KR20230038673A - Curable composition, dry film, cured product and printed wiring board - Google Patents

Abstract

The objective of the present invention is to provide a curable composition capable of forming a cured product with excellent strength, a high storage modulus, and a low coefficient of linear expansion (CTE) and providing a dry film with excellent lamination properties, a dry film having a resin layer acquired from the composition, a cured product of the resin layer of the composition or the dry film, and a printed circuit board including the cured product. According to the present invention, the curable composition comprises: a (A) curable component; a (B-1) inorganic filler; and a (B-2) inorganic filler having a different average particle diameter from that of the (B-1) inorganic filler, wherein the average particle diameter of the (B-1) inorganic filler is 5 or more times that of the (B-2) inorganic filler and the sum of the (B-1) inorganic filler and the (B-2) inorganic filler is 45% or more by mass of the total mass of the solid content.

Description

Curable composition, dry film, cured product, and printed wiring board

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

For example, in the production of printed wiring boards, curable compositions are generally employed for forming permanent films such as solder resist, and as such curable compositions, dry film compositions and liquid compositions have been developed (for example, patent Literature 1).

BACKGROUND OF THE INVENTION [0002] In recent years, with the rapid progress of semiconductor components, electronic devices tend to be made lighter, thinner, smaller, higher in performance, and multifunctional. Following this trend, miniaturization, thinning, and multi-pin semiconductor packages are being put into practical use. Specifically, instead of IC packages called QFP (Quad Flat Pack Package), SOP (Small Outline Package), etc., BGA (Ball Grid Array), CSP (Chip Scale Package), etc. An IC package called . In recent years, FC-BGA (flip chip ball grid array) has also been put into practical use as a higher density IC package.

Japanese Patent Laid-Open No. 61-243869 (claims)

Further thinning is requested|required of permanent films, such as a solder resist, formed on the printed wiring board (it is also called a package board|substrate) used for the above IC packages. However, when thinned, there was a problem that, for example, the storage modulus was relatively low, and the strength of the cured film, such as breaking strength, became insufficient. For such a problem, it is conceivable to increase the blending ratio of the inorganic filler. However, in the case of a dry film made of a curable composition in which the blending ratio of the inorganic filler is increased, when it is laminated on a printed wiring board having a circuit pattern, it may be difficult to sufficiently bring the resin layer of the dry film into contact with the deep part of the circuit pattern. Therefore, there is a possibility that various characteristics such as insulation reliability may be deteriorated.

Therefore, an object of the present invention is a curable composition capable of forming a cured product having excellent strength, a high storage modulus, and a low coefficient of linear expansion (CTE) and obtaining a dry film having excellent lamination properties, from the composition It is providing the dry film which has a resin layer obtained, the hardened|cured material of the resin layer of this composition or this dry film, and the printed wiring board which has this hardened|cured material.

As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by using together two types of inorganic fillers having different average particle diameters of 5 times or more as inorganic fillers to be blended into the composition, and further setting the blending ratio of the inorganic fillers to a specific value or more. It was found that it could be solved, and it came to complete the present invention.

That is, the curable composition of the present invention is a curable composition containing (A) a curable component, (B-1) an inorganic filler, and (B-2) an inorganic filler having a different average particle diameter from the inorganic filler (B-1). As a composition, the average particle diameter of the (B-1) inorganic filler is 5 times or more of the average particle diameter of the (B-2) inorganic filler, and the (B-1) inorganic filler and the (B-2) It is characterized by containing 45 mass % or more of the total mass of solid content in total of an inorganic filler.

In the curable composition of the present invention, it is preferable that the average particle diameter of the inorganic filler (B-1) is 8 times or more of the average particle diameter of the inorganic filler (B-2).

In the curable composition of the present invention, it is preferable that the maximum particle diameter of the inorganic filler (B-2) is 500 nm or less.

In the curable composition of the present invention, it is preferable that the average particle diameter of the inorganic filler (B-1) is 5 μm or less.

It is preferable that the curable composition of this invention contains 80 mass % or more of the total solid mass of the said (B-1) inorganic filler and the said (B-2) inorganic filler in total.

As for the curable composition of this invention, it is preferable that the said (A) curable component contains at least a photocurable component, and further contains a photoinitiator and a ultraviolet absorber.

In the curable composition of the present invention, it is preferable that the ultraviolet absorber is carbon black.

The dry film of the present invention is characterized by having a resin layer obtained from the curable composition.

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

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

ADVANTAGE OF THE INVENTION According to the present invention, a curable composition capable of forming a cured product having excellent strength, high storage modulus, and low coefficient of linear expansion (CTE) and obtaining a dry film having excellent laminating properties, and water obtained from the composition A dry film having a paper layer, 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, (B-1) an inorganic filler, and (B-2) an inorganic filler having a different average particle diameter from the inorganic filler (B-1). , The average particle diameter of the (B-1) inorganic filler is 5 times or more of the average particle diameter of the (B-2) inorganic filler, and the (B-1) inorganic filler and the (B-2) inorganic filler In total, 45% by mass or more of the total mass of the solid content is included.

By raising the blending ratio of the mass of the inorganic filler in the total mass of the curable composition, a cured product having excellent strength, a high storage modulus, and a low coefficient of linear expansion (CTE) can be formed. When the amount of the filler is increased, a problem of lamination property of the dry film occurs. Moreover, smoothing of the surface of a curable composition becomes difficult. These problems become remarkable when the compounding ratio of the inorganic filler in the total solid mass of the curable composition is 45% by mass or more, particularly 80% by mass or more.

