from a phenol resin to be described later as a photocurable resin, or a photocurable copolymer resin having a maleimide structure, and (C) silica coated with a specific organoalkoxysilane in combination , in addition to the improvement of the resolution and further flowability, the improvement of heat resistance and thermal stability was also confirmed.

Although the curable resin composition of this invention exposes by ultraviolet-ray (around 400 nm), the refractive index in D-line|line which appears widely and generally is used for control of refractive index. The curable resin composition of the present invention uses (A) photocurable resin having a refractive index in the D-line of 1.50 to 1.65 and (C) silica coated with an organoalkoxysilane having a refractive index in the D-line of 1.50 to 1.65 in combination. It turns out that the objective of this invention can fully be achieved by the combination adjusted by the refractive index in D line|wire from the point which was able to obtain the outstanding resolution.

Below, each component of curable resin composition of this invention is demonstrated.

[(A) photocurable resin]

(A) The photocurable resin is a photocurable resin whose refractive index in D-line (25 degreeC) is 1.50-1.65, The compound which has one or more ethylenically unsaturated groups in a molecule|numerator is used preferably. As the compound having an ethylenically unsaturated group, a known and conventional compound may be used, and a polymer such as an alkali-soluble resin having an ethylenically unsaturated group, a photopolymerizable oligomer that is a photosensitive monomer, a photopolymerizable vinyl monomer, etc. can be used, and a radically polymerizable monomer or a cationically polymerizable monomer. As an ethylenically unsaturated group, a vinyl group and a (meth)acryloyl group are mentioned. In the present specification, the (meth)acryloyl group is a term that generically refers to an acryloyl group, a methacryloyl group, and a mixture thereof, and the same applies to other similar expressions.

When the composition of this invention is alkali developing type, it is preferable that (A) photocurable resin is alkali-soluble resin. (A) When photocurable resin is alkali-soluble resin, especially the hardened|cured material excellent in resolution can be obtained. What is necessary is just resin which has an alkali-soluble group as alkali-soluble resin, As an alkali-soluble group, it is any 1 type among a phenolic hydroxyl group, a thiol group, and a carboxyl group, for example. Examples of the alkali-soluble resin include a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups. Among them, excellent developability Therefore, carboxyl group-containing resin is preferable. Among the carboxyl group-containing resins, a photocurable resin using a phenol resin as a starting material, a photocurable copolymer resin having a maleimide structure, and a photocurable resin having an epoxy acrylate structure are preferable. (A) Photocurable resin may be used individually by 1 type, and may be used in combination of 2 or more type.

(A) Although the following compounds (any of an oligomer and a polymer may be sufficient) are mentioned as a specific example of a photocurable resin, It is not limited to them.

(1) To a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid and an unsaturated group-containing compound such as styrene or α-methylstyrene, glycidyl (meth)acrylate, α-methylglycy The carboxyl group-containing photosensitive resin which has a copolymerization structure which adds the compound which has one epoxy group and one or more (meth)acryloyl group in molecules, such as dil (meth)acrylate.

(2) A carboxyl group having a urethane structure obtained by reacting a diisocyanate such as an aromatic diisocyanate, a carboxyl group-containing dialcohol compound, a diol compound, and a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule containing photosensitive resin.

(3-1) Carboxyl group-containing photosensitivity having a urethane structure by polyaddition reaction of a diisocyanate, a (meth)acrylate of a bifunctional epoxy resin, or a partial acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound profit.

(3-2) A carboxyl group-containing photosensitive resin having a urethane structure obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in the molecule to the carboxyl group-containing photosensitive resin of (3-1).

(3-3) a diisocyanate, a (meth)acrylate of a bifunctional epoxy resin or a partial acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, a diol compound, one hydroxyl group and one or more (meth) ) A carboxyl group-containing photosensitive resin having a urethane structure obtained by reacting a compound having an acryloyl group.

(3-4) a diisocyanate, a (meth)acrylate of a bifunctional epoxy resin or a partial acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, a diol compound, one isocyanate group in the molecule, and one or more (meth) ) A carboxyl group-containing photosensitive resin having a urethane structure obtained by reacting a compound having an acryloyl group.

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

(5) A carboxyl group-containing photosensitive resin in which a monocarboxylic acid containing an unsaturated group is reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of the bifunctional epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the generated hydroxyl group .

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

(7) An unsaturated group-containing monocarboxylic acid is reacted with 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, and a polybasic acid anhydride is added to the obtained reaction product Carboxyl group-containing photosensitive resin obtained by making it react.

(8) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid, and a polybasic acid anhydride is added to the obtained reaction product Carboxyl group-containing photosensitive resin obtained by making it react.

(9) An unsaturated group having a maleimide or maleimide derivative such as N-phenylmaleimide and N-benzylmaleimide, an unsaturated carboxylic acid such as (meth)acrylic acid, and a hydroxyl group such as hydroxyalkyl (meth)acrylate Glycidyl (meth)acrylate, α-methyl to a carboxyl group-containing copolymer resin containing a compound and an unsaturated group-containing compound having an aromatic ring such as styrene, α-methylstyrene, α-chlorostyrene and vinyltoluene as monomers A carboxyl group-containing photosensitivity having a copolymerized structure obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in molecules such as glycidyl (meth)acrylate and epoxycyclohexylmethyl (meth)acrylate profit.

(10) In the carboxyl group-containing photosensitive resin of (2) to (8) above, glycidyl (meth) acrylate, α-methyl glycidyl (meth) acrylate, epoxycyclohexylmethyl (meth) acrylate, etc. A carboxyl group-containing photosensitive resin formed by adding a compound having one epoxy group and one or more (meth)acryloyl groups in the molecule.

