TW201437277A - Curable resin composition - Google Patents

Abstract

The purpose of this invention is to provide a curable resin composition having the excellent film-like resin fluidity (fillability), having the lower arithmetic mean roughness for insulation layers in wet type roughening steps as well as the lower square mean square root roughness, allowing formation thereon with an electroplated conductor layer with the sufficient peel strength and having the lower linear thermal expansion coefficient. The solution comprises providing a curable resin composition characterized by containing: (1) an epoxy resin mixture containing (1-A) epoxy resin A having at least two structures selected from biphenyl structure, bixylenol structure, bisphenol acetophenone structure, and bisphenol fluorene structure, and (1-B) epoxy resin B other than the said epoxy resin A, wherein the epoxy equivalent of the epoxy resin A is 1500 to 4800 and the content of the epoxy resin A is 3 to 30 mass% relative to 100 mass% of the epoxy resin mixture; (2) a curing agent; and (3) an inorganic filler material.

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, with the miniaturization and high performance of electronic equipment, it is required to increase the number of layers in the multilayer printed wiring board, to make the wiring finer and higher in density.

Various combinations of proposals have emerged. For example, as disclosed in Patent Document 1, 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, movability, impact resistance, and adhesion are improved. (Request and paragraph number 0003, etc.). However, the resin composition of Patent Document 1 is a polymer epoxy resin having an epoxy equivalent of 5000 g/eq or more, but heat resistance of 5000 g/eq or less is insufficient (paragraph 0016).

Prior technical literature Patent literature

Patent Document 1: JP-A-2003-252951

The problem to be solved by the present invention is to provide a film-like resin excellent in fluidity (filling property). In the wet roughening step, not only the arithmetic mean roughness of the surface of the insulating layer is low, but also the self-average square root roughness is also higher. Low (low roughness), a curable resin composition having a plated conductor layer having sufficient tear strength and having a low coefficient of thermal expansion of the wire can be formed thereon.

In view of the above-mentioned problems, the present inventors have intensively reviewed and found that the epoxy resin composition containing (1) epoxy resin A having a specific structure and other epoxy resin B is composed of the above epoxy resin mixture. 100% by mass of the epoxy resin A is 3 to 30% by mass, the epoxy resin A has an epoxy equivalent of 1500 to 4800, an epoxy resin mixture, (2) a hardener, and (3) an inorganic filler. The curable resin composition of the material can achieve the above-mentioned excellent landfillability, low roughness, high tear strength and low linear thermal expansion coefficient, and the present invention has been completed.

That is, the present invention encompasses the following aspects.

[1] A curable resin composition comprising (1) containing (1-A) having a biphenyl structure, a bixylenol structure, a biphenyl benzene structure, and a bisphenol quinone structure selected Two or more types of epoxy resin A, and (1-B) other than the above epoxy resin A In the epoxy resin mixture of the epoxy resin B, when the epoxy resin resin mixture is 100 mass, the content of the epoxy resin A is 3 to 30% by mass, and the epoxy resin A has an epoxy equivalent of 1500 to 4800. Epoxy resin mixture, (2) hardener, and (3) inorganic filler.

[2] The curable resin composition according to [1], wherein the content of the epoxy resin A in the case where the nonvolatile content in the curable resin composition is 100% by mass is 0.5 to 10% by mass.

[3] The curable resin composition according to [1] or [2] wherein the (1-B) epoxy resin B is a bisphenol type epoxy resin, a crystalline bifunctional epoxy resin, and a bicyclic ring. A mixture of a pentadiene type epoxy resin, a naphthalene type epoxy resin, and a mixture of such epoxy resins is selected.

[4] The curable resin composition according to any one of [1] to [3] wherein the epoxy resin mixture of the (1) epoxy resin mixture has an epoxy equivalent of 50 to 3,000.

[5] The curable resin composition according to any one of [1], wherein the (2) hardener is one selected from the group consisting of a phenol resin, a cyanate resin, and an active ester resin. the above.

[6] The curable resin composition according to any one of [1], wherein the (3) inorganic filler has an average particle diameter of 0.01 to 5 μm.

[7] The curable resin composition according to any one of [1] to [6] wherein the (3) inorganic filler is surface-treated with a surface treatment agent.

[8] The curable resin composition according to any one of [1], wherein the (3) inorganic filler is cerium oxide.

[9] The curable resin composition according to any one of [1], wherein the content of the (2) hardener is when the nonvolatile component in the curable resin composition is 100% by mass. It is 1 to 30% by mass, and the content of the above (3) inorganic filler is 30 to 90% by mass.

[10] 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 [9].

[11] A curable resin composition for a buildup layer of a multilayer printed wiring board, which comprises the curable resin composition according to any one of [1] to [9].

[12] A flaky laminate comprising the curable resin composition according to any one of [1] to [9].

[13] The flaky laminate according to [12], wherein the thickness is 5 to 30 μm.

[14] A multilayer printed wiring board comprising the cured resin composition according to any one of [1] to [11] or the flaky laminate according to [12] or [13]. The resulting insulating layer is hardened.