In the present invention, as the inorganic filler, (B-1) inorganic filler and (B-1) inorganic filler and (B-2) inorganic filler having different average particle diameters are contained, and (B-1) the average of the inorganic filler (B-2) Inorganic filler is filled in the space|interval of (B-1) inorganic filler by making particle diameter into 5 times or more of the average particle diameter of (B-2) inorganic filler. Thereby, the remaining gap|interval can be reduced and curable resin composition with a small resin content, ie, the high ratio of the mass of the filler in total mass can be obtained. According to this curable resin composition, the ratio of the mass of the filler to the total mass is high, and not only can a cured product having excellent strength be obtained, but also the lamination property of the dry film is excellent. Moreover, smoothing of the surface of a composition can also be aimed at.

In addition, in the curable composition of the present invention, there is no upper limit of the ratio of the mass of the inorganic filler in the total mass, but as the upper limit of the volume ratio of the (B-1) and (B-2) inorganic fillers in the composition, an example is given. For example, it is 95% by volume or less. Moreover, in the curable composition of this invention, it can handle as liquid ink.

Below, each component of the curable composition of this invention is demonstrated. In addition, in this specification, (meth)acrylate is a term which collectively names acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

[(A) Curable Component]

(A) The curable component may contain at least one of a photocurable reactive group and a thermosetting reactive group, but preferably contains both a photocurable reactive group and a thermosetting reactive group. (A) As the curable component, a (A1) photocurable component contributing to a photocuring reaction by light irradiation and a (A2) thermosetting component contributing to a thermal curing reaction by heating are preferable.

Here, as the (A) curable component, it is more preferable to contain a photocurable component (A1) and a thermocurable component (A2). Further, the curable composition of the present invention is more preferably a composition containing (A1) a photocurable component, (A2) a compound having an alkali-soluble resin and a plurality of cyclic ether groups or cyclic thioether groups in a molecule as a thermosetting component. do.

Further, the photocurable component (A1) and the thermosetting component (A2) may be photocurable components that contribute to both the photocuring reaction and the thermal curing reaction, and such photocurable components may be photocurable components and (A1) the photocurable component and ( A2) It can be suitably used as a thermosetting component.

((A1) photocurable component)

(A1) As a photocurable component, it is a compound which has an ethylenically unsaturated group, and a polymer, an oligomer, a monomer, etc. are mentioned, These mixtures may be sufficient. By including a photocurable component, the strength of a 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, photopolymerizable oligomers, photopolymerizable vinyl monomers, etc., which are known and commonly used photocurable monomers, can be used.

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

As the photopolymerizable vinyl monomer, known and commonly used ones, for example, styrene derivatives such as styrene, chlorostyrene, and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate, or vinyl benzoate; Vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinylcyclohexyl ether, ethylene glycol monobutyl vinyl vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; Acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, etc. ( meta) acrylamides; allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isoboronyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (metha)acrylate ) esters of (meth)acrylic acid such as acrylates; 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 Alkylene polyol poly(meth)acrylates such as pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate; Polyoxyalkylene glycol polys such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane tri(meth)acrylate ( meta) acrylates; poly(meth)acrylates such as hydroxypivalic acid neopentyl glycol ester di(meth)acrylate; Isocyanurate-type poly (meth)acrylates, such as tris [(meth)acryloxyethyl] isocyanurate, etc. are mentioned.

A photocurable component can be used individually by 1 type or in combination of 2 or more types. The blending ratio of the photocurable component is, for example, 0 to 55% by mass, preferably 0 to 50% by mass, in the solid content excluding the solvent of the entire composition.

(photopolymerization initiator)

In the curable composition of the present invention, when the (A) curable component contains at least the (A1) photocurable component, it is preferable to further contain a photopolymerization initiator. As the photopolymerization initiator, any known photopolymerization initiator as a photopolymerization initiator or a photoradical generating agent may be used.

Examples of the photopolymerization initiator include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, and bis-(2,6- Dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis-(2,4, bisacylphosphine oxides such as 6-trimethylbenzoyl)-phenylphosphine oxide (IRGACURE819 manufactured by BASF Japan); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, p monoacyl phosphine oxides such as valoylphenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (IRGACURE TPO manufactured by BASF Japan); 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-phenylpropan- 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's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2- 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-carb oxime esters such as bazol-3-yl]- and 1-(O-acetyl oxime); Bis(η5-2,4-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; Phenyl disulfide 2-nitrofluorene, butyloin, anisoin ethyl 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. Among them, monoacylphosphine oxides and oxime esters (hereinafter also referred to as monoacylphosphine oxide photopolymerization initiators and oxime ester photopolymerization initiators, respectively) are preferable, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide , ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, and 1-(O-acetyloxime) are more preferable.

A photoinitiator can be used individually by 1 type or in combination of 2 or more types. The blending ratio 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.

((A2) thermosetting component)

(A2) The strength of a cured film can be improved by including a thermosetting component. (A2) The thermosetting component can be used individually by 1 type or in combination of 2 or more types.

