WO2018123695A1 - Curable composition, base resin, curing agent, dry film, cured product, and printed wiring board - Google Patents

Abstract

Provided are a curable composition with which it is possible to obtain a cured product having exceptional strength, a base resin, a curing agent, a dry film, a cured product, and a printed wiring board. A curable composition containing (A) a curable component and (B) a surface-treated filler, wherein the curable composition, etc., is characterized by containing (B-1) a surface-treated filler having photocurable reactive groups and thermosetting reactive groups as the (B) surface-treated filler.

Description

Curable composition, main agent and curing agent, dry film, cured product, and printed wiring board

The present invention relates to a curable composition, a main agent and a curing agent, a dry film, a cured product, and a printed wiring board.

In the production of printed wiring boards, curable compositions are generally employed for the formation of permanent films such as solder resists, and dry film type compositions and liquid compositions have been developed as such curable compositions. ing. Among these, in consideration of environmental problems, an alkali development type curable composition using a dilute alkaline aqueous solution as a developing solution has become the mainstream, and several composition systems have been proposed in the past (for example, patent documents). 1).

In recent years, with the rapid progress of semiconductor components, electronic devices tend to be lighter, thinner, smaller, higher performance, and multifunctional. Following this trend, miniaturization and multi-pin semiconductor packages have been put into practical use. Specifically, instead of IC packages called QFP (Quad Flat Pack Package), SOP (Small Outline Package), etc., BGA (Ball Grid Array), CSP (Chip Scale Package), etc. IC package called is used. In recent years, FC-BGA (Flip Chip Ball Grid Array) has been put to practical use as an IC package with higher density.

JP 61-243869 (Claims)

Further reduction in the thickness of permanent coatings such as solder resist formed on printed wiring boards (also referred to as package substrates) used in IC packages as described above is required. However, when the film thickness is reduced, there is a problem that the strength of the cured film such as the breaking strength becomes insufficient.

The inventors of the present invention tried to increase the strength of the cured film by increasing the amount of the acrylate compound, which is a photocurable component having an ethylenically unsaturated group, and increasing the crosslinking density. However, sufficient strength of the cured film could not be obtained.

Therefore, an object of the present invention is to provide a curable composition capable of forming a cured product having excellent strength, a main agent and a curing agent that are mixed to form the composition, a dry film having a resin layer obtained from the composition, and the composition Another object is to provide a cured product of the resin layer of the dry film and a printed wiring board having the cured product.

As a result of intensive studies in view of the above, the present inventors have used a surface treatment filler having a photocurable reactive group and a thermosetting reactive group as a filler to be blended in the composition, or a photocurable reactive group. It has been found that the above-mentioned problems can be solved by using the surface-treated filler having the surface-treated filler and the surface-treated filler having a thermosetting reactive group, and the present invention has been completed.

That is, the curable composition of the present invention is a curable composition containing (A) a curable component and (B) a surface treatment filler, wherein (B) the surface treatment filler is (B-1) It contains a surface treatment filler having a photocurable reactive group and a thermosetting reactive group.

Another curable composition of the present invention is a curable composition containing (A) a curable component and (B) a surface treatment filler, wherein (B) the surface treatment filler is (B-2) It contains a surface treatment filler having a photocurable reactive group and (B-3) a surface treatment filler having a thermosetting reactive group.

In the curable composition of the present invention, the amount of the (B) surface treatment filler is preferably 50 to 90% by mass in the solid content of the composition.

The curable composition of the present invention preferably contains a compound having an ethylenically unsaturated group as the (A) curable component.

The curable composition of the present invention preferably contains an alkali-soluble resin having an ethylenically unsaturated group as the (A) curable component.

The curable composition of the present invention preferably contains an epoxy resin as the (A) curable component.

The dry film of the present invention has a resin layer obtained from the curable composition.

The main agent and curing agent of the present invention contain at least (A) an alkali-soluble resin as a curable component and (B-2) a surface treatment filler having a photocurable reactive group, and the curing agent comprises It contains at least a compound having a plurality of cyclic ether groups or cyclic thioether groups in the molecule as the curable component (A) and a surface treatment filler having the thermosetting reactive group (B-3). Is.

The cured product of the present invention is obtained by curing the curable composition, the curable composition that is a mixture of the main agent and the curing agent, or the resin layer of the dry film.

The printed wiring board of the present invention is characterized by having the cured product.

According to the present invention, a curable composition capable of forming a cured product having excellent strength, a main agent and a curing agent mixed to form the composition, 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 a printed wiring board having the cured product can be provided.

The curable composition of the present invention is a curable composition containing (A) a curable component and (B) a surface treatment filler, wherein (B-1) light is used as the (B) surface treatment filler. It contains a surface treatment filler having a curable reactive group and a thermosetting reactive group, or (B-2) a surface treatment filler having a photocurable reactive group and (B-3) a surface treatment having a thermosetting reactive group. It is characterized by containing a filler. Usually, since the filler does not participate in the curing reaction, after the curing reaction, it is included in the cured product in a state surrounded by the crosslinked network, and therefore an interface is formed between the filler and the crosslinked network. Although the detailed mechanism is not clear, it is considered that the interface between the filler and the crosslinked network was a weak point in fracture, etc. In the present invention, by incorporating a specific surface treatment filler, photocuring reaction and thermosetting reaction In this case, the filler is taken into the cured product without causing an interface. As a result, it is considered that breakage or the like due to the above-described interface is less likely to occur. Moreover, the (B) surface treatment filler can form the hardened | cured material which was more excellent in intensity | strength, when the direction which has a photocurable reactive group and a thermosetting reactive group. According to the curable composition of the present invention, a cured product having a high storage elastic modulus and a low coefficient of linear expansion (CTE) can also be formed.

