JP2004277729A - Curable resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition which suffers from no decrease in surface roughness after a roughening treatment, even when the content of a filler is increased, and is suitable for an insulator excellent in adhesion for a printed wiring board. <P>SOLUTION: The curable resin composition comprises a curable resin (A) comprised of a polymer epoxy resin, an inorganic filler (B), a curing accelerator (C), where the inorganic filler (B) is silicon oxide of 0.01-10 μm having its surface treated with a silane coupling agent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable resin composition and a cured product thereof. More specifically, the present invention relates to a multilayer printed wiring board interlayer insulating material.

As an insulating material used for manufacturing an interlayer insulating substrate of a multilayer printed wiring board by build-up, a material having excellent dimensional stability is demanded from the viewpoint of reliability. There is known a method for improving the dimensional stability by reducing the coefficient of thermal expansion by including a filler. It is known that the dimensional stability is improved with an increase in the filler content (for example, Patent Document 1). ~ 3).
In addition, in the additive method (method of applying a conductor by plating), it is very important from the viewpoint of reliability that the surface of an insulating resin to which a conductor is applied can be roughened.

JP-A-6-120626 JP-A-6-196856 JP-A-2000-86871

However, when the content of the filler is increased, the surface roughness after the roughening is reduced, so that there is a problem that the adhesion between the resin and the conductor cannot be ensured.
An object of the present invention is to solve these problems and to provide a curable resin composition having excellent adhesion without lowering the surface roughness than before.

The present inventors have intensively studied to solve the above problems, and as a result, have reached the present invention.
That is, the gist of the present invention is that in a curable resin composition including a curable resin (A), an inorganic filler (B), and a curing accelerator (C), the inorganic filler is surface-treated with a silane coupling agent. I do.

  When the curable resin composition of the present invention is used, in the roughening step, the surface roughness becomes larger than before, and the peel strength of the conductor increases. In particular, the filler content of the curable resin composition is 33 to 85%. In the case of, there is an effect that a small linear expansion coefficient and a large adhesion are simultaneously provided.

  The curable resin of the present invention comprises a curable resin (A), an inorganic filler (B) surface-treated with a silane coupling agent, and a curing accelerator (C).

The inorganic filler (B) in the present invention is classified into a metal oxide and a metal salt.
Known metal oxides can be used, and specific examples thereof include titanium oxide, silicon oxide, and aluminum oxide. Known metal salts can be used, and specific examples thereof include calcium carbonate and barium sulfate.
Among these (B), metal oxides are preferred from the viewpoints of electrical properties (wet heat reliability / dielectric properties), heat resistance and chemical resistance, and more preferred are silicon oxide and titanium oxide. Particularly preferred is silicon oxide.

  The content (% by weight) of (B) is preferably from 3 to 85, more preferably 8 or more, and particularly preferably from the viewpoint of the linear expansion coefficient and the strength of the cured product, based on the weight of the curable resin composition. It is 13 or more, more preferably 70 or less, particularly preferably 60 or less.

  The volume average particle size (μm) of (B) is preferably from 0.01 to 10, more preferably from 0.02 to 8, and particularly preferably from the viewpoint of the complex viscosity of the curable resin and the coefficient of linear expansion of the cured product. 0.03 to 6. That is, the volume average particle size (μm) of the filler is preferably 0.01 or more, more preferably 0.02 or more, particularly preferably 0.03 or more, and preferably 10 or less, more preferably 8 or less, Particularly preferably, it is 6 or less.

  The melting point of (B) is preferably from 300 to 2000 ° C, more preferably from 400 to 1900 ° C, particularly preferably from 500 to 1800 ° C, from the viewpoints of the coefficient of linear expansion of the cured product and availability. That is, the melting point ° C of the inorganic filler is preferably 300 or more, more preferably 400 or more, particularly preferably 500 or more, and preferably 2000 or less, more preferably 1900 or less, and particularly preferably 1800 or less.

As the surface treatment agent for the inorganic filler particles, a known silane coupling agent can be used. Specifically, for example, a silane coupling agent represented by the following general formula (1) can be used.
_{Y- (CH 2) n-SiX} 3 (1)
In the formula (1), Y represents an organic functional group, for example, chlorine, amino group, mercapto group, vinyl group, methyl methacryl group, epoxy group, amide group and the like. Among them, an epoxy group is preferable from the viewpoint of dispersibility of the surface-treated particles.
X represents a hydrolyzable group, for example, a methoxy group, an ethoxy group, an ethyloxymethoxy group and the like. Among them, a methoxy group and an ethoxy group are preferred from the viewpoint of the reaction rate.
Specific examples of the silane coupling agent include α-glycidoxypropyltrimethoxysilane, N-phenyl-α-aminopropyltrimethoxysilane, α-mercaptotriethoxysilane, α-glycidoxyethyltriethoxysilane, α -Glycidoxypropyltripropyloxysilane, α-mercaptotrimethoxysilane, α-glycidoxybutyltrimethoxysilane and the like. Among them, α-glycidoxypropyltrimethoxysilane and α-glycidoxyethyltriethoxysilane are preferred from the viewpoint of reactivity and dispersibility.

Known methods can be used for the surface treatment. For example, there are a spray method of directly spraying a silane coupling agent, an aqueous solution method of preparing a dilute aqueous solution of the silane coupling agent and impregnating the same, and an organic solvent method of impregnating the silane coupling agent with an organic solvent. In the treatment of the silane coupling agent, an acid and an alkali can coexist.
As the dispersion medium in the organic solvent method, a known organic solvent can be used, but from the viewpoint of the solubility of the silane coupling agent, methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate and the like are preferable.

Examples of the curable resin (A) include a thermosetting resin and a photocurable resin.
Examples of the thermosetting resin include an epoxy resin (A1), a polyimide resin, and a resin having another reactive group. Examples of the thermosetting resin include an epoxy resin described in JP-A-2001-279116, and JP-A-2002-88242. A polyimide resin described in the gazette and a resin having another reactive group described in JP-A-2001-279110 can be used.
Examples of the photocurable resin include an epoxy resin and a resin having another reactive group. For example, the epoxy resin described in JP-A-2002-105117 and other resins described in JP-A-11-214815 are disclosed. Resins having a reactive group can be used.
Among these curable resins, a thermosetting resin is preferable from the viewpoint of simplicity of the curing reaction and the like, and an epoxy resin (A1) is more preferable from the viewpoint of cost and dielectric properties.

The epoxy resin (A1) is composed of an epoxide and a curing agent.
As the epoxide, the above-mentioned known compounds can be used, and for example, glycidyl ether epoxide, glycidyl ester epoxide, glycidylamine epoxide, alicyclic epoxide and the like can be used.