(A) When photocurable resin is alkali-soluble resin, the range of 40-200 mgKOH/g is suitable for the acid value, More preferably, it is the range of 45-120 mgKOH/g. (A) If the acid value of the photocurable resin is 40 mgKOH/g or more, alkali development becomes easy, and on the other hand, if it is 200 mgKOH/g or less, it is preferable because drawing of a normal cured product pattern becomes easy.

Examples of the photopolymerizable oligomer include epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate, and bisphenol epoxy (meth) acrylate, epoxy urethane (meth) acrylate, Polyester (meth)acrylate, etc. are mentioned.

As a photopolymerizable vinyl monomer, well-known and customary thing, for example, styrene derivatives, such as styrene, chlorostyrene, and (alpha)-methylstyrene, triallyl isocyanurate, diallyl phthalate, allyl compounds, such as diallyl isophthalate, phenyl (meth ) esters of (meth)acrylic acid such as acrylate and phenoxyethyl (meth)acrylate, isocyanurate-type poly(meth)acrylates such as tris[(meth)acryloxyethyl]isocyanurate, etc. can be heard

(A) It is preferable that it is 1.52 or more, and, as for the refractive index in D-line (25 degreeC) of photocurable resin, it is more preferable that it is 1.54 or more.

(A) The compounding quantity of photocurable resin is 10-50 mass % with respect to solid content whole quantity of curable resin composition, for example. Moreover, in curable resin composition of this invention, the refractive index in D-line (25 degreeC) may contain the photocurable compound which is less than 1.50. For example, as a compounding quantity of the photocurable compound whose refractive index is less than 1.50, the refractive index may just be less than 50 mass % with respect to the total amount of the photocurable resin whose refractive index is less than 1.50 and the photocurable resin whose refractive index is 1.50-1.65. As a photocurable compound whose refractive index is less than 1.50, For example, hydroxyalkyl (meth)acrylates, such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate ; Alkoxyalkylene glycol mono(meth)acrylates, such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, butanediol di(meth)acrylates, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , pentaerythritol tetra(meth)acrylate, and alkylene polyol poly(meth)acrylates such as dipentaerythritol hexa(meth)acrylate; Polyoxyalkylene glycol poly(es) such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane tri(meth)acrylate meth) acrylates; Poly(meth)acrylates, such as hydroxypivalic acid neopentyl glycol ester di(meth)acrylate, etc. are mentioned.

[(B) Photoinitiator]

(B) As a photoinitiator, if it is a well-known photoinitiator as a photoinitiator or a photoradical generator, any can also be used.

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

(B) The compounding quantity of a photoinitiator is 0.1-30 mass % with respect to solid content whole quantity of curable resin composition, for example.

[(C) Silica]

In this invention, (C) silica is coat|covered with the organoalkoxysilane whose refractive index in D-line (25 degreeC) is 1.50-1.65. Examples of the silica include fused silica, spherical silica, amorphous silica, crystalline silica, and sol silica, and spherical silica is preferable.

The organic alkoxysilane whose refractive index in D-line (25 degreeC) is 1.50-1.65 is not specifically limited, What is necessary is just to use a well-known and usual organoalkoxysilane. For example (hereinafter, the refractive index is the refractive index in the measurement of D-line (25° C., also referred to as sodium D-line)), Shin-Etsu Chemical KBM-202SS (dimethoxydiphenylsilane: refractive index 1.54), X -12-1156 (organosilane containing a methoxy group and a mercapto group: refractive index 1.52), X-12-1154 (organosilane containing a methoxy group and a mercapto group: refractive index: 1.51), KR-511 (containing a methoxy group and a vinyl group) Siloxane: refractive index 1.51), X-12-1159L (organosilane containing a methoxy group and an isocyanate group: refractive index 1.50), KBM-573 (N-phenyl-3-aminopropyltrimethoxysilane containing an amino group: refractive index 1.50), KBM -1403 (styryl trimethoxysilane: refractive index 1.50), SC-001 (fluorene-containing silane: refractive index 1.56) by Osaka Gas Chemical company, SC-003 (fluorene-containing silane: refractive index 1.53), etc. are mentioned. Especially, the alkoxysilane which has an aromatic ring is preferable, and the organoalkoxysilane which has a cardo structure is especially preferable. Moreover, from a heat resistant viewpoint as mentioned above, the organoalkoxysilane which has fluorene skeletons, such as SC-001 and SC-003, is preferable, and the organoalkoxysilane which has a fluorene skeleton of a cardo structure is more preferable. The alkoxy group of the said organoalkoxysilane is a C1-C5 alkoxy group, for example. The said organic alkoxysilane may match with the refractive index of (A) photocurable resin 1 type, or may combine 2 or more types.

As an organoalkoxysilane which has a fluorene skeleton of the said cardo structure, the organoalkoxysilane represented by following formula (1-1) and Formula (1-2) is mentioned.

(Wherein, n and m each independently represent an integer of 1 to 6.)

As a commercial item of the organic alkoxysilane represented by said Formula (1-1), the Osaka Gas Chemical company Ogsol SC-001 etc. are mentioned, for example. Moreover, as a commercial item of the organic alkoxysilane represented by said Formula (1-2), the Osaka Gas Chemical company Ogsol SC-003 etc. are mentioned, for example.

The said organoalkoxysilane may have a sclerosing|hardenable reactive group. The curable reactive group is not particularly limited as long as it is a group that cures and reacts with a component (eg, a photocurable resin or a thermosetting resin) to be blended with the curable resin composition, and may be a photocurable reactive group or a thermosetting reactive group.

