TW201500452A - Curable resin composition - Google Patents

Abstract

To provide a curable resin composition with not only excellent elongation rate at break, low arithmetic average coarseness on the surface of insulation layer and low root-mean-square coarseness in the wet coarsening step, but also capable of forming thereon the plating conductor layer having adequate peeling strength and low linear thermal expansion coefficient. The curable resin composition containing (A) a phenoxy resin containing anthracene structure, (B) an expoxy resin, and (C) a curing agent. Also, in the occasion in that the total of aforementioned (A) phenoxy resin, (B) expoxy resin, and (C) curing agent is 100 mass%, the curable resin composition is characterized in that the aforementioned (A) phenoxy resin is 1-15 mass% and the epoxy equivalent of the aforementioned (A) phenoxy resin is above 5000.

Description

Curable resin composition

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

In recent years, in the multilayer printed wiring board, the build-up of the multilayered printed wiring board has been stratified, and the wiring has been made finer and higher in density.

For this, there are various ways. For example, Patent Document 1 discloses that a polymer epoxy resin having a specific structure is used as a resin composition for a printed wiring board, and heat resistance, low water absorbability, electrical properties, moldability, flexibility, impact resistance, and adhesion are improved ( Request item and paragraph number 0003, etc.). However, Patent Document 1 does not disclose that a phenoxy resin having an oxime structure, an epoxy resin, and a curing agent are combined at a specific ratio, and a phenoxy resin having a specific epoxy equivalent is used. Further, although Patent Document 2 discloses an epoxy resin having a fluorene structure, it is not disclosed that a phenoxy resin, an epoxy resin, and a curing agent are combined at a specific ratio, and a phenoxy group having a specific epoxy equivalent is used. Resin.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-252951

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-255813

The problem to be solved by the present invention is to provide not only a specific strength (elongation at break) but also a low average arithmetic mean roughness of the surface of the insulating layer and a low root mean square roughness (low thickness) in the wet roughening step, and A plated conductor layer having sufficient peeling strength and a curable resin composition having a low coefficient of thermal expansion of the wire can be formed.

In order to solve the above problems, the inventors of the present invention have found that (A) a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a curing agent having a specific amount and a specific epoxy equivalent are contained. The resin composition and the thermosetting product thereof can achieve the above-described excellent strength, low thickness, high peeling strength, and low coefficient of linear thermal expansion, and the present invention has been completed.

That is, the present invention is intended to include the following aspects.

[1] A curable resin composition comprising (A) a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a curing agent, which is characterized by the aforementioned When the total of the (A) phenoxy resin, the (B) epoxy resin, and the (C) curing agent is 100% by mass, the (A) phenoxy resin is 1 to 15% by mass, and the above (A) The phenoxy resin has an epoxy equivalent of 5,000 or more.

[2] The curable resin composition according to [1], wherein the (A) phenoxy resin has a weight average molecular weight of 8,000 to 100,000.

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

[4] The curable resin composition according to any one of [1], wherein the (B) epoxy resin is a bisphenol type epoxy resin, a crystalline bifunctional epoxy resin, or the like. A mixture of a cyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a mixture of such epoxy resins is selected.

The curable resin composition of any one of the above-mentioned (C), wherein the (C) curing agent is a phenol curing agent, a cyanate ester curing agent, an active ester curing agent, and the like. A mixture of hardeners is selected as the group.

[6] The curable resin composition according to any one of [1], wherein the (C) curing agent is a cyanate ester curing agent or an active ester curing agent.

[7] The curable resin composition as described in any one of [1] to [6] In the case where the non-volatile component in the curable resin composition is 100% by mass, the content of the (A) phenoxy resin is 0.3 to 10% by mass, and the content of the (B) epoxy resin is 5 to 30% by mass, and the content of the (C) hardener is 3 to 20% by mass.

[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 (D) inorganic filler 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 (D) inorganic filler is (100% by mass) of the non-volatile component in the curable resin composition. 30 to 90% by mass.

[11] The curable resin composition according to any one of [8], wherein the (D) inorganic filler is cerium oxide.

[12] 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 [1] to [11].

[13] A curable resin composition for a build-up of a multilayer printed wiring board, characterized in that the curable resin composition according to any one of [1] to [11] is contained.

[14] A flaky laminate comprising the curable resin composition according to any one of [1] to [13].

[15] A multilayer printed wiring board comprising the curable resin composition according to any one of [1] to [13] or [14]. The insulating layer obtained by thermally curing the sheet-like laminate material.

[16] A semiconductor device characterized by comprising the multilayer printed wiring board according to [15].

Further, the present invention preferably includes the following aspects.

[I] contains (A) a phenoxy resin having a weight average molecular weight of 25,000 to 40,000, and having a fluorene structure and a tetramethylbiphenyl structure, (B) a bisphenol type epoxy resin, a crystalline 2 functional epoxy An epoxy resin selected from the group consisting of a resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a mixture of such epoxy resins, and (C) containing cyanic acid One or more kinds of curing agents selected from the ester ester curing agent and the active ester curing agent, and (D) a curable resin composition of an inorganic filler having ceria having an average particle diameter of 0.01 to 5 μm, which is characterized by When the total of (A) phenoxy resin, (B) epoxy resin, and (C) hardener is 100% by mass, the (A) phenoxy resin is 1 to 15% by mass, and the above (A) benzene The epoxy resin has an epoxy equivalent of 9000 to 15,000.

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

In particular, in the present invention, the above-described low thickness and high peeling strength can be attained by using the phenoxy resin having a specific fluorene structure of the component (A). Further, in general, an epoxy resin composition containing a large amount of inorganic filler is used in the case where the resin of the film is poor in flow and pores are formed between the laminated conductors, and the peeling strength is easily lowered. Ingredient (A) can increase the peeling strength.

[Best Mode for Carrying Out the Invention] [Curable resin composition]

The curable resin composition of one aspect of the present invention contains (A) a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a curing resin composition of a curing agent, and When the total of the (A) phenoxy resin, the (B) epoxy resin, and the (C) curing agent is 100% by mass, the (A) phenoxy resin is 1 to 15% by mass, and the above (A) The phenoxy resin has a curable resin composition characterized by an epoxy equivalent of 5,000 or more. Hereinafter, the curable resin composition of the present invention will be described in detail.

(A) Phenoxy resin having a ruthenium structure

The phenoxy resin having a fluorene structure which can be used in the present invention is A phenoxy resin having at least one type of ruthenium structure, for example, a ruthenium structure shown below, can be used.

蒽 Construction:

In the above formula (1), R ₁ may be the same or different from each other, and is a group selected from a group consisting of a hydrogen atom, a halogen element, and a hydrocarbon group of C _{1 to 10} , and n is an integer of 0 to 8. Here, the halogen element may be fluorine, chlorine, bromine, iodine or the like.

Further, (A) the phenoxy resin having a fluorene structure is preferably a phenoxy resin having at least one type of fluorene structure and at least one type of quinone resin other than the fluorene structure. Specifically, a phenoxy resin having a substituted or unsubstituted biphenyl structure and/or a bisphenol acetophenone structure is preferred. The substituted or unsubstituted biphenyl structure is as follows.

Substituted or unsubstituted biphenyl structure

In the above formula (2), R ₂ and R ₃ may be the same or different from each other, and are a group selected from a group consisting of a hydrogen atom, a halogen element and a hydrocarbon group of C _{1 to 10} , and m is an integer of 0 to 4. Here, the halogen element may be fluorine, chlorine, bromine, iodine or the like.