Examples of the glycidyl ether type epoxide include glycidyl ether of dihydric phenol, glycidyl ether of polyhydric phenol, glycidyl ether of dihydric alcohol, and glycidyl ether of polyhydric alcohol.
Examples of the glycidyl ether of a dihydric phenol include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol S diglycidyl ether.
Examples of the glycidyl ether of polyhydric phenol include dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, and dinaphthyltriol triglycidyl ether.
Examples of the glycidyl ether of a dihydric alcohol include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polyethylene glycol (weight average molecular weight (hereinafter, Mw): 150 to 4,000) diglycidyl ether and polypropylene glycol (Mw: 180 to 5,000) diglycidyl ether.
Examples of the glycidyl ether of a polyhydric alcohol include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, and poly (polymerization degree 2 to 5) glycerin polyglycidyl ether.

As the glycidyl ester type epoxide, glycidyl ester of carboxylic acid, glycidyl ester type polyepoxide and the like are used.
Examples of the glycidyl ester of a carboxylic acid include glycidyl methacrylate, diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, and triglycidyl trimellitate.

As the glycidylamine type epoxide, glycidyl aromatic amine, glycidyl alicyclic amine, glycidyl heterocyclic amine and the like are used.
Examples of the glycidyl aromatic amine include N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl Diaminodiphenyl sulfone and N, N, N ', N'-tetraglycidyldiethyldiphenylmethane.
Examples of the glycidyl alicyclic amine include bis (N, N-diglycidylaminocyclohexyl) methane (a hydrogenated compound of N, N, N ', N'-tetraglycidyldiaminodiphenylmethane) and N, N, N', N ' -Tetraglycidyldimethylcyclohexylenediamine (hydrogenated compound of N, N, N ', N'-tetraglycidylxylylenediamine) and the like.
Examples of the glycidyl heterocyclic amine include trisglycidylmelamine and N-glycidyl-4-glycidyloxypyrrolidone.

  Examples of the alicyclic epoxide include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ether and 3,4-epoxy-6-methyl. Cyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate and the like.

  Among these epoxides, glycidyl ether epoxides, glycidyl ester epoxides and glycidylamine epoxides are preferred from the viewpoints of cost and heat resistance, and more preferred are glycidyl ether epoxides and glycidyl ester epoxides. As these epoxides, these may be used alone, or two or more selected from them may be used as a mixture.

  The number of epoxy groups in the epoxide is preferably at least 2 in number average, more preferably from 2 to 500, and further preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. The number is most preferably 6 or more. The upper limit is more preferably 300 or less, particularly preferably 100 or less, still more preferably 50 or less, and most preferably 40 or less. When the number of epoxy groups is within this range, the curable resin film of the present invention tends to have better thermal shock resistance and dielectric properties.

  The weight average molecular weight (hereinafter, abbreviated as Mw) of the epoxide is preferably 300 to 10,000, more preferably 400 or more, particularly preferably 500 or more, and still more preferably 9, from the viewpoint of thermal shock resistance and the like. 000 or less, particularly preferably 5,000 or less.

Known curing agents can be used, for example, carboxylic acids, acid anhydrides, amine compounds, phenols, and the like.
As the carboxylic acid, an aromatic carboxylic acid and an alicyclic carboxylic acid are used.
Known aromatic carboxylic acids can be used, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid.
As the alicyclic carboxylic acid, known ones can be used, and cyclohexane-1,2-dicarboxylic acid (aromatic hydrogenation compound of phthalic acid) and cyclohexane-1,3-dicarboxylic acid (aromatic hydrogenation of isophthalic acid) can be used. Compounds) and the like.
Known acid anhydrides can be used, and examples thereof include phthalic anhydride, maleic anhydride, and 4-methylcyclohexane-1,2-dicarboxylic anhydride.

As the amine compound, an aromatic amine compound, an aliphatic amine compound, an alicyclic amine compound, or the like is used.
As the aromatic amine compound, known compounds can be used, and examples thereof include 1,3-phenylenediamine, 1,4-phenylenediamine, and 4,4′-diphenylmethanediamine.
As the aliphatic amine compound, known compounds can be used, and examples thereof include ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, and iminobispropylamine.
As the alicyclic amine compound, known compounds can be used, and cyclohexylene-1,3-diamine (aromatic hydrogenated compound of 1,3-phenylenediamine) and cyclohexylene-1,4-diamine (1,4 -Hydrogenated aromatic nucleus compound of phenylenediamine), bis (aminocyclohexyl) methane (hydrogenated compound of aromatic nucleus of 4,4'-diphenylmethanediamine) and the like.
Known phenols can be used, and cresol / novolak resin (Mw: 320 to 32,000), phenol novolak resin (Mw: 360 to 36,000), naphthyl cresol, tris (hydroxyphenyl) methane, and dinaphthyl Triol, tetrakis (4-hydroxyphenyl) ethane, 4,4′-oxybis (1,4-phenylethyl) tetracresol and the like can be mentioned.
Of these curing agents, phenol is preferred from the viewpoint of reliability. These curing agents may be used alone or as a mixture.

  The equivalent ratio of the epoxide to the curing agent (epoxide / curing agent) is preferably 0.7 to 1.3, more preferably 0.8 or more, and particularly preferably 0.9 from the viewpoint of the Tg and strength of the cured product. It is more preferably 1.2 or less, particularly preferably 1.1 or less.

A polyimide resin as a thermosetting resin comprises a diamine and a tetracarboxylic dianhydride.
As the diamine, the above-mentioned known ones can be used. For example, paraphenylenediamine, 2,2′-bis (4-aminophenoxyphenyl) propane, bis (2- (4-aminophenoxy) ethoxy) ethane and the like can be used. Can be used.
As the tetracarboxylic dianhydride, the above-mentioned known compounds and the like can be used. For example, pyromellitic dianhydride and benzophenonetetracarboxylic dianhydride can be used.

  The resin having another reactive group as the thermosetting resin includes a compound having a polymerizable double bond and the like, and the above-mentioned known compounds and the like can be used.For example, cyclooctadiene, dicyclopentadiene, methyl Tetrahydroindene, norbornadiene, 2-propenyl-2,5-norbornadiene, norbornene, propenoxyethyl vinyl ether, propenoxypropyl (meth) acrylate, propenoxypropyl vinyl ether, ethylene glycol diallyl ether, and the like can be used.

The epoxy resin as the photocurable resin is composed of the above-mentioned epoxide.
As the epoxide, the same epoxide or the like as described above can be used.

The other resin having a reactive group as the photocurable resin is a compound having a polymerizable double bond.
As the compound having a polymerizable double bond, a compound having a polymerizable double bond similar to the above can be used.

  These curable resins (A) may be used alone or in combination of two or more. As a combination of two or more, for example, a combination of an epoxy resin and a resin having another reactive group (for example, a combination described in JP-A-2002-80525) and a combination of an epoxy resin and a polyimide resin (for example, 2001-356519) and the like. Of these two or more combinations, it is preferable to combine the epoxy resin with another resin from the viewpoint of cost, dielectric properties, and the like.