[15] A multilayer printed wiring board comprising an insulating layer obtained by thermally curing a sheet-like laminate according to [12].

[16] A semiconductor device comprising the multilayer printed wiring board according to [14] or [15].

Further, the present invention preferably includes the following aspects.

[A] A curable resin composition for an insulating layer of a multilayer printed wiring board, comprising (1) a (1-A)-containing bixylenol-containing structure, a bisphenol acetonitrile structure, and a bisphenol fluorene structure. Epoxy resin A ₁ and (1-B) from bisphenol type epoxy resin, crystalline bifunctional epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin and the like the epoxy resin composition of the mixture in the selected groups of B ₁ in the epoxy resin to the epoxy resin mixture is 100% by mass of the epoxy resin a is _a content of 5 to 20% by mass, the ring The epoxy resin A _{1 has an} epoxy equivalent of 2000 to 4200, an epoxy resin mixture having an epoxy equivalent of 50 to 3000, and (2) one or more selected from the group consisting of a phenol resin, a cyanate resin, and an active ester resin. a hardener, and (3) cerium oxide used as an inorganic filler.

The insulating layer of the multilayer printed wiring board produced by thermally curing the curable resin composition of the present invention is excellent in fluidity (filling property) of a film-like resin, and not only the arithmetic mean roughness of the surface of the insulating layer in the wet roughening step. The degree is lower, the average square root roughness is also lower, and an electroplated conductor layer having sufficient tear strength can be formed thereon, and the coefficient of linear thermal expansion is also low.

In particular, the use of the component (1) in the present invention achieves the above-described low roughness and high tear strength. Further, an epoxy resin composition which generally contains a large amount of inorganic filler is a film-like resin having a poor flow, a void is formed between the laminated conductors, and tearing strength is easily lowered, but the component (1) is used by the present invention. It can improve landfill and tear strength.

Form of implementing the invention [Curable resin composition]

The curable resin composition according to one aspect of the present invention is characterized in that (1) contains (1-A) has a biphenyl structure, a bixylenol structure, a bisphenol acetophenone structure, and a bisphenol quinone structure. In the epoxy resin mixture of the two or more types of the selected epoxy resin A and the epoxy resin B other than the epoxy resin A (1-B), when the epoxy resin mixture is 100% by mass The content of the epoxy resin A is 3 to 30% by mass, the epoxy resin equivalent of the epoxy resin A is 1500 to 4800, (2) the hardener, and (3) the hardenability of the inorganic filler. Resin composition. The epoxy resin composition of the present invention will be described in detail below.

[ingredient (1)] (1-A) Epoxy Resin A

The epoxy resin A used in the present invention has two or more structures selected from a biphenyl structure, a bixylenol structure, a bisphenol acetonitrile structure, and a bisphenol fluorene structure. Each structure can be represented by the following formulas (1) to (4).

Biphenyl structure

Dimethyl phenol structure

Bisphenol acetophenone structure (Ref. 2003-252951)

(In the formula (3), R ₁ is the same or a different one selected from the group consisting of a hydrogen atom, a hydrocarbon group of C _1-10 and a halogen element, and R ₂ is a hydrogen atom, a hydrocarbon group of C _1-10 And a group selected from the group consisting of halogen elements, R ₃ is a hydrogen atom or a C _1-10 hydrocarbon group, and m is an integer of 0 to 5).

Bisphenolphthalein structure (Ref. 2003-252951)

(In the formula (4), R ₄ is the same or different selected from the group consisting of a hydrogen atom, a hydrocarbon group of C _1-10 and a halogen element, and R ₅ is the same or different from a hydrogen atom, C _a hydrocarbon group selected from _{1 to 10} and a selected one of the halogen elements, and n is the same or a different integer of 0 to 4).

In a preferred embodiment, R ₁ in the formula (3) is the same or a different hydrogen atom or a hydrocarbon group of C _1-8 , preferably a hydrogen atom or a C _1-6 alkyl group, more preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, and R ₂ is a hydrogen atom or a C _1-8 hydrocarbon group, preferably a hydrogen atom or a C _1-6 alkyl group, more preferably a hydrogen atom or a methyl group, particularly preferably hydrogen. The atom, R ₃ is a hydrogen atom or a hydrocarbon group of C _1-8 , preferably a hydrogen atom or a C _1-6 alkyl group, more preferably a hydrogen atom or a methyl group, particularly preferably a methyl group, and m is 0 to 3 It is better to use an integer of 1~2.

Further, in the formula (4), R ₄ is the same or a different hydrogen atom or a hydrocarbon group of C _1-8 , preferably a hydrogen atom or a C _1-6 alkyl group, more preferably a hydrogen atom or a methyl group. R ₅ is the same or a different hydrogen atom or a C _1-8 hydrocarbon group, preferably a hydrogen atom or a C _1-6 alkyl group, more preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, n is The same or different 0~3, and the integer of 1~2 is preferred.