The main agent and the curing agent of the present invention contain at least the (A) alkali-soluble resin as the curable component and the (B-2) surface treatment filler having a photocurable reactive group, The agent contains at least (A) a compound having a plurality of cyclic ether groups or cyclic thioether groups in the molecule as the curable component and (B-3) a surface treatment filler having a thermosetting reactive group. It is what. Storage stability becomes favorable by being two-components which consist of such a main ingredient and a hardening | curing agent.

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

[(A) Curing component]
(A) The curable component may be any component that reacts with at least one of the photocurable reactive group and the thermosetting reactive group of the (B) surface treatment filler, but the photocurable reactive group and the thermosetting reactive group. It is preferable that it reacts with both. (A) The curable component is preferably (A1) a photocurable component that contributes to a photocuring reaction by light irradiation, and (A2) a thermosetting component that contributes to a thermosetting reaction by heating.
Here, as (A) curable component, it is more preferable to contain (A1) photocurable component and (A2) thermosetting component. The curable composition of the present invention comprises (A1) a photocurable component, (A2) an alkali-soluble resin as a thermosetting component, and a compound having a plurality of cyclic ether groups or cyclic thioether groups in the molecule. More preferably, the composition contains
The (A1) photocurable component and the (A2) thermosetting component may be light and thermosetting components that contribute to both the photocuring reaction and the thermosetting reaction. The sexual component can be suitably used as (A1) a photocurable component and (A2) a thermosetting component.
In addition, (A) curable component is a component different from (B) surface treatment filler.

((A1) photocurable component)
(A1) As a photocurable component, it is a compound which has an ethylenically unsaturated group, A polymer, an oligomer, a monomer, etc. are mentioned, Mixtures thereof may be sufficient. By including the photocurable component, it reacts with the photocurable reactive group of the (B) surface treatment filler, so that the strength of the cured film can be improved. (A1) A photocurable component can be used individually by 1 type or in combination of 2 or more types.
As the compound having an ethylenically unsaturated group, a photopolymerizable oligomer, a photopolymerizable vinyl monomer, or the like that is a known and commonly used photocurable monomer can be used.

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

As the photopolymerizable vinyl monomer, known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide (Meth) acrylamides such as rilamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl Esters of (meth) acrylic acid such as (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol Hydroxyalkyl (meth) acrylates such as tri (meth) acrylate; Alkyl such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Coxyalkylene glycol mono (meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tri Alkylene polyol poly (meth) acrylates such as methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Polyoxyalkylene glycol poly (such as ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri (meth) acrylate) Poly (meth) acrylates such as hydroxypivalic acid neopentyl glycol ester di (meth) acrylate; isocyanurate-type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate Can be mentioned.

The photocurable component can be used alone or in combination of two or more. The blending amount of the photocurable component is preferably 10 to 50% by mass in the solid content excluding the solvent of the entire composition.

(Photopolymerization initiator)
The curable composition of the present invention preferably contains a photopolymerization initiator. Any photopolymerization initiator can be used as long as it is a known photopolymerization initiator as a photopolymerization initiator or a photoradical generator.

Examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide Bisacylphosphine oxides such as (IRSFACURE 819 manufactured by BASF Japan); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid Monoacylphosphine oxides such as methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (IRGACURE TPO manufactured by BASF Japan Ltd.) 1-hydroxy-cyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1 Propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-hydroxy-2 -Hydroxyacetophenones such as methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl Ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimeth Xyl-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [ Acetophenones such as 4- (4-morpholinyl) phenyl] -1-butanone and N, N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl Thioxanthone, 2-chlorothioxanthone, 2, Thioxanthones such as diisopropylthioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; acetophenone Ketals such as dimethyl ketal and benzyl dimethyl ketal; benzoates such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1 -[4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Oxime esters such as 1,-(O-acetyloxime); bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) Phenyl) titanium, titanocenes such as bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium; phenyl disulfide 2-nitrofluorene , Butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like. A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type. Of these, monoacylphosphine oxides and oxime esters (hereinafter also referred to as monoacylphosphine oxide photopolymerization initiators and oxime ester photopolymerization initiators) are preferred, respectively. 2,4,6-trimethylbenzoyldiphenylphosphine Oxide, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is more preferred.

The photopolymerization initiator can be used alone or in combination of two or more. The blending amount of the photopolymerization initiator is, for example, 0.01 to 30 parts by mass with respect to 100 parts by mass of the photocurable component. When the photopolymerization initiator is an oxime ester photopolymerization initiator, the amount is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the photocurable component. When the photopolymerization initiator is other than the oxime ester photopolymerization initiator, it is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the photocurable component.

((A2) thermosetting component)
By including the (A2) thermosetting component, it reacts with the thermosetting reactive group of the (B) surface treatment filler, so that the strength of the cured film can be improved. (A2) A thermosetting component can be used individually by 1 type or in combination of 2 or more types.
(A2) Any known thermosetting component can be used. For example, known amino resins such as melamine resin, benzoguanamine resin, melamine derivative, benzoguanamine derivative, isocyanate compound, block isocyanate compound, cyclocarbonate compound, epoxy compound, oxetane compound, episulfide resin, bismaleimide, carbodiimide resin, alkali-soluble resin, etc. These thermosetting components can be used. Particularly preferred are compounds having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) and alkali-soluble resins in the molecule.