These curable resins (A) have at least two epoxy groups in the molecule from the viewpoint of thermal shock resistance and strength of the cured film, have a glass transition temperature before curing of 50 to 150 ° C., and have a weight It is desirable that a high molecular weight epoxy resin (A1-1) having an average molecular weight (abbreviated as Mw) of 10,000 to 1,000,000 is contained as a part thereof.
From the viewpoint of the complex viscosity of the curable resin composition and the strength of the cured product, the content (% by weight) of the polymer epoxy resin (A1-1) is 2 to 70 based on the total weight of the curable resin. It is preferably 5 or more, more preferably 10 or more, further preferably 50 or less, particularly preferably 30 or less.

As the polymer epoxy resin (A1-1), known resins such as those described in JP-A-2001-279116 can be used, and a styrene / glycidyl (meth) acrylate copolymer (Mw: 2,000 to 500,000, styrene : 5 to 95% by weight), styrene / glycidyl (meth) acrylate / alkyl (meth) acrylate (Mw: 2,000 to 500,000, styrene: 5 to 95% by weight, alkyl (meth) acrylate: 1 to 40% by weight %) Copolymers and glycidyl ester-type polyepoxides such as polyglycidyl (meth) acrylate.
Among these high-molecular epoxy resins, glycidyl ester type polyepoxide is preferable from the viewpoint of cost and reliability, and styrene / glycidyl methacrylate copolymer and styrene / glycidyl methacrylate / alkyl (meth) acrylate are more preferable from the viewpoint of dielectric properties. It is a copolymer.
As the curing agent, the thermosetting catalyst, and the photocuring catalyst for the high-molecular epoxy resin, those similar to the above-mentioned epoxides are used, and the respective amounts used are the same as above.

It is desirable to add the following thermoplastic resin (Q) to these curable resins (A) from the viewpoint of thermal shock resistance and peel strength from copper plating.
That is, as the thermoplastic resin (Q), the absolute value of the difference between the solubility parameters of the polymer epoxy resins (A1-1) and (Q) is 0.5 to 3.0, and the weight average molecular weight is 5 A thermoplastic resin having a molecular weight of from 1,000 to 1,000,000 is preferred.

  The absolute value of the difference between the solubility parameters (hereinafter abbreviated as SP value) between the polymer epoxy resin (A1-1) and the thermoplastic resin (Q) is preferably 0.5 to 3.0, and more preferably. 0.6-2.5, even more preferably 0.7-2.0, particularly preferably 0.8-1.8, even more preferably 0.9-1.5, most preferably 1.0- 1.2. When the solubility parameter is in this range, an insulator excellent in thermal shock resistance can be easily obtained, and the peel strength with copper plating is improved.

The SP value is represented by the following equation.
SP value (δ) = (ΔH / V) ^1/2
Here, in the formula, ΔH represents a molar heat of evaporation (cal), and V represents a molar volume (cm ³ ). ΔH and V are “POLYMER ENGINEERING AND
FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 151 to 153) ", the sum (V) of the molar heat of vaporization (△ ei) of the atomic group (ΔH) and the molar volume (△ vi) can be used.

  The weight average molecular weight of (Q) is preferably 5,000 to 1,000,000, more preferably 5,000 to 800, from the viewpoint of the complex viscosity of the curable resin composition and the elastic modulus of the cured product. 000, even more preferably 10,000 to 600,000, particularly preferably 50,000 to 400,000, most preferably 60,000 to 100,000.

Next, the chemical structure of the thermoplastic resin (Q) will be described.
As (Q), a thermoplastic resin (Q1) having a carbon-carbon double bond and a thermoplastic resin (Q2) having a carbon-nitrogen bond can be used.
Examples of the thermoplastic resin (Q1) having a carbon-carbon double bond include ring-opening polymerization of polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, and norbornene. And the like, and can be easily obtained as the following commercial products.

Examples of commercially available products (trade names) include JSR BR series as polybutadiene, JSR IR series as polyisoprene, JSR TR series as styrene-butadiene copolymer, and JSR TR series as styrene-isoprene copolymer.
Examples of the SIS series and the ring-opening polymer of norbornene include the No Solex series (above, manufactured by JSR Corporation).

  Examples of the thermoplastic resin (Q2) having a carbon-nitrogen bond include polyamide, polyurethane, polyurea, polyimide, polyamino acid, and a reaction product (q) between a bifunctional epoxy (p) and a monofunctional primary amine (r). Is used.

As the polyamide, a polyamide obtained by reacting a diamine having 2 to 18 carbon atoms with a dicarboxylic acid having 6 to 20 carbon atoms or more is used.
Examples of the diamine include diamine (l) having a primary amino group and diamine (m) having a secondary amino group.

  As the diamine (l) having a primary amino group, an aliphatic diamine (2 to 18 carbon atoms) (11), an alicyclic polyamine (4 to 15 carbon atoms) (12) and the like can be used.

As the aliphatic diamine (11), an alkylenediamine having 2 to 6 carbon atoms, an aromatic diamine containing an aromatic ring (8 to 15 carbon atoms), or the like is used.
Examples of the alkylenediamine include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, and hexamethylenediamine.
Examples of the aromatic ring-containing aliphatic diamine include xylylenediamine and tetrachloro-p-xylylenediamine.

  Examples of the alicyclic diamine (12) include 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, and 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline).

  As the diamine (m) having a secondary amino group, those obtained by substituting the primary amino group (-NH2 group) in (1) with -NH-R (R is an alkyl group having 1 to 4 carbon atoms) are used. Examples thereof include di (methylamino) ethylene, di (ethylamino) hexane, and 1,3-di (methylamino) cyclohexane.

Examples of the dicarboxylic acid include divalent aromatic polycarboxylic acids (C6 to C20 or more) (n1) and divalent aliphatic or alicyclic dicarboxylic acids (C6 to C20 or more) (N2) and the like can be used.
Examples of the aromatic dicarboxylic acid (n1) include phthalic acid, isophthalic acid, and terephthalic acid.
Examples of the aliphatic or alicyclic dicarboxylic acid (n2) include hydrogenated aromatic nuclei of the above aromatic dicarboxylic acid (n1), dimer acid, oxalic acid, maleic acid, succinic acid, adipic acid, dodecenyl succinic acid, and the like. Is mentioned.

  In the reaction for obtaining the polyamide, an amine compound other than the diamine, a carboxyl group-containing compound other than the dicarboxylic acid, and the like can be used in addition to the diamine and the dicarboxylic acid for the purpose of adjusting the molecular weight and the like.

  Examples of the polyurethane as the thermoplastic resin (Q2) having a carbon-nitrogen bond include those obtained from the reaction of a dihydric phenol or dihydric alcohol having 2 to 100 or more carbon atoms with a diisocyanate having 6 to 20 carbon atoms. Used.