(A2) As the thermosetting component, all known ones can be used. For example, melamine resin, benzoguanamine resin, melamine derivative, amino resin such as benzoguanamine derivative, isocyanate compound, block isocyanate compound, cyclocarbonate compound, epoxy compound, oxetane compound, episulfide resin, bismaleimide , known thermosetting components such as carbodiimide resins and alkali-soluble resins 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) in the molecule and alkali-soluble resins.

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 ring cyclic (thio) ether groups in the molecule, for example, a compound having a plurality of epoxy groups in the molecule. , that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in a molecule, that is, a multifunctional oxetane compound, a compound having a plurality of thioether groups in a molecule, that is, an episulfide resin, and the like.

As a polyfunctional epoxy compound, it is epoxidized vegetable oil; bisphenol A type epoxy resin; Hydroquinone type epoxy resin; Bisphenol type epoxy resin; Thioether type epoxy resin; brominated epoxy resin; novolak-type epoxy resins; biphenol novolac type epoxy resin; bisphenol F-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 resins or mixtures thereof; bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylolethane type epoxy resin; heterocyclic epoxy resins; diglycidyl phthalate resin; tetraglycidylxylenoylethane resin; naphthalene group-containing epoxy resins; Epoxy resins having a dicyclopentadiene skeleton; glycidyl methacrylate copolymerization type epoxy resin; Copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives; Although CTBN-modified epoxy resins 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 types. 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 preferred.

Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl] ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl] ether, and 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 methacrylate In addition to polyfunctional oxetanes such as latex and their oligomers or copolymers, oxetane alcohol, novolak resins, poly(p-hydroxystyrene), cardotype bisphenols, calixarenes, calixresorcin arenes or siloxanes Ether compounds with resins having a hydroxyl group, such as sesquioxane, are exemplified. In addition, copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate are also exemplified.

Bisphenol A type episulfide resin etc. are mentioned as a compound which has several cyclic thioether groups in a molecule|numerator. Moreover, episulfide resin etc. which substituted the oxygen atom of the epoxy group of a novolak-type epoxy resin with the sulfur atom using the same synthesis 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 the isocyanate compound, a polyisocyanate compound can be blended. As the polyisocyanate compound, 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-trene 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 illustrated previously, the biuret body, the 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 blocking agent and the isocyanate compound which can react, the polyisocyanate compound etc. mentioned above are mentioned, for example. As an isocyanate blocking agent, it is a phenol type blocking agent, for example; lactam-based blocking agents; active methylene-based blocking agents; alcohol-based blocking agents; oxime-based blocking agent; mercaptan-based blocking agent; acid amide blocking agents; imide-based blocking agents; amine-based blocking agent; imidazole-based blocking agents; Immigration block system etc. are mentioned.

(thermal curing catalyst)

It is preferable that the curable composition of this invention contains a thermosetting catalyst. As a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine 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-triazine 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 adducts can also be used, and compounds that also function as these adhesion imparting agents are preferably used in combination with a heat curing catalyst.

A thermosetting catalyst can be used individually by 1 type or in combination of 2 or more types. The blending ratio of the thermosetting catalyst is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the thermosetting component.

In addition, as the (A2) thermosetting component, it is preferable to include 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. Especially, when the alkali-soluble resin is a carboxyl group-containing resin or a phenol resin, it is preferable because the adhesion to the substrate is improved. In particular, since it is excellent in developability, it is more preferable that the alkali-soluble resin is a carboxyl group-containing resin. It is preferable that carboxyl group-containing resin is carboxyl group-containing photosensitive resin which has an ethylenically unsaturated group, but carboxyl group-containing resin which does not have an ethylenically unsaturated group may be sufficient. When the alkali-soluble resin has an ethylenically unsaturated group, it also functions as a photocurable component and corresponds to the above-described photo- and thermosetting components. In addition, when the curable composition of the present invention contains an alkali-soluble resin, it may be used not only for alkali-developing applications but also for alkali-free applications.

As a specific example of carboxyl group-containing resin, the compounds enumerated below (either an oligomer or a polymer may be used) are mentioned.

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or 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, and polycarbonate-based polyols and polyether-based polyols , Polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide adduct diol, carboxyl group-containing urethane resin by polyaddition reaction of diol compounds such as compounds having a phenolic hydroxyl group and an alcoholic hydroxyl group .

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

(4) Bifunctional epoxy resins such as diisocyanate, 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, and biphenol type epoxy resin A carboxyl group-containing urethane resin by a polyaddition reaction of (meth)acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

(5) During the synthesis of the resin of (2) or (4) above, 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 ( Meta) acrylated carboxyl group-containing urethane resin.

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

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

(8) A carboxyl group-containing resin obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of the bifunctional epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the generated hydroxyl group.

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

(10) A polybasic acid anhydride is formed by reacting a monocarboxylic acid containing an unsaturated group 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. Carboxyl group-containing resin obtained by making it react.

(11) 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, reacting a monocarboxylic acid containing an unsaturated group with a reaction product obtained by reacting a polybasic acid anhydride with a reaction product obtained Carboxyl group-containing resin obtained by making it react.

(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 an unsaturated compound such as (meth)acrylic acid A polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic anhydride is reacted with the alcoholic hydroxyl group of the reaction product obtained by reacting a group-containing monocarboxylic acid. Carboxyl group-containing resin.

