CN108976709B - Curable resin composition - Google Patents

Abstract

The present invention addresses the problem of providing a curable resin composition which has excellent elongation at break, has low arithmetic mean roughness and low root mean square roughness of the surface of an insulating layer in a wet roughening step, can form a plated conductor layer having sufficient peel strength, and has a low coefficient of linear thermal expansion. The present invention provides a curable resin composition containing (A) a phenoxy resin having an anthracene structure, (B) an epoxy resin, and (C) a curing agent, wherein the total amount of the phenoxy resin (A), the epoxy resin (B), and the curing agent (C) is 100% by mass, the phenoxy resin (A) is 1 to 15% by mass, and the epoxy equivalent of the phenoxy resin (A) is 5000 or more.

Description

Curable resin composition

The present application is a divisional application of chinese patent application having application number 201410134634.6, application date 4/2014, and invention name "curable resin composition".

Technical Field

The present invention relates to a curable resin composition. The present invention also relates to a curable resin composition for an insulating layer, a sheet-like laminate, a multilayer printed wiring board, and a semiconductor device, each containing the curable resin composition.

Background

In recent years, electronic devices have been reduced in size and improved in performance, and multilayer printed wiring boards have been provided with a plurality of build-up (build dup) layers, and thus miniaturization and high-density wiring are required.

Various efforts have been made to do so. For example, patent document 1 discloses the use of a polymer epoxy resin having a specific structure as a resin composition for a printed wiring board to improve heat resistance, low water absorption, electrical characteristics, moldability, flexibility, impact resistance and adhesiveness (claims, paragraph No. 0003, etc.). However, patent document 1 does not disclose any combination of a phenoxy resin having an anthracene structure, an epoxy resin, and a curing agent in a specific ratio, and use of a phenoxy resin having a specific epoxy equivalent. In addition, patent document 2 discloses an epoxy resin having an anthracene structure, but does not disclose any combination of a phenoxy resin, an epoxy resin, and a curing agent at a specific ratio, and use of a phenoxy resin having a specific epoxy equivalent.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent application laid-open No. 2003-252951

[ patent document 2] Japanese patent application laid-open No. 2005-255813.

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a curable resin composition that has a specific strength (elongation at break), has a low arithmetic mean roughness and a low root mean square roughness of the surface of an insulating layer in a wet roughening step (low roughness), can form a plated conductor layer having a sufficient peel strength, and has a low linear thermal expansion coefficient.

Means for solving the problems

The present inventors have made diligent studies to solve the above problems and, as a result, have found that: the resin composition containing (a) a phenoxy resin having an anthracene structure in a specific amount and having a specific epoxy equivalent, and containing (B) an epoxy resin and (C) a curing agent, and a heat-cured product thereof can realize the above-mentioned excellent strength, low roughness, high peel strength, and low coefficient of linear thermal expansion, thereby completing the present invention.

That is, the present invention includes the following aspects:

[1] a curable resin composition comprising (A) a phenoxy resin having an anthracene structure, (B) an epoxy resin, and (C) a curing agent, wherein the amount of the phenoxy resin (A) is 1 to 15% by mass and the epoxy equivalent of the phenoxy resin (A) is 5000 or more, when the total amount of the phenoxy resin (A), the epoxy resin (B), and the curing agent (C) is 100% by mass;

[2] the curable resin composition according to [1], wherein the phenoxy resin (A) has a weight-average molecular weight of 8000 to 100000;

[3] the curable resin composition according to [1] or [2], wherein the phenoxy resin (A) further has an unsubstituted or substituted biphenyl structure;

[4] the curable resin composition according to any one of [1] to [3], wherein the epoxy resin (B) is selected from the group consisting of a bisphenol-type epoxy resin, a crystalline 2-functional epoxy resin, a dicyclopentadiene-type epoxy resin, a naphthalene-type epoxy resin, a biphenyl-type epoxy resin, and a mixture of these epoxy resins;

[5] the curable resin composition according to any one of [1] to [4], wherein the (C) curing agent is selected from a phenol curing agent, a cyanate ester curing agent, an active ester curing agent, and a mixture of these curing agents;

[6] the curable resin composition according to [5], wherein the curing agent (C) is a cyanate ester curing agent or an active ester curing agent;

[7] the curable resin composition according to any one of [1] to [6], wherein the phenoxy resin (A) is contained in an amount of 0.3 to 10% by mass, the epoxy resin (B) is contained in an amount of 5 to 30% by mass, and the curing agent (C) is contained in an amount of 3 to 20% by mass, based on 100% by mass of nonvolatile components in the curable resin composition;

[8] the curable resin composition according to any one of [1] to [7], further comprising (D) an inorganic filler;

[9] the curable resin composition according to [8], wherein the inorganic filler (D) has an average particle diameter of 0.01 to 5 μm;

[10] the curable resin composition according to [8] or [9], wherein the content of the inorganic filler (D) is 30 to 90% by mass, based on 100% by mass of nonvolatile components in the curable resin composition;

[11] the curable resin composition according to any one of [8] to [10], wherein the inorganic filler (D) is silica;

[12] a curable resin composition for insulating layers of multilayer printed wiring boards, which comprises the curable resin composition according to any one of [1] to [11 ];

[13] a curable resin composition for multilayer printed wiring boards, which comprises the curable resin composition according to any one of [1] to [11 ];

[14] a sheet-like laminate material comprising the curable resin composition according to any one of [1] to [13 ];

[15] a multilayer printed wiring board comprising an insulating layer obtained by thermally curing the curable resin composition according to any one of [1] to [13] or the sheet-like layered material according to [14 ];

[16] a semiconductor device comprising the multilayer printed wiring board according to [15 ].

Further, the present invention preferably includes the following means,

[I] a curable resin composition comprising: (A) a phenoxy resin having a weight average molecular weight of 25000 to 40000 and having an anthracene structure and a tetramethylbiphenyl structure,

(B) An epoxy resin selected from the group consisting of bisphenol type epoxy resins, crystalline 2-functional epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins and mixtures of these epoxy resins,

(C) Containing 1 or more curing agents selected from cyanate ester curing agents and active ester curing agents, and

(D) an inorganic filler which is silica having an average particle diameter of 0.01 to 5 μm,

the curable resin composition is characterized in that,

the phenoxy resin (A) is 1 to 15% by mass based on 100% by mass of the total amount of the phenoxy resin (A), the epoxy resin (B) and the curing agent (C),

the phenoxy resin (A) has an epoxy equivalent of 9000 to 15000.

ADVANTAGEOUS EFFECTS OF INVENTION

The insulating layer of a multilayer printed wiring board produced by heat-curing the curable resin composition of the present invention has excellent strength (elongation at break), and at the same time, not only the arithmetic mean roughness but also the root mean square roughness of the surface of the insulating layer are low in the wet roughening step, and a plated conductor layer having sufficient peel strength can be formed and the coefficient of linear thermal expansion is also low.

In particular, in the present invention, the above-described low roughness and high peel strength can be achieved by using a specific phenoxy resin having an anthracene structure of the component (a). In addition, in general, an epoxy resin composition containing a large amount of an inorganic filler is poor in resin flow in a film state, and voids may be generated between laminated conductors, and further, the peel strength is liable to be lowered.

Detailed Description

[ curable resin composition ]

A curable resin composition according to one aspect of the present invention is a curable resin composition containing (A) a phenoxy resin having an anthracene structure, (B) an epoxy resin, and (C) a curing agent, wherein the sum of the phenoxy resin (A), the epoxy resin (B), and the curing agent (C) is 100% by mass, the phenoxy resin (A) is 1 to 15% by mass, and the phenoxy resin (A) has an epoxy equivalent weight of 5000 or more. The curable resin composition of the present invention will be described in detail below.

(A) Phenoxy resin with anthracene structure

As the phenoxy resin having an anthracene structure that can be used in the present invention, any phenoxy resin can be used as long as it has at least 1 or more anthracene structures, for example, the anthracene structures shown below.

An anthracene structure:

in the above formula (1), R₁May be the same or different from each other and is selected from the group consisting of a hydrogen atom, a halogen element and C_1～10N is an integer of 0 to 8. Wherein, the halogen element can be fluorine, chlorine, bromine, iodine, etc.