Examples of the dihydric phenol include bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S, halogenated bisphenol A (eg, tetrachlorobisphenol A, etc.), catechin, resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, Dihydroxybiphenyl, octachloro-4,4′-dihydroxybiphenyl, tetramethylbiphenyl, 9,9′-bis (4-hydroxyphenyl) fluorene and the like.
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, polyethylene glycol (Mw 150 to 4,000), polypropylene glycol (Mw 180 to 5,000), and polytetramethylene glycol ( Mw 200 to 5,000), neopentyl glycol, and EO and / or PO (1 to 20 mol) adduct of bisphenol A.

  As the diisocyanate, an aromatic diisocyanate (o1) having 6 to 20 carbon atoms (excluding the carbon in the NCO group; the same applies hereinafter), an aliphatic diisocyanate (o2) having 2 to 18 carbon atoms, and a 4 to 15 carbon atoms Alicyclic diisocyanate (o3) and araliphatic diisocyanate (o4) having 8 to 15 carbon atoms can be used.

  Examples of the aromatic diisocyanate (o1) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 2,4′- or 4,4′- Diphenylmethane diisocyanate (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, Examples thereof include 1,5-naphthylene diisocyanate.

  Examples of the aliphatic diisocyanate (o2) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and bis (2-isocyanatoethyl). ) Fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate;

  Examples of the alicyclic diisocyanate (o3) include, for example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic polyisocyanate (o4) include m- or p-xylylene diisocyanate (XDI).

  In the reaction for obtaining a polyurethane, an isocyanate compound other than diisocyanate can be used for the purpose of adjusting the molecular weight and the like.

As the polyurea as the thermoplastic resin (Q2) having a carbon-nitrogen bond, those obtained from the reaction of a diamine having 2 to 18 carbon atoms and a diisocyanate having 6 to 20 carbon atoms are used.
Examples of the diamine include the diamines described above.
Examples of the diisocyanate include the aforementioned diisocyanates.

  In the reaction for obtaining polyurea, an amine compound other than diamine or an isocyanate group-containing compound other than diisocyanate can be used for the purpose of adjusting the molecular weight and the like.

As the polyimide as the thermoplastic resin (Q2) having a carbon-nitrogen bond, a polyimide obtained by reacting a diamine having 2 to 18 carbon atoms with a dicarboxylic acid having 6 to 20 or more carbon atoms is used.
Examples of the diamine include the diamines described above.
Examples of the dicarboxylic acid include the dicarboxylic acids described above.
In the reaction for obtaining the polyimide, an amine compound other than diamine or a carboxyl group-containing compound other than dicarboxylic acid can be used for the purpose of adjusting the molecular weight and the like.

Examples of the polyamino acid as the thermoplastic resin (Q2) having a carbon-nitrogen bond include a condensate of an aminocarboxylic acid having 2 to 12 carbon atoms and a ring-opening polymer of a lactam having 6 to 12 carbon atoms.
Examples of the aminocarboxylic acid include, for example, amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocaprin Acids, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Examples of the lactam include caprolactam, enantholactam, laurolactam, and undecanolactam.
In the reaction for obtaining a polyamino acid, the above-mentioned diamine compound, another amino compound, the above-mentioned dicarboxylic acid, another carboxyl group-containing compound, or the like can be used for the purpose of adjusting the molecular weight or the like.

Examples of the thermoplastic resin (Q2) having a carbon-nitrogen bond include a reaction product (q) of a bifunctional epoxy (p) and a monofunctional primary amine (r).
Examples of the bifunctional epoxy (p) include diglycidyl ether (p1) of dihydric phenol (C6 to C30); dihydric alcohol [alkylene glycol having 2 or more carbon atoms or dihydric phenol having 6 or more carbon atoms] Diglycidyl ether (p2); divalent glycidyl ester (p3); divalent glycidylamine (p4); divalent alicyclic epoxide ( p5) and the like.
In the following description, alkylene oxides having 2 to 4 carbon atoms are abbreviated as AO; ethylene oxide as EO; and propylene oxide as PO.

  Examples of the diglycidyl ether (p1) of dihydric phenol (C6 to C30) include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, and bisphenol S diglycidyl. Ether, halogenated bisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, dihydroxybiphenyldiglycidyl ether, octachloro -4,4'-dihydroxybiphenyldiglycidyl ether, tetramethylbiphenyldiglyci Ether, 9,9'-bis (4-hydroxyphenyl) furo diglycidyl ether and diglycidyl ether obtained from bisphenol A2 moles and 3 moles of epichlorohydrin in the reaction, and the like.

  Examples of the diglycidyl ether (p2) of a dihydric alcohol [alkylene glycol having 2 or more carbon atoms or an AO of 1 to 90 mol adduct of dihydric phenol having 6 or more carbon atoms] include ethylene glycol diglycidyl ether and propylene glycol diglycidyl. Ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol (Mw 150 to 4,000) diglycidyl ether, polypropylene glycol (Mw 180 to 5,000) diglycidyl ether, polytetramethylene glycol ( Mw 200-5,000) Diglycidyl ether, neopentyl glycol diglycidyl ether, and a jig of EO and / or PO (total 1-20 mol) adduct of bisphenol A Glycidyl ether and the like.

As the divalent glycidyl ester (p3), for example, the following (p31) to (p32) can be used.
(P31) Diglycidyl esters of divalent aromatic polycarboxylic acids (C6 to C20 or more) such as diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate.
(P32) Diglycidyl esters of divalent aliphatic or alicyclic carboxylic acids (C6 to C20 or more).
(P31) Aromatic nucleus water additive, diglycidyl dimer acid ester, diglycidyl oxalate, diglycidyl malate, diglycidyl succinate, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimerate and the like.

As the divalent glycidylamine (p4), for example, the following (p41) to (p43) can be used.
(P41) Examples of the diglycidyl aromatic amine having two glycidyl groups (aromatic amine having 6 to 20 or more carbon atoms) include N, N-diglycidylaniline and N, N-diglycidyltoluidine.

(P42) Examples of the polyglycidyl alicyclic amine having two glycidyl groups (alicyclic amine having 6 to 20 or more carbon atoms) include N, N, N ′, N′-tetraglycidylxylylenediamine. Hydrogenated compounds and the like.
(P43) Examples of the diglycidyl heterocyclic amine having two glycidyl groups (heterocyclic amine having 6 to 20 carbon atoms or more) include N-glycidyl-4-glycidyloxypyrrolidone.