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

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

As the compound having a phenolic hydroxyl group, for example, a compound having a biphenyl skeleton or a phenylene skeleton or both skeletons, 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, and the like, and synthesized phenolic resins having various skeletons.

In addition, as a compound having a phenolic hydroxyl group, for example, phenol novolac resin, alkylphenol novolac resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinyl Known and commonly used phenolic resins such as phenols, bisphenol F, bisphenol S-type phenolic resins, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes.

Examples of commercially available phenolic resins include HF1H60 (manufactured by Maywa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (manufactured by Dainippon Insatsu Co., Ltd.), Vesmol CZ-256-A (manufactured by DIC Corporation), and Shonol. BRG-555, Shounol BRG-556 (manufactured by Showa Denko), CGR-951 (manufactured by Maruzen Sekiyu Co., Ltd.), polyvinylphenol CST70, CST90, S-1P, S-2P (manufactured by Maruzen Sekiyu Co., Ltd.). can

The acid value of the alkali-soluble resin is preferably in the range of 20 to 200 mgKOH/g, more preferably in the range of 40 to 150 mgKOH/g. (A) 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 becomes good. On the other hand, when the acid value is 200 mgKOH/g or less, dissolution of the exposed area by the developer can be suppressed, so the line becomes thinner than necessary, or in some cases, the exposed area and the unexposed area are dissolved and peeled off with the developer without distinction. It is suppressed, and a resist pattern can be drawn satisfactorily.

Although the weight average molecular weight of alkali-soluble resin differs according to resin frame|skeleton, the range of 1500-50,000 and also 1500-30,000 is preferable. When the weight average molecular weight is 1500 or more, the touch-drying performance is good, the moisture resistance of the coating film after exposure is good, the film shrinkage during development is suppressed, and the decrease in resolution can be suppressed. On the other hand, when the weight average molecular weight is 50,000 or less, developability is good and storage stability is also excellent.

Alkali-soluble resin can be used individually by 1 type or in combination of 2 or more types. The blending ratio of the alkali-soluble resin is, for example, 0 to 55% by mass, preferably 0 to 50% by mass, in the solid content excluding the solvent of the entire composition.

(A2) The thermosetting component can be used individually by 1 type or in combination of 2 or more types. (A2) The blending ratio of the thermosetting component is, for example, 0 to 55% by mass, preferably 0 to 50% by mass, in the solid content excluding the solvent of the entire composition.

[(B) inorganic filler ((B-1) inorganic filler and (B-2) inorganic filler)]

The curable composition of the present invention contains (B-1) an inorganic filler and (B-2) an inorganic filler having a different average particle diameter from the (B-1) inorganic filler, and (B-1) an average particle of the inorganic filler The diameter is 5 times or more of the average particle diameter of the (B-2) inorganic filler, and the total of the inorganic filler (B-1) and the inorganic filler (B-2) is 45% by mass of the total mass of the solid content of the composition. include more The curable composition of the present invention is more effective when the total amount of the inorganic filler (B-1) and the inorganic filler (B-2) is 50% by mass or more and 60% by mass or more of the total solid content of the composition. , 70% by mass or more, 80% by mass or more, and particularly effective at 83% by mass or more.

Here, in the present specification, the average particle diameter of the inorganic fillers (B-1) and (B-2) is the average particle diameter including not only the particle diameter of the primary particles but also the particle diameter of the secondary particles (aggregates) ( D50). (B-1) and (B-2) The average particle diameter of an inorganic filler is a value of D50 measured by the laser diffraction method. As a measuring device by the laser diffraction method, Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. is mentioned. In addition, the maximum particle diameter (D100) and particle diameter (D10) of the (B-1) and (B-2) inorganic fillers can be similarly measured with the above-mentioned apparatus.

As described above, the present invention can reduce the remaining gaps by filling the gaps of the (B-1) inorganic fillers with the (B-2) inorganic filler, and the resin content is small, that is, the mass of the filler in the total mass It is to obtain a curable resin composition with a high ratio. Even within the same product of normal commercial products, there is originally a 2 to 3 times change in particle diameter, but at that ratio, fine particles do not enter the gap effectively, so both (B-1) and (B-2) A difference of 5 times or more is required for the average particle diameter of the filler. (B-1), (B-2) The larger the average particle diameter ratio of both fillers, the better. It is more preferably 8 times or more, and even more preferably 10 times or more.

(B-1) It is preferable that the average particle diameter of an inorganic filler is 5 micrometers or less. (B-1) The average particle diameter of the inorganic filler differs depending on the use of the curable composition, but is preferably 5 µm or less for use in forming a cured film on an IC package substrate, for example, and cured on a printed wiring board for a motherboard. It is preferably 30 μm or less for film forming applications, and preferably 40 μm or less for mold (sealing) applications. Also, the maximum particle size of the (B-2) inorganic filler is preferably 500 nm or less. Moreover, it is preferable that the particle diameter (D10) of (B-1) inorganic filler is 5 times or more of the average particle diameter (D50) of (B-2) inorganic filler. When this ratio is 5 times or more, the filling efficiency of the (B-2) inorganic filler into the gap between the (B-1) inorganic fillers is improved, and the balance between the strength of the cured product and the laminating properties of the dry film is excellent.