Bisphenol acetophenone structure (Japanese Patent Laid-Open No. 2003-252951)

(In the formula (3), R ₄ may be the same or different from each other, and is a group selected from a hydrogen atom, a hydrocarbon group of C _{1 to 10} , and a group of halogen elements, and R ₅ is a hydrogen atom, and C _{1 to 10} A group selected from the group consisting of a hydrocarbon group and a halogen element, and R ₆ is a hydrogen atom or a hydrocarbon group of C _{1 to 10} , and m is an integer of 0 to 5).

In a preferred aspect, in the formula (1), R ₁ may be the same or different from each other, and is a hydrogen atom or a C _1-8 hydrocarbon group, more preferably a hydrogen atom or a C _{1 to 6} alkyl group. Preferably, it is a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom, and n may be the same or different from each other, and is an integer of 0 to 6, more preferably 0 to 4.

In a preferred embodiment, in the formula (2), R ₂ and R ₃ may be the same or different from each other, and are a hydrogen atom or a C _1-8 hydrocarbon group, more preferably a hydrogen atom or a C _1-6 alkyl group. Further, it is preferably a hydrogen atom or a methyl group, more preferably a tetramethylbiphenyl structure, and m is an integer of from 0 to 3, more preferably from 1 to 2.

In a preferred aspect, in the formula (3), R ₄ may be the same or different from each other, and is a hydrogen atom or a C _1-8 hydrocarbon group, more preferably a hydrogen atom or a C _{1 to 6} alkyl group. Preferably, it is a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, and R ₅ is a hydrogen atom or a C _1-8 hydrocarbon group, more preferably a hydrogen atom or a C _1-6 alkyl group, still more preferably a hydrogen atom or a group. More preferably, the group is a hydrogen atom, and R ₆ is a hydrogen atom or a C _1-8 hydrocarbon group, more preferably a hydrogen atom or a C _1-6 alkyl group, still more preferably a hydrogen atom or a methyl group, and particularly preferably A. The base, m is an integer from 0 to 3, more preferably from 1 to 2.

An example of a method for producing a phenoxy resin having a fluorene structure 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 to 0.8:1, more preferably 1.3:1 to 0.9:1. , 1.1:1~1:1 is better.

When the content of the phenoxy resin having a fluorene structure is 100% by mass based on the total of the (A) phenoxy resin, the epoxy resin (B) described later, and the curing agent (C) described later, (A) phenoxy The base resin is from 1 to 15% by mass, preferably from 2 to 13% by mass, more preferably from 5 to 10% by mass. When the content of the phenoxy resin is 1% by mass or more, the arithmetic mean roughness and the low root mean square roughness are low, and when the content is 15% by mass or less, the crosslinking portion is sufficiently maintained, so that the arithmetic mean is low. The thickness and the low root mean square roughness, and the low coefficient of linear thermal expansion can be maintained.

Further, when the total of the (A) phenoxy resin and the epoxy resin (B) described later is 100% by mass, the (A) phenoxy resin is preferably 2 to 30% by mass, more preferably 4 to 20% by mass. %.

The epoxy equivalent of the phenoxy resin having a fluorene structure (the mass of the epoxy group-containing resin) is, for example, 5,000 (g/eq) or more, preferably 5,000 to 30,000 (g/equivalent), more preferably Good for 7000~ 20000 (g / equivalent), more preferably 9000 ~ 15000 (g / equivalent). When the epoxy equivalent of the phenoxy resin having a fluorene structure is 5,000 or more, the elongation at break is excellent, and the crosslinking portion is sufficiently maintained at 30,000 or less, so that the arithmetic mean roughness and the low root mean square roughness are low. And, a low coefficient of linear thermal expansion can be maintained. Further, the epoxy equivalent can be measured in accordance with JIS K7236 (2001).

The weight average molecular weight of the phenoxy resin having a fluorene structure is, for example, 8,000 to 100,000, preferably 15,000 to 80,000, more preferably 20,000 to 60,000, still more preferably 25,000 to 40,000. When the weight average molecular weight of the phenoxy resin is 8,000 or more, the elongation at break is excellent, and when it is 100,000 or less, the compatibility with the resin composition is improved, and the arithmetic mean roughness and the low root mean square roughness can be obtained. The weight average molecular weight of the phenoxy resin can be determined by a colloidal permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is used in the measurement apparatus using LC-9A/RID-6A manufactured by Shimadzu Corporation, and the column is Shodex K-800P/K-804L manufactured by Showa Denko Co., Ltd. /K-804L, the mobile phase is measured at a column temperature of 40 ° C using chloroform or the like, and can be calculated using a calibration curve of standard polystyrene.

When the non-volatile component in the curable resin composition is 100% by mass, the content of the phenoxy resin having a fluorene structure (A) is preferably from 0.3 to 10% by mass, more preferably from 0.5 to 7% by mass, More preferably, it is 0.7 to 5% by mass.

(B) Epoxy resin

The epoxy resin of the component (B) is an epoxy resin different from the phenoxy resin of the component (A). The epoxy resin of the component (B) preferably has an epoxy equivalent different from the phenoxy resin of the component (A). The epoxy equivalent of the epoxy resin of the component (B) (the mass of the epoxy group-containing resin) is preferably 50 to 3000 (g/eq), more preferably 100 to 2000 (g/equivalent), It is more preferably 150 to 1000 (g/eq), and particularly preferably 200 to 500 (g/equivalent). Thereby, the crosslinking density of the insulating layer obtained from the curable resin composition becomes sufficient, which contributes to low thickness. Further, the epoxy equivalent can be measured in accordance with JIS K7236 (2001).

Further, the epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule.

Specific examples of the epoxy resin of the component (B) include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol AF epoxy resin bisphenol ring. Oxygen resin, dicyclopentadiene type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthyl group Ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, linear fat Group epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, screw-containing epoxy resin, cyclohexane dimethanol epoxy resin, trimethylol Type epoxy resin, halogenated epoxy resin, crystalline bifunctional epoxy resin, and the like. More preferably, (B) epoxy resin is 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 such epoxy resins are selected from the group consisting of. These may be used alone or in combination of two or more.

Among these epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, crystalline bifunctional epoxy resin, dicyclopentadiene type epoxy resin, naphthalene, from the viewpoint of heat resistance improvement A type epoxy resin and a mixture of two or more kinds thereof are preferred. Specifically, for example, a mixed epoxy resin of bisphenol A type and F type ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd.), and a bisphenol A type epoxy resin ("EPIKOTE828EL" manufactured by Mitsubishi Chemical Corporation", "YL980" ""jER1009"), bisphenol F type epoxy resin ("JER806H" and "YL983U" manufactured by Mitsubishi Chemical Corporation), and naphthalene type 2-functional epoxy resin (HP4032" and "HP4032D" manufactured by DIC Corporation , "HP4032SS", "EXA4032SS"), naphthalene type 4-functional epoxy resin ("HP4700", "HP4710" made by DIC), and naphthol type epoxy resin ("Nippon Steel Chemical Co., Ltd." 475V"), epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.), epoxy resin having a biphenyl structure ("NC3000H" manufactured by Nippon Kayaku Co., Ltd.," NC3000L", "NC3100"), tetramethylbiphenyl type epoxy resin ("XX4000", "YX4000H", "YX4000HK", "YL6121" manufactured by Mitsubishi Chemical Corporation), 蒽-type epoxy resin (Mitsubishi Chemical) "YX8800" (manufactured by the company), a naphthyl ether epoxy resin (EXA-7310, "EXA-7311", "EXA-7311L", "EXA7311-G3") made from DIC) Ester type epoxy tree Fat ("Ag711", "EX721", "R540" made by Printec, Nagasechemtex), dicyclopentadiene type epoxy tree Fat ("HP-7200H" made by DIC).