As the divalent alicyclic epoxide (p5), for example, an alicyclic epoxide having 6 to 50 or more carbon atoms, Mw of 98 to 5,000, and 2 epoxy groups can be used, and for example, vinylcyclohexene Dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, and the like.
Of these (p), (p2) is preferable from the viewpoint of reducing the elastic modulus of the reactant (q), and (p1) and (p2) from the viewpoint of adjusting the glass transition temperature of the reactant (q). Particularly preferred is the combination of

As a reactant (q) as a thermoplastic resin (Q2) having a carbon-nitrogen bond, as a monofunctional primary amine (r) as a reaction partner of a bifunctional epoxy (p), for example, one having 1 to 18 carbon atoms Examples thereof include an aliphatic amine (r1) and an aromatic amine (r2) having 6 to 18 carbon atoms.
Examples of the aliphatic amine (r1) include methylamine, dimethylamine, methylbutylamine, undecylamine, decalylamine, and octadecylamine.
Examples of the aromatic amine (r2) include aniline, p-methylaniline, p-undecylaniline, m-methoxyaniline, and naphthylamine.
(R) is preferably (r1) from the viewpoint of lowering the elastic modulus of the reactant (q).
As a reaction product (q) of the bifunctional epoxy and the monofunctional primary amine, one or more of (p1) and (p2) is used as the bifunctional epoxy (p), and (r1) is used as the monofunctional primary amine. Are preferred.
In the reaction between the bifunctional epoxy and the monofunctional primary amine, an epoxy group-containing compound other than those described above, an amine compound, and the like can be used for the purpose of adjusting the molecular weight and the like.

  Among these thermoplastic resins (Q), from the viewpoint of the dielectric constant, the thermoplastic resin (Q1) having a carbon-carbon double bond and the reaction product (q) of a bifunctional epoxy and a monofunctional primary amine are: preferable. More preferred are polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, norbornene ring-opening polymer, and reaction product of bifunctional epoxy and monofunctional primary amine.

The content of the carbon-carbon double bond or carbon-nitrogen bond in (Q) is from 5 × 10 ^{−5 to} 3.5 × 10 ⁻² mol / g per 1 g of (Q) from the viewpoint of adhesion and the like. g is preferable, and 1.0 × 10 ^{−4 to} 3.5 × 10 ⁻² mol / g is more preferable in the case of a carbon-carbon double bond, and 1 × 10 ^{−4 to} 3.5 × in the case of a carbon-nitrogen bond. 10 ^-2 mol / g is more preferred. In particular, from the viewpoint of the dielectric constant, it is preferably 1.0 × 10 ^{−3 to} 2.5 × 10 ⁻² mol / g in the case of a carbon-carbon double bond, and 5 × 10 ⁻⁴ to 2.times.2 in the case of a carbon-nitrogen bond. 5 × 10 ^-2 mol / g is preferred.

When the content of the carbon-carbon double bond or carbon-nitrogen bond is in this range, the thermoplastic resin on the surface of the insulating layer is easily eluted by the oxidizing agent, and fine irregularities are formed, and the adhesiveness to electroless plating is improved. Becomes better.
The carbon-carbon double bond or carbon-nitrogen bond may be present in either the main chain skeleton or the side chain skeleton of the resin as long as it is present in (Q), but is present in the main chain skeleton of the resin. Is preferred.

  The weight ratio of (A1-1) to (Q) is preferably from 40/60 to 98/2 as a weight ratio in terms of pure content excluding the solvent, and more preferably from 50/50 to from the viewpoint of resin strength. 96/4, from the viewpoint of heat resistance, particularly preferably 55/45 to 90/10, most preferably 60/40 to 85/15.

  When the curable resin contains (Q), it is preferable that (Q) is uniformly dispersed in (A1-1).

When (Q) is dispersed in (A1-1), the dispersion average particle size of (Q) is not particularly limited, but is preferably 0.001 to 50 μm, and further from the viewpoint of resin strength, It is preferably from 0.005 to 20 μm, particularly preferably from 0.01 to 10 μm, and particularly preferably from 0.05 to 5 μm, most preferably from 0.1 to 2 μm from the viewpoint of adhesion to a conductor.
The dispersion average particle diameter is obtained by subjecting the curable resin composition to a curing treatment at 180 ° C. for 3 hours, observing the cross section with a scanning electron microscope, and calculating the arithmetic average of the particle diameters of at least 10 (Q) particles. Desired.

Known curing accelerators can be used as the curing accelerator (C). In the case of a thermosetting resin type epoxy resin, an imidazole catalyst, a tertiary amine, or the like can be used. When the thermosetting resin is a resin having a reactive group other than an epoxy group, a thermal radical generator can be used.
In the case of a photocurable resin type epoxy resin, a cationic polymerization catalyst or the like can be used. When the photocurable resin is a resin having a reactive group other than an epoxy group, a photoradical generator or the like can be used.

As the imidazole catalyst, known catalysts can be used. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2 -Methylimidazole and 1-cyanoethyl-2-methylimidazole.
As the tertiary amine, known ones can be used, and examples thereof include benzylmethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, triethylamine and DBU.
As the thermal radical generator, known compounds (such as those described in JP-A-08-134178) can be used, and for example, peroxides, azo compounds, disulfide compounds, and the like can be used.
As the cationic polymerization catalyst, known catalysts (for example, those described in JP-A-08-134178) can be used. For example, aromatic pyridinium salts, aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, benzylsulfonium salts , Cinnamylsulfonium salts, aromatic selenium salts and the like, and as counter ions thereof, anions such as PF ₆ ⁻ , AsF ₆ ⁻ and BF ₄ ⁻ are used.
As the photo-radical generator, known compounds (described in JP-A-08-134178) and the like can be used, and for example, peroxides, azo compounds, disulfide compounds and the like can be used.

  The addition amount (% by weight) of these curing accelerators is preferably 0.1 to 10, more preferably 0.3 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. And still more preferably 7 or less, particularly preferably 5 or less.

  The content (% by weight) of the curable resin (A) is preferably from 15 to 97, more preferably from 30 to 92, based on the weight of the curable resin composition, from the viewpoint of dimensional stability and mechanical strength. And particularly preferably 40 to 87. That is, the content (% by weight) of the curable resin is preferably 15 or more, more preferably 30 or more, particularly preferably 40 or more, and preferably 97 or less, based on the weight of the curable resin composition. It is more preferably at most 92, particularly preferably at most 87.

  Additives can be added to the curable resin composition of the present invention as needed. Additives added as needed include, for example, flame retardants, thickeners, defoamers, leveling agents, and the like. As the flame retardant, known flame retardants such as phosphorus-based flame retardants and halogen-based flame retardants (the above-mentioned patent publications) can be used. When a flame retardant is used, the addition amount (% by weight) of the flame retardant is preferably from 0.5 to 30 based on the total weight of the curable resin composition, and more preferably from the viewpoint of exhibiting flame retardancy. 1 to 15, particularly preferably 2 to 10. That is, in this case, the addition amount (% by weight) of the flame retardant is preferably 0.5 or more, more preferably 1 or more, particularly preferably 2 or more, based on the total weight of the curable resin composition. It is preferably 30 or less, more preferably 15 or less, and particularly preferably 10 or less.