The blending ratio of (B-1) and (B-2) inorganic fillers is preferably (B-1):(B-2) = 5:5 to 9:1, and 6:4 to 8:1 by volume. It is more preferable that it is 2. If it is within the said range, coexistence of the strength of hardened|cured material and the lamination property of a dry film is further aimed at.

The material of (B-1) and (B-2) inorganic filler is not particularly limited, and examples thereof include silica, barium sulfate, barium titanate, Neuburg diatomaceous earth, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, Titanium oxide, aluminum hydroxide, silicon nitride, aluminum nitride, etc. are mentioned. Among them, silica is preferable, and curing shrinkage of the cured product of the curable composition is suppressed, resulting in a lower CTE, and also improves properties such as adhesion and hardness. As silica, fused silica, spherical silica, amorphous silica, crystalline silica, etc. are mentioned.

(B-1) and (B-2) The presence or absence of surface treatment of the inorganic filler is not particularly limited. However, as described above, since the curable composition of the present invention has a low resin content, it is preferable that the inorganic fillers (B-1) and (B-2) are surface-treated to increase dispersibility.

In addition, the surface treatment method of (B-1) and (B-2) inorganic filler is not specifically limited, A well-known and usual method may be used, The surface treatment agent which has a curable reactive group, for example, which has a curable reactive group as an organic group The surface of the filler may be treated with a coupling agent or the like.

(B-1) and (B-2) It is preferable that the surface treatment of the inorganic filler is surface treatment by a coupling agent. As a coupling agent, coupling agents, such as a silane type, a titanate type, an aluminate type, and a zirco aluminate type, can be used. Among them, a silane-based coupling agent is preferable. Examples of such silane-based 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-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. can be mentioned, and these can be used alone or in combination. It is preferable that these silane-type coupling agents are previously immobilized on the surface of a filler by adsorption or reaction. Here, it is preferable that the processing amount of the coupling agent with respect to 100 mass parts of fillers is 0.5-10 mass parts. In addition, in this invention, the coupling agent given to a filler shall not be contained in the compound which has an ethylenically unsaturated group.

As a photocurable reactive group, ethylenically unsaturated groups, such as a vinyl group, a styryl group, a methacryl group, and an acryl group, are mentioned. Especially, at least 1 sort(s) of arbitrary of a vinyl group and a (meth)acryl group is preferable.

As a thermosetting reactive group, a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, an oxazoline group, etc. are mentioned. Among them, at least one of an amino group and an epoxy group is preferable.

In addition, the surface-treated inorganic filler of (B-1) and (B-2) inorganic filler should just be contained in the curable composition of the present invention in a surface-treated state, and the surface-untreated inorganic filler and surface treatment agent are separately Although the inorganic filler may be separately blended and surface treated in the composition, it is preferable to blend an inorganic filler surface-treated in advance. By blending the previously surface-treated inorganic filler, it is possible to prevent a decrease in crack resistance or the like due to a surface treatment agent not consumed by the surface treatment that may remain when separately blended. In the case of surface treatment in advance, it is preferable to mix a pre-dispersion liquid obtained by pre-dispersing an inorganic filler in a solvent or curable component, and pre-disperse the surface-treated inorganic filler in a solvent and blend the pre-dispersion liquid into the composition, or the surface is not treated. When pre-dispersing the inorganic filler in a solvent, after sufficient surface treatment, it is more preferable to blend the pre-dispersion into the composition.

(B-1) and (B-2) inorganic fillers may be blended with (A) component or the like in a powder or solid state depending on the usage form of the curable composition of the present invention, and after mixing with a solvent or dispersant to form a slurry You may mix|blend with (A) component etc.

[UV absorbent]

In the curable composition of the present invention, when the (A) curable component contains at least (A1) a photocurable component and a photopolymerization initiator, (B-1) inorganic filler and (B-2) inorganic filler are blended The higher the ratio, the more difficult it is to form openings. However, by further containing an ultraviolet absorber, openings can be easily formed even when the blending ratio of (B-1) inorganic filler and (B-2) inorganic filler is high. The upper limit of the blending ratio of the (B-1) inorganic filler and the (B-2) inorganic filler is preferably 90% by mass or less, and more preferably 88% by mass or less, from the viewpoint of resolution.

Any ultraviolet absorber according to the present invention can be used as long as it absorbs light with a wavelength of 300 nm to 450 nm.

Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as carbon black and black titanium oxide (also referred to as titanium black), organic ultraviolet absorbers, and the like. Among these, carbon black is the most preferable from the viewpoint of the resolution of the cured product.

Examples of organic UV absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, and dibenzoylmethane derivatives. Specific examples of benzophenone derivatives include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and 2 , 4-dihydroxy benzophenone etc. are mentioned. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, p-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4 -Hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, etc. are mentioned. Specific examples of the benzotriazole derivative include 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-( 2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5 -Chlorobenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole, etc. can be heard Specific examples of the triazine derivative include hydroxyphenyltriazine, bisethylhexoxyoxyphenol methoxyphenyltriazine, and the like.

The ultraviolet absorber may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (or above). , BASF Japan Co., Ltd. product, brand name), etc. are mentioned.

It is preferable to use the organic ultraviolet absorber described above in combination with carbon black. Resolution is more stable by using together with carbon black.