The (a) phenoxy resin having an anthracene structure is preferably a phenoxy resin having at least 1 or more anthracene structures and any structure other than at least 1 or more anthracene structures. Specifically, a phenoxy resin having a substituted or unsubstituted biphenyl structure and/or a bisphenol acetophenone structure is preferable. The substituted or unsubstituted biphenyl structure is shown below.

Substituted or unsubstituted biphenyl structure

In the above formula (2), R₂And R₃May be the same or different from each other and is selected from the group consisting of a hydrogen atom, a halogen element and C_1～10M is an integer of 0 to 4. Wherein, the halogen element can be fluorine, chlorine, bromine, iodine, etc.

Bisphenol acetophenone structure (refer to Japanese patent laid-open No. 2003-252951)

(in the formula (3), R₄May be the same or different from each other and is selected from a hydrogen atom, C_1～10Of the hydrocarbon group and halogen element, R₅Is selected from hydrogen atom, C_1～10Of the hydrocarbon group and halogen element, R₆Is a hydrogen atom or C_1～10M is an integer of 0 to 5. )

Preferably, in the formula (1), R₁May be the same or different from each other, is a hydrogen atom or C_1～8More preferably a hydrogen atom or C_1～6The alkyl group (b) is more preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, and n may be the same or different and is an integer of 0 to 6, more preferably 0 to 4.

Preferably, in the formula (2), R₂And R₃May be the same or different from each other, is a hydrogen atom or C_1～8More preferably a hydrogen atom or C_1～6The alkyl group of (1) is more preferably a hydrogen atom or a methyl group, particularly preferably a tetramethylbiphenyl structure, and m is an integer of 0 to 3, more preferably 1 to 2.

Preferably, in the formula (3), R₄May be the same or different from each other, is a hydrogen atom or C_1～8More preferably a hydrogen atom or C_1～6Further, the alkyl group of (A) is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, R₅Is a hydrogen atom or C_1～8More preferably a hydrogen atom or C_1～6Further, the alkyl group of (A) is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, R₆Is a hydrogen atom or C_1～8More preferably a hydrogen atom or C_1～6The alkyl group of (1) is more preferably a hydrogen atom or a methyl group, particularly preferably a methyl group, and m is an integer of 0 to 3, more preferably 1 to 2.

As an example of a method for producing a phenoxy resin having an anthracene structure, it can be produced by reacting an epoxy group of a substituted or unsubstituted biphenyl-type epoxy resin with a hydroxyl group of a dihydroxyanthracene derivative. Specifically, the ratio of the number of epoxy groups of the substituted or unsubstituted biphenyl type epoxy resin to the number of hydroxyl groups of the dihydroxyanthracene derivative is preferably 1.5: 1-0.8: 1, more preferably 1.3: 1-0.9: 1, more preferably 1.1: 1-1: 1.

the content of the phenoxy resin having an anthracene structure is 1 to 15% by mass, preferably 2 to 13% by mass, and more preferably 5 to 10% by mass, based on 100% by mass of the total amount of the phenoxy resin (A), the epoxy resin (B), and the curing agent (C). When the content of the phenoxy resin is 1% by mass or more, a low arithmetic mean roughness and a low root mean square roughness are formed, and when it is 15% by mass or less, the crosslinked site is sufficiently maintained, so that a low arithmetic mean roughness and a low root mean square roughness are still formed, and a low coefficient of linear thermal expansion can be maintained.

The phenoxy resin (A) is preferably 2 to 30% by mass, more preferably 4 to 20% by mass, based on 100% by mass of the total amount of the phenoxy resin (A) and the epoxy resin (B).

The epoxy equivalent (the mass of the resin containing 1 equivalent of epoxy group) of the phenoxy resin having an anthracene structure is, for example, preferably 5000 (g/equivalent) or more, preferably 5000 to 30000 (g/equivalent), more preferably 7000 to 20000 (g/equivalent), and further preferably 9000 to 15000 (g/equivalent). The phenoxy resin having an anthracene structure has excellent elongation at break if the epoxy equivalent is 5000 or more, and also sufficiently retains a crosslinked portion if 30000 or less, so that a low arithmetic average roughness and a low root-mean-square roughness are formed, and a low linear thermal expansion coefficient can be maintained. The epoxy equivalent can be measured according to JIS K7236 (2001).

The weight average molecular weight of the phenoxy resin having an anthracene structure is, for example, 8000 to 100000, preferably 15000 to 80000, more preferably 20000 to 60000, and further preferably 25000 to 40000. The phenoxy resin has excellent elongation at break when the weight average molecular weight is 8000 or more, and has improved compatibility with the resin composition when it is 100000 or less, and can be formed to have low arithmetic mean roughness and low root mean square roughness. The weight average molecular weight of the phenoxy resin can be measured by Gel Permeation Chromatography (GPC). Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be calculated as follows: using LC-9A/RID-6A manufactured by Shimadzu corporation as a measuring apparatus, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko K.K. K-800 as a column, chloroform or the like as a mobile phase, the measurement was carried out at a column temperature of 40 ℃ and the calculation was carried out using a standard curve of standard polystyrene.

The content of the phenoxy resin having an anthracene structure (a) is preferably 0.3 to 10% by mass, more preferably 0.5 to 7% by mass, and still more preferably 0.7 to 5% by mass, based on 100% by mass of the nonvolatile component in the curable resin composition.

(B) Epoxy resin

(B) The epoxy resin of the component (A) is different from the phenoxy resin of the component (A). The epoxy resin as the component (B) is preferably an epoxy resin having an epoxy equivalent different from that of the phenoxy resin as the component (a). (B) The epoxy equivalent (mass of the resin containing 1 equivalent of epoxy group) of the epoxy resin of component (a) is preferably 50 to 3000 (g/equivalent), more preferably 100 to 2000 (g/equivalent), still more preferably 150 to 1000 (g/equivalent), and particularly preferably 200 to 500 (g/equivalent). This makes the crosslinking density of the insulating layer obtained from the curable resin composition sufficient, and is advantageous for reducing the roughness. The epoxy equivalent can be measured according to JIS K7236 (2001).

Further, the epoxy resin is preferably an epoxy resin having 2 or more epoxy groups in 1 molecule.

Specific examples of the epoxy resin of the component (B) include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins and other bisphenol type epoxy resins, dicyclopentadiene type epoxy resins, phenol novolac type epoxy resins, t-butyl-catechol type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, naphthylene ether type epoxy resins, glycidylamine type epoxy resins, and glycidyl ester type epoxy resins, cresol formaldehyde type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing a spiro ring, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, crystalline 2-functional epoxy resin, and the like. More preferably, (B) the epoxy resin is selected from the group consisting of bisphenol type epoxy resins, crystalline 2-functional epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, and mixtures of these epoxy resins. These epoxy resins may be used in 1 kind or in combination of 2 or more kinds.

Among these epoxy resins, bisphenol a type epoxy resins, bisphenol F type epoxy resins, crystalline 2-functional epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, and mixtures of 2 or more of these epoxy resins are preferable from the viewpoint of improving heat resistance. Specifically, examples thereof include bisphenol a-type and F-type mixed epoxy resins ("ZX 1059" manufactured by shin-iron chemical corporation), bisphenol a-type epoxy resins ("エピコート 828 EL", "YL 980", "jER 1009" manufactured by shin-iron chemical corporation), bisphenol F-type epoxy resins ("jER 806H", "YL 983U" manufactured by shin-iron chemical corporation), naphthalene-type 2-functional epoxy resins ("HP 4032", "HP 4032D", "HP 4032 SS", "EXA 4032 SS" manufactured by shin-iron chemical corporation), naphthalene-type 4-functional epoxy resins ("HP 4700" and "HP 4710" manufactured by shin-iron chemical corporation), naphthalene-type epoxy resins ("ESN-475V" manufactured by shin-iron chemical corporation), epoxy resins having a butadiene structure ("PB-3600" manufactured by ダイセル chemical industry (manufactured by shin-x 3100 ") and epoxy resins having a biphenyl structure (" NC3000H "manufactured by shin-3000L" manufactured by shin-iron chemical corporation ", manufactured by japan chemical corporation, "YX 4000H", "YX 4000 HK", "YL 6121"), anthracene-type epoxy resin ("YX 8800" manufactured by Mitsubishi chemical Co., Ltd.), naphthylene ether-type epoxy resin ("EXA-7310", "EXA-7311L", "EXA 7311-G3" manufactured by DIC Co., Ltd.), glycidyl ester-type epoxy resin ("EX 711", "EX 721", manufactured by ナガセケムテックス "," R540 "manufactured by プリンテック, and dicyclopentadiene-type epoxy resin (" HP-7200H "manufactured by DIC Co., Ltd.), and the like.