  As the thickener, known thickeners such as asbestos and benton (the above patent publications and the like) can be used. When a thickener is used, the amount (% by weight) of the thickener is preferably 0.01 to 5, more preferably 0.1 to 4, and particularly preferably 0.1 to 4, based on the total weight of the curable resin composition. Preferably it is 0.5-3. That is, in this case, the addition amount (% by weight) of the thickener is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. The number is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less.

  As the antifoaming agent, known antifoaming agents such as silicone-based antifoaming agents, polyether-based antifoaming agents, alcohol-based antifoaming agents, and oil-based antifoaming agents can be used. When an antifoaming agent is used, the amount (% by weight) of the antifoaming agent is preferably from 0.01 to 5, more preferably from 0.1 to 4, based on the total weight of the curable resin composition. Preferably it is 0.5-3. That is, in this case, the amount (% by weight) of the defoaming agent is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. The number is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less.

  As the leveling agent, known leveling agents such as a silicone leveling agent, a polyether-based leveling agent, and an alcohol-based leveling agent (the above-mentioned patent publications) can be used. When a leveling agent is used, the amount (% by weight) of the leveling agent is preferably from 0.01 to 10, more preferably from 0.1 to 7, and particularly preferably based on the total weight of the curable resin composition. 0.5 to 5. That is, in this case, the amount (% by weight) of the leveling agent is preferably 0.01 or more, more preferably 0.1 or more, and particularly preferably 0.5 or more, based on the total weight of the curable resin composition. And preferably 10 or less, more preferably 7 or less, particularly preferably 5 or less.

The curable resin composition can be obtained by uniformly mixing a filler, a curable resin, and additives to be added as necessary with a known mixing device or the like.
The temperature (° C.) for uniform mixing is usually 0 to 150, preferably 10 to 130, more preferably 20 to 110, and particularly preferably 30 to 100. That is, the temperature (° C.) is usually 0 or higher, preferably 10 or higher, more preferably 20 or higher, particularly preferably 30 or higher, and usually 150 or lower, preferably 130 or lower, and further preferably It is 110 or less, particularly preferably 100 or less. As the mixing device, any device can be used as long as it can mix the filler with the liquid material. For example, a planetary mixer, a bead mill, a three-roller, a two-roller and the like can be used. The stirring and mixing time is, for example, a time until most of the aggregates contained in the filler are eliminated (for example, determined while measuring the particle size distribution) and the like, and is appropriately determined. If necessary, the curable resin composition may remove coarse particles and the like by filtration.

The curable resin composition of the present invention may be used as it is, or may be used after being processed into a curable resin film. The curable resin film is obtained by dissolving and / or dispersing the curable resin composition in a solvent to form a resin solution (resin dispersion solution), and applying the resin solution on a support film by a known film manufacturing apparatus such as a roll coater. Can be manufactured.
The solvent used in the production of the curable resin film is not particularly limited as long as it can dissolve and / or disperse the curable resin composition and can adjust the resin solution to the physical properties (viscosity, etc.) applicable to the film production apparatus. For example, known solvents such as N-methylpyrrolidone, N, N-dimethylformamide, dimethylsulfoxide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, acetone and xylene can be used. Among these solvents, those having a boiling point of 200 ° C. or less (toluene, ethanol, cyclohexane, methanol, methyl ethyl ketone, ethyl acetate, acetone, and xylene) are preferable from the viewpoint of the drying temperature of the film.

  The support film used in processing the curable resin film is a support used for the purpose of facilitating the handling of the curable resin film, and may have a certain strength, and a known support film or the like can be used. For example, a polyethylene terephthalate (PET) film, a polypropylene film, a polyethylene film, and the like can be used.

  The thickness (μm) of the curable resin film is preferably from 1 to 100, more preferably from 5 to 80, and particularly preferably from 10 to 60. That is, the thickness (μm) of the curable resin film of the present invention is preferably 1 or more, more preferably 5 or more, particularly preferably 10 or more, and preferably 100 or less, more preferably 80 or less, and particularly preferably. Is 60 or less.

  The amount of residual solvent (% by weight) after drying of the curable resin film is determined from the viewpoint of the penetration of the curable resin film into the through-hole and the handling (breaking of the film) of the curable resin film (before curing). Is preferably from 0.1 to 5.0, more preferably from 0.2 to 4.0, and particularly preferably from 0.3 to 3.0, based on the weight of. That is, the amount (% by weight) of the residual solvent after curing (drying) of the curable resin film of the present invention is preferably 0.1 or more, more preferably 0, based on the weight of the curable resin film (before curing). 0.2 or more, particularly preferably 0.3 or more, and preferably 5.0 or less, more preferably 4.0 or less, particularly preferably 3.0 or less.

The cured product of the present invention can be easily produced by thermally curing the above curable resin film.
The conditions for the heat curing are as follows: 80 to 250 ° C (preferably 120 to 200 ° C, more preferably 150 to 200 ° C) for 0.1 to 15 hours (preferably 0.2 to 5 hours, more preferably 0.1 to 5 hours). 5 to 3 hours).

The boiling water absorption of the cured product of the present invention is 3.00 to 0.001%, preferably 2.50 to 0.005%, more preferably 2.00 to 0.01%, and particularly preferably 1. 0 to 0.05%.
The boiling water absorption is measured in accordance with JIS K7209 (2000) 6.3B method.
The volume resistivity of the cured product of the present invention is 10 ¹⁰ to 10 ¹⁹ Ω / cm, preferably 10 ^{12 to} 5 × 10 ¹⁸ Ω / cm, more preferably 10 ¹⁴ to 10 ¹⁸ Ω / cm, and particularly preferably 10 10 to 10 ¹⁸ Ω / cm. ^{It is 16 to} 5 × 10 ¹⁷ Ω / cm, and is excellent in electrical insulation as compared with conventionally used insulating materials such as epoxy resin and polyimide resin.
The volume resistance is measured according to JIS K6011 (1995).

The heat resistance of the cured product of the present invention is the same as that of a conventional insulator, and even if it is brought into contact with a solder at 300 ° C. for 1 minute, no abnormality such as sagging of the pattern, breakage and blistering is observed, and it is resistant to various solvents. The chemical resistance is also very good.
The cured product of the present invention is also excellent in 10% sulfuric acid resistance, 10% hydrochloric acid resistance, 10% nitric acid resistance and 10% sodium hydroxide resistance as measured by the method specified in JIS K6911 (1995) 5.32. .