Moreover, the structural formula of the main component of HP4032SS is as follows.

Also, the structure of the YX4000HK is as follows.

(wherein Gr is a glycidyl group).

Also, the structural formula of the HP-7200H is as follows.

(where n is an integer from 1 to 20).

Also, the structure of the NC3000L is as follows.

(where n is an integer from 1 to 20).

(B) The content of the epoxy resin is preferably 30 to 80% by mass in the case where the total of the (A) phenoxy resin and the (B) epoxy resin and the (C) curing agent are 100% by mass. More preferably, it is 35 to 75 mass%, and more preferably 40 to 70 mass%.

The content of the (B) epoxy resin in the curable resin composition of the present invention is not particularly limited, but the curable resin is composed of a low-thickness and high peeling strength of the insulating layer. When the nonvolatile content in the product is 100% by mass, it is preferably 5 to 30% by mass, more preferably 7 to 25% by mass, even more preferably 10 to 20% by mass.

(C) hardener

The curing agent used in the present invention is not particularly limited as long as it can be cured by crosslinking the phenoxy resin and the epoxy resin, and contains a phenol curing agent (phenol resin) and a cyanate ester curing agent (cyanic acid). One or more selected from the group consisting of an ester ester resin and an active ester curing agent (active ester resin) are preferred. These phenolic hardeners, cyanate ester hardeners, and active ester hardeners can meaningfully reduce the surface roughness of the insulating layer.

The phenol resin is not particularly limited, and a biphenyl type phenol resin, a naphthalene type phenol resin, a phenol novolac resin, a stretch naphthyl ether type phenol resin, and a triazine skeleton phenol resin are preferable. Specifically, for example, MEH-7700, MEH-7810, MEH-7851 (manufactured by Megumi Kasei Co., Ltd.), naphthol type phenol resin, NHN, CBN, and GPH of a biphenyl type phenol resin (Nippon Chemical Co., Ltd.) System), SN-170, SN-180, SN-190, SN-475, SN- 485, SN-495, SN-375, SN-395 (Nippon Steel Chemical Co., Ltd.), EXB9500 (DIC), phenolic novolac resin TD2090 (made by DIC), naphthyl EXB-6000 (manufactured by DIC Co., Ltd.) of an ether type phenol resin, LA-3018, LA-7052, LA-7054, LA-1356 (manufactured by DIC Co., Ltd.) containing a triazine skeleton phenol resin. These may be used alone or in combination of two or more.

Further, the structural formula of SN-485 is as shown in the following formula (4).

(n is an integer from 1 to 20).

Further, the structural formula of LA-7054 is as shown in the following formula (5).

(n is an integer from 1 to 20).

The cyanate ester resin is not particularly limited, and examples thereof include a novolac type cyanate ester resin, a dicyclopentadiene type cyanate ester resin, a bisphenol type cyanate ester resin, and the like. Triazineated prepolymers and the like. Specifically, a phenol novolac type polyfunctional cyanate ester resin (manufactured by LONZA Japan Co., Ltd., PT30S: number average molecular weight 380, PT60: number average molecular weight 560) represented by the following formula (6), and the following formula ( 7) expressed A bisphenol A type cyanate ester resin (LONZA Nippon Co., Ltd., BA230S75) in which a part or all of the bisphenol A type cyanate ester resin is triazine-formed to form a prepolymer of a trimer, and the following formula (8) A dicyclopentadiene type cyanate ester resin (manufactured by LONZA Japan Co., Ltd., DT-4000, DT-7000) or the like. Specifically, the number average molecular weight is used for the measurement device using LC-9A/RID-6A manufactured by Shimadzu Corporation, the column is Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd., and the mobile phase is chloroform. Etc., measured at a column temperature of 40 ° C, can be calculated using a standard polystyrene calibration line. These may be used alone or in combination of two or more.

[In the formula, the average value of the n system is an arbitrary number (preferably 0 to 20, more preferably 1 to 10)].

(In the formula, the average value of n is 0 to 5).

The active ester resin which can be used in the present invention is a resin compound having one or more active ester groups in one molecule. Here, the "active ester group" means an ester group which reacts with an epoxy resin. The active ester resin is preferably a resin compound which can react with an epoxy resin and has two or more active ester groups in one molecule. A resin compound having two or more reactive ester groups in one molecule selected from the group consisting of phenol esters, thiophenol esters, N-hydroxylamine esters and heterocyclic hydroxy ester esters, preferably used as an active ester resin . The active ester resin may be used singly or in combination of two or more kinds.

From the viewpoint of improvement in heat resistance, an active ester resin obtained by subjecting a carboxylic acid compound and/or a thiocarboxylic acid compound to a condensation reaction with a hydroxy compound and/or a thiol compound is more preferable. The active ester resin obtained by reacting one or two or more selected from a phenol compound, a naphthol compound, and a thiol compound with a carboxylic acid compound is more preferable. Further, an aromatic resin compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is more preferable. An aromatic resin compound obtained by reacting at least two or more carboxylic acid compounds with an aromatic compound having a phenolic hydroxyl group in one molecule, and having two or more active ester groups in one molecule of the aromatic resin compound It An aromatic resin compound is particularly preferred. The active ester resin may be linear or multi-branched. In addition, when a compound having at least two or more carboxylic acids in one molecule is an aliphatic chain-containing compound, compatibility with a resin composition can be improved, and a compound having an aromatic ring can improve heat resistance.

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 preferred from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable. The thiocarboxylic acid compound is specifically thioacetic acid, thiobenzoic acid or the like.

In the above phenol compound or naphthol compound, specifically, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, acid phenolphthalein, methylated bisphenol A, methylated double Phenol 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, dicyclopentadiene Diphenol, phenol novolac, etc. Among them, from the viewpoints of improvement in heat resistance and improvement in solubility, 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, four Hydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene diphenol, phenol novolac, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 ,6- Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene diphenol, phenol novolac lacquer, preferably 1, 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene diphenol , phenol novolac varnish is better, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, phenol novolac varnish is better, 1,5- Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diol are particularly preferred, and dicyclopentadiene diol is particularly preferred. The thiol compound is specifically, for example, benzenedithiol, triazinedithiol or the like.

In terms of the active ester resin, specifically, an active ester resin having a structure composed of a dicyclopentadiene diphenol, an active ester resin containing a naphthalene structure, an active ester resin containing an acetal of a phenol novolac, and a phenol novolac The active ester resin of benzamidine is preferred, and an active ester resin having a naphthalene structure or an active ester resin having a dicyclopentadiene diphenol structure is more preferred. In the case of a commercially available product, an active ester resin containing a dicyclopentadiene diphenol structure may, for example, be EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC), and an active ester resin containing a naphthalene structure may be exemplified. For example, EXB9416-70BK (manufactured by DIC Co., Ltd.), an active ester resin containing a phenolic novolac-based acetal varnish, for example, DC808 (manufactured by Mitsubishi Chemical Corporation), and a benzamidine-based phenol phenolic aldehyde The ester resin may, for example, be YLH1026 (manufactured by Mitsubishi Chemical Corporation).

A particularly preferred active ester resin is the general formula (9) (wherein m is 0 or 1, n is an average value of 0.25 to 1.5, preferably 0.4 to 1.2), and the dicyclopentadiene diphenol is represented by a structure, and each of the terminals has an X-group and an XO-group ( Here, X is a resin compound of a phenyl group or a naphthyl group which may have a substituent. The weight average molecular weight of the active ester resin is preferably from 1,500 to 4,000, more preferably from 2,000 to 3,000.