The structural formula of the main component of HP4032SS is shown below.

Further, the structural formula of YX4000HK is shown below,

(wherein Gr is a glycidyl group.).

Further, the structural formula of HP-7200H is shown below,

(wherein n is an integer of 1-20.).

Further, the structural formula of NC3000L is shown below,

(wherein n is an integer of 1-20.).

The content of the epoxy resin (B) is preferably 30 to 80% by mass, more preferably 35 to 75% by mass, and still more preferably 40 to 70% by mass, based on 100% by mass of the total amount of the phenoxy resin (A), the epoxy resin (B), and the curing agent (C).

The content of the epoxy resin (B) in the curable resin composition of the present invention is not particularly limited, but is preferably 5 to 30% by mass, more preferably 7 to 25% by mass, and even more preferably 10 to 20% by mass, when the nonvolatile component in the curable resin composition is 100% by mass, from the viewpoint of achieving both low roughness and high peel strength of the insulating layer.

(C) Curing agent

The curing agent used in the present invention is not particularly limited as long as it is a curing agent capable of crosslinking and curing the phenoxy resin and the epoxy resin, and preferably contains 1 or more selected from a phenol curing agent (phenol resin), a cyanate curing agent (cyanate resin), and an active ester curing agent (active ester resin). These phenol curing agents, cyanate ester curing agents and active ester curing agents can significantly reduce the surface roughness of the insulating layer.

The phenol resin is not particularly limited, but is preferably a biphenyl-type phenol resin, a naphthalene-type phenol resin, a phenol novolac resin, a naphthylene ether-type phenol resin, or a phenol resin having a triazine skeleton. Specifically, there may be mentioned MEH-7700, MEH-7810, MEH-7851 (manufactured by Meihe Kabushiki Kaisha Co., Ltd.), NHN, CBN, GPH (manufactured by Nippon Kasei Co., Ltd.), SN-170, SN-180, SN-190, SN-475, SN-485, SN-495, SN-375, SN-395 (manufactured by Nippon iron chemical Co., Ltd.), EXB9500 (manufactured by DIC Co., Ltd.), TD 0 (manufactured by DIC Co., Ltd.) as a phenol resin of novolak type, EXB-6000 (manufactured by DIC Co., Ltd.) as a phenol resin of naphthylene ether type, LA-3018, LA-7052, LA-7054, LA-1356 (manufactured by DIC Co., Ltd.) as a phenol resin having a triazine skeleton, and the like. These phenolic resin can use 1 or more than 2.

The structural formula of SN-485 is shown in the following formula (4),

(n is an integer of 1-20.).

In addition, the structural formula of LA-7054 is shown in the following formula (5),

(n is an integer of 1-20.).

The cyanate ester resin is not particularly limited, and a novolac type cyanate ester resin, a dicyclopentadiene type cyanate ester resin, a bisphenol type cyanate ester resin, a prepolymer in which a part of them is triazinized, and the like can be cited. Specifically, there may be mentioned a novolak type polyfunctional cyanate ester resin represented by the following formula (6) (manufactured by ロンザジャパン, PT 30S: number average molecular weight 380, PT 60: number average molecular weight 560), a bisphenol A type cyanate ester resin (manufactured by ロンザジャパン, manufactured by BA230S75) which is a prepolymer in which a part or all of the bisphenol A type cyanate ester resin represented by the following formula (7) is triazinized to form a trimer, a dicyclopentadiene type cyanate ester resin (manufactured by ロンザジャパン, manufactured by DT-4000, DT-7000) represented by the following formula (8), and the like. Specifically, the number average molecular weight can be calculated as follows: using LC-9A/RID-6A manufactured by Shimadzu corporation as a measuring apparatus, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko K.K. K-800 as a column, chloroform or the like as a mobile phase, the measurement was carried out at a column temperature of 40 ℃ and the calculation was carried out using a standard curve of standard polystyrene. These cyanate ester resins may be used in combination of 1 or 2 or more;

[ in the formula, n represents an arbitrary number (preferably 0 to 20, more preferably 1 to 10) in average. ].

(in the formula, n represents the number of 0-5 in average).

The active ester resin that can be used in the present invention is a resin compound having 1 or more active ester groups in 1 molecule. Wherein "active ester group" means an ester group which reacts with an epoxy resin. The active ester resin is preferably a resin compound having 2 or more active ester groups in 1 molecule, which is reactive with the epoxy resin. Generally, a resin compound having 2 or more ester groups with high reactivity in 1 molecule selected from phenol esters, thiophenol esters, N-hydroxylamine esters and heterocyclic hydroxy compound esters can be preferably used as the active ester resin. The active ester resin can use 1 or more than 2.

From the viewpoint of improving heat resistance, an active ester resin obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound is more preferable. More preferably, the resin is an active ester resin obtained by reacting 1 or 2 or more selected from the group consisting of a phenol compound, a naphthol compound and a thiol compound with a carboxylic acid compound. Still more preferably, the aromatic resin compound has 2 or more active ester groups in 1 molecule, which is obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group. More preferably, the aromatic resin compound is an aromatic resin compound obtained by reacting a compound having at least 2 carboxylic acids in 1 molecule with an aromatic compound having a phenolic hydroxyl group, and the aromatic resin compound has 2 or more active ester groups in 1 molecule. The active ester resin may be linear or branched. Further, the compound having at least 2 or more carboxylic acids in 1 molecule can improve the compatibility with the resin composition if it is a compound having an aliphatic chain, and can improve the heat resistance if it is a compound having an aromatic ring.

Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable, from the viewpoint of heat resistance. Specific examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.

Specific examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac (phenol novolac). Among these, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac are preferable, catechol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac are more preferable, 1, 5-dihydroxynaphthalene, dienyl, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac is further preferable, and 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, phenol novolac, more preferably 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dicyclopentadienyl diphenol, phenol novolac, particularly preferably 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dicyclopentadienyl diphenol, and particularly preferably dicyclopentadienyl diphenol. Specific examples of the thiol compound include benzenedithiol and triazinedithiol.

As the active ester resin, specifically, an active ester resin containing a dicyclopentadienyl diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylate of a phenol novolac, and an active ester resin containing a benzoylate of a phenol novolac are preferable, and among them, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadienyl diphenol structure are more preferable. Commercially available active ester resins having a dicyclopentadienyl diphenol structure include EXB9451, EXB9460S, HPC-8000-65T (manufactured by DIC corporation), active ester resins having a naphthalene structure include EXB9416-70BK (manufactured by DIC corporation), active ester resins having an acetylated phenol novolac include DC808 (manufactured by mitsubishi chemical corporation), active ester resins having a benzoylate phenol novolac include YLH1026 (manufactured by mitsubishi chemical corporation).

Particularly preferred active ester resins are resin compounds containing a dicyclopentadienyl diphenol structure represented by the following general formula (9) having X-group and XO-group (wherein X is phenyl or naphthyl group which may have a substituent) at the terminal, respectively,

(wherein m is 0 or 1, and n is 0.25 to 1.5, preferably 0.4 to 1.2, in average). The weight average molecular weight of the active ester resin is preferably 1500-4000, more preferably 2000-3000.

An especially more preferred active ester resin is HPC-8000-65T, which is an active ester resin having a dicyclopentadienyl diphenol structure represented by the following formula (10), having X-group and XO-group (wherein X is naphthyl group which may have substituent) at the terminals, respectively, a weight average molecular weight of about 2700,

(wherein m is 0 or 1, and n is 0.4 to 1.2 in average).

The content of the curing agent (C) in the curable resin composition of the present invention is not particularly limited, but is preferably 3 to 20% by mass, more preferably 5 to 18% by mass, and still more preferably 7 to 15% by mass, based on 100% by mass of the nonvolatile component in the curable resin composition, from the viewpoint of achieving both low roughness and high peel strength of the insulating layer.

When the number of epoxy groups of all the epoxy resins is 1, the number of reaction groups of the curing agent is preferably 0.2 to 2, more preferably 0.3 to 1.5, and still more preferably 0.4 to 1. The term "the number of epoxy groups of all the epoxy resins" refers to the total of all the epoxy resins, which is obtained by dividing the mass of the solid content of each epoxy resin present in the curable resin composition by the epoxy equivalent weight. The "reactive group" refers to a functional group capable of reacting with an epoxy group, and the "number of reactive groups" refers to a total value obtained by dividing the mass of the solid content of the curing agent present in the resin composition by the equivalent of the reactive group.