Specifically, the epoxy resin A is preferably an epoxy resin having three or more structures selected from the group consisting of a biphenyl structure, a bixylenol structure, a bisphenol acetonide structure, and a bisphenol fluorene structure. An epoxy resin having a bixylenol structure, a bisphenol acetonitrile structure and a bisphenol fluorene structure, and an epoxy resin having a biphenyl structure, a bixylenol structure, a bisphenol acetonitrile structure, and a bisphenol hydrazine structure. good. More specifically, the bisphenol acetonitrile structure is preferably such that, in the formula (3), R ₁ is a hydrogen atom, R ₂ is a hydrogen atom, and R ₃ is a methyl group. The bisphenol fluorene structure is preferably such that R ₄ in the formula (4) has a hydrogen atom and a methyl group, and R ₅ is a hydrogen atom.

Method for Producing Epoxy Resin A For example, an epoxy group of a biphenyl type epoxy resin and a bixylenol type epoxy resin is reacted with a phenol group of a bisphenol acetonitrile derivative and a bisphenol hydrazine derivative. Got it. Specifically, the ratio of the epoxy group of the biphenyl type epoxy resin and the bixylenol type epoxy resin to the phenol group number derived from the bisphenol acetonitrile derivative and the bisphenol hydrazine derivative is preferably 1:1 to 1.5. :1, preferably 1.05:1~1.4:1, more preferably 1.1:1~1.3:1. Therefore, the epoxy equivalent of the epoxy resin A is easily 1,500 to 4,800. Further, the ratio of the phenol group number derived from the bisphenol acetonitrile derivative to the phenol group number derived from the bisphenol hydrazine derivative is preferably from 1:5 to 1:15, more preferably from 1:7 to 1:10. Thereby, the heat resistance of the epoxy resin A can be improved.

The content of the epoxy resin A is 3 to 30% by mass, preferably 4 to 25% by mass, and more preferably 5 to 20% by mass, based on 100% by mass of the epoxy resin mixture of the component (1). When the content of the epoxy resin A is 3% by mass or more, a lower arithmetic mean roughness and a lower self-average square root roughness can be obtained, and when the content is 30% by mass or less, the cross-linking portion can be sufficiently retained. Low arithmetic mean roughness and lower self-averaged average square root roughness, and can maintain a lower coefficient of linear expansion.

The epoxy equivalent of the epoxy resin A (the mass of the resin containing 1 equivalent of the epoxy group) is 1500 to 4800 (g/eq), preferably 1700 to 4600 (g/equivalent), and 1900 to 4400 (g/). The equivalent weight is preferably from 2,000 to 4,300 (g/equivalent), and particularly preferably from 2,000 to 4,200 (g/equivalent). When the epoxy equivalent of epoxy resin A is 1500 or more, a lower arithmetic mean roughness and a lower self-centered average square root roughness can be obtained, and when the epoxy resin A is less than 4800, the crosslinked portion can be sufficiently retained, so that the lower portion can be obtained. The arithmetic mean roughness and the lower self-averaged average square root roughness, and can maintain a lower coefficient of linear expansion.

Further, the epoxy equivalent of the entire epoxy resin mixture of the component (1) is preferably from 50 to 3,000 (g/eq), more preferably from 100 to 2,000 (g/eq), more preferably from 150 to 1,000 (g/). Equivalent), particularly preferably from 200 to 500 (g/equivalent). The insulating layer thus obtained from the curable resin composition has a sufficient crosslinking density, which contributes to low roughness. The epoxy equivalent is measured in accordance with JIS K7236 (2001).

When the nonvolatile content in the curable resin composition is 100% by mass, the content of the epoxy resin A is preferably 0.5 to 10% by mass, more preferably 0.5 to 7% by mass, still more preferably 0.5 to 5% by mass. %.

(1-B) Epoxy Resin B

The epoxy resin B is an epoxy resin other than the epoxy resin A. The epoxy resin B is preferably an epoxy resin having two or more epoxy groups in one molecule.

Specific epoxy resin B, such as bisphenol A epoxy resin, bisphenol F Type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin like bisphenol type epoxy resin, dicyclopentadiene type epoxy resin, phenol novolak type epoxy resin, tert-butyl - phenol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthalene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac Epoxy resin, biphenyl type epoxy resin, bismuth type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, An epoxy resin containing a spiro ring, a cyclohexanedimethanol type epoxy resin, a trimethylol epoxy resin, a halogenated epoxy resin, a crystalline bifunctional epoxy resin, or the like. More preferably, the epoxy resin B is in the group of a bisphenol type epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, and a mixture of the epoxy resins. Selected. These may be used alone or in combination of two or more.