A more preferred active ester resin is a dicyclopentadiene diphenol structure represented by the following formula (10), and each of the terminals has an X-group and an XO- group (wherein X is a naphthyl group which may have a substituent) ) HPC-8000-65T, an active ester resin having a weight average molecular weight of about 2,700.

(where m is 0 or 1, and the average value of n is 0.4 to 1.2)

The content of the (C) curing agent in the curable resin composition of the present invention is not particularly limited, but the curable resin composition is obtained from the viewpoint of reducing the thickness of the insulating layer and the high peeling strength. When the nonvolatile content is 100% by mass, it is preferably 3 to 20% by mass, more preferably 5 to 18% by mass, and still more preferably 7 to 15% by mass.

When the number of epoxy groups in the entire epoxy resin is 1, the number of reactive 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. Here, the "number of epoxy groups in the entire epoxy resin" means a value obtained by dividing the solid content of each epoxy resin present in the curable resin composition by the epoxy equivalent as the total epoxy resin value. Further, "reactive group" means a functional group reactive with an epoxy group, and "reaction group number" means The solid content mass of the hardener present in the resin composition divided by the value of the reactive group equivalent is taken as the total value.

(D) Inorganic filling materials

The inorganic filler which can be used in the present invention may, for example, be cerium oxide, aluminum oxide, mica, mica, ceric acid salt, barium sulfate, magnesium hydroxide, titanium oxide or the like, preferably cerium oxide or aluminum oxide, especially Preferably, cerium oxide such as cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide, spherical cerium oxide, etc., spherical cerium oxide, and molten cerium oxide are more preferable. good. From the viewpoint of improving the filling property of the inorganic filler of the sheet-like laminate of the present invention containing a curable resin composition, it is more preferable to melt the cerium oxide in a spherical shape. One type or two or more types of inorganic fillers can be used. Commercially available spherical molten cerium oxide, for example, "SOC2" and "SOC1" manufactured by Admatechs.

The average particle diameter of the inorganic filler is not particularly limited, and is preferably 5 μm or less, more preferably 3 μm or less, more preferably 1 μm or less, and more preferably 0.8 μm or less, and 0.6 μm or less from the viewpoint of forming fine wiring on the insulating layer. Especially good. On the other hand, when the curable resin composition is used as a varnish, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, more preferably 0.07 μm or more, and more preferably 0.1 μm or more from the viewpoint of preventing the viscosity of the varnish from increasing and improving the workability. Preferably. The average particle size of the above inorganic filler can be laser diffraction according to the Mie scattering theory. Determined by scattering method. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median diameter is taken as the average particle diameter. Line measurement. It is preferable to use a sample in which the inorganic filler is dispersed in water by ultrasonic waves. For the laser diffraction scattering type particle size distribution measuring apparatus, LA-950 or the like manufactured by Horiba Co., Ltd. can be used.

The content of the inorganic filler is not particularly limited, and the inorganic filler is used when the non-volatile component in the curable resin composition is 100% by mass from the viewpoint of preventing the flexibility of the sheet form of the sheet-like laminate. The amount is preferably from 30 to 90% by mass, more preferably from 40 to 85% by mass, even more preferably from 50 to 85% by mass. In particular, in the present invention, even if the curable resin composition containing 50% by mass or more of the inorganic filler is used, the peeling strength can be improved.

The inorganic filler is preferably subjected to surface treatment (coating) by a coupling agent or the like in order to improve moisture resistance and improve dispersibility. The surface treatment agent (coupling agent) is selected from an epoxy decane coupling agent, an amino decane coupling agent, a mercapto decane coupling agent, a decane coupling agent, an organic decazane compound, and a titanate coupling agent. One or more of them are preferred. Among these, the amino decane coupling agent is excellent in moisture resistance, dispersibility, and properties of a cured product, and a phenylamino decane coupling agent is more preferable. For example, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyl) manufactured by Shin-Etsu Chemical Co., Ltd. "Methoxy decane", "KBE903" (3-aminopropyltriethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-amino group) manufactured by Shin-Etsu Chemical Co., Ltd. "propyl trimethoxy decane", "SKM103" (phenyl trimethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., and "SZ-" manufactured by Shin-Etsu Chemical Co., Ltd. 31" (hexamethyldioxane) and the like.

[Other ingredients]

The curable resin composition of the present invention may be appropriately blended with a curing accelerator, a thermoplastic resin, a vinyl benzyl compound, an acrylic compound, a maleimide compound, or a blocked isocyanate compound, in addition to the above components. Curable resin; flame retardant such as phosphorus compound or metal hydroxide; organic filler such as barium powder, nylon powder, fluorine powder, rubber particles; organic solvent; tackifier of Orben, Penton, etc. A fluorine-based or polymer-based antifoaming agent; an adhesion imparting agent such as an imidazole-based, a thiazole-based, a triazole-based or a decane coupling agent; and a phthalocyanine. Blue, turnip. Green, Iodine. Green, Disazo Yellow, carbon black and other coloring agents; additives, etc.

In the case of the hardening accelerator, if the above-mentioned curing agent can promote crosslinking and hardening of the above epoxy resin, any curing accelerator can be used, for example, an amine compound, a cerium compound, an imidazole compound, a cerium compound, and a metal-based hardening accelerator. Agents, etc. These may be used alone or in combination of two or more.

The amine compound which can be used in the invention is not particularly limited, and examples thereof include a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine (DMAP), and benzyldimethyl group. Amine, 2,4,6,-paraxyl (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU). Ethamamine compounds and the like. These may be used alone or in combination of two or more. These may be used alone or in combination of two or more.

The imidazole compound which can be used in the present invention may be the following general formula (11) (Wherein, R ₇ ~ R ₁₀ are each the same or different, is a hydrogen atom, a halogen atom, cyano, nitro, methyl acyl, C _{1 ~ 20} alkyl group, C _{2 ~ 20} alkylene group, C _{2 ~ 20} alkynyl group, C _{3 ~ 20} allyl, C _{4 ~ 20} alkyldienyl group, C _{4 ~ 20} polyalkenyl group, C _{6 ~ 20} aryl group, C _{6 ~ 20} aryl group, C _{6 ~ 20} aryl An alkyl group, a C _4-20 cycloalkyl group, a C _4-20 cycloalkenyl group, a (C _5-10 cycloalkyl) C _1-10 alkyl group, a decyl group which may have a C _1-10 hydrocarbon group, derived from a ring The compound represented by the hydroxyethyl group of the oxygen resin may also be used.

More specifically, the imidazole compound may be 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-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'-undecidamidazolyl-(1')]-ethyl-S-triazine, 2,4-diamino- 6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-S-triazine, 2,4-diamino-6-[2'-methylimidazolyl- (1')]-Ethyl-S-triazine iso-cyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole , 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-methylimidazole, an adduct of an imidazole compound and an epoxy resin, and 2,4-diamino-6- A selected compound of the group formed by vinyl-S-triazine. These may be used alone or in combination of two or more.