(D) Inorganic filler

Examples of the inorganic filler used in the present invention include silica, alumina, mica (mica), silicate, barium sulfate, magnesium hydroxide, titanium oxide, etc., and silica and alumina are preferable, and silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is particularly preferable, and spherical silica and fused silica are more preferable. The inorganic filler is more preferably spherical fused silica from the viewpoint of improving the filling property of the sheet-like layered material of the present invention containing the curable resin composition. 1 or 2 or more kinds of inorganic filler materials may be used. Examples of commercially available spherical fused silica include "SOC 2" and "SOC 1" manufactured by strain アドマテックス.

The average particle size of the inorganic filler is not particularly limited, but from the viewpoint of forming fine wiring on the insulating layer, the average particle size is preferably 5 μm or less, more preferably 3 μm or less, further preferably 1 μm or less, further more preferably 0.8 μm or less, and particularly preferably 0.6 μm or less. On the other hand, the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.03 μm or more, even more preferably 0.07 μm or more, and even more preferably 0.1 μm or more, from the viewpoint of preventing an increase in viscosity and a decrease in workability of a varnish when the curable resin composition is formed into a varnish. The average particle diameter of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size is measured as an average particle size. As the measurement sample, a sample in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by horiba, Ltd., can be used.

The content of the inorganic filler is not particularly limited, and the amount of the inorganic filler is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and still more preferably 50 to 85% by mass, based on 100% by mass of the nonvolatile component in the curable resin composition, from the viewpoint of preventing a decrease in sheet-form flexibility of the sheet-like layered material. In particular, in the present invention, the peel strength can be improved even in a curable resin composition containing 50% by mass or more of an inorganic filler.

The inorganic filler is preferably surface-treated (coated) with a coupling agent for the purpose of improving moisture resistance and dispersibility. The surface treatment agent (coupling agent) is preferably 1 or more selected from epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, organosilicon nitrogen compounds, and titanate coupling agents. Among these, the aminosilane-based coupling agent is preferable because it is excellent in moisture resistance, dispersibility, properties of a cured product, and the like, and the phenylaminosilane-based coupling agent is more preferable. Examples of commercially available products include "KBM 403" (3-glycidoxypropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., "KBM 803" (3-mercaptopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., "KBE 903" (3-aminopropyltriethoxysilane) available from shin-Etsu chemical Co., Ltd., "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., "KBM 103" (phenyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) available from shin-Etsu chemical Co., Ltd.,.

[ other ingredients ]

In the curable resin composition of the present invention, in addition to the above components, a curing accelerator may be added as another component; a thermoplastic resin; thermosetting resins such as vinylbenzyl compounds, acrylic compounds, maleimide compounds and blocked isocyanate compounds; flame retardants such as phosphorus compounds and metal hydroxides; organic fillers such as silica powder, nylon powder, fluorine powder, and rubber particles; an organic solvent; オルベン, ベントン, and the like, silicone, fluorine, and polymer defoaming agents; adhesion imparting agents such as imidazole-based, thiazole-based, triazole-based and silane coupling agents; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, and carbon black; additives, and the like.

As the curing accelerator, any curing accelerator can be used as long as it can accelerate crosslinking and curing of the epoxy resin using the curing agent, and examples thereof include amine compounds, guanidine compounds, imidazole compounds, phosphonium compounds, and metal-based curing accelerators. These curing accelerators may be used in 1 kind or in combination of 2 or more kinds.

The amine compound that can be used in the present invention is not particularly limited, and examples thereof include amine compounds such as trialkylamine such as triethylamine and tributylamine, and amine compounds such as 4-Dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). These amine compounds may be used in 1 kind or in combination of 2 or more kinds.

The imidazole compound that can be used in the present invention may be a compound represented by the following general formula (11),

(in the formula, R₇～R₁₀Are respectively the same or different and are hydrogen atom, halogen atom, cyano group, nitro group, formyl group, C_1～20Alkyl radical, C_2～20Alkenyl radical, C_2～20Alkynyl, C_3～20Allyl radical, C_4～20Alkyldienyl radical, C_4～20Polyalkenyl radical, C_6～20Aryl radical, C_6～20Alkylaryl group, C_6～20Arylalkyl radical, C_4～20Cycloalkyl radical, C_4～20Cycloalkenyl group, (C)_5～10Cycloalkyl) C_1～10Alkyl, may have C_1～10Silyl groups of hydrocarbon groups, hydroxyethyl groups derived from epoxy resins).

More specifically, the imidazole compound may be selected from the group consisting of 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-S-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1') ] -ethyl-S-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1') ] -ethyl-S-triazine, and mixtures thereof, 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-S-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-methylimidazole, an adduct of an imidazole compound with an epoxy resin, and a compound of 2, 4-diamino-6-vinyl-S-triazine. These compounds may be used in combination of 1 or more than 2.

The metal-based curing accelerator that can be used in the present invention is not particularly limited, and examples thereof include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetonate (co (II) Ac) and cobalt (III) acetylacetonate (co (III) Ac), organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These metal-based curing accelerators may be used in combination of 1 kind or 2 or more kinds.

The content of the curing accelerator is preferably in the range of 0.005 to 3% by mass, and more preferably in the range of 0.01 to 1% by mass, based on 100% by mass of the total amount of the nonvolatile components in the curable resin composition.

Examples of the thermoplastic resin include (a) phenoxy resins other than the phenoxy resin having an anthracene structure, polyvinyl acetal resins, polyimide resins, polyamideimide resins, polyethersulfone resins, cycloolefin polymers, polysulfone resins, and the like, and polyvinyl acetal resins are preferable to the extent that the effects of the present invention are not impaired. These thermoplastic resin can use 1 or more than 2 combination.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably 8000 to 70000, more preferably 10000 to 60000, and still more preferably 20000 to 60000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be measured by a Gel Permeation Chromatography (GPC) method in the same manner as the method for measuring the weight average molecular weight of the phenoxy resin (a).

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as mineral spirit, toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. The organic solvent may be used in combination of 2 or more.

[ preparation of curable resin composition ]

The curable resin composition of the present invention can be prepared by appropriately mixing the above components, and if necessary, kneading or mixing the mixture by a kneading apparatus such as a three-roll mill, a ball mill, a bead mill, or a sand mill, or a stirring apparatus such as a high-speed rotary mixer, a high-speed mixer, or a planetary mixer. The resin varnish may be prepared by further adding the above-mentioned organic solvent.

The curable resin composition of the present invention has a low arithmetic mean roughness and a low root mean square roughness of the surface of the insulating layer, and can form a plated conductor layer having a sufficient peel strength, and therefore, the curable resin composition can be suitably used as a curable resin composition for insulating layers of a multilayer printed wiring board in the production of a multilayer printed wiring board. Further, the curable resin composition can be suitably used as a curable resin composition for forming a conductor layer by plating (a resin composition for an insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating), and further as a curable resin composition for a stacked layer of a multilayer printed wiring board.

The form of the curable resin composition of the present invention is not particularly limited, and the curable resin composition can be suitably used for a sheet-like laminate such as an adhesive film or a prepreg, a circuit board (for laminate applications, multilayer printed wiring board applications, etc.). The curable resin composition of the present invention can be applied to a circuit board in the form of a varnish to form an insulating layer, but is generally industrially preferably used in the form of a sheet-like laminate such as an adhesive film or a prepreg. The softening point of the curable resin composition is preferably 40 to 150 ℃ from the viewpoint of the laminatability of the sheet-like laminate material.

[ multilayer printed Wiring Board ]

The curable resin composition of the present invention can be used as a curable resin composition for an insulating layer of a multilayer printed wiring board. The multilayer printed wiring board usable in the present invention is a multilayer printed wiring board containing an insulating layer obtained by thermosetting the curable resin composition of the present invention and a sheet-like laminate material.

The conditions for the heat curing may be appropriately selected depending on the type, content, etc. of the epoxy resin in the curable resin composition, and for example, the curing is performed by heating at a curing temperature of 90 to 220 ℃, preferably 160 to 210 ℃, for a curing time of 10 to 180 minutes, preferably 20 to 120 minutes. In addition, the heat curing can be performed in 2 stages.