A ultraviolet absorber may be used individually by 1 type, and may be used in combination of 2 or more type. The ultraviolet absorber is effective in a small amount, and preferably contains 0.01 to 10% by mass of the total solid mass of the composition, and is more preferably 0.02 to 7% by mass from the viewpoint of deep curability that affects the resolution of the cured product. As the UV absorber, when carbon black is contained, it is preferably contained in an amount of 0.01 to 1% by mass of the total mass of the solid content of the composition, and contains 0.02 to 0.5% by mass of the total mass of the solid content of the composition, from the viewpoint of resolution of the cured product. It is more preferable to do it, and it is especially preferable to contain 0.05 to 0.30 mass% of the total mass of the solid content of the composition.

(organic solvent)

The curable composition of the present invention may contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when applied to a substrate or carrier film. As an organic solvent, 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, butyl cellosolve acetate, carbitol acetate, butyl carbitol 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 common organic solvent such as petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha can be used. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

(other optional ingredients)

In the curable composition of the present invention, if necessary, a photoinitiation aid, a cyanate compound, an elastomer, a mercapto compound, a thermosetting catalyst, a urethanization catalyst, a thixotropy agent, an adhesion accelerator, a block copolymer, a chain transfer agent, and a polymerization inhibitor , antifreeze agent, antioxidant, rust preventive, ultraviolet absorber, finely divided silica, organic bentonite, thickener such as montmorillonite, silicone type, fluorine type, polymer type antifoaming agent and/or leveling agent, such as imidazole type, thiazole type, triazole type silane, etc. Components such as coupling agents, flame retardants such as phosphorus compounds such as phosphinic acid salts, phosphoric acid ester derivatives, and phosphazene compounds, and colorants can be further blended. Those known in the field of electronic materials can be used.

The curable composition of the present invention may be used in the form of a dry film or as a liquid. When used as a liquid phase, 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 film strength even if it is a thin film, a pattern on a printed wiring board requiring thinning, such as an IC package substrate (printed wiring board used for an IC package) It can be used suitably also for formation of a layer. In addition, the cured product obtained from the curable composition of the present invention has a high modulus of elasticity and a low CTE, so it can be said that it can be suitably used for forming a pattern layer in an IC package substrate having a thin total thickness and lacking in rigidity.

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

As the carrier film, a plastic film is used, and it is preferable to use 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. The thickness of the carrier film is not particularly limited, but is generally appropriately selected from the range of 10 to 150 μm.

After forming a film of the curable composition of the present invention on a 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, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used. It is only necessary if the adhesive force of is smaller than that.

Moreover, in this invention, a resin layer may be formed by apply|coating and drying the curable composition of this invention on the said cover film, and a carrier film may be laminated|stacked 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 to which the curable composition of this invention is apply|coated.

The printed wiring board of the present invention has a cured product obtained from the resin layer of the curable composition or dry film of the present invention. As a method for producing the printed wiring board of the present invention, for example, the curable composition of the present invention is adjusted to a viscosity suitable for the coating method using the above organic solvent, and then, on a substrate, dip coating method, flow coating method, roll coating method, After coating by a method such as a bar coater method, screen printing method, or curtain coating method, a touch-drying resin layer is formed by volatilizing and drying (pre-drying) the organic solvent contained in the composition at a temperature of 60 to 100 ° C. . In addition, in the case of a dry film, after bonding on a base material so that a resin layer may contact a base material by a laminator etc., the resin layer is formed on a base material by peeling off a carrier film.

As the substrate, in addition to printed wiring boards and flexible printed wiring boards formed with circuits of copper or the like in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabric epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin・Copper-clad laminates of all grades (FR-4, etc.) made of materials such as copper-clad laminates for high frequency circuits using polyethylene/polyphenylene ether, polyphenylene oxide/cyanate, etc., as well as metal substrates and polyimides A film, a PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, etc. are mentioned.

The volatilization drying performed after applying the curable composition of the present invention is carried out in a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, etc. and a method of spraying from a nozzle to a support).

After forming a resin layer on the printed wiring board, it is selectively exposed to active energy rays through a photomask having a predetermined pattern formed thereon, and the unexposed portion is dipped in a dilute alkali aqueous solution (for example, 0.3 to 3% by mass aqueous sodium carbonate solution). developed to form a pattern of the cured product. In addition, after irradiation of active energy rays to the cured product, heat curing (for example, 100 to 220 ° C.), or by irradiation of active energy rays after heat curing or final finish curing (main curing) only by heat curing, adhesion, hardness, etc. Forms a cured film with excellent various properties.

The exposure machine used for the active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and irradiating ultraviolet rays in the range of 350 to 450 nm, or direct drawing. A device (for example, a laser direct imaging device that directly draws an image with a laser by CAD data from a computer) can also be used. As the lamp light source or laser light source of the weaving machine, the maximum wavelength may be 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 generally be within the range of 10 to 1000 mJ/cm 2 , preferably 20 to 800 mJ/cm 2 .

The developing method may be a dipping method, a shower method, a spray method, a brush method, and the like, and as a developing solution, an alkali aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, or amines may be used. can

The curable composition of the present invention may be used not only for forming a pattern of a cured film with a developing solution as described above, but also for a non-patterning application, such as a mold application (sealing application).

[Example]

Examples and comparative examples will be shown below and the present invention will be described in detail, but the present invention is not limited to the following examples. In addition, "part" and "%" below are all based on mass unless otherwise indicated.