As a method of using the curable resin composition of the present invention as an insulator, for example, (1) when using the curable resin composition solution or the curable resin composition dispersion of the present invention on a base material when used as an interlayer insulating material, After coating, drying and heat-curing, if necessary, processing such as roughening and formation of a conductive circuit is performed, and this operation is repeated. 2) After laminating a resin film of the curable resin composition of the present invention on a substrate, hot press and pressure bonding. Thereafter, only the support film is peeled off and cured by heating. After heat-curing, if necessary, roughening, conductive circuit formation, etc. are performed, and further, a substrate is laminated, this operation is repeated, and further, if necessary, heat-curing to form a multilayer, etc. .
When the curable resin composition is used as a part of a substrate material of a multilayer substrate, (3) a curable resin solution or a curable resin dispersion is applied to a substrate, dried, and then, if necessary, a hole is formed. A process such as opening is performed, and this operation is repeated. Finally, a method of forming a multilayer by heating and curing is used, or (4) a curable film is bonded to a substrate, and then hot pressed and pressed. Thereafter, only the support film is peeled off and removed. A method of forming a multilayer by performing processing such as drilling as necessary, repeating this operation, and finally heat-curing.
In addition, it can also be used as a printed wiring board as it is, without using a base material.

  When used as an interlayer insulating material such as a multilayer circuit board of an electronic circuit, one interlayer insulating layer may be composed of a single layer or multiple layers, and its thickness (after curing) is preferably 1 to 100 μm, more preferably 15 to 100 μm. 50 μm.

The conditions of the hot press include a temperature of 25 to 180 ° C. (preferably 50 to 150 ° C.), a pressure of 0.01 MPa to 10 MPa (preferably 0.1 to 1 MPa), and a time of 1 to 1200 seconds (preferably 10 to 300 seconds). Are preferred.
Holes (via holes, through holes, etc.) for conducting between the layers of the multilayer substrate can be formed by a usual method, and for example, a method using a laser (carbon dioxide, YAG, excimer, etc.), a drill or the like can be used.
Roughening can be performed by a usual method, for example, a method described in JP-B-6-49852 can be used.

[Example]
Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, parts mean parts by weight and% means% by weight.

Production Example 1
100 parts of commercially available spherical silicon oxide powder (manufactured by Admatech Co., Ltd., average particle size 0.4 μm “Admafine SO-C2”) was added to a silane coupling agent (available from Shin-Etsu Chemical Co., Ltd., α-glycidoxypropyltrimethoxysilane “ KBM-403 ") A mixture of 2 parts of water and 10 parts of water is sprayed, followed by heat treatment in a circulating drier at 260 ° C. for 2 hours to obtain a surface-treated silicon oxide of the present invention. A powder (B1) was obtained.
An infrared spectrum was measured by a diffuse reflection method, and it was determined that the silicon oxide surface had been surface-treated with the silane coupling agent since the peak specific to the silanol group observed around 3750 cm ^-1 disappeared.

Production Example 2
Five parts of methyl ethyl ketone (hereinafter abbreviated as MEK) were charged into a reaction vessel purged with nitrogen, heated to 80 ° C., and 20 parts of glycidyl methacrylate and styrene 20 uniformly dissolved in another vessel purged with nitrogen. , A mixture of 5 parts of 2-hydroxyethyl acrylate, 20 parts of MEK, and 1.5 parts of azobisisobutyronitrile was dropped into the reaction vessel over 4 hours. After completion of the dropwise addition, the mixture was aged at 100 ° C. for 5 hours to obtain a styrene (hereinafter abbreviated as St) / glycidyl methacrylate (hereinafter abbreviated as GMA) / 2-ethylhexyl acrylate (hereinafter abbreviated as 2EHA) copolymer (X1). The Mw of this copolymer (X1) was 30,000, the epoxy equivalent was 320 (JIS), and the glass transition temperature was 58 ° C.
This copolymer (X1) was diluted with MEK to a solid content of 50% to obtain a polymer epoxy resin solution (X11) of the present invention.

Production Example 3
Production Example 1 is the same as Production Example 2 except that in addition to monomers such as glycidyl methacrylate, 30 parts of a styrene-butadiene copolymer (JSR-TR2250 manufactured by JSR Corporation; hereinafter abbreviated as SBS resin) is further blended and polymerized. Thus, St / GMA / 2EHA copolymer (X2) in which SBS resin was dispersed was obtained. The Mw of the copolymer (X2) was 155,000, and the epoxy equivalent was 527.
This copolymer (X2) was diluted with MEK to a solid content of 50% to obtain a mixture solution (X21) of the polymer epoxy resin and the thermoplastic resin of the present invention.
The SBS resin, which is a thermoplastic resin used here, has an Mw of 115,000 and a calculated SP value of 9.3. The calculated SP value of the GMA / St / 2EHA copolymer having this ratio is 10.7.

Production Example 4
Silane coupling was carried out in the same manner as in Production Example 1, except that a commercially available titanium oxide powder ("JR" manufactured by Teica, average particle diameter: 0.3 µm) was used instead of the commercially available spherical silicon oxide powder of Production Example 1. A titanium oxide powder (B2) surface-treated with the agent was prepared.

Production Example 5
In the same manner as in Production Example 1, except that a commercially available silicon oxide powder ("Admafine SO-C5" manufactured by Admatech, volume average particle size 1.4 μm) was used instead of the commercially available spherical silicon oxide powder of Production Example 1. Thus, silicon oxide (B3) surface-treated with a silane coupling agent was prepared.
Example 1
12 parts of a glycidyl ether type epoxy resin (Epicoat 154, manufactured by Japan Epoxy Resin Co., Ltd.), 6.6 parts of a polymer epoxy resin solution (X11) prepared in Production Example 2, and surface-treated silicon oxide (B1) prepared in Production Example 1 46 parts, phenolic hardener (phenol novolak resin, PSM-4326 manufactured by Gunei Chemical Industry Co., Ltd.), 8 parts, flame retardant (brominated epoxy resin, YDB-500 manufactured by Toto Kasei Co., Ltd.) and epoxy ring-opening catalyst (SAN APRO Was added to 19 parts of MEK to obtain a curable resin composition (Y1) of the present invention.

  This composition (Y1) was applied to a 50 μm-thick PET film (600 mm × 600 mm) with a roll coater so that the resin thickness after drying was 50 μm, and then dried at 90 ° C. for 7 minutes, followed by curing. A resin film (Z1) was obtained.

This curable resin film (Z1) was vacuum-pressed on both sides to a copper-clad BT resin substrate.
The used BT resin substrate (30 mm square) is CCL-HL830 (trade name, manufactured by Mitsubishi Gas Chemical Industry Co., Ltd.), and the copper surface on both sides is roughened by 2 μm (mech etch bond CZ-8100 manufactured by MEC Corporation). Processing).
The vacuum compression bonding was performed at 80 ° C., a pressure of 0.8 kgf / cm ² , and a degree of vacuum of ² mmHg or less using a pressure-type vacuum laminator (V130 manufactured by Nichigo Morton Co., Ltd.).
After the substrate on which the film was pressed was allowed to cool to 30 ° C., the support film (PET) was peeled off. This substrate was cured at 170 ° C. for 30 minutes to obtain a cured resin substrate (Z11).
With respect to this substrate (Z11), the surface roughness after roughening and the peel strength (adhesion) were measured by the methods described later. The results are shown in Table 1.