The metal-based hardening accelerator which can be used in the present invention is not particularly limited, and examples thereof include organometallic complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetamidineacetone (Co(II)Ac), cobalt (III) acetamidineacetone (Co(III)Ac), and copper. (II) an organic copper complex such as acetonitrile acetone, an organic zinc complex such as zinc (II) acetamidine, an organic iron complex such as iron (III) acetamidine, or nickel (II) acetamidine. An organic nickel complex such as acetone or an organic manganese complex such as manganese (II)acetonitrile or the like. Examples of the organic metal salt include zinc octoate, tin octylate, zinc naphthalate, cobalt naphthalate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

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

In the thermoplastic resin, for example, (A) a phenoxy resin other than a phenoxy resin having a fluorene structure, a polyvinyl acetal resin, a polyimine resin, and a polyfluorene may be mentioned as long as it does not inhibit the effects of the present invention. Amino acetal resin, a polyether oxime resin, a cycloolefin polymer, a polyfluorene resin, etc. are preferable, and a polyvinyl acetal resin is preferable. These may be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is equal to the weight of the (A) phenoxy resin The method for determining the average molecular weight can also be measured by a colloidal permeation chromatography (GPC) method.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbene. An acetate such as an alcohol acetate, a cellosolve, a carbitol such as butyl carbitol, a petroleum-soluble petroleum spirit, an aromatic hydrocarbon such as toluene or xylene, dimethylformamide or the like. A guanamine-based solvent such as methyl acetamide or N-methylpyrrolidone. Two or more types of organic solvents can be used in combination.

[Modulation of Curable Resin Composition]

The curable resin composition of the present invention can be suitably mixed by the above-mentioned components, and if necessary, a kneading means such as a three-roller, a ball mill, a bead mill, a sand mixer, or a high-speed rotary mixer or a quick mixer. The stirring means such as a planetary mixer is mixed or mixed to prepare. Further, it can be prepared by adding the above organic solvent as a resin varnish.

In the curable resin composition of the present invention, not only the arithmetic mean roughness of the surface of the insulating layer is low, but also the square root thickness is low, and a plated conductor layer having sufficient peeling strength can be formed thereon, so that the multilayer printed wiring board is formed. In the production, a curable resin composition for an insulating layer as a multilayer printed wiring board can be suitably used. Further, it is more preferably 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 on which a conductor layer is formed by plating), and is more preferably used as a multilayer printed wiring board. The layer is made of a curable resin composition.

The form of the curable resin composition of the present invention is not particularly limited, and a sheet-like laminate such as a film or a prepreg or a circuit board (for laminate use, multilayer printed wiring board use, etc.) can be applied. The resin composition may be applied to the circuit board in a varnish state to form an insulating layer. However, it is generally used in the form of a sheet-like laminate which is followed by a film or a prepreg, and the softening point of the curable resin composition. From the viewpoint of the lamination property of the sheet-like laminate, it is preferably from 40 to 150 °C.

[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 which can be used in the present invention is a multilayer printed wiring board including an insulating layer obtained by thermally curing the curable resin composition or the sheet-like laminate of the present invention.

Here, the conditions of the thermosetting may be appropriately selected depending on the type and content of the epoxy resin in the curable resin composition, for example, the curing temperature is 90 to 220 ° C, preferably 160 ° C to 210 ° C, and the hardening time is 10 The heating is carried out in minutes to 180 minutes, preferably in 20 to 120 minutes. Further, it is also possible to perform thermal hardening in two stages.

The linear thermal expansion coefficient (CTE) (JIS K7197) of the insulating layer is measured by an average linear thermal expansion coefficient of 25 to 150 ° C, preferably 20 ppm / ° C or less, more preferably 19 ppm / ° C or less. The lower limit is not particularly limited and is generally 4 ppm/° C. Thereby, deformation of the insulating layer (addition layer) and the conductor layer (wiring) can be prevented, and a multi-layer printing with high reliability can be obtained. Brush the wiring board.

The surface of the insulating layer can be roughened. The dry roughening treatment may, for example, be plasma treatment or the like. The wet roughening treatment can be carried out, for example, by using various treatment liquids. For example, a method of swelling with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid are sequentially performed. Therefore, the treatment liquid can be a set of such a swelling liquid, an oxidizing agent, and a neutralizing liquid.

The wet roughening processor is preferable in terms of high productivity because it can process a large area or a plurality of pieces at a time.

The swelling treatment of the swelling liquid is carried out by immersing the insulating layer at 50 to 80 ° C for 5 to 20 minutes (preferably 55 to 70 ° C for 8 to 15 minutes). The swelling liquid may, for example, be an alkali solution or a surfactant solution, and is preferably an alkali solution. The alkali solution may, for example, be a sodium hydroxide solution or a potassium hydroxide solution. Commercially available swelling liquids include, for example, Swelling Dip Securiganth P) manufactured by Atotech Japan Co., Ltd., Swelling Dip Securiganth SBU, and the like.

The oxidizing agent is subjected to roughening treatment, and the insulating layer is immersed in an oxidizing agent solution at 60 to 80 ° C for 10 to 30 minutes (preferably 70 to 80 ° C for 15 to 25 minutes). The oxidizing agent may, for example, be 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, nitric acid or the like. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. The commercially available oxidizing agent may, for example, be an alkaline permanganic acid solution such as concentrates Compact CP or Dosing Solution security Gans P manufactured by Atotech Japan Co., Ltd.

The mixture is neutralized by a neutralizing solution, and immersed in a neutralizing solution at 30 to 50 ° C for 3 to 10 minutes (preferably 35 to 45 ° C for 3 to 8 minutes). In the case of the neutralizing liquid, an acidic aqueous solution is preferred, and in the case of a commercial product, for example, a reduction solution Shin security Gantt P manufactured by Atotech Japan Co., Ltd. may be mentioned.

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

The surface roughness of the surface of the insulating layer after the roughening treatment is preferably 30 nm or less in arithmetic mean roughness (Ra), more preferably 300 nm or less, more preferably 250 nm or less, or more preferably 100 nm or less in order to improve the fine wiring. The lower limit of the arithmetic mean roughness (Ra) is not limited, but is generally 10 nm or more, 40 nm or more, 70 nm or more. The root mean square roughness (Rq) is preferably 500 nm or less, more preferably 450 nm or less, more preferably 350 nm or less, and particularly preferably 150 nm or less. The lower limit of the square root roughness (Rq) is not limited, but is generally 20 nm or more, 50 nm or more, 90 nm or more. Further, the root mean square roughness (Rq) is a partial state of the surface of the insulating layer, and by grasping Rq, it is confirmed that the surface of the insulating layer is denser and smoother, and the peeling strength is stabilized. This is equivalent to the surface roughness of the insulating layer after the heat-hardening of the curable resin composition and the roughening treatment.

The peeling strength is preferably 0.45 kgf/cm (4.41 N/cm) or more, and 0.50 kgf/cm (4.90 N/cm) or more in order to make the insulating layer and the layer adjacent thereto, for example, sufficiently adhered to the conductor layer. Preferably. The upper limit of the peeling strength is preferably as high as possible, and is not particularly limited, and is generally 1.5 kgf/cm (14.7 N/cm) or less and 1.2 kgf/cm (11.8 N/cm) or less. 1.0 kgf/cm (9.81 N/cm) or less, 0.8 kgf/cm (7.85 N/cm) or less.

The tensile strength of the cured product obtained by thermally hardening the curable resin composition was measured in accordance with JIS K7127. Specifically, a test piece cut out of the cured product into a dumbbell shape was prepared, and the PET film was peeled off and measured using a tensile tester RTC-1250A manufactured by Orientec. 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 laminate]

The sheet-like laminate used in the present invention is a sheet-like material before curing in which the curable resin composition is layered. The sheet-like laminate can be applied to a resin varnish in which the resin composition is dissolved in the above organic solvent by a conventional method of the above, and the resin varnish can be applied to the support using a pattern coater or the like. The organic solvent is dried by heating or hot air blowing, and a resin composition layer (sheet-like laminate) is formed on the support to produce a support sheet-like laminate. Further, the resin varnish may be impregnated and dried by a hot melt method or a solvent method on a sheet-like reinforcing substrate such as a glass mesh, or the sheet-like laminate may be used as a prepreg. Further, there is also a case where the support sheet-like laminate is referred to as a film.