(Synthesis of alkali-soluble resin)

In an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, 119.4 parts of novolak type cresol resin (trade name "Shonol CRG951", manufactured by Showa Denko, OH equivalent: 119.4), 1.19 parts of potassium hydroxide And 119.4 parts of toluene were introduced, the inside of the system was substituted with nitrogen while stirring, and the temperature was raised by heating. Then, 63.8 parts of propylene oxide were gradually added dropwise and reacted at 125 to 132°C and 0 to 4.8 kg/cm 2 for 16 hours. Thereafter, it is cooled to room temperature, and 1.56 parts of 89% phosphoric acid is added to the reaction solution to neutralize potassium hydroxide, and the novolak-type cresol having a non-volatile content of 62.1% and a hydroxyl value of 182.2 mgKOH/g (307.9 g/eq) is mixed. A propylene oxide reaction solution of the resin was obtained. This was obtained by adding an average of 1.08 mol of propylene oxide per 1 equivalent of phenolic hydroxyl group.

293.0 parts of the obtained propylene oxide reaction solution of the novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer and an air suction tube, and 10 ml of air was introduced. It was blown in at a rate of /min and reacted at 110°C for 12 hours while stirring. 12.6 parts of water distilled out the water produced|generated by reaction as an azeotropic mixture with toluene. Thereafter, the reaction solution obtained by cooling to room temperature was neutralized with 35.35 parts of 15% sodium hydroxide aqueous solution, followed by washing with water. Thereafter, toluene was distilled off while being substituted with 118.1 parts of diethylene glycol monoethyl ether acetate in an evaporator to obtain a novolak-type acrylate resin solution. Then, 332.5 parts of the obtained novolak-type acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air suction pipe, and air was blown at a rate of 10 ml/min to tetrahydrogenate while stirring. 60.8 parts of phthalic anhydride was added gradually, it was made to react at 95-101 degreeC for 6 hours, and it took out after cooling. In this way, a solution of photosensitive carboxyl group-containing resin A-1 having a solid content of 65% and an acid value of 87.7 mgKOH/g of the solid content was obtained. Hereinafter, the solution of this carboxyl group-containing photosensitive resin is called resin solution A-1.

((B-1) Preparation of Inorganic Filler 1)

Dispersion treatment was performed using 700 g of spherical silica (Adma Fine SO-E2) manufactured by Adma Tech Co., Ltd., 300 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 0.5 µm zirconia beads in a bead mill. This was repeated three times and filtered with a 3 µm filter to prepare a silica slurry having an average particle size of 500 nm. In addition, this (B-1) inorganic filler 1 has a particle diameter D10 of 250 nm and a maximum particle diameter D100 of 3 µm.

((B-1) Preparation of Inorganic Filler 2)

Dispersion treatment was performed using 700 g of spherical silica (Admafine SO-E1) manufactured by Admatech Co., Ltd., 300 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 0.5 µm zirconia beads in a bead mill. This was repeated three times and filtered with a 3 µm filter to prepare a silica slurry having an average particle diameter of 250 nm. In addition, this (B-1) inorganic filler 2 has a particle diameter D10 of 100 nm and a maximum particle diameter D100 of 1 µm.

((B-2) Manufacture of Inorganic Filler)

A silica slurry (YA050C, PMA (propylene glycol monomethyl ether acetate) solvent) having an average particle diameter of 50 nm and having a vinyl group manufactured by Admatech was used. In addition, this (B-2) inorganic filler has a particle diameter D10 of 20 nm and a maximum particle diameter D100 of 0.2 µm.

(Examples 1 to 11 and Comparative Examples 1 to 3)

The various components shown in the table below were blended at the ratios (parts by mass) shown in the table, premixed with a stirrer, and then kneaded with a bead mill to prepare a curable composition. Each of the obtained curable compositions was applied onto a 38 μm polyester film using an applicator, and dried at 80° C. for 20 minutes to prepare a dry film having a resin layer having a thickness of 20 μm.

(lamination)

As a pre-treatment, an etching treatment corresponding to 1.0 μm was performed by Macke's CZ-8101 treatment on a double-sided printed wiring board having a copper thickness of 15 μm and L (line: wiring width) / S (space: spacing width) having the following comb pattern. Subsequently, the dry films of each Example and Comparative Example were laminated using a vacuum laminator (CVP-300: manufactured by Nikko Materials Co., Ltd.) in a first chamber at 80 ° C. under conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds, and then press pressure Pressing was performed on conditions of 0.5 MPa and a press time of 30 seconds to obtain a substrate for evaluation. Evaluation after lamination Whether or not the resin layer of the dry film was in contact with the bottom surface (surface of the substrate) of the space of the substrate was observed with a scanning electron microscope (SEM, magnification: 1000 times).

◎: In the case of L/S = 10/10, the resin layer of the dry film was in contact with the bottom surface of the space (surface of the substrate).

○: In the case of L/S = 20/20, the resin layer of the dry film was in contact with the bottom face of the space.

(triangle|delta): In the case of L/S=50/50, the resin layer of the dry film contacted the bottom surface of the space.

x: In the case of L/S = 50/50, the resin layer of the dry film was not in contact with the bottom surface of the space.