The coefficient of linear thermal expansion (CTE) (JIS K7197) of the insulating layer is measured as an average coefficient of linear thermal expansion of 25-150 ℃, and is preferably 20 ppm/DEG C or less, and more preferably 19 ppm/DEG C or less. The lower limit is not particularly limited, but is generally 4 ppm/DEG C. This prevents the insulating layer (stacked layer) and the conductor layer (wiring) from being deformed, and thus a highly reliable multilayer printed wiring board can be obtained.

The surface of the insulating layer may be roughened. As the dry roughening treatment, plasma treatment and the like can be mentioned. The wet roughening treatment can be performed by applying various treatment liquids, for example. There is a method of sequentially performing a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralizing treatment using a neutralizing liquid. Thus, the treatment solution may be a kit of these swelling solutions, oxidizing agents, and neutralizing solutions. The wet roughening treatment is preferable in view of the availability of a large area, the disposal of a plurality of sheets at once, and high productivity.

The swelling treatment using the swelling solution is performed, for example, by immersing the insulating layer in the swelling solution at 50 to 80 ℃ for 5 to 20 minutes (preferably at 55 to 70 ℃ for 8 to 15 minutes). Examples of the swelling solution include an alkali solution and a surfactant solution, preferably an alkali solution, and examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include スウェリング, ディップ and セキュリガンス P (spinning Dip securigant P), スウェリング, ディップ and セキュリガンス SBU (spinning Dip securigant SBU), manufactured by アトテックジャパン (strain), and the like.

The roughening treatment using an oxidizing agent can be performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ℃ for 10 to 30 minutes (preferably at 70 to 80 ℃ for 15 to 25 minutes). Examples of the oxidizing agent include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide/sulfuric acid, and nitric acid. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10 mass%. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as コンセントレート, コンパクト CP and ド ー ジ ン グ ソ リ ュ ー シ ョ ン セキュリガンス P manufactured by アトテックジャパン (ltd.).

The neutralization treatment using the neutralization solution can be carried out by immersing the substrate in the neutralization solution at 30 to 50 ℃ for 3 to 10 minutes (preferably at 35 to 45 ℃ for 3 to 8 minutes). The neutralizing solution is preferably an acidic aqueous solution, and commercially available products include リダクションソリューシン · セキュリガンス P manufactured by アトテックジャパン (ltd.).

After the roughening treatment, the insulating layer may be dried at 50 to 120 ℃ for 10 to 60 minutes (preferably, dried at 60 to 100 ℃ for 20 to 40 minutes).

The surface roughness of the surface of the insulating layer after the roughening treatment is preferably 350nm or less, more preferably 300nm or less, still more preferably 250nm or less, and particularly preferably 100nm or less in order to improve the formation of fine wiring. The lower limit of the arithmetic average roughness (Ra) is not particularly limited, but it is generally 10nm or more, 40nm or more, 70nm or more, or the like. The root mean square roughness (Rq) is preferably 500nm or less, more preferably 450nm or less, still more preferably 350nm or less, and particularly preferably 150nm or less. The lower limit of the root mean square roughness (Rq) is not particularly limited, and is generally 20nm or more, 50nm or more, 90nm or more, or the like. Since the root mean square roughness (Rq) reflects a local state of the surface of the insulating layer, it was confirmed that a denser and smoother insulating layer surface was formed and the peel strength was stabilized by grasping Rq. This corresponds to the surface roughness of the insulating layer after the thermosetting of the curable resin composition and the roughening treatment.

In order to sufficiently adhere the insulating layer to a layer adjacent thereto, for example, a conductor layer, the peel strength is preferably 0.45kgf/cm (4.41N/cm) or more, and more preferably 0.50kgf/cm (4.90N/cm) or more. The higher the upper limit value of the peel strength, the better, but not particularly limited, it is generally 1.5kgf/cm (14.7N/cm) or less, 1.2kgf/cm (11.8N/cm) or less, 1.0kgf/cm (9.81N/cm) or less, 0.8kgf/cm (7.85N/cm) or less, and the like.

The tensile strength of a cured product obtained by heat curing the curable resin composition was measured for the elongation at break in accordance with JIS K7127. Specifically, a dumbbell-shaped test piece was prepared from the cured product, and the PET film was peeled off and measured using a tensile tester RTC-1250A manufactured by オリエンテック. The elongation at break is preferably 1.5% or more, more preferably 1.6% or more, and still more preferably 1.7% or more.

[ sheet-like laminated Material ]

The sheet-like laminate material used in the present invention is a sheet-like material before curing in which the curable resin composition is formed into a layer. The sheet-like layered material can be produced as a sheet-like layered material with a support by a method known to those skilled in the art, for example, a method in which a resin varnish in which a resin composition is dissolved in the above-mentioned organic solvent is prepared, the resin varnish is applied to a support using a die coater or the like, and the organic solvent is dried by heating, blowing hot air, or the like to form a resin composition layer (sheet-like layered material) on the support. The sheet-shaped laminate material may be formed into a prepreg by impregnating a sheet-shaped reinforcing base material such as glass cloth with a resin varnish by a hot melt method or a solvent method and drying the resin varnish. The sheet-like laminate with a support may be referred to as an adhesive film.

The drying conditions are not particularly limited as long as the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. The amount of the organic solvent in the varnish and the boiling point of the organic solvent vary, but for example, a resin composition layer can be formed by drying a varnish containing 30 to 60 mass% of the organic solvent at 50 to 150 ℃ for about 3 to 10 minutes.

The thickness of the sheet-like laminate material obtained is not particularly limited, but is, for example, preferably in the range of 1 to 150. mu.m, more preferably in the range of 2 to 100. mu.m, still more preferably in the range of 3 to 50 μm, and particularly preferably in the range of 5 to 30 μm.

In the sheet-like laminate, the resin composition layer may be a plurality of layers, and the resin composition layer may have a support on one surface and a protective film on the other surface.

[ support ]

Examples of the support usable in the present invention include a plastic film and a metal foil. Specifically, examples of the plastic film include polyesters such as polyethylene terephthalate (hereinafter sometimes referred to simply as "PET") and polyethylene naphthalate, polycarbonates, polyethylenes, polypropylenes, acrylic, cyclic polyolefins, triacetyl celluloses, polyether sulfides, polyether ketones, and polyimides. Among these, polyethylene terephthalate films and polyethylene naphthalate films are preferable, and particularly, polyethylene terephthalate films which are inexpensive and easily available are preferable.

Examples of the metal foil include copper foil and aluminum foil.

In view of general versatility, a plastic film is preferred, and when a plastic film is used, a support whose surface to be in contact with the layer containing the curable resin composition is subjected to a release treatment is preferably used in order to improve releasability. The release agent used in the release treatment is not particularly limited as long as the layer containing the curable resin composition can be released from the support, and examples thereof include a silicone-based release agent, an alkyd-based release agent, a polyolefin resin, a polyurethane resin, and a fluororesin. As the support subjected to the releasing treatment, a commercially available plastic film with a releasing layer can be used, and preferable examples thereof include PET films having a releasing layer containing an alkyd resin-based releasing agent as a main component, that is, SK-1, AL-5, AL-7 (manufactured by リンテック Co., Ltd.), and the like. The plastic film may be subjected to matting treatment or corona treatment, or a release layer may be formed on the treated surface. On the other hand, the metal foil may be removed by an etching solution, or the metal foil may be used as a conductor layer without being removed.

The thickness of the support is not particularly limited, but is preferably in the range of 10 to 150. mu.m, more preferably in the range of 20 to 50 μm, and still more preferably in the range of 25 to 45 μm.

The protective film usable in the present invention may be provided for the purpose of preventing dust and the like from adhering to a layer containing the curable resin composition, and the like. As the protective film, a plastic film similar to the support can be used. The protective film may be subjected to surface treatment such as matting treatment or corona treatment, or may be subjected to release treatment as described above. The thickness of the protective film is preferably 3 to 30 μm, and more preferably 5 to 20 μm.

[ multilayer printed Wiring Board Using sheet-like laminate Material ]

Next, an example of a method for manufacturing a multilayer printed wiring board using the sheet-like laminate material manufactured as described above will be described.