The drying conditions are not particularly limited, and the content of the organic solvent of 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 varies depending on the boiling point of the organic solvent, for example, by using a varnish containing 30 to 60% by mass of an organic solvent. It is dried at 50 to 150 ° C for about 3 to 10 minutes to form a resin composition layer.

The thickness of the obtained sheet-like laminate is not particularly limited, and is preferably in the range of preferably 1 to 150 μm, more preferably in the range of 2 to 100 μm, 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 one side of the resin composition layer may have a support, and the other surface may have a protective film.

[Support]

The support which can be used in the present invention may, for example, be a plastic film or a metal foil. Specific examples of the plastic film include polyethylene terephthalate (hereinafter referred to as "PET"), polyester such as polyethylene-naphthalate, polycarbonate, polyethylene, and poly. Propylene, acrylic acid, cyclic polyolefin, triethylenesulfonyl cellulose, polyether sulfide, polyether ketone, polyimine, and the like. Among them, a polyethylene terephthalate film or a polyethylene p-naphthalate film is preferable, and a polyethylene terephthalate film which is inexpensive and easily available is preferable.

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

In the case of a plastic film, in the case of a plastic film, in order to improve the peeling property, it is preferable to use a support which is a release film in contact with a layer containing a curable resin composition. In the release agent used for the release treatment, the layer containing the curable resin composition is not particularly limited, and is, for example, a bismuth release agent, an alkyd resin release agent, a polyolefin resin, and an amine group. Ethyl formate resin, fluororesin, and the like. Again As the support for the release treatment, a commercially available plastic film having a release layer may be used, and for example, SK-1, AL having a PET film having a release layer containing an alkyd resin release agent as a main component may be preferably used. -5, AL-7 (Lintec system) and the like. Further, the plastic film may be subjected to a matting treatment or a corona treatment, and 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.

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

The protective film which can be used in the present invention can be prevented from being attached to the layer containing the curable resin composition for the purpose of adhering dust or the like. For the protective film, the same plastic film as the support can be used. Further, the protective film may be subjected to a surface treatment such as matting treatment or corona treatment, or the same release treatment as described above may be applied. The thickness of the protective film is preferably 3 to 30 μm, more preferably 5 to 20 μm.

[Multilayer Printed Wiring Board Using Sheet Laminate]

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

First, the sheet-like laminate is laminated on one side or both sides of a circuit board 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, and a thermosetting polyphenylene ether substrate. In addition, the circuit board means a conductor layer (circuit) formed by patterning on one surface or both surfaces of the above-described substrate. And the conductor layer and the insulating layer are alternately laminated In the multilayer printed wiring board, the one or both sides of the outermost layer of the multilayer printed wiring board are also included in the patterned circuit board. Further, the surface of the conductor layer may be subjected to a roughening treatment in advance, such as blackening treatment or copper etching.

In the laminate, when the sheet-like laminate has a protective film, after removing the protective film, the sheet-like laminate and the circuit substrate are preheated, and the sheet-like laminate is pressed and heated while laminating. On the circuit board. In the sheet-like laminate of the present invention, a method of laminating to a circuit board under reduced pressure by vacuum lamination is preferably used. The lamination conditions are not particularly limited. For example, the air pressure is 20 mmHg (26.7 hPa) or less, and the pressure is reduced for about 10 to 120 seconds. Thereafter, the pressing temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure (layer) The pressing pressure is preferably 0.1 to 1.5 MPa, more preferably 0.5 to 1.2 MPa, and the pressing time (lamination time) is preferably 5 to 180 seconds. Further, the lamination method may be a batch type or a continuous type of rolls. Vacuum lamination can be carried out using a commercially available vacuum laminator. The commercially available vacuum laminating machine may, for example, be a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum press laminator manufactured by Nippon Machine Co., Ltd., or a roll dryer manufactured by Hitachi Industries Co., Ltd. A coater, a vacuum laminator made by Hitachi AIC Inc., and the like.

Thereafter, after cooling to the vicinity of room temperature (25 ° C), the support is 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 of the heat curing can be appropriately selected depending on the kind and content of the resin component in the resin composition, for example, the curing temperature is 100 to 220 ° C, preferably 160 ° C to 210 ° C, and the hardening time is 20 minutes. The clock is heated for 180 minutes, preferably 30 to 120 minutes. Further, it is also possible to perform thermal hardening in two stages. After the insulating layer is formed, if the support is not peeled off before the hardening, the peeling may be performed here as necessary.

Further, the sheet-like laminate may be laminated on one surface or both surfaces of the circuit board using a vacuum presser. The laminating step of heating and pressurizing under reduced pressure can be carried out using a general vacuum heat press. For example, the metal plate such as a heated SUS plate can be pressurized by the support side. The pressurization condition is 70 to 250 ° C, preferably 100 to 230 ° C, and the degree of pressure reduction is usually 0.01 MPa or less, preferably 0.001 MPa or less, and the pressure is 0.5 to 4 MPa. The pressing time is preferably 30 to 150 minutes. The heating and the pressurization can be carried out in one step, and it is preferable to carry out two or more stages from the viewpoint of controlling the bleeding of the resin. For example, in the first stage, the pressure is 70 to 150 ° C, the pressure is 0.1 to 1.5 MPa, and the second stage is pressurized at a temperature of 150 to 200 ° C and a pressure of 0.5 to 4 MPa. Preferably. The time of each stage is preferably 20 to 120 minutes. By thermally hardening the resin composition layer in this manner, an insulating layer can be formed on the circuit board. For example, MNPC-V-750-5-200 (manufactured by Nippon Seiki Co., Ltd.), VH1-1603 (made by Kitagawa Seiki Co., Ltd.), and the like can be used.

Next, the insulating layer formed on the circuit board is subjected to a hole drilling process to form a via hole and a through hole. Open hole processing, for example, a conventional method such as a drill, a laser, a plasma, etc., and may be performed in combination with such a method, and a laser of a carbon dioxide gas laser, a YAG laser, or the like is processed as the most The general method. Where the support is not peeled off before the hole processing, Stripping is performed here.

Next, the surface of the insulating layer is subjected to the above-described roughening treatment, and a conductor layer is formed on the insulating layer by dry plating or wet plating. For dry plating, a conventional method such as vapor deposition, sputtering, or ion coating can be used. Examples of the wet plating include a method in which electroless plating and electrolytic plating are combined, a method of forming a conductor layer, a plating resist which forms a reverse pattern with a conductor layer, and a method of forming a conductor layer only by electroless plating. . The method of pattern formation thereafter can be, for example, a multilayer printed wiring board of a multi-stage laminated build-up layer by repeating the above-described series of steps several times using the conventional Subtractive Method, semi-additive method, or the like. In the present invention, it is preferable to use as a build-up layer of a multilayer printed wiring board because of low thickness and high peeling strength.

[semiconductor device]

A semiconductor device can be manufactured by using the multilayer printed wiring board manufactured as described above. In the conduction of the multilayer printed wiring board which can be used in the present invention, a semiconductor device can be manufactured by mounting a semiconductor wafer. “Conduit” means “where the electrical signal is transmitted in a multilayer printed wiring board”, which may be a surface or embedded. Further, if it is turned on, it may be a conductive portion such as a part of the conductor layer or a connector other than the conductor layer. The "semiconductor wafer" is a circuit element made of a semiconductor, and is not particularly limited.

The method for mounting a semiconductor wafer in the manufacture of the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can be effectively operated. Specifically, for example, a wire bonding mounting method, a flip chip mounting method, and no bump increase Layer (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, etc.