(storage modulus)

Place the GTS-MP foil (manufactured by Furukawa Circuit Foil Co., Ltd.) on the glossy surface side (copper foil), and vacuum laminator in the same manner as above so that the dry films according to Examples and Comparative Examples produced above are in contact with the copper foil. By joining together using , a resin layer was formed on the copper foil and the carrier film was peeled off. This was cured by heating at 170°C for 60 minutes after irradiating with ultraviolet rays on conditions of a cumulative exposure amount of 1000 mJ/cm 2 in a UV conveyor furnace. Then, after peeling the cured film from the copper foil, a sample was cut out to a measurement size (size (length x width x thickness) of 5 mm x 50 mm x 20 µm). The sample was applied to DMS6100 (manufactured by Hitachi High-Tech Science Co., Ltd.), and the storage modulus at 25°C was measured at a frequency of 1 Hz.

○: The storage modulus at 25°C is 10 GPa or more.

x: The storage modulus at 25°C is less than 10 GPa.

(coefficient of linear expansion (CTE))

Place the GTS-MP foil (manufactured by Furukawa Circuit Foil Co., Ltd.) on the glossy surface side (copper foil), and vacuum laminator in the same manner as above so that the dry films according to Examples and Comparative Examples produced above are in contact with the copper foil. By joining together using , a resin layer was formed on the copper foil and the carrier film was peeled off. This was cured by heating at 170°C for 60 minutes after irradiating with ultraviolet rays on conditions of a cumulative exposure amount of 1000 mJ/cm 2 in a UV conveyor furnace. Then, after peeling the cured film from the copper foil, a sample was cut out to a measurement size (size (length × width × thickness) of 5 mm × 50 mm × 20 μm) and used for TMA6100 manufactured by Seiko Instruments. In the TMA measurement, the temperature of the sample was raised from room temperature at a heating rate of 10°C/min with a test weight of 5 g, and the measurement was performed twice in succession. The intersection point of the two tangents having different linear expansion coefficients in the second time was regarded as the glass transition temperature (Tg), and evaluated as the linear expansion coefficient (CTE (α1)) in the region below Tg. The criterion for judgment is as follows.

○: CTE below Tg temperature is 20 ppm or less.

×: CTE at Tg temperature or lower exceeds 20 ppm.

(Resolution)

Each curable composition of Examples 7 to 11 was coated on the entire surface on copper foil, dried at 80 ° C. for 30 minutes, and irradiated with light with a direct imaging exposure device (light source: high-pressure mercury) so that the exposure amount on the composition was 50 mJ / cm 2, It developed with 1% sodium carbonate aqueous solution at 30 degreeC, and the pattern of the hardened|cured material was formed. After pattern formation, it was evaluated whether an opening diameter of 80 µm could be formed and the shape was good.

◎: The opening can be formed, and the wall surface of the opening has a straight shape.

○: An opening can be formed.

×: An opening cannot be formed.

*1: Solution A-1 of alkali-soluble resin synthesized above

*2: IGM OmniradTPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) (photopolymerization initiator)

*3: DIC Epiclon N-870 (bisphenol A novolac type epoxy resin)

*4: Laromer manufactured by BASF (compound having an ethylenically unsaturated group)

*5: Inorganic filler 1 (B-1) prepared above

*6: Inorganic filler 2 (B-1) prepared above

*7: Inorganic filler (B-2) prepared above

*8: MA-100 manufactured by Mitsubishi Chemical Corporation

*9: 13M-C manufactured by Mitsubishi Material Co., Ltd.

*10: BASF TINUVIN460

From the results shown in the table above, it is understood that a curable composition having a high percentage of the mass of the filler in the total solid mass can be obtained by using two types of fillers having different average particle diameters of 5 times or more. In addition, from the results shown in the table above, it can be seen that even in the case of a resin composition having a high filler mass ratio, the dry film has excellent lamination properties.

In addition, when the curable composition of the present invention obtained in this way is used, it is found that the cured product has excellent strength, high storage modulus, and low linear expansion coefficient (CTE), as well as excellent dry film lamination properties.

In addition, it can be seen that as the ultraviolet absorber, carbon black is most preferable from the viewpoint of the resolution of the cured product.

Claims (8)

A dry film having a resin layer obtained from a curable composition on a support,
The resin layer,
(A) contains a curable component, (B-1) an inorganic filler, and (B-2) an inorganic filler having a different average particle diameter from the inorganic filler (B-1),
The average particle diameter of the (B-1) inorganic filler is 5 times or more of the average particle diameter of the (B-2) inorganic filler,
The dry film characterized by containing 80 mass % or more of the total mass of the solid content of the said curable composition in total of said (B-1) inorganic filler and said (B-2) inorganic filler. The dry film according to claim 1, wherein the average particle diameter of the inorganic filler (B-1) is 8 times or more of the average particle diameter of the inorganic filler (B-2). The dry film according to claim 1 or 2, wherein the (B-2) inorganic filler has a maximum particle diameter of 500 nm or less. The dry film according to claim 1 or 2, wherein the inorganic filler (B-1) has an average particle diameter of 5 µm or less. The method according to claim 1 or 2, wherein the (A) curable component contains at least a photocurable component,
A dry film characterized by further comprising a photopolymerization initiator and an ultraviolet absorber. The dry film according to claim 5, wherein the ultraviolet absorber is carbon black. A cured product obtained by curing the resin layer of the dry film according to claim 1 or 2. A printed wiring board comprising the cured product according to claim 7.