First, a sheet-like laminate is laminated (laminated) on one or both surfaces of a circuit substrate using a vacuum laminator. Examples of the substrate used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Here, the circuit board is a substrate having a conductor layer (circuit) patterned on one or both surfaces of the substrate. In addition, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a circuit board in which a conductor layer (circuit) subjected to patterning is formed on one surface or both surfaces of the outermost layer of the multilayer printed wiring board is also included in the circuit board described herein. The surface of the conductive layer may be roughened in advance by blackening treatment, copper etching, or the like.

In the above lamination, when the sheet laminate has a protective film, the protective film is removed, and then the sheet laminate and the circuit board are preheated as necessary, and the sheet laminate is laminated on the circuit board while being pressurized and heated. For the sheet-like laminate material of the present invention, a method of laminating on a circuit substrate under reduced pressure by a vacuum lamination method is suitably used. The lamination conditions are not particularly limited, but lamination is preferably performed under a reduced pressure of about 10 to 120 seconds to an air pressure of 20mmHg (26.7hPa) or less, and then the pressure bonding temperature (lamination temperature) is preferably 70 to 140 ℃, the pressure bonding pressure (lamination pressure) is preferably 0.1 to 1.5MPa, more preferably 0.5 to 1.2MPa, and the pressure bonding time (lamination time) is preferably 5 to 180 seconds. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum laminators manufactured by ニチゴー & モートン, vacuum pressure laminators manufactured by nippon machine, roll dry coater manufactured by hitachi インダストリイズ, and vacuum laminators manufactured by hitachi エーアイーシー.

Then, after cooling to around room temperature (25 ℃), the support is peeled off when peeled off, and the resin composition is thermally cured to form a cured product, whereby an insulating layer can be formed on the circuit board. The conditions for heat curing may be appropriately selected depending on the kind, content, etc. of the resin component in the resin composition, and for example, the heat curing is performed by heating at a curing temperature of 100 to 220 ℃, preferably 160 to 210 ℃, and for a curing time of 20 to 180 minutes, preferably 30 to 120 minutes. In addition, the heat curing may be performed in 2 stages. After the insulating layer is formed, if the support is not peeled before curing, the support may be peeled off at that time as necessary.

Further, the sheet-like laminate material may be laminated on one surface or both surfaces of the circuit board by using a vacuum press. The lamination step of heating and pressing under reduced pressure can be performed by using a common vacuum thermocompressor. For example, the lamination step can be performed by pressing a heated metal plate such as SUS plate from the support layer side. The pressurizing conditions are preferably 70 to 250 ℃, preferably 100 to 230 ℃, under reduced pressure with a vacuum degree of usually 0.01MPa or less, preferably 0.001MPa or less, a pressurizing pressure in the range of 0.5 to 4MPa, and a pressurizing time of 30 to 150 minutes. The heating and pressing may be performed in one stage, but it is preferable to perform the heating and pressing in two or more stages from the viewpoint of controlling bleeding of the resin. For example, the first stage of pressurization is preferably carried out at a temperature of 70 to 150 ℃ and a pressurization pressure of 0.1 to 1.5MPa, and the second stage of pressurization is preferably carried out at a temperature of 150 to 200 ℃ and a pressure of 0.5 to 4 MPa. The time of each stage is preferably 20 to 120 minutes. By thus thermally curing the resin composition layer, an insulating layer can be formed on the circuit substrate. Examples of the commercially available vacuum hot press include MNPC-V-750-5-200 (manufactured by KANTIANJIAO Co., Ltd.) and VH1-1603 (manufactured by KANTIANJINGJI Co., Ltd.).

Then, a via hole (via hole) or a through hole (through hole) is formed in the insulating layer formed on the circuit board. The hole opening processing can be performed by a known method such as a drill, a laser, plasma, or the like, or a combination of these methods as needed, and the hole opening processing using a laser such as a carbon dioxide gas laser, a YAG laser, or the like is the most common method. When the support was not peeled before the punching, the support was peeled at this time.

Next, the surface of the insulating layer is roughened as described above, and a conductor layer can be formed on the insulating layer by dry plating or wet plating. As the dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. Examples of the wet plating include a method in which a conductor layer is formed by a combination of electroless plating and electrolytic plating; a method of forming a resist pattern having a pattern reverse to that of the conductor layer and forming the conductor layer by electroless plating alone. As a method of forming a pattern later, for example, a subtractive (reactive) method, a semi-additive method, or the like, which is well known to those skilled in the art, can be used, and the above series of steps are repeated a plurality of times, whereby a multilayer printed wiring board in which stacked layers are stacked in multiple stages can be formed. In the present invention, since the film has low roughness and high peeling, it can be suitably used as a stacked layer of a multilayer printed wiring board.

[ semiconductor device ]

By using the multilayer printed wiring board manufactured as described above, a semiconductor device can be manufactured. The semiconductor device can be manufactured by mounting a semiconductor chip on the conductive portion of the multilayer printed wiring board used in the present invention. The "conductive portion" refers to a "portion for conducting an electrical signal in the multilayer printed wiring board", and the position thereof may be either a surface portion or a buried portion. The conductive layer may be a part of the conductive layer, or may be a conductive part such as a connector other than the conductive part. The "semiconductor chip" is not particularly limited as long as it is a circuit element made of a semiconductor.

The method of mounting a semiconductor chip in the manufacture of the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, and specific examples thereof include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bump-free stacked layer (BBUL), a mounting method using an Anisotropic Conductive Film (ACF), a mounting method using a non-conductive film (NCF), and the like.

[ examples ]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following description, "part" means "part by mass" unless otherwise specified, and "%" means "% by mass" unless otherwise specified.

< measuring method, evaluation method >

First, various measurement methods and evaluation methods will be described.

[ preparation of samples for measuring peeling Strength, arithmetic average roughness (Ra value), root mean Square roughness (Rq value) ]

(1) Substrate treatment of laminated board

Both surfaces of a glass cloth substrate epoxy resin double-sided copper clad laminate (copper foil 18 μm thick, substrate 0.3mm thick, R5715ES manufactured by matsushita corporation) were etched by 1 μm using CZ8100 manufactured by メック corporation, and the copper surface was roughened.

(2) Lamination of adhesive films

The adhesive films prepared in examples and comparative examples were laminated on both sides of the epoxy resin double-sided copper clad laminate subjected to the above roughening treatment using a batch type vacuum press MVLP-500 (manufactured by nomenclatures corporation). Lamination was performed as follows: the pressure was reduced for 30 seconds to 13hPa or less, and then the pressure was bonded at 100 ℃ for 30 seconds and 0.74 MPa.

(3) Curing of resin compositions

After a polyethylene terephthalate (PET) film as a support was peeled off from the laminated adhesive film, the resin composition was cured under curing conditions of 100 ℃ for 30 minutes and then 180 ℃ for 30 minutes to form an insulating layer.

(4) Roughening treatment

The laminate having the insulating layer formed thereon was immersed in スウェリング · ディップ · セキュリガンス P (ethylene glycol ethers, aqueous sodium hydroxide solution) containing diethylene glycol monobutyl ether of アトテックジャパン strain as a swelling solution at 60 ℃ for 5 minutes (example 1, comparative examples 1, 4, 5) or 10 minutes (examples 2, 3, comparative examples 2, 3). Then, the resultant was dissolved in コンセントレート, コンパクト P (KMnO) of アトテックジャパン (Kabushiki Kaisha) as a roughening solution₄: 60g/L, NaOH: 40g/L aqueous solution) at 80 ℃ for 15 minutes (examples 1, comparative examples 1, 4, 5) and 20 minutes (examples 2, 3, comparative examples 2, 3). Finally アト as a neutralizing liquidテックジャパン (strain リダクションソリューシン. セキュリガント P (aqueous solution of sulfuric acid) was immersed at 40 ℃ for 5 minutes. After drying at 80 ℃ for 30 minutes, this substrate was designated as evaluation substrate A.

(5) Plating using a semi-additive process

The evaluation substrate a was plated to form a conductor layer. Specifically, the evaluation substrate A was treated to contain PdCl₂The electroless copper plating solution of (1) is immersed at 40 ℃ for 5 minutes and then immersed at 25 ℃ for 20 minutes in an electroless copper plating solution. After annealing treatment by heating at 150 ℃ for 30 minutes, an etching resist was formed, patterning was performed by etching, and copper sulfate plating was performed to form a conductor layer with a thickness of 30 μm. Followed by an annealing treatment at 190 ℃ for 60 minutes. This substrate was designated as evaluation substrate B.