[Examples]

Hereinafter, the invention will be more specifically described by way of examples, but the invention is not limited to the examples. In addition, the "part" in the following description means "parts by mass", and "%" means "mass%" unless otherwise specified.

<Measurement method. Evaluation method>

First, explain the various measurement methods. evaluation method.

[Modulation of peeling strength, arithmetic mean roughness (Ra value), and square root mean roughness (Rq value)] (1) Underlayer treatment of laminates

The glass cloth substrate epoxy resin was coated on both sides of a copper laminate (18 μm thick copper foil, 0.3 mm thick substrate, R5715ES manufactured by Matsushita Electric Works Co., Ltd.), and 1 μm was etched by CZ8100 manufactured by MEC Co., Ltd. to perform copper surface etching. Coarse processing.

(2) subsequent lamination of the film

The adhesive film produced in the examples and the comparative examples was laminated on both sides of the double-sided copper-clad laminate of the epoxy resin subjected to the above-mentioned roughening treatment using a batch type vacuum pressure laminator MVLP-500 (manufactured by Nago Seisakusho Co., Ltd.). . Lamination After depressurization for 30 seconds, the gas pressure was 13 hPa or less, and then pressing was carried out for 30 seconds, 100 ° C, and a pressure of 0.74 MPa.

(3) Hardening of resin composition

After peeling off the polyethylene terephthalate (PET) film of the support by the laminated adhesive film, the resin composition was cured at 100 ° C for 30 minutes, followed by hardening conditions of 180 ° C for 30 minutes to form an insulation. Floor.

(4) roughening treatment

The laminate forming the insulating layer is immersed in a swelling liquid, that is, Atotech Japan's diethylene glycol monobutyl ether-containing Swelling Dip Securiganth P (glycol ether, aqueous sodium hydroxide solution), impregnated at 60 ° C. Minutes (Example 1, Comparative Examples 14, 5) or 10 minutes (Examples 2, 3, Comparative Examples 2, 3). Subsequently, it was immersed in a concentration of Atotech Japan's concentrates Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L) as a roughening solution at 80 ° C for 15 minutes (Example 1, Comparative Examples 1, 4, 5) ), 20 minutes (Examples 2, 3, Comparative Examples 2, 3). Finally, as a neutralizing solution, Atotech Japan's reduction solution Shin security GanttP (aqueous solution of sulfuric acid) was immersed at 40 ° C for 5 minutes. After drying at 80 ° C for 30 minutes, the substrate was used as the evaluation substrate A.

(5) Plating of semi-additive method

The evaluation substrate A is plated to form a conductor layer. Specifically, the substrate A was evaluated in a solution for electroless plating containing PdCl ₂ , immersed at 40 ° C for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C for 20 minutes. After heating at 150 ° C for 30 minutes and annealing treatment, an etching resist was formed, and after the pattern of etching was formed, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. The annealing treatment was then carried out at 190 ° C for 60 minutes. This substrate was used as the evaluation substrate B.

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

The evaluation substrate A was subjected to a non-contact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments Co., Ltd.), and the Ra value and the Rq value were determined from the values obtained by measuring the measurement range at 121 μm × 92 μm by a VSI contact mode and a 50-fold lens. . The measurement was performed by obtaining an average value of 10 points.

[Determination of peeling strength of plated conductor layer]

For the evaluation of the conductor layer of the substrate B, a cut of a portion having a width of 10 mm and a length of 100 mm was set, and the one end was peeled off and clamped by a jig (stock company TSE type tester AC-50C-SL), and measured at room temperature ( In 25 ° C), the load (kgf / cm (N / cm)) when peeling 35 mm in the vertical direction at a speed of 50 mm / minute.

[Determination of linear thermal expansion coefficient (CTE)]

By bringing the film obtained in the examples and the comparative examples at 200 ° C The film was heated for 90 minutes to be thermally hardened, and peeled off from the PET film of the support to obtain a flaky cured product. The cured product was cut into a test piece having a width of 5 mm, a length of 15 mm, and a thickness of 30 mm, and subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Co., Ltd.). After the test piece was placed in the above apparatus, the measurement was carried out twice in succession under the measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C /min. The average linear thermal expansion coefficient (ppm) at 25 ° C to 150 ° C in the second measurement was calculated.

[Measurement of elongation at break]

The adhesive film obtained in the examples and the comparative examples was heated at 200 ° C for 90 minutes to be thermally cured, and the cured product was cut into a dumbbell shape to peel off the PET film to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester RTC-1250A manufactured by Orientec Co., Ltd. in accordance with JIS K7127, and the elongation at break at 23 ° C was determined.

<Synthesis Example 1> Synthesis of phenoxy resin with oxime structure and tetramethylbiphenyl structure

In the reaction vessel, tetramethylbiphenyl type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185) 191 g, 9,10-dihydroxyanthracene (phenolic hydroxyl equivalent 210) 210 g, and cyclohexane were added. 150 g of the ketone was stirred to dissolve. Next, 0.5 g of a tetramethylammonium chloride solution was dropped, and the reaction was carried out for 5 hours at 180 ° C in a nitrogen atmosphere. After completion of the reaction, filtration was carried out using a filter cloth, and phenoxy resin A was obtained by dilution with a solvent.

. Epoxy equivalent: 11000

. Weight average molecular weight: 35000

. Solid solution of 30% by mass of 1:1 solution of MEK and cyclohexanone

Further, the phenoxy resin A has the following structure.

<Synthesis Example 2> Synthesis of phenoxy resin with tetramethylbiphenyl structure and bisphenol acetophenone structure

In the reaction vessel, tetramethylbiphenyl type epoxy resin ("YX4000" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185) 100 g, bisphenol acetophenone (phenolic hydroxyl equivalent 145) 80 g, and cyclohexane were added. 150 g of the ketone was stirred to dissolve.

Next, 0.5 g of a tetramethylammonium chloride solution was dropped, and the reaction was carried out for 5 hours at 180 ° C in a nitrogen atmosphere. After completion of the reaction, filtration was carried out using a filter cloth, and phenoxy resin B was obtained by dilution with a solvent. Further, the phenoxy resin B has a fluorene structure and is a reference example of the present invention.

. Epoxy equivalent: 13000

. Weight average molecular weight: 38000

. 1:1 dissolution of MEK and cyclohexanone as a solid fraction of 30% by mass liquid.

Further, the phenoxy resin B has the following structure.

<Example 1>

A bisphenol type epoxy resin (ZX1059 manufactured by Nippon Steel 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 (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185) 10 parts, dicyclopentadiene type epoxy resin ("HP-7200H" manufactured by DIC Co., Ltd., epoxy equivalent 275) 20 parts 35 parts of the coal-soluble petroleum spirit was dissolved while heating while stirring. After cooling to room temperature (25 ° C), phenoxy resin A was mixed therein: 12 parts, and a triazine-based phenol-based hardener (TC-7, a solid content of "LA-7054" having a hydroxyl equivalent of 125% by DIC) was mixed. MEK solution) 12 parts, naphthalene type hardener ("SK-485", 70% of MEK solution of hydroxyl equivalent of 215, of Nippon Steel Chemical Co., Ltd.) 15 parts, hardening accelerator (4-dimethylamino group) Pyridine (DMAP), 2% by mass of MEK solution) 3 parts, flame retardant ("HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydrogen-9, manufactured by Sanguang Co., Ltd.) - Oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts, phenylamino decane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") 150 parts of 矽 (average particle diameter: 0.24 μm, "SOC1" manufactured by Admatechs, 0.36 mg/m ² per unit area) was uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. Then, the thickness of the resin composition layer after drying was 30 μm on the release surface of the polyethylene terephthalate film ("AL5" manufactured by Lintec Co., Ltd., thickness: 38 μm). The resin varnish was uniformly applied, and dried at 80 to 120 ° C (average 100 ° C) for 4 minutes to prepare a film.