The compound having a plurality of cyclic (thio) ether groups in the molecule is preferably a compound having a plurality of 3, 4 or 5-membered cyclic (thio) ether groups in the molecule. A compound having a plurality of epoxy groups, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, that is, an episulfide resin, and the like can be mentioned.

Polyfunctional epoxy compounds include epoxidized vegetable oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins; bisphenol type epoxy resins; thioether type epoxy resins; brominated epoxy resins; novolac type epoxy resins; biphenol novolac type epoxy resins; Type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin; Bisphenol A novolak type epoxy resin; Tetraphenylol ethane type epoxy resin; Heterocyclic epoxy resin; Phthalate resin; Tetraglycidylxylenoylethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Glycidyl methacrylate copolymer epoxy resin; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Polybutadiene rubber derivatives; CTBN-modified epoxy resins and the like can be mentioned, but are not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, novolak type epoxy resins, bisphenol type epoxy resins, bixylenol type epoxy resins, biphenol type epoxy resins, biphenol novolac type epoxy resins, naphthalene type epoxy resins or mixtures thereof are particularly 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- In addition to polyfunctional oxetanes such as oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin , Poly (p-hydroxystyrene), cardo type bi Phenols, calixarenes, calix resorcin arenes or etherified products such as the resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.

As the isocyanate compound, a polyisocyanate compound can be blended. Polyisocyanate compounds include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, and Aromatic polyisocyanates such as 2,4-tolylene 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 heptane triisocyanate; and adducts of the isocyanate compounds listed above, Yuretto body and isocyanurate products thereof.

As the blocked isocyanate compound, an 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 above-mentioned polyisocyanate compound etc. are mentioned, for example. As an isocyanate block agent, for example, phenol block agent; lactam block agent; active methylene block agent; alcohol block agent; oxime block agent; mercaptan block agent; acid amide block agent; imide block agent; Examples include amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents.

Further, (A2) the thermosetting component preferably contains an alkali-soluble resin having an alkali-soluble 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 these, it is preferable that the alkali-soluble resin is a carboxyl group-containing resin or a phenol resin because adhesion with the base is improved. In particular, since the developability is excellent, the alkali-soluble resin is more preferably a carboxyl group-containing resin. The carboxyl group-containing resin is preferably a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group, but may be a carboxyl group-containing resin having no ethylenically unsaturated group. When alkali-soluble resin has an ethylenically unsaturated group, it functions also as a photocurable component, and corresponds to said light and a thermosetting component. In addition, when the curable composition of this invention contains alkali-soluble resin, you may use it for the use which does not carry out alkali image development as well as the use which carries out alkali image development.

Specific examples of the carboxyl group-containing resin include the compounds listed below (any of oligomers and polymers).

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

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

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

(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound.

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

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

(7) A carboxyl group obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the hydroxyl group present in the side chain Containing resin.

(8) A carboxyl group-containing resin in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. .

(9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

(10) Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a product.

(11) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a reaction product with a polybasic acid anhydride.

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

(13) In addition to the carboxyl group-containing resins described in the above (1) to (12) and the like, in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate, one epoxy group and one or more ( A carboxyl group-containing resin obtained by adding a compound having a (meth) acryloyl group.

Among the carboxyl group-containing resins, the carboxyl group-containing resins described in (1), (7), (8), (10) to (13) are preferable.

Examples of the compound having a phenolic hydroxyl group include a compound having a biphenyl skeleton and / or a phenylene skeleton, phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4-xylenol, 2 , 5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol, etc. And phenol resins having various skeletons synthesized.

Examples of the compound having a phenolic hydroxyl group include a phenol novolac resin, an alkylphenol volac resin, a bisphenol A novolac resin, a dicyclopentadiene type phenol resin, an Xylok type phenol resin, a terpene modified phenol resin, a polyvinylphenol, and bisphenol F. And bisphenol S-type phenol resins, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes.

Commercially available phenol resins include, for example, HF1H60 (Maywa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (Dai Nippon Printing Co., Ltd.), Vesmol CZ-256-A (Dic Co., Ltd.), Show Nord BRG-555, Shounol BRG-556 (manufactured by Showa Denko), CGR-951 (manufactured by Maruzen Petroleum), polyvinylphenol CST70, CST90, S-1P, S-2P (manufactured by Maruzen Petroleum) .

The acid value of the alkali-soluble resin is desirably in the range of 20 to 200 mgKOH / g, more preferably in the range of 40 to 150 mgKOH / g. When the acid value of the alkali-soluble resin is 20 mgKOH / g or more, the adhesion of the coating film is good and the alkali development is good. On the other hand, when the acid value is 200 mgKOH / g or less, the dissolution of the exposed part by the developer can be suppressed, so the line can be thinned more than necessary, or in some cases, dissolution and peeling with the developer without distinguishing the exposed part and the unexposed part It is possible to satisfactorily draw a resist pattern.

The weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is preferably in the range of 1,500 to 50,000, more preferably 1,500 to 30,000. When the weight average molecular weight is 1,500 or more, the tack-free performance is good, the moisture resistance of the coated film after exposure is good, the film loss during development can be suppressed, and the resolution can be suppressed from decreasing. On the other hand, when the weight average molecular weight is 50,000 or less, the developability is good and the storage stability is also excellent.