Among these epoxy resins, from the viewpoint of improving heat resistance, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene type epoxy resin, or the like is preferable. A naphthalene type epoxy resin and a mixture of two or more of these. Specifically, for example, a mixed epoxy resin of bisphenol A type and F type (Nippon Steel Chemical Co., Ltd. "ZX1059"", a bisphenol A type epoxy resin ("Jipi 828EL" 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), naphthol type epoxy tree Grease ("ESN-475V" manufactured by Nippon Steel Chemical Co., Ltd.), epoxy resin with butadiene structure ("PB-3600" manufactured by Daischer Chemical Co., Ltd.), and biphenyl type epoxy resin ( Nippon Chemical Co., Ltd. "NC3000H", "NC3000L", "NC3100"), Dimethyl phenol type epoxy resin ("XX4000", "YX4000H", "YX4000HK", "YL6121" manufactured by Mitsubishi Chemical Corporation ), bismuth epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Corporation), naphthalene ether epoxy resin (EXA-7310, "EXA-7311", "EXA-7311L", "" EXA7311-G3"), glycidyl ester epoxy resin ("EX711", "EX721" manufactured by Nagase Co., Ltd., "R540" manufactured by Principal), dicyclopentadiene epoxy resin (DIC (share) system "HP-7200H") and so on.

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

Further, the structural formula of the NC3000L is as follows.

(n is an integer from 1 to 20).

Also, the structure of the YX4000HK is as follows.

(wherein Gr is a glycidyl group).

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

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

Further, the structural formula of jER1009 is as follows.

The content of the epoxy resin B is 70 to 97% by mass, preferably 75 to 96% by mass, and more preferably 80 to 95% by mass, based on 100% by mass of the epoxy resin mixture of the component (1).

(2) Hardener

(2) The hardener may be capable of crosslinking the above epoxy resin mixture and hardening As the substance, any hardener such as a phenol resin, a cyanate resin, a benzoxazine resin, an active ester resin or the like can be used. Among them, the phenol resin, the cyanate resin and the reactive resin can significantly reduce the surface roughness of the insulating layer.

The active ester resin used in the present invention is a resin compound having one or more active ester groups in one molecule. The "active ester group" means an ester group reactive with an epoxy resin. The active ester resin is preferably a resin compound having two or more active ester groups in one molecule which can be reacted with an epoxy resin. It is generally preferred to use 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. For active ester resins. The active ester resin may be used singly or in combination of two or more kinds.

From the viewpoint of improving heat resistance, an active ester resin obtained by condensation reaction of a carboxylic acid compound and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound is preferred. More preferably, it is an active ester resin obtained by reacting one or more selected from a phenol compound, a naphthol compound, and a thiol compound with a carboxylic acid compound. 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, and it is particularly preferable to have at least two or more molecules per molecule. An aromatic resin compound obtained by reacting a compound of a carboxylic acid with an aromatic compound having a phenolic hydroxyl group and having two or more active ester groups in one molecule of the aromatic resin compound. The active ester resin may be linear or branched. Further, when the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, the composition of the resin can be improved. The compatibility of the substance is such that when it is a compound containing an aromatic ring, heat resistance can be improved.

Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, citric acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, succinic acid, maleic acid, itaconic acid, citric acid, isophthalic acid, and terephthalic acid are preferred from the viewpoint of heat resistance, and more preferably isophthalic acid or terephthalic acid. Specific examples of the sulfuric acid compound are, for example, sulfuric acid, sulfuric acid, and the like.

Specific examples of the above phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol porphyrin, methylated bisphenol A, methylated bisphenol F, and methyl group. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pyrogallol, benzenetriol, dicyclopentadienyl diphenol, phenol Novolac and the like. Among them, the viewpoint of improving heat resistance and solubility is preferably 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, pyrogallol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, etc., and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene , 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pyrogallol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac Varnish is preferred, more preferably 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, phenol novolac, and 1, 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyl diphenol, phenol novolac, more preferably 1,5-dihydroxynaphthalene, 1, 6-Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and dicyclopentadienyldiphenol are particularly preferred, and particularly preferred is dicyclopentadienyl diphenol. Specific examples of the thiol compound include benzenedithiol, triazinedithiol and the like.

Specifically, the active ester resin is preferably an active ester resin containing a dicyclopentadienyl diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated phenol novolak, and a phenol novolac. The active ester resin of benzoquinone is more preferably an active ester resin containing a naphthalene structure or an active ester resin containing a dicyclopentadienyl diphenol structure. Commercially available active ester resins containing a structure of a dicyclopentadienyl diphenol such as EXB9451, EXB9460, EXB9460S, HPC8000-65T (manufactured by DIC), an active ester resin containing a naphthalene structure such as EXB9416-70BK ( DIC (manufactured by the DIC), an active ester resin containing acetal phenol varnish, such as DC808 (manufactured by Mitsubishi Chemical Corporation), an active ester resin containing phenol phenolic novolac benzoate, such as YLH1026 (Mitsubishi Chemical ( Stock system) and so on.

The most preferred active ester resin contains the following general formula (I)

(where m is 0 or 1, n is an average of 0.25 to 1.5, preferably 0.4 The structure of the dicyclopentadienyl diphenol represented by ~1.2), which has a resin compound having an X-group and an XO- group at the terminal (the X is 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.

More specifically, the active ester resin has a dicyclopentadienyl diphenol structure represented by the following formula (5), and has an X-group and an XO- group at the terminal (the X is a naphthyl group which may have a substituent), HPC 8000-65T of an active ester resin having a weight average molecular weight of about 2,700.

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

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

Further, the structural formula of SN-485 is as follows.

(n is an integer from 1 to 20).