The coating method is not specifically limited, For example, what is necessary is just to carry out by well-known and usual methods, such as the method of processing a silica using the said organoalkoxysilane as a silane coupling agent.

The coating|cover with the organic alkoxysilane whose refractive index in D line|wire (25 degreeC) is 1.50-1.65 is 1-50 mass parts with respect to 100 mass parts of silica.

(C) It is preferable that the silica is coat|covered with at least 2 types of said organoalkoxysilane, or coat|covered with the said organoalkoxysilane and organoalkoxysilane other than the said organoalkoxysilane. By blending the silica coated in this way, a cured product having excellent low CTE and excellent cold-and-heat resistance can be obtained. Such a coating process may be before, after, or simultaneous with the coating process by the said organic alkoxysilane.

The organic alkoxysilane whose refractive index in D line|wire (25 degreeC) is 1.50-1.65 may or may not have a sclerosing|hardenable reactive group. When the organic alkoxysilane whose refractive index in D-line (25 degreeC) is 1.50-1.65 does not have a sclerosing|hardenable reactive group, it is preferable to use together with the organoalkoxysilane which has a sclerosing|hardenable reactive group. By using in this way, heat resistance, thermal stability, and crack resistance at the time of a cooling-heat cycle improve.

Examples of the organic silane other than the organic alkoxysilane include KBM-502 (refractive index: 1.43), KBM-503 (refractive index: 1.43), KBE-502 (refractive index: 1.43), KBE-503 (refractive index: 1.43), KBM-5803 ( Refractive index: 1.44), methacrylsilane such as KR-503 (refractive index: 1.45), KBM-5103 (refractive index: 1.43), X-12-1048 (refractive index: 1.45), X-12-1050 (refractive index: 1.48), and silane having a refractive index of less than 1.50, such as KR-513 (refractive index: 1.45) and KBM-1003 (refractive index: 1.39). It is preferable that organic silanes other than the said organic alkoxysilane are silanes which have a reactive group with (A) component. Especially, it is preferable that it is methacrylsilane from a viewpoint of physical properties, such as tensile strength. In addition, epoxy silanes, such as KBM-403 (refractive index: 1.43), etc. may be mixed and added for refractive index control.

When further coat|covering with organosilanes other than the said organoalkoxysilane, the coat|cover with organosilanes other than the said organoalkoxysilane is 1-50 mass parts with respect to 100 mass parts of silicas.

In addition, (C) silica may be further coat|covered with the inorganic substance. It does not specifically limit as an inorganic substance, For example, the hydrated oxide of silicon, hydrated oxide of aluminum, hydrated oxide of zirconium, hydrated oxide of zinc, hydrated oxide of titanium, etc. are mentioned.

In the case of further coating with an inorganic substance, the coating amount with an inorganic substance is, for example, 1 to 40 parts by mass with respect to 100 parts by mass of silica.

(C) The average particle diameter of silica is 0.01-0.8 micrometer, for example. Here, in this specification, (C) the average particle diameter of 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 a value of D50 measured by laser diffraction method . As a measuring apparatus by a laser diffraction method, Microtrac MT3300EXII made from a Microtrac Bell company is mentioned.

(C) Silica may adjust an average particle diameter, for example, it is preferable to pre-disperse with a bead mill or a jet mill. In addition, it is preferable to mix|blend an inorganic filler in a slurry state, and by mix|blending in a slurry state, high dispersion|distribution is easy, aggregation is prevented, and handling becomes easy.

(C) Silica may be used individually by 1 type, and may be used in combination of 2 or more type. (C) The compounding quantity of silica may be 10 mass % or more with respect to solid content whole quantity of curable resin composition, for example, 20 mass % or more, Furthermore, 30 mass % or more may be sufficient. As an upper limit of the compounding quantity of a silica, it is 80 mass % or less, for example.

Curable resin composition of this invention may contain well-known and usual inorganic fillers other than (C) silica in the range which does not impair the effect of this invention. Examples of such an inorganic filler include silica other than silica coated with an organoalkoxysilane having a refractive index in the D-line (25°C) of 1.50 to 1.65, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate. inorganic fillers such as calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, and zinc oxide.

(thermosetting resin)

The curable resin composition of this invention may contain a thermosetting resin. Heat resistance of hardened|cured material improves by a thermosetting resin, and adhesiveness with a base material improves. As the thermosetting resin, an isocyanate compound, a blocked isocyanate compound, an amino resin, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, an epoxy compound, a polyfunctional oxetane compound, an episulfide resin, and other known and usual thermosetting resins can be used. can Among these, an epoxy compound, a polyfunctional oxetane compound, and the compound which has two or more thioether groups in a molecule|numerator, ie, episulfide resin, are preferable, and an epoxy compound is more preferable. A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more type.

The said epoxy compound is a compound which has an epoxy group, Any conventionally well-known thing can be used. The polyfunctional epoxy compound etc. which have several epoxy groups in a molecule|numerator are mentioned. Moreover, the hydrogenated epoxy compound may be sufficient.

Examples of the polyfunctional epoxy compound include epoxidized vegetable oil; bisphenol A epoxy resin; hydroquinone type epoxy resin; bisphenol-type epoxy resin; thioether type epoxy resin; Brominated epoxy resin; novolac-type epoxy resin; Biphenol novolak type epoxy resin; bisphenol F-type epoxy resin; hydrogenated bisphenol A epoxy resin; glycidylamine type epoxy resin; hydantoin-type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; Bixylenol-type or biphenol-type epoxy resins or mixtures thereof; bisphenol S-type epoxy resin; bisphenol A novolak-type epoxy resin; tetraphenylolethane type epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl xylenoyl ethane resin; naphthalene group-containing epoxy resin; an epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer-based epoxy resin; Copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives; Although CTBN modified|denatured epoxy resin etc. are mentioned, It is not limited to these. These epoxy resins can be used individually by 1 type or in combination of 2 or more type. Among these, a novolak-type epoxy resin, a bisphenol-type epoxy resin, a bixylenol-type epoxy resin, a biphenol-type epoxy resin, a biphenol novolak-type epoxy resin, a naphthalene-type epoxy resin, or a mixture thereof is especially preferable.

Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)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-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylic In addition to polyfunctional oxetanes such as lactate and their oligomers or copolymers, oxetane alcohol and novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcinarenes, or The etherified product with resin which has hydroxyl groups, such as silsesquioxane, etc. are mentioned. In addition, the copolymer etc. of the unsaturated monomer which have an oxetane ring, and alkyl (meth)acrylate are mentioned.

Bisphenol A type episulfide resin etc. are mentioned as a compound which has several cyclic thioether group in a molecule|numerator. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthetic|combination method can also be used.

As amino resins, such as a melamine derivative and a benzoguanamine derivative, a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, etc. are mentioned.

As an isocyanate compound, a polyisocyanate compound can be mix|blended. Examples of the polyisocyanate compound include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- aromatic polyisocyanates such as xylylene diisocyanate and 2,4-tolylene isocyanate dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate) and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; And the adduct body of the isocyanate compound mentioned previously, a biuret body, an isocyanurate body, etc. are mentioned.

As a block isocyanate compound, the addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. As an isocyanate compound which can react with an isocyanate blocking agent, the polyisocyanate compound etc. which were mentioned above are mentioned, for example. As an isocyanate blocking agent, For example, a phenol type blocking agent; lactam block agent; active methylene-based blocking agent; alcohol-based blocking agent; oxime-based blocking agent; mercaptan-based blocking agent; acid amide blocking agent; imide block agent; amine blocking agent; imidazole-based blocking agents; An immigration-based block system, etc. are mentioned.

The compounding quantity of a thermosetting resin is 1-50 mass % in solid content whole quantity of a composition, for example.

(curing accelerator)

The curable resin composition of the present invention may contain a curing accelerator. Examples of the curing accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 imidazole derivatives such as cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-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 dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid S-triazine derivatives, such as an adduct, can also be used. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

The compounding quantity of a hardening accelerator is 0.01-30 mass % in solid content whole quantity of a composition, for example.

(coloring agent)

The colorant may be contained in the curable resin composition of this invention. As a coloring agent, well-known coloring agents, such as red, blue, green, yellow, black, and white, can be used, Any of a pigment, dye, and a pigment|dye may be sufficient. However, it is preferable not to contain halogen from the viewpoint of reducing the environmental load and affecting the human body. A coloring agent may be used individually by 1 type, and may be used in combination of 2 or more type.

The compounding quantity of a coloring agent is 0.01-10 mass % in solid content whole quantity of a composition, for example.

(organic solvent)

The curable resin composition of this invention can be made to contain the organic solvent for the purpose of preparation of a composition, viscosity adjustment at the time of apply|coating to a board|substrate or a film, etc. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether glycol ethers such as acetate and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butylcellosolve acetate, carbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; A well-known and usual organic solvent, such as petroleum solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

(Other optional ingredients)

In addition, you may mix|blend with the curable resin composition of this invention other well-known and usual additives in the field|area of an electronic material. Examples of the other additives include a thermal polymerization inhibitor, a UV absorber, a silane coupling agent, a plasticizer, a flame retardant, an antistatic agent, an anti-aging agent, an antioxidant, an antibacterial/mildew inhibitor, an antifoaming agent, a leveling agent, a thickener, an adhesion imparting agent, and a thixotropic imparting agent. , a light initiation auxiliary agent, a sensitizer, an organic filler, an elastomer, a thermoplastic resin, a mold release agent, a surface treatment agent, a dispersing agent, a dispersion auxiliary agent, a surface modifier, a stabilizer, a phosphor, and the like.

Moreover, in the curable resin composition of this invention, you may contain alkali-soluble resin and solvent-soluble resin which are not (A) photocurable resin in the range which does not impair the effect of this invention.

The curable resin composition of this invention is not specifically limited, For example, a photocurable thermosetting resin composition may be sufficient and the photocurable resin composition which is not thermosetting may be sufficient. Moreover, an alkali developing type may be sufficient and a solvent developing type may be sufficient. That is, when the composition of the present invention is an alkali developing type containing alkali-soluble resin, a negative pattern cured film can be obtained by active energy ray irradiation and alkali developing solution, and when alkali-soluble resin is not included, active energy A negative-type pattern cured film can be obtained by line irradiation and a developing solution containing an organic solvent.

What is necessary is just to select a well-known and usual component for the arbitrary component which curable resin composition of this invention contains according to sclerosis|hardenability and a use.

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

The dry film of this invention has a resin layer obtained by apply|coating and drying the curable resin composition of this invention on a carrier film. When forming a dry film, first, the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, It is applied to a uniform thickness on the carrier film by a gravure coater, a spray coater, or the like. Thereafter, the resin layer can be formed by drying the applied composition at a temperature of usually 40 to 130° C. for 1 to 30 minutes. Although there is no restriction|limiting in particular about the coating film thickness, Generally 3 - 150 micrometers as a film thickness after drying, Preferably it selects suitably in the range of 5-60 micrometers.

A plastic film is used as a carrier film, For example, polyester films, such as a polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, etc. can be used. Although there is no restriction|limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers. More preferably, it is the range of 15-130 micrometers.