[ measurement of arithmetic average roughness (Ra value) and root mean square roughness (Rq value) after roughening ]

For the evaluation substrate A, values were obtained in a VSI contact mode, a 50-fold lens, and a measurement range of 121 μm × 92 μm using a non-contact surface roughness meter (WYKO NT3300, manufactured by ビーコインスツルメンツ Co., Ltd.), and from the obtained values, an Ra value and an Rq value were obtained. The measurement was performed by obtaining an average value of 10 points.

[ measurement of tear Strength (peeling Strength) of plated conductor layer ]

A10 mm wide and 100mm long portion of the conductor layer of the evaluation substrate B was cut, one end of the cut was peeled off, the substrate was held by a jig (TSE, model オートコム tester AC-50C-SL), and the load (kgf/cm (N/cm)) at which the substrate was peeled off by 35mm in the vertical direction at a speed of 50 mm/min at room temperature (25 ℃) was measured.

[ measurement of coefficient of Linear thermal expansion (CTE) ]

The adhesive films obtained in examples and comparative examples were heated at 200 ℃ for 90 minutes to be thermally cured, and peeled from the PET film as a support to obtain a sheet-like cured product. The cured product was cut into a test piece having a width of 5mm, a length of 15mm and a thickness of 30mm, and subjected to thermomechanical analysis by a tensile load method using Thermo Plus TMA8310 (manufactured by LTD リガク). After the test piece was mounted in the above-mentioned apparatus, the measurement was continuously performed 2 times under the measurement conditions of a load of 1g and a temperature rise rate of 5 ℃/min. The average linear thermal expansion coefficient (ppm) at 25 ℃ to 150 ℃ in the measurement of the 2 nd time was calculated.

[ determination of elongation at Break ]

The adhesive films obtained in examples and comparative examples were heated at 200 ℃ for 90 minutes to be thermally cured, the cured products were cut into dumbbell shapes, and the PET films were peeled off to obtain test pieces. The tensile strength of the test piece was measured by using a tensile tester RTC-1250A manufactured by オリエンテック Co., Ltd, according to JIS K7127, and the elongation at break at 23 ℃ was determined.

< Synthesis example 1 >

Synthesis of phenoxy resin having anthracene structure and tetramethylbiphenyl structure

In a reaction vessel, 191g of tetramethylbiphenyl type epoxy resin (YX 4000, epoxy equivalent 185, manufactured by Mitsubishi chemical corporation), 210g of 9, 10-dihydroxyanthracene (phenolic hydroxyl equivalent 210), and 150g of cyclohexanone were charged and dissolved by stirring. Next, 0.5g of tetramethylammonium chloride solution was added dropwise thereto, and the reaction was carried out at 180 ℃ for 5 hours under a nitrogen atmosphere. After the reaction, the reaction mixture was filtered through a filter cloth and diluted with a solvent to obtain a phenoxy resin A,

epoxy equivalent: 11000

Weight average molecular weight: 35000

Solid content 30 mass% of 1: 1 solution of

Note that the phenoxy resin a has the following structure:

< Synthesis example 2 >

Synthesis of phenoxy resin with tetramethyl biphenyl structure and bisphenol acetophenone structure

100g of tetramethylbiphenyl-type epoxy resin ("YX 4000" manufactured by Mitsubishi chemical corporation, epoxy equivalent 185), 80g of bisphenol acetophenone (phenolic hydroxyl equivalent 145), and 150g of cyclohexanone were charged into a reaction vessel and dissolved by stirring. Next, 0.5g of tetramethylammonium chloride solution was added dropwise thereto, and the reaction was carried out at 180 ℃ for 5 hours under a nitrogen atmosphere. After the reaction, the reaction mixture was filtered through a filter cloth and diluted with a solvent to obtain phenoxy resin B. Note that, the phenoxy resin B does not have an anthracene structure, and therefore is a reference example of the present invention,

epoxy equivalent: 13000

Weight average molecular weight: 38000

1: 1, dissolving;

note that the phenoxy resin B has the following structure:

< example 1 >

A bisphenol type epoxy resin ("ZX 1059" manufactured by Nippon iron chemical Co., Ltd., a 1: 1 mixture of bisphenol A type and bisphenol F type, and an epoxy equivalent of 169)10 parts, a crystalline 2-functional epoxy resin ("YX 4000 HK" manufactured by Mitsubishi chemical Co., Ltd., an epoxy equivalent of about 185)10 parts, a dicyclopentadiene type epoxy resin ("HP-7200H" manufactured by DIC Co., Ltd., an epoxy equivalent of 275)20 parts, and the mixture was heated and dissolved in 35 parts of a solvent oil while stirring. After cooling to room temperature (25 ℃), 12 parts of phenoxy resin A, 12 parts of a triazine skeleton-containing phenol curing agent ("LA-7054" made by DIC corporation as a 60% MEK solution having a hydroxyl equivalent of 125 as a solid content), 15 parts of a naphthalene type curing agent ("SN-485" made by Nippon iron chemical corporation as a 60% MEK solution having a hydroxyl equivalent of 215 as a solid content), 3 parts of a curing accelerator (4-Dimethylaminopyridine (DMAP) and a 2% by mass MEK solution as a solid content), 2 parts of a flame retardant ("HCA-HQ" made by Sanguang corporation as a flame retardant, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 2 parts of an average particle size, and a phenylaminosilane coupling agent (made by shin chemical industries, Ltd.) were mixed therein, "KBM 573") was surface-treated with spherical silica (average particle diameter: 0.24 μm, "SOC 1" manufactured by Tokaki Kaisha アドマテックス, and carbon content per unit area: 0.36mg/m²)150 parts by weight, and uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish. Subsequently, a resin varnish was uniformly applied to the release surface of the polyethylene terephthalate film (38 μm in thickness, "AL 5" manufactured by リンテック K.) subjected to the release treatment so that the thickness of the dried resin composition layer was 30 μm, and the resin composition layer was dried at 80 to 120 ℃ (average 100 ℃) for 4 minutes to prepare an adhesive film.

< example 2 >

5 parts of a liquid naphthalene-type epoxy resin ("HP 4032 SS" manufactured by DIC corporation), 5 parts of a crystalline 2-functional epoxy resin ("YX 4000 HK" manufactured by Mitsubishi chemical corporation, epoxy equivalent of about 185), 12 parts of a biphenyl-type epoxy resin ("NC 3000L" manufactured by Nippon Kabushiki Kaisha, epoxy equivalent of 269), and 30 parts of a solvent oil were dissolved by heating while stirring. After cooling to room temperature (25 ℃), 5 parts of phenoxy resin a, 20 parts of a prepolymer of bisphenol a dicyanate ester ("BA 230S 75" manufactured by ロンザジャパン, having a cyanate equivalent of about 232 and a non-volatile component of 75 mass% MEK solution), a novolac-type polyfunctional cyanate resin ("PT 30S" manufactured by ロンザジャパン, having a cyanate equivalent of about 133 and a non-volatile component of 85 mass% MEK solution) 6 parts of a curing accelerator (4-dimethylaminopyridine, a MEK solution having a solid component of 2 mass%), a curing accelerator (manufactured by tokyo chemical corporation, cobalt (III) acetylacetonate (co (III) Ac)), 3 parts of a MEK solution having a solid component of 1 mass%, 2 parts of rubber particles (manufactured by ガンツ chemical corporation, スタフィロイド Ac3816N), and a flame retardant ("HCA-HQ" manufactured by mitsui chemical corporation, 2 parts of 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide having an average particle diameter of 2 μm, and 2 parts of spherical silica (average particle diameter of 0.5 μm, SOC2, manufactured by KBM573, Ltd.) surface-treated with a phenylaminosilane-based coupling agent (manufactured by shin-Etsu chemical Co., Ltd., "SOC 2", carbon content per unit area of 0.39mg/m²)100 parts of the dispersion liquid was uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. Next, an adhesive film was produced in the same manner as in example 1.