Further, the structural formula of LA-7054 is as follows.

(n is an integer from 1 to 20).

The cyanate resin is not particularly limited, and examples thereof include a novolak type cyanate resin, a dicyclopentadiene type cyanate resin, a bisphenol type cyanate resin, and a prepolymer which is partially triazineized. . Specifically, a phenol novolac type polyfunctional cyanate resin represented by the following formula (6) (manufactured by Lonza Japan Co., Ltd., PT30S: number average molecular weight 380, PT60: number average molecular weight 560), and the following formula ( 7) A bisphenol A type cyanate resin which is a part or all of a bisphenol A type cyanate resin which is partially or completely triazineated and trimerized (made by Lonza Japan Co., Ltd.), BA230S75) A dicyclopentadiene type cyanate resin represented by the following formula (8) (manufactured by Lonza Japan Co., Ltd., DT-4000, DT-7000). Specifically, the number average molecular weight is determined by using the LC-9A/RID-6A manufactured by Shimadzu Corporation and the Shodex K-800P/K- by the Showa Denko Co., Ltd. 804L/K-804L, the mobile phase was measured using a chloroform or the like, and was measured at a column temperature of 40 ° C using a calibration curve of standard polystyrene. These may be used alone or in combination of two or more.

[wherein, n represents an arbitrary number of average values (preferably 0 to 20, more preferably 1 to 10)].

(where n represents the average value of 0 to 5).

The content of the curing agent in the curable resin composition of the present invention is not particularly limited, and the low roughness of the insulating layer and the high tearing strength are simultaneously established, and the nonvolatile content in the cured resin composition is 100 mass. The % is preferably from 1 to 30% by mass, more preferably from 2 to 20, more preferably from 5 to 15% by mass.

Further, when the epoxy group number of the entire epoxy resin mixture is 1, the reaction group of the curing agent is preferably 0.2 to 2, more preferably 0.3 to 1.5, still more preferably 0.4 to 1. In this case, the "epoxy group number of the entire epoxy resin mixture" means the total value of the relevant epoxy resin obtained by dividing the epoxy equivalent by the solid content of each epoxy resin present in the curable resin composition. . Further, the "reactive group" means a functional group reactive with an epoxy group, and the "number of reactive groups" means a value obtained by dividing the equivalent of the reactive group by the mass of the solid component of the hardener present in the resin composition. Total value.

(3) Inorganic filler

The inorganic filler used in the present invention is, for example, ceria, alumina, mica, Mica, silicate, barium sulfate, magnesium hydroxide, titanium oxide, etc., preferably cerium oxide, aluminum oxide, particularly preferably Shaped cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide, spherical cerium oxide, etc., wherein spherical cerium oxide and molten cerium oxide are used. good. The viewpoint of improving the filling property of the inorganic filler with respect to the sheet-like laminate of the present invention containing the curable resin composition is more preferably spherical molten cerium oxide. One or two or more types can be used. Inorganic filler material. Commercially available spherical molten cerium oxide, for example, "SOC2" and "SOC1" manufactured by Aideman Co., Ltd.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, more preferably 1 μm or less, and even more preferably 0.8 μm or less from the viewpoint of forming fine wiring on the insulating layer. It is particularly preferably 0.6 μm or less. When the curable resin composition is used for painting, it is preferably 0.01 μm or more, more preferably 0.03 μm or more, and more preferably 0.07 μm or more, from the viewpoint of preventing the viscosity of the coating from rising and causing deterioration in handleability. More preferably, it is 0.1 μm or more. The average particle diameter of the above inorganic filler can be measured by a laser diffraction scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the equal diameter can be obtained as an average particle diameter. The measurement sample is preferably obtained by dispersing an inorganic filler in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, LA-950 or the like manufactured by Horiba, Ltd. can be used.

The content of the inorganic filler is not particularly limited, but the amount of the inorganic filler is 100% by mass in terms of the non-volatile content in the curable resin composition from the viewpoint of preventing the flexibility of the sheet form of the sheet-like laminated resin. It is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, still more preferably 50 to 85% by mass. In particular, in the present invention, the hardenable resin composition containing 50% by mass or more of the inorganic filler can also improve the landfill property and the peeling strength.

Inorganic filler materials are used to improve moisture resistance and dispersibility. It is preferably a surface treated (coated) by a coupling agent or the like. The surface treatment agent (coupling agent) is preferably an epoxy decane coupling agent, an amino decane coupling agent, a mercapto decane coupling agent, a decane coupling agent, an organic decazane compound, or a titanate coupling agent. One or more selected ones. Further, the amine decane coupling agent preferably has excellent moisture resistance, dispersibility, properties of a cured product, and the like, and more preferably a phenylamino decane coupling agent. Commercial products such as "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. "Keta" (3-aminopropyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. "Oxyoxane", "KBM103" (phenyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "SZ-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd.