Example 2
Instead of “6.6 parts of the polymer epoxy resin solution (X11) prepared in Production Example 2” described in Example 1, a mixture solution (X21) 11 of a polymer epoxy resin and a thermoplastic resin prepared in Production Example 3 was used. A curable resin film (Z2) was obtained in the same manner as in Example 1 except that the parts were used.
Then, using this curable resin film (Z2), a substrate (Z21) was obtained in the same manner as in Example 1.

Example 3
Example 2 was repeated except that 46 parts of the surface-treated titanium oxide (B2) prepared in Production Example 4 was used instead of “46 parts of the surface-treated silicon oxide (B1) prepared in Production Example 1”. In the same manner as in 2, a curable resin film (Z3) was obtained. A substrate (Z31) was obtained in the same manner as in Example 1 using this curable resin film (Z3).

Example 4
In Example 1 described above, 46 parts of the surface-treated silicon oxide (B3) prepared in Production Example 5 was used instead of “46 parts of the surface-treated silicon oxide (B1) prepared in Production Example 1”. In the same manner as in 2, a curable resin film (Z4) was obtained. A substrate (Z41) was obtained in the same manner as in Example 1 using this curable resin film (Z4).

Example 5
Example 2 was repeated except that 46 parts of the surface-treated silicon oxide (B3) prepared in Production Example 5 was used instead of “46 parts of the surface-treated silicon oxide (B1) prepared in Production Example 1”. In the same manner as in 2, a curable resin film (Z5) was obtained. A substrate (Z51) was obtained in the same manner as in Example 1 using this curable resin film (Z5).

Comparative Example 1
A comparison was made in the same manner as in Example 1 except that 46 parts of the surface-treated silicon oxide (B1) described in Example 1 was replaced with untreated silicon oxide powder ("Admafine SO-C2" manufactured by Admatech Co., Ltd.). Of a curable resin film (Z6) and a substrate (Z61).

Comparative Example 2
In the same manner as in Example 3 except that untreated titanium oxide powder ("JR" manufactured by Teica Corporation) was used instead of "46 parts of the surface-treated titanium oxide (B2) prepared in Production Example 4" in Example 3. Thus, a comparative curable resin film (Z7) and a substrate (Z71) were obtained.

<Surface roughness after roughening>
The substrate prepared above was immersed in a swelling aqueous solution at 80 ° C. (sodium hydroxide: 3 g / L, diethylene glycol monobutyl ether: 250 g / L) for 5 minutes, washed with water, and then roughened at 80 ° C. (permanganic acid: 60 g). / L, sodium hydroxide: 40 g / L) for 15 minutes to perform a roughening treatment. Then, after immersing in a 40 degreeC neutralization aqueous solution (hydroxylamine sulfate 16g / L, sulfuric acid: 48g / L) for 5 minutes, it wash | cleaned with water. Further, the substrate was immersed in an alkaline cleaner solution (sodium hydroxide: 5 g / L) at 60 ° C. for 5 minutes, washed with water, and dried at 25 ° C. for 12 hours. The substrate was subjected to laser microscope (KEYENCE: VF-7500). The surface roughness (arithmetic mean roughness Ra) was measured at a measurement magnification of 1250 times in accordance with JIS-B0601.

<Peel strength>
After roughening by the above method, the substrate is immersed in a palladium catalyst (manufactured by ATOTEC, trade name: Neoganth 834), activated, and then placed in an electroless plating solution (copper sulfate 12 g / L, formaldehyde 7.5 g / L). At 32 ° C. for 20 minutes to form an electroless plating layer having a plating film thickness of 2 μm. Thereafter, electrolytic plating with a thickness of 50 μm was further performed in a copper sulfate electrolytic plating bath. With respect to the substrate thus prepared, the adhesion between the substrate and the copper plating film was measured by the peel strength measuring method described in JIS C6481.

In the results shown in Table 1, the cured products of the examples all had a sufficiently large surface roughness of 0.5 μm or more, whereas the cured products of the comparative examples were insufficiently 0.2 μm. In addition, the peel strength of each of the cured products of the examples is 0.5 kgf / cm or more, which is sufficiently high, whereas the comparative examples are all insufficient at about 0.24 kgf / cm.
From these comparisons, it is clear that the cured product of the present invention has both excellent surface roughness and peel strength.

When the curable resin composition of the present invention is used, in the roughening step, the surface roughness becomes larger than before, and the peel strength becomes larger. A small coefficient of linear expansion and a large peel strength can be achieved at the same time, and it is suitable as a through-hole filling agent and interlayer insulating material in a build-up substrate manufacturing process.
Furthermore, the curable resin film of the present invention having a filler content of 33 to 85% is suitable as an interlayer insulating material also serving as a hole-filling agent for through holes in a build-up substrate manufacturing process. When applied to this application, since the smoothness around the through-hole opening is extremely high, even if the through-hole is filled and the interlayer insulating layer is formed at the same time, the reduction in the yield of the conductor circuit formation in the next step is extremely small. Further, the substrate using the curable resin film of the present invention and simultaneously forming the through-hole filling and the interlayer insulating layer is suitable for use as a printed wiring board by a build-up method. And the printed wiring board by such a build-up method is used for electric products such as a personal computer, a camera-integrated VTR, a digital video camera, a mobile phone, a car navigation system, and a digital camera.

Claims (10)

  A curable resin composition comprising a curable resin (A), an inorganic filler (B), and a curing accelerator (C), wherein the inorganic filler (B) is surface-treated with a silane coupling agent. Resin composition.   The curable resin composition according to claim 1, wherein (A) is an epoxy resin (A1).   (A) a high-molecular epoxy resin having at least two epoxy groups in a molecule, a glass transition temperature before curing of 50 to 150 ° C., and a weight average molecular weight of 10,000 to 1,000,000 The curable resin composition according to claim 1, comprising (A1-1).   The curable resin composition according to claim 3, comprising (A1-1) in an amount of 2 to 70% by weight based on the weight of the curable resin.   It further contains a thermoplastic resin (Q), the absolute value of the difference between the solubility parameter of the (A1-1) and the solubility parameter of the (Q) is 0.5 to 3.0, and the weight average of the (Q) The curable resin composition according to claim 3, wherein the molecular weight is 5,000 to 1,000,000.   The curable resin composition according to claim 5, wherein (Q) is dispersed in the curable resin composition, and the average dispersed particle size is 0.01 to 10 µm.   The curable resin composition according to any one of claims 1 to 6, wherein (B) is silicon oxide or titanium oxide having a volume average particle diameter of 0.01 to 10 µm.   The curable resin composition according to any one of claims 1 to 7, wherein the content of (B) is 3 to 85% by weight based on the weight of the curable resin composition.   A cured product obtained by curing the curable resin composition according to claim 1. An insulator comprising the cured product according to claim 9.