When the alkali-soluble resin has an ethylenically unsaturated group, the double bond equivalent is, for example, 500 to 3,500 eq. / G, and 700 to 3,000 eq. From the viewpoint of resolution. / G is preferable.

Alkali-soluble resins can be used singly or in combination of two or more. The blending amount of the alkali-soluble resin is preferably 5 to 50% by mass, more preferably 10 to 50% by mass in the solid content excluding the solvent of the entire composition. In the case of 5 to 50% by mass, the coating film strength is better, the viscosity of the composition is moderate, and coatability and the like can be improved.

(A2) The thermosetting component can be used singly or in combination of two or more. The blending amount of the (A2) thermosetting component is preferably 10 to 50% by mass in the solid content excluding the solvent of the whole composition.

(Thermosetting catalyst)
The curable composition of the present invention preferably contains a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Examples include amines, amine compounds such as 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, and the like. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adducts can also be used. A compound that also functions in combination with a thermosetting catalyst.
A thermosetting catalyst can be used individually by 1 type or in combination of 2 or more types. The blending amount of the thermosetting catalyst is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermosetting component.

[(B) Surface treatment filler]
The curable composition of the present invention contains (B-1) a surface treatment filler having a photocurable reactive group and a thermosetting reactive group as (B) a surface treatment filler, or (B-2) a photocuring agent. And (B-3) a surface treatment filler having a thermosetting reactive group. Two or more types of the surface treatment fillers (B-1) to (B-3) may be used, and each of the surface treatment fillers (B-1) and (B-2) and / or (B-3) These surface treatment fillers may be used in combination. The method for producing the surface treatment fillers of (B-1) to (B-3) is not particularly limited, and may be introduced using a known and commonly used method. A surface treatment agent having a curable reactive group, for example, curable What is necessary is just to process the surface of a filler with the coupling agent etc. which have a reactive group as an organic group.

The filler to be surface-treated is not particularly limited and may be an organic filler or an inorganic filler, but an inorganic filler is preferable. Examples of the inorganic filler include silica, barium sulfate, barium titanate, Neuburg silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, titanium oxide, aluminum hydroxide, silicon nitride, and aluminum nitride. Among them, silica is preferable, and cure shrinkage of the cured product of the curable composition is suppressed, the CTE becomes lower, and the properties such as adhesion and hardness are improved. Examples of silica include fused silica, spherical silica, amorphous silica, and crystalline silica.

(B) The surface-treated filler is preferably a filler surface-treated with a coupling agent. As the coupling agent, coupling agents such as silane, titanate, aluminate and zircoaluminate can be used. Of these, silane coupling agents are preferred. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino. Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like. These can be used alone or in combination. These silane coupling agents are preferably immobilized on the surface of the filler in advance by adsorption or reaction. Here, the treatment amount of the coupling agent with respect to 100 parts by mass of the filler is preferably 0.5 to 10 parts by mass. In the present invention, the coupling agent applied to the filler is not included in the compound having an ethylenically unsaturated group.

Examples of the photocurable reactive group include ethylenically unsaturated groups such as vinyl group, styryl group, methacryl group, and acrylic group. Among these, at least one of a vinyl group and a (meth) acryl group is preferable.

Examples of thermosetting reactive groups include hydroxyl groups, carboxyl groups, isocyanate groups, amino groups, imino groups, epoxy groups, oxetanyl groups, mercapto groups, methoxymethyl groups, methoxyethyl groups, ethoxymethyl groups, ethoxyethyl groups, oxazoline groups, etc. Is mentioned. Among these, at least one of an amino group and an epoxy group is preferable.

(B) The ratio of the photocurable reactive group and the thermosetting reactive group in the surface treatment filler is preferably 1.0: 0.5 to 1.0: 2.5 by mass ratio, and 1.0: It is preferably 0.8 to 1.0: 2.0. Within the above range, the photocuring reaction and thermosetting reaction of the filler proceed in a well-balanced manner, and a cured film having excellent coating strength can be obtained.

(B) The average particle diameter of the surface treatment filler is preferably 1 μm or less.

(B) The blending amount of the surface treatment filler is preferably 50 to 90% by mass in the solid content excluding the solvent of the composition. (B) When the compounding quantity of a surface treatment filler is the said range, the intensity | strength and storage elastic modulus of a cured film will become high and CTE can be made low. Here, the blending ratio when (B-2) the surface treatment filler having a photocurable reactive group and (B-3) the surface treatment filler having a thermosetting reactive group is (B- 2): (B-3) = 1.0: 0.5 to 1.0: 2.5 is preferable, and 1.0: 0.8 to 1.0: 2.0 is preferable. . Within the above range, (B-2) the photocuring reaction of the surface treatment filler and (B-3) the thermosetting reaction of the surface treatment filler proceed in a balanced manner, and a cured film having excellent strength can be obtained.

(B) The surface treatment filler should just be contained in the curable composition of this invention in the surface-treated state, mix | blends a surface untreated filler and a surface treating agent separately, and is a filler in a composition. Although surface treatment may be carried out, it is preferable to blend a filler that has been surface-treated in advance. By blending the surface-treated filler in advance, it is possible to prevent a decrease in crack resistance or the like due to the surface treatment agent that has not been consumed by the surface treatment that can remain when blended separately. When the surface treatment is performed in advance, it is preferable to blend a pre-dispersed liquid in which a filler is pre-dispersed in a solvent or a curable component. More preferably, after pre-dispersing the surface-untreated filler in the solvent, the pre-dispersed liquid is blended into the composition.