[Other ingredients]

In addition to the above components, the curable resin composition of the present invention may be appropriately added with other components such as a curing accelerator; a thermoplastic resin; a vinyl benzyl compound, an acrylic compound, a maleimide compound, and a blocked isocyanate compound. Curable resin; flame retardant such as phosphorus compound or metal hydroxide; organic filler such as strontium powder, nylon powder, fluorine powder, rubber granule; organic solvent; Orben, Benton, etc. A tackifier; a polyoxyalkylene-based, fluorine-based or polymer-based antifoaming agent; an adhesion-promoting agent such as an imidazole-based, a thiazole-based, a triazole-based or a decane coupling agent; Blue, phthalocyanine, green, iodine, green, diazo yellow, carbon black and other coloring agents; additives.

The hardening accelerator may be one in which the above-mentioned epoxy resin is crosslinked and hardened by the above-mentioned curing agent, and any hardening accelerator such as an amine compound, a pulse compound, an imidazole compound, an anthraquinone compound, and a metal-based hardening accelerator may be used. . These may be used alone or in combination of two or more.

The amine compound which can be used in the present invention is not particularly limited, and for example, a trialkylamine such as triethylamine or tributylamine, 4-dimethylpyridine, benzyldimethylamine, 2,4,6-tri ( An amine compound such as dimethylaminomethyl)phenol or 1,8-diazabicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU). These may be used alone or in combination of two or more.

The imidazole compound used in the present invention may be the following general formula (9)

(wherein R ₆ to R ₉ are each the same or different hydrogen atom, a halogen atom, a cyano group, a nitro group, a decyl group, a C _1-20 alkyl group, a C _2-20 alkenyl group, a C _{2 - 20} alkynyl, C _3-20 allyl, C _4-20 alkadienyl, C _{4-20 polyalkenyl} , C _6-20 aryl, C _6-20 alkaryl, C _6-20 aralkyl , C _4-20 cycloalkyl, C _4-20 cycloalkenyl, (C _5-10 cycloalkyl) C _1-10 alkyl, decyl group which may have a C _1-10 hydrocarbyl group, derived from epoxy A compound represented by a hydroxyethyl group of a resin.

More specifically, the imidazole compound is 1-benzyl-2-phenylimene. Oxazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano Ethyl-2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-S-triazine, 2,4-diamino- 6-[2'-undecyl imidazolyl-(1')]-ethyl-S-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazole -(1')]-ethyl-S-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-S-triazine trimer Isocyanate adduct, 2-phenylimidazole trimer isocyanate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxyl a compound selected from the group consisting of imidazole, 2-phenyl-4-methylimidazole, an imidazole compound and an epoxy resin, and a 2,4-diamino-6-vinyl-S-triazine . These may be used alone or in combination of two or more.

The metal-based hardening accelerator used in the present invention is not particularly limited, and is, for example, an organometallic complex or an organic metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese or tin. Specific examples of the organometallic complex include, for example, an organic cobalt complex such as cobalt (II) acetoacetate, cobalt (III) acetoacetate, or copper (II) acetoacetate. Compound, an organic zinc complex such as zinc (II) acetoacetate, an organic iron complex such as iron (III) acetoacetate, or an organic nickel such as nickel (II) acetoacetate A complex compound, an organic manganese complex such as manganese (II) acetoacetate or the like. The organic metal salt is, for example, zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like. These may be used alone or in combination of two or more.

The content of the hardening accelerator is preferably 0.005 when the total amount of the nonvolatile components in the curable resin composition is 100% by mass. The range of ~3 mass% is more preferably in the range of 0.01 to 1 mass%.

The thermoplastic resin is, for example, a phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyamidoximine resin, a polyether oxime resin, a cycloolefin polymer, a polyfluorene resin, etc., preferably a phenoxy resin, Polyethylene acetal resin. 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, still more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be measured by gel permeation chromatography (GPC). Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be obtained by using the LC-9A/RID-6A manufactured by Shimadzu Corporation and the column using Shodex K-800P/K-made by Showa Denko Co., Ltd. 804L/K-804L, the mobile phase was measured using a chloroform or the like, and was measured at a column temperature of 40 ° C using a calibration curve of standard polystyrene. Further, when the thermoplastic resin is a phenoxy resin, the epoxy equivalent of the phenoxy resin is from 10,000 to 20,000 (g/eq).

Organic solvents such as ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate An aromatic hydrocarbon such as an acetate, a cellosolve or a butyl carbitol, a solvent oil, an aromatic hydrocarbon such as toluene or xylene, dimethylformamide or dimethylacetamide. A guanamine-based solvent such as N-methylpyrrolidone. The organic solvent may be used in combination of two or more kinds.

[Preparation of hardenable resin composition]

The curable resin composition of the present invention can be suitably mixed with the above components, or if necessary, a kneading method using a three-seat roll, a ball mill, a bead mill, a sand mill, or the like, or a high-speed rotary mixer or an ultra-mixer, A stirring method such as a planetary mixer is obtained by kneading or mixing and modulating. Further, the above organic solvent may be added and prepared as a resin paint.