<Example 2>

5 parts of a liquid naphthalene type epoxy resin (epoxy equivalent 144, "HP4032SS" manufactured by DIC Co., Ltd.), a crystalline bifunctional epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, and an epoxy equivalent of about 185) 12 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269) 12 parts were dissolved in 30 parts of coal-soluble petroleum spirit while stirring. After cooling to room temperature (25 ° C), phenoxy resin A was mixed therein: 5 parts of a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by LONZA Japan Co., Ltd., cyanate equivalent: about 232 20 parts by mass of a MEK solution having a nonvolatile content of 75% by mass, a phenol novolac type polyfunctional cyanate ester resin ("PT30S" manufactured by LONZA Japan Co., Ltd., a cyanate equivalent of about 133, and a nonvolatile content of 85% by mass) MEK solution) 6 parts, hardening accelerator (4-dimethylaminopyridine, solid content 2% by mass of MEK solution) 1 part, hardening accelerator (Tokyo Chemical Co., Ltd., cobalt (III) acetonitrile ( Co(III)Ac)), 3 parts by mass of MEK solution in solid content) 3 parts, 2 parts of rubber particles (manufactured by GANZ Chemical Co., Ltd., Stafyloid AC3816N), and a flame retardant (HCA-HQ, manufactured by Sanguang Co., Ltd.) 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxo-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts, phenylamino decane coupling agent ( Shin-Etsu Chemical Co., Ltd., "KBM573"), spherical cerium oxide (average particle size: 0.5 μm, "SOC2" manufactured by Admatechs, carbon content per unit area: 0.39 mg/m ² ) 100 parts, The resin varnish was prepared by uniformly dispersing in a high-speed rotary mixer. Next, a film of the following film was produced in the same manner as in Example 1.

<Example 3>

Bisphenol type epoxy resin (ZX1059 made by Nippon Steel Chemical Co., Ltd.), 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169) 10 parts, biphenyl type epoxy 12 parts of resin (Nippon Chemical Co., Ltd. "NC3000L", epoxy equivalent 269) was dissolved in 30 parts of coal-soluble petroleum spirit while stirring. After cooling to room temperature, phenoxy resin A was mixed therein: 17 parts, an active ester compound ("HPC8000-65T" manufactured by DIC), a weight average molecular weight of about 2700, and an active group equivalent of about 223. 34 parts by mass of toluene solution), 6 parts of hardening accelerator (4-dimethylaminopyridine, solid content of 2% by mass of MEK solution), flame retardant ("HCO-HQ" manufactured by Sanguang Co., Ltd., 10 -(2,5-dihydroxyphenyl)-10-hydro-9-oxo-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts, phenylamino decane-based coupling agent (Shin-Etsu 150 parts of spherical ceria (average particle size 0.5 μm, "SOC2" manufactured by Admatcchs, 0.39 mg/m ² per unit area) surface-treated by Chemical Industry Co., Ltd., "KBM573") The high-speed rotary mixer is uniformly dispersed to produce a resin varnish. Next, a film of the following film was produced in the same manner as in Example 1.

<Comparative Example 1>

In addition, the phenoxy resin A of Example 1 was changed to 12 parts by weight to a bisphenol A type phenoxy resin ("E1256B40" manufactured by Mitsubishi Chemical Corporation, a MEK solution having a solid content of 40% by mass, an epoxy equivalent of 8000, and a weight. A film was produced in the same manner as in Example 1 except that the average molecular weight was about 50,000).

<Comparative Example 2>

An adhesive film was produced in the same manner as in Example 2 except that the phenoxy resin A of Example 2 was changed to 5 parts of the phenoxy resin B of Synthesis Example 2: 5 parts.

<Comparative Example 3>

An adhesive film was produced in the same manner as in Example 3 except that the phenoxy resin A of Example 3 was changed to 17 parts of the phenoxy resin B of Synthesis Example 2.

The results are shown in Tables 1 and 2.

<Comparative Example 4>

In addition, the phenoxy resin A of Example 1 was changed from 12 parts to a fluorene type epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 181). A film was produced in the same manner as in Example 1 except for 3.6 parts. Also, the structure of "YX8800" is as follows.

<Comparative Example 5>

A film was produced in the same manner as in Example 1 except that the phenoxy resin A of Example 1 was changed from 12 parts to 43 parts. Further, in Comparative Example 5, when the total of (A) phenoxy resin, (B) epoxy resin, and (C) curing agent is 100% by mass, the (A) phenoxy resin is 18.8% by mass. Therefore, it is outside the scope of the present invention.

The results are shown in Tables 1 and 2.

As a result of Tables 1 and 2, in Examples 1 to 3 using the curable resin composition of the present invention, it has a low thickness, a sufficient peeling strength, a low coefficient of linear thermal expansion, and a sufficient elongation at break. On the other hand, in Comparative Examples 1 to 5, when the curable resin composition of the present invention is not used, there is a case where the arithmetic mean roughness and the square root thickness become large, and when the peeling strength is small, the linear thermal expansion coefficient becomes In the case of large, the occasion where the fracture extension is lowered.

Claims (17)

A curable resin composition comprising (A) a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a curing agent, which is characterized by the aforementioned (A) When the total of the phenoxy resin, the (B) epoxy resin, and the (C) curing agent is 100% by mass, the (A) phenoxy resin is 1 to 15% by mass, and the (A) phenoxy group. The epoxy equivalent of the resin is 5,000 or more. The curable resin composition according to claim 1, wherein the (A) phenoxy resin has a weight average molecular weight of 8,000 to 100,000. The curable resin composition according to claim 1, wherein the (A) phenoxy resin further has an unsubstituted or substituted biphenyl structure. The curable resin composition according to claim 1, wherein the epoxy resin (B) is a bisphenol epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene epoxy resin, or a naphthalene type. An epoxy resin, a biphenyl type epoxy resin, and a mixture of such epoxy resins are selected as a group. The curable resin composition according to claim 1, wherein the (C) curing agent is selected from the group consisting of a phenol curing agent, a cyanate ester curing agent, an active ester curing agent, and a mixture of such curing agents. The curable resin composition according to claim 1, wherein the (C) curing agent is a cyanate ester curing agent or an active ester curing agent. In the case where the non-volatile component in the curable resin composition is 100% by mass, the content of the (A) phenoxy resin is 0.3 to 10% by mass, before The content of the (B) epoxy resin is 5 to 30% by mass, and the content of the (C) curing agent is 3 to 20% by mass. The curable resin composition according to claim 1, further comprising (D) an inorganic filler. The curable resin composition according to claim 8, wherein the (D) inorganic filler has an average particle diameter of 0.01 to 5 μm. In the case where the non-volatile component in the curable resin composition is 100% by mass, the content of the (D) inorganic filler is 30 to 90% by mass. The curable resin composition according to claim 8, wherein the (D) inorganic filler is cerium oxide. 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 11. A curable resin composition for a build-up of a multilayer printed wiring board, characterized in that the curable resin composition according to any one of claims 1 to 11 is contained. A sheet-like laminate comprising the curable resin composition according to any one of claims 1 to 11. A multilayer printed wiring board comprising the insulating layer obtained by thermally curing the curable resin composition according to any one of claims 1 to 11. A multilayer printed wiring board characterized by comprising an insulating layer obtained by thermally curing the sheet-like laminate described in claim 14. A semiconductor device characterized by comprising the multilayer printed wiring board of claim 16.