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

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

What is necessary is just to use a conventionally well-known method as a manufacturing method of the printed wiring board using the curable resin composition of this invention. Taking the case of an alkali developing type photocurable thermosetting resin composition as an example, 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 the dip coating method or the flow coating method is applied to the substrate. , roll coat method, bar coater method, screen printing method, curtain coat method, etc., followed by volatilization drying (temporary drying) of the organic solvent contained in the composition at a temperature of 60 to 100 ° C. A resin layer is formed. Moreover, in the case of a dry film, after bonding on a board|substrate so that a resin layer may contact with a board|substrate with a laminator etc., a resin layer is formed on a board|substrate by peeling a carrier film.

Examples of the substrate include printed wiring boards and flexible printed wiring boards formed with copper or the like in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin · Copper-clad laminates of all grades (FR-4, etc.), other metal substrates, polyimide films, A PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, etc. are mentioned. Pretreatment may be given to the circuit, for example, GliCAP manufactured by Shikoku Chemical Co., Ltd., New Organic AP (Adhesion promoter) manufactured by Mack Corporation, Nova Bond manufactured by Atotech Japan, etc. Adhesiveness, etc. with with can be improved, or you may pre-process with a rust preventive agent.

The volatilization drying performed after applying the curable resin composition of the present invention is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. It can be carried out using a method of making the substrate and spraying it from a nozzle to a support).

After forming the resin layer on the printed wiring board, it is selectively exposed with an active energy ray through the photomask in which the predetermined pattern was formed, and an unexposed part is diluted alkali aqueous solution (for example, 0.3-3 mass % sodium carbonate aqueous solution) to form a pattern of the cured product. In addition, by irradiating the cured product with active energy rays and then heat curing (for example, 100 to 220 ° C.), or by irradiating active energy rays after heat curing or final curing (main curing) only by heat curing, adhesion, hardness It forms a cured film excellent in various characteristics, such as.

As the exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc. is mounted, and any device irradiating active energy rays in the range of 350 to 450 nm is sufficient, and A projection exposure machine using a projection lens or a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used as maskless exposure that is not in contact with the substrate. As a lamp light source or a laser light source of a straight drawing machine, what exists in the range of 350-450 nm of maximum wavelength may be sufficient. The exposure amount for image formation varies depending on the film thickness and the like, but can be generally within the range of 10 to 1000 mJ/cm 2 , preferably 20 to 800 mJ/cm 2 .

As the developing method, a dipping method, showering method, spraying method, brush method, etc. can be used. As the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines is used. can

Curable resin composition of this invention is used suitably for forming a cured film on an electronic component, especially for forming a cured film on a printed wiring board, More suitably, it is used for forming a permanent film, More preferably, it is used for a soldering resist, an interlayer Used to form insulating layers, coverlays, and sealing materials. Moreover, it is suitable for formation of the permanent film (especially soldering resist) for printed wiring boards which high reliability is requested|required, for example, a package board|substrate, especially FC-BGA. Moreover, even if the roughness of the circuit surface is small, the curable resin composition of this invention can be used suitably also for the printed wiring board provided with a wiring pattern, for example, for high frequency printed wiring boards. For example, even if surface roughness Ra is 0.05 micrometer or less, especially 0.03 micrometer or less, it can use suitably. Moreover, it can use suitably also when forming a cured film on the base material of a low polarity, for example, the base material containing an active ester. Moreover, in order to form a cured film on the wafer or glass substrate without roughening, it is used suitably.

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, in the following, "part" and "%" are both based on mass unless otherwise indicated.

[Synthesis of photocurable resin]

(Photocurable resin A-1)

In a flask equipped with a cooling tube and a stirrer, 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin were put, the temperature was maintained at 40° C. or lower, and 228 parts of a 25% aqueous sodium hydroxide solution was added, and after the addition was completed, 50 The reaction was carried out at °C for 10 hours. After completion of the reaction, the mixture was cooled to 40°C and neutralized to pH4 with a 37.5% aqueous phosphoric acid solution while maintaining the temperature at 40°C or lower. Thereafter, it was allowed to stand to separate the aqueous layer. After separation, 300 parts of methyl isobutyl ketone was added and dissolved uniformly, washed three times with 500 parts of distilled water, and then water and solvent were removed under reduced pressure at a temperature of 50° C. or less. The obtained polymethylol compound was melt|dissolved in 550 parts of methanol, and 1230 parts of methanol solutions of a polymethylol compound were obtained.

When a part of the methanol solution of the obtained polymethylol compound was dried at room temperature in a vacuum dryer, solid content was 55.2%.

500 parts of methanol solutions of the obtained polymethylol compound and 440 parts of 2,6-xylenol were thrown into the flask provided with a cooling tube and a stirrer, and it melt|dissolved uniformly at 50 degreeC. After uniformly dissolving, methanol was removed under reduced pressure at a temperature of 50° C. or less. After that, 8 parts of oxalic acid was added, and it reacted at 100 degreeC for 10 hours. After completion of the reaction, the distillate was removed at 180°C and under a reduced pressure of 50 mmHg to obtain 550 parts of novolak resin A.

130 parts of novolak resin A, 2.6 parts of a 50% aqueous sodium hydroxide solution, toluene/methylisobutylketone (mass ratio = 2/1) 100 The system was replaced with nitrogen while stirring, followed by heating and heating, and gradually introducing 60 parts of propylene oxide at 150°C and 8 kg/cm 2 to react. After the reaction was continued for about 4 hours until the gauge pressure became 0.0 kg/cm 2 , it was cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid solution was added and mixed to neutralize sodium hydroxide. The neutralization reaction product was diluted with toluene, washed with water 3 times, and desolvated in an evaporator to obtain a propylene oxide adduct of novolak resin A having a hydroxyl value of 189 g/eq. In this case, an average of 1 mole of propylene oxide was added per equivalent of phenolic hydroxyl groups.