The curable composition of the present invention may contain a filler that has not been surface-treated within a range that does not impair the effects of the present invention, but preferably does not contain a filler that has not been surface-treated.

(Coloring agent)
The curable composition of the present invention can contain a colorant. As the colorant, known and commonly used colorants such as red, blue, green, yellow, white and black can be used, and any of pigments, dyes and pigments may be used. Specific examples include color index (CI; issued by The Society of Dyer's and Colorists) number. However, it is preferable that the colorant does not contain a halogen from the viewpoint of reducing environmental burden and affecting the human body.

Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Examples of blue colorants include metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds that are classified as pigments. Similarly, the green colorant includes metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based materials. Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. Examples of the white colorant include rutile type, anatase type titanium oxide and the like. Black colorants include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, and aniline. Examples thereof include pigments, molybdenum sulfide, and bismuth sulfide. In addition, a colorant such as purple, orange or brown may be added for the purpose of adjusting the color tone.

Coloring agents can be used alone or in combination of two or more. The blending amount of the colorant is not particularly limited, but is preferably 0.1 to 5% by mass in the solid content excluding the solvent of the entire composition.

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

(Other optional ingredients)
If necessary, the curable composition of the present invention may further include a photoinitiator, a cyanate compound, an elastomer, a mercapto compound, a thermosetting catalyst, a urethanization catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, Chain transfer agents, polymerization inhibitors, copper damage inhibitors, antioxidants, rust inhibitors, UV absorbers, thick silica, organic bentonites, montmorillonites, thickeners such as silicones, fluorines, and polymers Components such as foaming agents and / or leveling agents, silane coupling agents such as imidazole, thiazole, and triazole, flame retardants such as phosphinates, phosphoric ester derivatives, and phosphorus compounds such as phosphazene compounds can be blended. . As these, those known in the field of electronic materials can be used.

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

The curable composition of the present invention is useful for forming a pattern layer as a permanent film of a printed wiring board such as a solder resist, a cover lay, and an interlayer insulating layer, and is particularly useful for forming a solder resist. In addition, since the curable composition of the present invention can form a cured product having excellent coating strength even with a thin film, a printed wiring board that is required to be thin, such as an IC package substrate (printed wiring board used for an IC package). It can also be suitably used for forming a pattern layer. Furthermore, the cured product obtained from the curable composition of the present invention is preferably used for forming a pattern layer on an IC package substrate having a thin total thickness and insufficient rigidity even in terms of high elastic modulus and low CTE. I can say that.

The curable composition of the present invention can also be in the form of a dry film comprising a carrier film (support) and a resin layer made of the curable composition formed on the carrier film. In forming a dry film, the curable composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, A film can be obtained by applying a uniform thickness on a carrier film with a gravure coater, spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes. The coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 1 to 150 μm, preferably 10 to 60 μm.

As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. The thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 μm.

After forming the curable composition of the present invention on the carrier film, it is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. . As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

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

The main agent and the curing agent of the present invention contain at least (A) an alkali-soluble resin as a curable component and (B-2) a surface treatment filler having a photocurable reactive group, and the curing agent is at least (A). The molecule as a curable component contains a compound having a plurality of cyclic ether groups or cyclic thioether groups and (B-3) a surface treatment filler having a thermosetting reactive group. (A) an alkali-soluble resin as a curable component, (B-2) a surface treatment filler having a photocurable reactive group, and (A) a molecule having a plurality of cyclic ether groups or cyclic thioether groups as a curable component. Components other than the compound and (B-3) the surface treatment filler having a thermosetting reactive group may be contained in either the main agent or the curing agent. For example, the photopolymerization initiator is contained in the curing agent. It is preferable that the thermosetting catalyst is contained in the main agent. In the main agent and the curing agent of the present invention, the blending amount of each component is not particularly limited as long as it is mixed to be the blending amount in the curable composition as described above. For example, (A) the alkali-soluble resin as the curable component The blending amount is preferably 10 to 60% by mass in the solid content excluding the solvent of the main agent. Further, (B-2) the surface treatment filler having a photocurable reactive group is preferably 30 to 90% by mass in the solid content excluding the solvent of the main agent. (A) The compounding amount of the compound having a plurality of cyclic ether groups or cyclic thioether groups in the molecule as the curable component is preferably 3 to 40% by mass in the solid content excluding the solvent of the curing agent. (B-3) The amount of the surface treatment filler having a thermosetting reactive group is preferably 50 to 95% by mass in the solid content excluding the solvent of the curing agent.

The printed wiring board of the present invention has a cured product obtained from the curable composition of the present invention or the resin layer of the dry film. As a method for producing a printed wiring board of the present invention, for example, the curable composition of the present invention is adjusted to a viscosity suitable for a coating method using the organic solvent, and a dip coating method, a flow is performed on a substrate. After coating by a coating method, roll coating method, bar coater method, screen printing method, curtain coating method or the like, the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of 60 to 100 ° C. Thus, a tack-free resin layer is formed. Moreover, in the case of a dry film, after bonding together on a base material so that a resin layer may contact a base material with a laminator etc., a resin layer is formed on a base material by peeling a carrier film.

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

Volatile drying performed after the application of the curable composition of the present invention is performed by using a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a hot air in a dryer using an air heating type heat source by steam). Can be carried out by using a counter current contact method and a method of spraying a nozzle on a support.