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 self-average square root roughness is low, and an electroplated conductor layer having sufficient tear strength can be formed thereon, thereby manufacturing multilayer printing. The wiring board is applied to a curable resin composition for an insulating layer of a multilayer printed wiring board. Further, it is preferably used as a curable resin composition for forming a conductor layer by electroplating (a resin composition for an insulating layer of a multilayer printed wiring board in which a conductor layer is formed by electroplating), and is also applied as a build-up layer of a multilayer printed wiring board. A curable resin composition is used.

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

[Multilayer printed wiring board]

The curable resin composition of the present invention is suitably used as a curable resin composition for an insulating layer of a multilayer printed wiring board. Multilayer printing with the invention The wiring board is a multilayer printed wiring board containing the insulating layer obtained by thermally curing the curable resin composition or the sheet-like laminate of the present invention.

The conditions of the heat hardening at this time may be appropriately selected depending on the kind 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 minutes. Heating is carried out for ~180 minutes, preferably for 20 to 120 minutes. Moreover, the heat hardening can be performed in two stages.

In this case, the linear thermal expansion coefficient (JIS K7197) of the insulating layer is preferably 20 ppm/° C. or less, more preferably 19 ppm/° C. or less, as measured by an average linear thermal expansion coefficient of 25 to 150° C. The lower limit is not particularly limited and is generally 4 ppm/°C. In this way, it is possible to prevent the insulating layer (addition layer) and the conductor layer (wiring) from being deformed, and it is possible to obtain a multilayer printed wiring board having high reliability.

The surface of the insulating layer can be roughened. Dry roughening treatment such as plasma treatment. The wet roughening treatment is carried out, for example, with various treatment liquids. For example, it is subjected to a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid. Therefore, the treatment liquid may be a combination of the swelling liquid, the oxidizing agent, and the neutralizing liquid. The wet roughening treatment is preferred because it can be processed in large areas or in several pieces and has high productivity.

The swelling treatment using the swelling liquid is to immerse the insulating layer in the swelling liquid at 50 to 80 ° C for 5 to 20 minutes (preferably at 55 to 70 ° C for 8 to 15 minutes). The swelling solution such as an alkali solution, a surfactant solution or the like is preferably an alkali solution. The alkali solution is, for example, a sodium hydroxide solution, a potassium hydroxide solution or the like. Commercially available swelling liquids such as Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc., manufactured by Aite Iron Co., Ltd.

The roughening treatment using an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 to 80 ° C for 10 to 30 minutes (preferably at 70 to 80 ° C for 15 to 25 minutes). An oxidizing agent such as potassium permanganate or sodium permanganate dissolved in an aqueous solution of sodium hydroxide, an alkaline permanganic acid solution, dichromate, odor, hydrogen peroxide/sulfuric acid, nitric acid, or the like. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably from 5 to 10% by mass. Commercially available oxidizing agents such as a constant permanganic acid solution such as Concentrate Compact CP and Dosingsolution Securiganth P manufactured by Aite Iron Co., Ltd.

The neutralization treatment using the neutralization solution is immersed in the neutralization solution at 30 to 50 ° C for 3 to 10 minutes (preferably 3 to 8 minutes at 35 to 45 ° C). The neutralizing liquid is preferably an acidic aqueous solution, and a commercial product such as Reduction Solution Securiganth P manufactured by Aite Iron Co., Ltd.

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 for 20 to 40 minutes).

In order to enhance the formation of the fine wiring, the arithmetic mean roughness (Ra) of the surface roughness of the surface of the insulating layer after the roughening treatment is preferably 350 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, and particularly preferably 100 nm. the following. The lower limit of the arithmetic mean roughness (Ra) is not limited, and is generally 10 nm or more, 40 nm or more, 70 nm or more. The calculation average square root roughness (Rq) is preferably 450 nm or less, more preferably 350 nm or less, still more preferably 250 nm or less, and particularly preferably 150 nm or less. The lower limit of the self-average square root roughness (Rq) is not limited, and is generally 20 nm or more, 50 nm or more, 90 nm or more. Moreover, the self-equalized average square root roughness (Rq) reflects the local state of the surface of the insulating layer, By grasping Rq, the surface of the smooth and smooth insulating layer can be confirmed, and the tearing strength can be stabilized. This corresponds to the surface roughness of the insulating layer obtained by subjecting the curable resin composition to heat curing.

The tearing strength is preferably 0.45 kgf/cm (4.41 N/cm) or more, more preferably 0.50 kgf/cm (4.90 N/cm) or more, in order to sufficiently close the insulating layer to the layer adjacent thereto, for example, the conductor layer. The upper limit of the tearing 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, 1.2 kgf/cm (11.8 N/cm) or less, and 1.0 kgf/cm (9.81 N/ Below cm), 0.8 kgf/cm (7.85 N/cm) or less.

[Sheet laminate]

The sheet-like laminate used in the present invention is a sheet-like material before curing obtained by molding the above-mentioned curable resin composition into a layer. The sheet-like laminate may be applied to a support by a resin coating method, for example, by modulating a resin obtained by dissolving a resin composition in the organic solvent, and then applying the resin to a support using a die coater or the like. The organic solvent is dried by blowing hot air or the like to form a resin composition layer (sheet-like laminate) on the support, and a sheet-like laminate having a support is obtained. Further, a sheet-like reinforcing substrate such as a glass fiber woven fabric may be impregnated with a resin by a hot melt method or a solvent method, and then dried to obtain a prepreg sheet-like laminate. Further, the sheet-like laminate material with the support may also be referred to as an adhesive film.