189 parts of the propylene oxide adduct of the obtained novolak resin A, 36 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 parts of hydroquinone monomethyl ether, and 140 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air intake tube, and air It stirred while blowing, the temperature was raised to 115 degreeC, and it cooled to room temperature after making it react for further 4 hours, distilling off the water produced|generated by reaction as an azeotropic mixture with toluene. After the obtained reaction solution was washed with water using 5% NaCl aqueous solution and toluene was removed by distillation under reduced pressure, diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a solid content of 67%.

Next, 322 parts of the obtained acrylate resin solution, 0.1 parts of hydroquinone monomethyl ether, and 0.3 parts of triphenylphosphine were put into a four-neck flask having a stirrer and a reflux condenser, and the mixture was heated to 110°C and tetrahydrophthalic anhydride. 60 parts were added, it was made to react for 4 hours, and it took out after cooling. Thus, the obtained photosensitive carboxyl group-containing resin solution A-1 had a solid content of 70% and a solid content acid value of 81 mgKOH/g. In addition, the numerical value of Table 1 is a mass part of solid content which does not contain a solvent.

(photocurable resin A-2)

81.5 parts of carbitol acetate was thrown into the separable flask which has a cooling tube as a reaction tank, and after nitrogen substitution, it heated up at 80 degreeC. On the other hand, 30 parts of N-phenylmaleimide and 120 parts of carbitol acetate were mixed in dropping tank 1, 29 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate were mixed in dripping tank 2, dripping In tank 3, 21 parts of acrylic acid and 10.6 parts of carbitol acetate were mixed, and in dropping tank 4, Luperox 11 as a polymerization initiator (trade name; manufactured by Arkema Yoshitomi, a hydrocarbon containing 70% of t-butylperoxypivalate) 10 parts of solution) and what mixed 21.2 parts of carbitol acetate were each inject|thrown-in. While maintaining the reaction temperature at 80°C, it was dripped from the dropping tanks 1, 2, and 4 over 3 hours and from the dropping tank 3 over 2.5 hours. After completion of the dropwise addition, the reaction was continued at 80°C for 30 minutes. Then, the reaction temperature was raised to 95 degreeC, reaction was continued for 1.5 hours, and the polymer solution before radically polymerizable double bond introduction reaction was obtained.

Next, to this polymer solution, 9.9 parts of glycidyl methacrylate, 7.4 parts of carbitol acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, and Anteji W-400 as a polymerization inhibitor (manufactured by Kawaguchi Chemical Industry Co., Ltd.) 0.2 parts were added, and it was made to react at 115 degreeC, bubbling the mixed gas (oxygen concentration of 7%) of nitrogen and oxygen, and the photosensitive carboxyl group containing radically polymerizable polymer solution A-2 was obtained. This photosensitive carboxyl group-containing copolymer resin had a solid content of 32% and a solid content of 120 mgKOH/g. In addition, the numerical value of Table 1 is a mass part of solid content which does not contain a solvent.

(Photocurable resin A-3)

To 700 g of diethylene glycol monoethyl ether acetate, 1,070 g of orthocresol novolak type epoxy resin [manufactured by DIC Corporation, EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average number of functional groups 7.6] (the number of glycidyl groups (aromatic rings) Total number): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were added, and the mixture was heated and stirred at 100° C. to dissolve uniformly. Next, 4.3 g of triphenylphosphine was added, and after heating at 110°C and reaction for 2 hours, 1.6 g of triphenylphosphine was further added, the temperature was raised to 120°C, and reaction was performed for another 12 hours. 562 g of aromatic hydrocarbons (Sorvesso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were added to the obtained reaction liquid, and reaction was performed at 110 degreeC for 4 hours. Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylate was thrown into the obtained reaction liquid, reaction was performed at 115 degreeC for 4 hours, and the carboxyl group-containing resin solution was obtained. Thus, solid content of the obtained photosensitive carboxyl group-containing resin solution A-3 was 65 %, and the acid value of solid content was 87 mgKOH/g. In addition, the numerical value of Table 1 is a mass part of solid content which does not contain a solvent.

[Preparation of inorganic filler]

C-1:

60 g of spherical silica (SFP-20M manufactured by Denka Corporation, 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-202SS: D from Shin-Etsu Chemical Co., Ltd.) 2 g of refractive index at a line (25°C) of 1.54) was uniformly dispersed to obtain a silica solvent dispersion product C-1.

C-2:

60 g of spherical silica (SFP-20M manufactured by Denka Corporation, average particle diameter: 400 nm), 40 g of MEK (methyl ethyl ketone) as a solvent, a methoxy group, and a silane coupling agent having a fluorene skeleton having a cardo structure (Osaka Gas) 2 g of SC-001 by Chemical Corporation: refractive index 1.56 in D-line (25 degreeC)) was disperse|distributed uniformly, and the silica solvent dispersion product C-2 was obtained.

C-3:

60 g of spherical silica (SFP-20M manufactured by Denka Corporation, average particle diameter: 400 nm), 40 g of MEK (methyl ethyl ketone) as a solvent, a methoxy group, and a silane coupling agent having a fluorene skeleton having a cardo structure (Osaka Gas) 2 g of SC-003 by Chemical Corporation: refractive index 1.53 in D-line (25 degreeC)) was disperse|distributed uniformly, and the silica solvent dispersion product C-3 was obtained.