After forming a resin layer on the printed wiring board, it is selectively exposed with an active energy ray through a photomask having a predetermined pattern. ) To form a cured product pattern. Further, the cured product is irradiated with active energy rays and then heat-cured (for example, 100 to 220 ° C.), irradiated with active energy rays after heat-curing, or is subjected to final finish curing (main curing) only by heat-curing. A cured film having excellent properties such as properties and hardness is formed.

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

The developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
The curable composition of the present invention may be used not only for the purpose of forming a cured film pattern with the developer as described above but also for the purpose of not forming a pattern.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

[Synthesis of alkali-soluble resin]
(Synthesis Example 1: Synthesis of alkali-soluble resin A-1)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 119.4 parts of a novolac-type cresol resin (trade name “Shonol CRG951”, manufactured by Showa Denko KK, OH equivalent: 119.4), 1.19 parts of potassium hydroxide and 119.4 parts of toluene were introduced, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1%, and the hydroxyl value was 182.2 mgKOH / g (307. 9 g / eq.) Of a novolak-type cresol resin propylene oxide reaction solution. This was an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
293.0 parts of a propylene oxide reaction solution of the obtained novolac-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer and a temperature. It was introduced into a reactor equipped with a meter and an air blowing tube, and air was blown at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min. With stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled and taken out. Thus, a solution of photosensitive carboxyl group-containing resin A-1 having a solid content of 65% and a solid content acid value of 87.7 mgKOH / g was obtained. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as Resin Solution A-1.

(Synthesis Example 2: Synthesis of alkali-soluble resin A-2)
A flask equipped with a condenser and a stirrer was charged with 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin, and kept at a temperature of 40 ° C. or lower, and 228 parts of 25% aqueous sodium hydroxide solution was added. The reaction was carried out at 0 ° C. for 10 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. and neutralized to pH 4 with a 37.5% phosphoric acid aqueous solution while maintaining the temperature at 40 ° C. or lower. Thereafter, the mixture was allowed to stand to separate the aqueous layer. After separation, 300 parts of methyl isobutyl ketone was added and dissolved uniformly, and then washed three times with 500 parts of distilled water, and water, solvent, and the like were removed under reduced pressure at a temperature of 50 ° C. or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound.
When a part of the methanol solution of the obtained polymethylol compound was dried at room temperature in a vacuum dryer, the solid content was 55.2%.
In a flask equipped with a condenser and a stirrer, 500 parts of a methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were charged and uniformly dissolved at 50 ° C. After dissolving uniformly, methanol was removed under reduced pressure at a temperature of 50 ° C. or lower. Thereafter, 8 parts of oxalic acid was added and reacted at 100 ° C. for 10 hours. After completion of the reaction, the distillate was removed under reduced pressure at 180 ° C. and 50 mmHg to obtain 550 parts of novolak resin A.
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 130 parts of novolak resin A, 2.6 parts of 50% aqueous sodium hydroxide, toluene / methyl isobutyl ketone (mass ratio = 2/1) 100 parts were charged, and the system was purged with nitrogen while stirring. Next, the temperature was raised by heating, and 60 parts of propylene oxide was gradually introduced and reacted at 150 ° C. and 8 kg / cm ² . The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg / cm ^2, and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and the solvent was removed with an evaporator. The hydroxyl value was 189 g / eq. A propylene oxide adduct of novolak resin A was obtained. This was an average of 1 mole of propylene oxide added per equivalent of phenolic hydroxyl group.
189 parts of propylene oxide adduct of the obtained novolak 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 were stirred, a thermometer, and an air blowing tube. Was stirred while blowing air, heated to 115 ° C., reacted for an additional 4 hours while distilling off the water produced by the reaction as an azeotrope with toluene, and then brought to room temperature. Cooled down. The obtained reaction solution was washed with 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, in a four-necked flask equipped with a stirrer and a reflux condenser, 322 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were charged. Then, 60 parts of tetrahydrophthalic anhydride was added, reacted for 4 hours, cooled and taken out. The photosensitive carboxyl group-containing resin solution thus obtained had a solid content of 70% and a solid content acid value of 81 mgKOH / g. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as Resin Solution A-2.

(Preparation of silica slurry)
Dispersion processing was performed using 700 g of spherical silica manufactured by Admatech Co., Ltd., 300 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 0.7 μm zirconia beads in a bead mill. This was repeated three times and filtered through a 3 μm filter to prepare a silica slurry having an average particle size of 0.7 μm.

[Preparation of surface treatment filler]
(Preparation of silica B-1-1 treated with a surface treatment agent having a methacryl group and an epoxy group)
The silica slurry having an average particle size of 0.7 μm obtained above (PMA (propylene glycol monomethyl ether acetate), solid content: 70% by mass)) was used, and 4 wt% (methacrylic silane: epoxy silane = 1: 1.4 (mass ratio)) was added, and the mixture was treated with a bead mill for 10 minutes to obtain surface-treated filler B-1-1. In addition, Shin-Etsu Silicone KBM-503 was used as the methacrylic silane, and Shin-Etsu Silicone KBM-403 was used as the epoxy silane.

(Preparation of silica B-1-2 having methacryl and amino groups)
The silica slurry having an average particle size of 0.7 μm obtained above (PMA (propylene glycol monomethyl ether acetate), solid content: 70% by mass)) was used, and 4 wt% (methacrylic silane: aminosilane = 1: 1) with respect to silica. .4 (mass ratio)) was added and treated with a bead mill for 10 minutes to obtain surface-treated filler B-1-2. The methacrylic silane used was Shin-Etsu Silicone KBM-503, and the aminosilane was Shin-Etsu Silicone KBM-573.