< example 3 >

Bisphenol epoxy resin ("ZX 105" manufactured by Nippon iron chemical Co., Ltd.)9 ", 1: 1 part of a mixture, 169 epoxy equivalent), 12 parts of a biphenyl type epoxy resin ("NC 3000L" manufactured by japan chemical corporation, 269 epoxy equivalent), and 30 parts of a solvent oil dissolved therein under heating with stirring. After cooling to room temperature, 17 parts of phenoxy resin A, 34 parts of an active ester compound (a toluene solution having a weight average molecular weight of about 2700 and a nonvolatile component having an active group equivalent of about 223 of 65% by mass, "HPC 8000-65T", manufactured by DIC), 6 parts of a curing accelerator (4-dimethylaminopyridine, a MEK solution having a solid content of 2% by mass), 2 parts of a flame retardant (HCA-HQ, manufactured by Sanko corporation, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2 parts of an average particle diameter of 2 μm), a spherical silica surface-treated with a phenylaminosilane coupling agent (a spherical silica having an average particle diameter of 0.5 μm, manufactured by shin-Etsu chemical Co., Ltd., "SOC 2", manufactured by アドマテックス, and the like were mixed therein, The amount of carbon per unit area was 0.39mg/m²)150 parts by weight of the dispersion liquid were uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. Next, an adhesive film was produced in the same manner as in example 1.

< comparative example 1 >

An adhesive film was produced in exactly the same manner as in example 1, except that 10 parts of bisphenol a type phenoxy resin ("E1256B 40" manufactured by mitsubishi chemical corporation, MEK solution having a solid content of 40 mass%, epoxy equivalent 8000, and weight average molecular weight of about 50000) was used instead of 12 parts of phenoxy resin a in example 1.

< comparative example 2 >

An adhesive film was produced in the same manner as in example 2 except that 5 parts of the phenoxy resin a in example 2 was changed to 5 parts of the phenoxy resin B in synthesis example 2.

< comparative example 3 >

An adhesive film was produced in the same manner as in example 3 except that 17 parts of the phenoxy resin a in example 3 was changed to 17 parts of the phenoxy resin B in synthesis example 2.

The results are shown in tables 1 and 2.

< comparative example 4 >

An adhesive film was produced in the same manner as in example 1 except that 3.6 parts of an anthracene-based epoxy resin ("YX 8800" manufactured by mitsubishi chemical corporation and having an epoxy equivalent of 181) was used instead of 12 parts of the phenoxy resin a in example 1. The structural formula of "YX 8800" is shown below.

< comparative example 5 >

An adhesive film was produced in the same manner as in example 1 except that the amount of phenoxy resin a 12 parts in example 1 was changed to 43 parts. In comparative example 5, the total amount of the phenoxy resin (a), the epoxy resin (B), and the curing agent (C) was 100 mass%, and the phenoxy resin (a) was 18.8 mass%, which was outside the scope of the present invention.

The results are shown in tables 1 and 2.

[ Table 1]

[ Table 2]

From the results shown in tables 1 and 2, it is understood that examples 1 to 3 using the curable resin composition of the present invention have low roughness, sufficient peel strength, low coefficient of linear thermal expansion, and sufficient elongation at break. On the other hand, in comparative examples 1 to 5, since the curable resin composition of the present invention was not used, there were cases where the arithmetic average roughness and the root mean square roughness were increased, the peel strength was decreased, the linear thermal expansion coefficient was increased, and the elongation at break was decreased.

Claims (32)

1. A curable resin composition comprising (A) a phenoxy resin having an anthracene structure, (B) an epoxy resin, and (C) a curing agent, characterized in that,

the above-mentioned phenoxy resin (A) further has a substituted or unsubstituted biphenyl structure,

the phenoxy resin (A) is 1 to 15% by mass based on 100% by mass of the total amount of the phenoxy resin (A), the epoxy resin (B) and the curing agent (C),

the phenoxy resin (A) has an epoxy equivalent of 5000 or more and

the curing agent (C) is a phenol curing agent.

2. The curable resin composition according to claim 1, wherein the phenoxy resin (A) is 2 to 13% by mass, based on 100% by mass of the total amount of the phenoxy resin (A), the epoxy resin (B), and the curing agent (C).

3. The curable resin composition according to claim 1, wherein the phenoxy resin (A) is 2 to 30% by mass, based on 100% by mass of the total amount of the phenoxy resin (A) and the epoxy resin (B).

4. The curable resin composition according to claim 1, wherein the phenoxy resin (A) is 4 to 20% by mass, based on 100% by mass of the total amount of the phenoxy resin (A) and the epoxy resin (B).

5. The curable resin composition according to claim 1, wherein the phenoxy resin (A) has an epoxy equivalent of 5000 to 30000.

6. The curable resin composition according to claim 1, wherein the phenoxy resin (A) has an epoxy equivalent of 7000 to 20000.

7. The curable resin composition according to claim 1, wherein the phenoxy resin (A) has an epoxy equivalent of 9000 to 15000.

8. The curable resin composition according to claim 1, wherein the weight-average molecular weight of the phenoxy resin (A) is 8000 to 100000.

9. The curable resin composition according to claim 1, wherein the weight average molecular weight of the phenoxy resin (A) is 15000 to 80000.

10. The curable resin composition according to claim 1, wherein the weight average molecular weight of the phenoxy resin (A) is 20000 to 60000.

11. The curable resin composition according to claim 1, wherein the weight average molecular weight of the phenoxy resin (A) is 25000 to 40000.

12. The curable resin composition according to claim 1, wherein the epoxy resin (B) is selected from the group consisting of a bisphenol-type epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene-type epoxy resin, a naphthalene-type epoxy resin, a biphenyl-type epoxy resin, and a mixture of these epoxy resins.

13. The curable resin composition according to claim 1, wherein the epoxy resin (B) has an epoxy equivalent of 50 to 3000.

14. The curable resin composition according to claim 1, wherein the epoxy resin (B) has an epoxy equivalent of 100 to 500.

15. The curable resin composition according to claim 1, wherein the epoxy resin (B) is 30 to 80% by mass, based on 100% by mass of the total amount of the phenoxy resin (A), the epoxy resin (B), and the curing agent (C).

16. The curable resin composition according to claim 1, wherein the epoxy resin (B) is 40 to 70% by mass, based on 100% by mass of the total amount of the phenoxy resin (A), the epoxy resin (B), and the curing agent (C).

17. The curable resin composition according to claim 1, wherein the curing agent (C) is selected from the group consisting of a biphenyl-type phenol resin, a naphthalene-type phenol resin, a novolak-type phenol resin, a naphthylene ether-type phenol resin, and a triazine skeleton-containing phenol resin.

18. The curable resin composition according to claim 17, wherein the curing agent (C) is a biphenyl-type phenol resin, a naphthalene-type phenol resin or a naphthylene ether-type phenol resin.

19. The curable resin composition according to claim 1, wherein the phenoxy resin (A) is contained in an amount of 0.3 to 10% by mass, the epoxy resin (B) is contained in an amount of 5 to 30% by mass, and the curing agent (C) is contained in an amount of 3 to 20% by mass, based on 100% by mass of nonvolatile components in the curable resin composition.

20. The curable resin composition according to claim 1, wherein the phenoxy resin (A) is contained in an amount of 0.7 to 5% by mass, the epoxy resin (B) is contained in an amount of 10 to 20% by mass, and the curing agent (C) is contained in an amount of 7 to 15% by mass, based on 100% by mass of nonvolatile components in the curable resin composition.

21. The curable resin composition according to claim 1, further comprising (D) an inorganic filler.

22. The curable resin composition according to claim 21, wherein the inorganic filler (D) has an average particle diameter of 0.01 to 5 μm.

23. The curable resin composition according to claim 21, wherein the inorganic filler (D) has an average particle diameter of 0.01 to 0.6. mu.m.

24. The curable resin composition according to claim 21, wherein the content of the inorganic filler (D) is 30 to 90% by mass, based on 100% by mass of non-volatile components in the curable resin composition.

25. The curable resin composition according to claim 21, wherein the content of the inorganic filler (D) is 50 to 85% by mass, based on 100% by mass of nonvolatile components in the curable resin composition.

26. The curable resin composition according to claim 21, wherein the inorganic filler (D) is silica.

27. The curable resin composition according to claim 1, further comprising a curing accelerator.

28. A curable resin composition for an insulating layer of a multilayer printed wiring board, which comprises the curable resin composition according to any one of claims 1 to 27.

29. A curable resin composition for multilayer printed wiring boards, which comprises the curable resin composition according to any one of claims 1 to 27.

30. A sheet-like laminate material comprising the curable resin composition according to any one of claims 1 to 29.

31. A multilayer printed wiring board comprising an insulating layer obtained by thermally curing the curable resin composition according to any one of claims 1 to 29 or the sheet-like layered material according to claim 30.

32. A semiconductor device comprising the multilayer printed wiring board according to claim 31.