C-4:

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

C-5:

60 g of spherical silica (SFP-20M manufactured by Denka Corporation, average particle diameter: 400 nm), 40 g of MEK (methyl ethyl ketone) as a solvent, a methoxy group, and a silane coupling agent having a fluorene skeleton having a cardo structure (Osaka Gas) After uniformly dispersing 2 g of SC-001 manufactured by Chemical Corporation: refractive index 1.56 at D-line (25° C.)), a silane coupling agent having a methoxy group and an amino group (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.: D line) (Refractive index 1.43 in (25 degreeC)) 1 g was made to disperse|distribute uniformly, and the silica solvent dispersion product C-5 was obtained.

R-1:

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

R-2:

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

R-3:

60 g of barium sulfate (B-30NC (surface untreated product) manufactured by Sakai Chemical Industry Co., Ltd., average particle size: 300 nm, refractive index 1.65 at D-line (25° C.)) and 40 g of MEK (methyl ethyl ketone) as a solvent are uniformly dispersed and a barium solvent dispersion product R-3 was obtained.

These were mix|blended so that it might become solid content of the numerical value of an Example and a comparative example.

<Method of measuring refractive index>

The refractive index of the photocurable resin, the organic alkoxysilane, and the inorganic filler adjusted above was measured using a refractive index meter ER-7MW manufactured by ERMA, applied to each sample on glass, dried, and measured on the D-line and at 25°C conditions.

[Examples 1 to 6, Comparative Examples 1 and 2]

The above-mentioned resin solution (varnish) was mix|blended in the ratio (mass part) which shows the various components shown in a table|surface, and after pre-mixing with a stirrer, it knead|mixed with 3 roll mill and prepared curable resin composition.

<Production of dry film>

To the curable resin composition adjusted as mentioned above, 300 g of methyl ethyl ketone was added and diluted, and it stirred for 15 minutes with a stirrer, and obtained the coating liquid. The coating solution was applied on a 38 µm-thick polyethylene terephthalate film (carrier film: Envet PTH-25 manufactured by Unitica Corporation), and was usually dried at a temperature of 80°C for 15 minutes to form a resin layer having a thickness of 20 µm. Next, the biaxially stretched polypropylene film (cover film: OPP-FOA by Futamura Corporation) was bonded on the resin layer, and the dry film was produced.

<Resolution>

On the copper of the copper clad laminate in which the dry film of each Example and the comparative example was acid-treated, using a vacuum laminator (CVP-600: manufactured by Nikko Materials Co., Ltd.) in the first chamber at 100° C. under the conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds After lamination, it pressed on the conditions of 0.5 Mpa of press pressure and 30 second of press time, and the evaluation board|substrate was obtained. Subsequently, DI exposure device after the exposure of the opening pattern φ30㎛ the obtained exposure amount is 10 at step tablet (41) to the (light source mercury short arc lamp), peeling off the PET film, and the phenomenon (1 wt% Na ₂ CO ₃ , 30 degreeC, 0.2 Mpa) was performed for 60 second, and the pattern of the resin layer was formed. Subsequently, after irradiating the resin layer with an exposure amount of 1 J/cm 2 in a UV conveyor furnace equipped with a high-pressure mercury lamp, heating at 160° C. for 60 minutes to completely cure the resin layer to produce an evaluation substrate having a pattern cured film, and a photosensitive cured coating film was measured.

◎: Top 30㎛, Bottom opening 95 to 100%

○: Top 30㎛, Bottom opening 85% or more and less than 95%

(triangle|delta): Opening precision of 80-90% in both Top and Bottom

×: halation or undercut occurs

<Breedability and BHAST resistance>

After acid treatment of a substrate on which a circuit pattern having a conductor thickness of 10 µm L/S = 8 µm/8 µm is formed, laminating, exposing, developing and curing a dry film in the same manner as in the <resolution> evaluation above, and confirming embedding properties Then, BHAST was performed at 130 degreeC, 85 %, and 3V, and insulation reliability was evaluated.

◎: Filled without voids and achieved insulation reliability of BHAST 300hrs or more

○: Filled without voids, achieving insulation reliability of BHAST 200 or more and less than 300hrs

△: Voids of about 1 to 2 μm were confirmed, and insulation resistance was less than 200 hrs.

x: Omission of 5 micrometers or more was confirmed.

<High temperature leaving test>

On the copper of the copper clad laminate in which the dry film of each Example and the comparative example was processed with CZ8101 manufactured by Mack Corporation, using a vacuum laminator (CVP-600: manufactured by Nikko Materials Co., Ltd.) in the first chamber at 100° C., a vacuum pressure of 3 hPa, a vacuum time of 30 After laminating under the conditions of second, it pressed on the conditions of 0.5 Mpa of press pressure and 30 second of press time, and obtained the evaluation board|substrate. Thereafter, the PET film is peeled off after exposure so as to form an exclusion pattern of φ200 μm with an exposure amount obtained by 10 steps in a step tablet (41 steps) with a DI exposure machine, and development (1% by mass Na ₂ CO ₃ , 30° C., 0.2 MPa) was performed for 60 seconds, and the pattern of the resin layer was formed. Subsequently, after irradiating the resin layer with an exposure amount of 1 J/cm 2 in a UV conveyor furnace equipped with a high-pressure mercury lamp, the resin layer was completely cured by heating at 160° C. for 60 minutes to prepare an evaluation substrate having a pattern cured film.

The board|substrate was put into the thermostat of 175 degreeC oxygen atmosphere, and the time for which peeling in the cellophane tape peel does not generate|occur|produce was confirmed.