(Preparation of silica B-1-3 having vinyl group and epoxy group)
The silica slurry (PMA (propylene glycol monomethyl ether acetate) obtained in the above) having a mean particle size of 0.7 μm obtained above was used and 4 wt% (vinylsilane: epoxysilane = 1: 1) with respect to silica. .4 (mass ratio)) was added and treated with a bead mill for 10 minutes to obtain surface-treated filler B-1-3. As the vinyl silane, Shin-Etsu Silicone KBM-1003 was used, and as the epoxy silane, Shin-Etsu Silicone KBM-403 was used.

(Preparation of silica B-1-4 having vinyl group and amino group)
The silica slurry having an average particle size of 0.7 μm obtained above (PMA (propylene glycol monomethyl ether acetate), solid content: 70% by mass)) was used, and 4 wt% (vinylsilane: aminosilane = 1: 1. 4 (mass ratio)) was added and treated with a bead mill for 10 minutes to obtain a surface-treated filler B-1-4. As the vinyl silane, Shin-Etsu Silicone KBM-1003 was used, and as the amino silane, Shin-Etsu Silicone KBM-573 was used.

(Preparation of silica B-2-1 having methacryl group)
Using the silica slurry (PMA (propylene glycol monomethyl ether acetate) obtained in the above) having a mean particle size of 0.7 μm obtained above, 4 wt% methacrylsilane was added to the silica, and a bead mill was used. After 10 minutes of treatment, a surface treated filler B-2-1 was obtained. As the methacryl silane, KBM-503 manufactured by Shin-Etsu Silicone Co., Ltd. was used.

(Preparation of epoxy group-containing silica B-3-1)
Using the silica slurry having an average particle diameter of 0.7 μm obtained above (in PMA (propylene glycol monomethyl ether acetate), solid content: 70% by mass), 4 wt% of epoxysilane was added to silica, Treatment for 10 minutes gave surface-treated filler B-3-1. As the epoxy silane, KBM-403 manufactured by Shin-Etsu Silicone Co., Ltd. was used.

(Preparation of Silica B-2-2 Having Vinyl Group)
Using the silica slurry having an average particle diameter of 0.7 μm obtained above (in PMA, solid content: 70% by mass), adding 4 wt% vinylsilane to silica, treating with a bead mill for 10 minutes, surface treatment filler B-2-2 was obtained. As the vinyl silane, KBM-1003 manufactured by Shin-Etsu Silicone Co., Ltd. was used.

(Preparation of silica B-3-2 having amino group)
Using the silica slurry having the average particle size of 0.7 μm obtained above (in PMA, solid content: 70% by mass), adding 4 wt% aminosilane to silica, treating with a bead mill for 10 minutes, surface treatment filler B-3-2 was obtained. As the aminosilane, KBM-573 manufactured by Shin-Etsu Silicone Co., Ltd. was used.

(Silica BR without surface treatment)
The silica slurry having an average particle size of 0.7 μm obtained above was used as the silica BR that was not surface-treated.

(Examples 1 to 18 and Comparative Examples 1 to 3)
The various components shown in Tables 1 and 2 below were blended in the proportions (parts by mass) shown in Tables 1 and 2, premixed with a stirrer, and then kneaded with a three-bead mill. 1-3 curable compositions were prepared.
In addition, the various components shown in Table 3 below were blended in the proportions (parts by mass) shown in Table 3, premixed with a stirrer, kneaded with a three-bead mill, and the main agents and curing agents of Examples 17 and 18 Was prepared. Then, the main ingredient and the hardening | curing agent were mixed and the curable composition of Examples 17 and 18 was prepared.

(Production of dry film)
The curable compositions of Examples 1 to 18 and Comparative Examples 1 to 3 were each applied onto a 38 μm polyester film using an applicator and dried at 80 ° C. for 20 minutes.

(Breaking strength)
A vacuum laminator is used so that the resin layers are in contact with the substrates on the glossy side (copper foil) of GTS-MP foil (manufactured by Furukawa Circuit Foil) on the glossy side (copper foil). The resin layer was formed on the copper foil by pasting together using the. The carrier film was peeled after exposure at the optimum exposure amount using an exposure apparatus equipped with a high-pressure mercury short arc lamp. This was irradiated with ultraviolet rays under the condition of an integrated exposure amount of 1000 mJ / cm ² in a UV conveyor furnace, and then cured by heating at 160 ° C. for 60 minutes. Then, after peeling a cured film from copper foil, the sample was cut out to measurement size (a size of 10 mm x 100 mm, 40 micrometers). In accordance with JIS K 7127, the elongation rate (tensile elongation at break) was measured under the conditions of a tensile speed of 1.0 mm / min and 23 ° C.
The judgment criteria are as follows.
◎: Break strength 120 Mpa or more ○: Break strength 110 Mpa or more Δ: Break strength 100 Mpa or more ×: Break strength 100 Mpa or less

(Storage modulus)
(Break strength) A sample having a measurement size (5 mm × 50 mm, 40 μm size) was prepared in the same manner as described in the test. The sample was subjected to DMS6100 (manufactured by Hitachi High-Tech Science Co., Ltd.), and the storage elastic modulus at 25 ° C. was measured at a frequency of 1 Hz. The judgment criteria are as follows.
A: Storage elastic modulus at 25 ° C. of 8 GPa or more ○: Storage elastic modulus at 25 ° C. of 5 GPa or more and less than −8 GPa ×: Storage elastic modulus at 25 ° C. of less than 5 GPa

(Linear expansion coefficient (CTE))
(Break strength) A sample having a measurement size (3 mm × 50 mm size) was prepared in the same manner as described in the test, and subjected to TMA6100 manufactured by Seiko Instruments Inc. In the TMA measurement, the test weight was 5 g, and the sample was heated from room temperature at a heating rate of 10 ° C./min, and was measured twice continuously. The intersection of two tangents having different linear expansion coefficients in the second round was defined as the glass transition temperature (Tg), and the linear expansion coefficient (CTE (α1)) in a region below Tg was evaluated. The judgment criteria are as follows.
A: CTE below Tg temperature is 20 ppm or less. C: CTE below Tg temperature is 50 ppm or less. Δ: CTE below Tg temperature is 80 ppm or less. X: CTE below Tg temperature is more than 80 ppm.