◎: No peeling over 2000hrs

○: Slight peeling occurs in 1500 hrs or more and less than 2000 hrs

△: peeling occurs in 1000 hrs or more and less than 1500 hrs

×: peeling occurs within 1000 hrs

<CTE>

The cured film was formed on the copper foil of a low profile on the conditions similar to the said <high temperature standing test>. The obtained cured film was peeled from copper foil, the sample was cut out so that a measurement size (3 mm x 10 mm size) might be obtained, and CTE was measured with TMA6100 by a Hitachi High-tech company. Measurement conditions were repeated twice in which a test load of 5 g and the sample was heated from room temperature at a temperature increase rate of 10° C./min, and a coefficient of linear expansion (CTE(α2)) equal to or less than Tg in the second time was obtained. It turns out that it is excellent in thermal stability, so that this CTE is small.

◎: 30ppm or less

○: More than 30ppm and less than 40ppm

△: more than 40 ppm and less than 50 ppm

×: more than 50 ppm

<Evaluation of cold and heat resistance>

Each dry film was laminated on the BT board|substrate on which the copper line pattern of 2 mm was formed similarly to the said <high temperature standing test> and <resolution> evaluation, and it thermosetted by exposure, image development, and UV. However, the pattern at the time of exposure was changed so that it might become a 3 mm square cured film pattern on one side, and the evaluation board|substrate which formed the 3 mm square cured film pattern on one side was produced in the copper line. This substrate was placed in a cooling/heating cycler in which a temperature cycle was performed between -50°C and 150°C, and TCT (Thermal Cycle Test) was performed. And the crack at the time of evaluating up to 1000 cycles was confirmed.

(double-circle): No crack generation|occurrence|production until 1000 cycles.

○: Cracks occurred in 500 to 750 cycles.

(triangle|delta): The crack generate|occur|produced in 250 cycles or more and less than 500 cycles.

x: The crack generate|occur|produced in less than 250 cycles.

* The difference in the refractive index in D-line (25 degreeC) of (A) photocurable resin and organic alkoxysilane in Example 2 is the difference with the photocurable resin of *2

*1: Solution A-1 of the photocurable resin synthesized above (refractive index 1.56 at D-line (25°C))

*2: Solution A-2 of the photocurable resin synthesized above (refractive index 1.55 at D-line (25°C))

*3: Solution A-3 of the photocurable resin synthesized above (refractive index 1.56 at D-line (25°C))

*4: Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by IGM Resins

*5: Omnirad907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one) manufactured by IGM Resins

*6: DPHA made by Nippon Kayaku (dipentaerythritol hexaacrylate, refractive index 1.48 in D-line (25°C))

*7: Mitsubishi Chemical Corporation jER828 (bisphenol A type epoxy resin)

*8: Nippon Kayaku Co., Ltd. NC-6000(2-(4-hydroxyphenyl)-2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propane glycidyl ether compound )

*9: Nippon Kayaku Co., Ltd. NC-3000H (biphenol novolak type epoxy resin)

*10: phthalocyanine blue

*11: dicyandiamide

*12: Melamine

C-1: Solvent dispersion product C-1 of silica coated with the above-adjusted silane coupling agent having a methoxy group (refractive index 1.54 at D-line (25°C))

C-2: Solvent dispersion product of silica coated with a silane coupling agent (refractive index 1.56 in D line (25°C)) having a methoxy group and a fluorene skeleton having a cardo structure adjusted above C-2

C-3: Solvent dispersion product C-3 of silica coated with a silane coupling agent (refractive index 1.53 at D-line (25°C)) having a methoxy group and a fluorene skeleton having a cardo structure adjusted above

C-4: A silane coupling agent having a methoxy group and a fluorene skeleton having a cardo structure (refractive index 1.56 in the D-line (25° C.)) adjusted above, and a silane couple having a methoxy group and a methacryl group Solvent dispersion C-4 of silica coated with a ring agent (refractive index 1.43 at D-line (25°C))

C-5: A silane coupling agent having a methoxy group and a fluorene skeleton having a cardo structure (refractive index 1.56 in the D-line (25°C)) adjusted above, and a silane coupling agent having a methoxy group and an amino group Solvent dispersion C-5 of silica coated with (refractive index 1.43 in D-line (25°C))

R-1: Solvent dispersion product of silica coated with a silane coupling agent having a methoxy group and a methacryl group (refractive index 1.43 at D-line (25°C)) adjusted above R-1

R-2: Solvent dispersion R-2 of silica (refractive index 1.42 at D-line (25°C)) adjusted above

R-3: Solvent dispersion product of barium (refractive index 1.65 in D-line (25°C)) adjusted above R-3

From the result shown in the said table|surface, it turns out that the hardened|cured material excellent in resolution and embedding property of a high-density wiring pattern is obtained from the curable resin composition of Examples 1-6 of this invention.

Claims (6)

(A) a photocurable resin;
(B) a photoinitiator, and
(C) silica
As a curable resin composition comprising a,
The (A) photocurable resin has a refractive index of 1.50 to 1.65 on the D line measured at 25° C.,
Said (C) silica is coat|covered with the organoalkoxysilane whose refractive index in D-line measured at 25 degreeC is 1.50-1.65, Curable resin composition characterized by the above-mentioned. The curable resin composition according to claim 1, wherein the organic alkoxysilane has a cardo structure. The compound according to claim 1 or 2, wherein the silica (C) is coated with at least two kinds of the organic alkoxysilanes or coated with the organic alkoxysilanes and organic alkoxysilanes other than the organic alkoxysilanes. Curable resin composition characterized in that. It has a resin layer obtained by apply|coating and drying the curable resin composition in any one of Claims 1-3 to a film, The dry film characterized by the above-mentioned. It is obtained by hardening|curing the resin layer of the curable resin composition in any one of Claims 1-3, or the dry film of Claim 4, The hardened|cured material characterized by the above-mentioned. It has the hardened|cured material of Claim 5, The electronic component characterized by the above-mentioned.