(Storage stability)
The main agent and the curing agent of Examples 17 and 18 were allowed to stand at 40 ° C. for the following time, and then the main agent and the curing agent were mixed to prepare a curable composition. The obtained curable composition was applied on the entire surface of a printed wiring board on which a circuit was formed with a film thickness of about 30 μm by screen printing, and was heated and dried at 80 ° C. for 30 minutes. Thereafter, a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 90 seconds under the condition of a spray pressure of 0.2 MPa, and evaluated according to the following criteria. The evaluation criteria are as follows.
A: Development residue did not occur even after standing for 2 months or longer.
○: Development residue did not occur even after standing for 1 month or more.
X: Development residue was generated in less than 1 month.

* 1: Solution A-1 of an alkali-soluble resin having an ethylenically unsaturated group synthesized above
* 2: Solution A-2 of an alkali-soluble resin having an ethylenically unsaturated group synthesized above
* 3: Irgacure TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by BASF Japan
* 4: Kayacure DETX-S (2,4-diethylthioxanthone) manufactured by Nippon Kayaku Co., Ltd.
* 5: JMT784 (titanocene photopolymerization initiator) manufactured by Yueyang Jinmao Technology Co., Ltd.
* 6: Irgacure OXE02 manufactured by BASF Japan Ltd. (Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime)
* 7: Epicron N-730A (phenol novolac type epoxy resin) manufactured by DIC
* 8: Epicron N-870 (bisphenol A novolac type epoxy resin) manufactured by DIC, solid content 85%
* 9: Surface treatment filler having methacrylic group and epoxy group prepared above * 10: Surface treatment filler having methacrylic group and amino group prepared above * 11: Surface treatment having vinyl group and epoxy group prepared above Filler * 12: Surface treatment filler having vinyl group and amino group prepared above * 13: Surface treatment filler having methacryl group prepared above * 14: Surface treatment filler having epoxy group prepared above * 15: Above Surface treatment filler having a vinyl group prepared in step * 16: Surface treatment filler having an amino group prepared above * 17: Silica that has not been surface treated as prepared above * 18: DPHA (dipentaerythritol manufactured by Nippon Kayaku Co., Ltd.) Hexaacrylate)
* 19: Phthalocyanine green

From the result shown in the said table | surface, according to the curable composition of this invention, it turns out that the hardened | cured material excellent in intensity | strength can be formed.

Claims (15)

1. A curable composition containing (A) a curable component, and (B) a surface treatment filler,
   A curable composition comprising (B-1) a surface treatment filler having a photocurable reactive group and a thermosetting reactive group as the (B) surface treated filler.
2. A curable composition containing (A) a curable component, and (B) a surface treatment filler,
   The (B) surface treatment filler contains (B-2) a surface treatment filler having a photocurable reactive group, and (B-3) a surface treatment filler having a thermosetting reactive group. A curable composition.
3. The curable composition according to claim 1, wherein the blending amount of the (B) surface treatment filler is 50 to 90% by mass in the solid content of the composition.
4. 2. The curable composition according to claim 1, comprising a compound having an ethylenically unsaturated group as the (A) curable component.
5. 2. The curable composition according to claim 1, comprising (A) an alkali-soluble resin having an ethylenically unsaturated group as the curable component.
6. 2. The curable composition according to claim 1, comprising an epoxy resin as the (A) curable component.
7. The curable composition according to claim 2, wherein the blending amount of the (B) surface treatment filler is 50 to 90% by mass in the solid content of the composition.
8. 3. The curable composition according to claim 2, comprising a compound having an ethylenically unsaturated group as the (A) curable component.
9. 3. The curable composition according to claim 2, comprising an alkali-soluble resin having an ethylenically unsaturated group as the (A) curable component.
10. 3. The curable composition according to claim 2, comprising an epoxy resin as the (A) curable component.
11. A main agent and a curing agent that are mixed to form the curable composition according to claim 2,
    The main agent contains at least (A) an alkali-soluble resin as a curable component and (B-2) a surface treatment filler having a photocurable reactive group,
    The curing agent contains at least (A) a compound having a plurality of cyclic ether groups or cyclic thioether groups in the molecule as the curable component and (B-3) a surface treatment filler having a thermosetting reactive group. Main agent and curing agent characterized by
12. A dry film comprising a resin layer obtained from the curable composition according to claim 1.
13. A dry film comprising a resin layer obtained from the curable composition according to claim 2.
14. Curing the curable composition according to any one of claims 1 to 10, the curable composition being a mixture of the main agent and the curing agent according to claim 11, or the resin layer of the dry film according to claim 12 or 13. A cured product characterized by being obtained as described above.
15. A printed wiring board comprising the cured product according to claim 14.