The drying conditions are not particularly limited, and the content of the organic solvent in the resin composition can be dried to 10% by mass or less, preferably 5% by mass or less. It varies depending on the amount of organic solvent in the paint and the boiling point of the organic solvent. For example, a paint containing 30 to 60% by mass of an organic solvent can be dried at 50 to 150 ° C for 3 to 10 minutes to form a resin composition layer.

The thickness of the obtained sheet-like laminate is not particularly limited, and is, for example, preferably in the range of 1 to 150 μm, 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.

The sheet-like laminate may have a plurality of layers of the resin composition, or one of the surface of the resin composition layer has a support, or the other surface may have a protective film.

[support]

The support used in the present invention is, for example, a mold or a metal foil. Specific molds such as polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate, polyester, polycarbonate, polyethylene, polypropylene, acrylate, Cyclic polyolefin, triacetyl cellulose, polyether sulfide, polyether ketone, polyimine, and the like. Among them, polyethylene terephthalate or polyethylene naphthalate is preferred, and a polyethylene terephthalate film which is inexpensive and easily available is particularly preferred.

Metal foils such as copper foil, aluminum foil, and the like.

From the viewpoint of general use, it is preferably a plastic film, and in order to improve the peeling property when a plastic film is used, it is preferred to use a support which is subjected to release treatment by contacting a surface of a layer containing a curable resin composition. The release agent used in the mold release treatment may be one in which the layer containing the curable resin composition can be peeled off from the support, and is not particularly limited, and examples thereof include an oxime release agent, an alkyd resin release agent, and a polyolefin resin. A urethane resin, a fluorine resin, or the like. Again, after being subjected to mold release treatment As the support, a commercially available plastic film with a release layer may be used, and preferably, a PET film SK-1, AL-5, AL-7 having a release layer whose main component is an alkyd resin release agent is used. Iron storage (stock) system, etc. Further, the plastic film may be subjected to a matte treatment or a corona treatment, and a release layer may be formed on the treated surface. Alternatively, 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 μm, more preferably in the range of 20 to 50 μm, still more preferably in the range of 25 to 45 μm.

The protective film used in the present invention is intended to prevent dust or the like from adhering to the layer containing the curable resin composition. The protective film can use the same plastic film as the support. Further, the protective film may be subjected to a surface treatment such as matte treatment or corona treatment, or the same release treatment as described above may be carried out. The thickness of the protective film is preferably from 3 to 30 μm, more preferably from 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 material was laminated on one side or both sides (lamination) of the circuit substrate using a vacuum laminator. The substrate used for the circuit board is, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT grease substrate, a thermosetting polyphenylene ether substrate, or the like. Moreover, the circuit board at this time means that the conductor layer (circuit) processed by the pattern is formed on one surface or both surfaces of the substrate. And the result of alternating laminated conductor layers and insulating layers In the layer printed wiring board, the conductor layer (circuit) of the pattern processing is formed on one side or both sides of the outermost layer of the multilayer printed wiring board, and is also incorporated in the circuit board. Further, the surface of the conductor layer may be subjected to a blackening treatment or a pre-roughening treatment by copper etching or the like.

In the laminating process, when the sheet-like laminate material has a protective film, after removing the protective film, the sheet-like laminate material and the circuit substrate may be preheated if necessary, and then the sheet-like laminate material is pressurized and heated while the layer is laminated. Pressed on the circuit board. The sheet-like laminate of the present invention is suitable for laminating on a circuit board under reduced pressure by a vacuum laminator. The laminating conditions are not particularly limited. Preferably, the pressure is 10 mm to 120 seconds, the air pressure is 20 mmHg (26.7 hPa) or less, and thereafter the pressing temperature (lamination temperature) is preferably 70 to 140 ° C, and the pressing pressure is ( The lamination pressure is preferably 0.1 to 1.5 MPa, more preferably 0.5 to 1.2 MPa, and the lamination time (lamination time) is preferably 5 to 180 seconds. Further, the lamination method may be a batch type or a continuous type using a roll. A vacuum laminator commercially available can be used for vacuum lamination. Commercially available vacuum laminating machines such as vacuum coating machines manufactured by Nikki Co., Ltd., vacuum pressure laminating machines manufactured by Nihon Seisakusho Co., Ltd., Hitachi Indas Roll Dry Coating Machines, Hitachi AIC ( Stock) vacuum laminator, etc.

Thereafter, the mixture is cooled to near room temperature, and when the support is peeled off, the resin composition is thermally cured to form a cured product after peeling, and an insulating layer can be formed on the circuit board. The curing conditions 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 to 210 ° C, and the curing time is 20 minutes to 180 minutes. Heat for 30 to 120 minutes. Also, can be divided into 2 orders The section is thermally hardened. When the insulating layer is formed and the support is not peeled off before hardening, it may be peeled off if necessary.

Further, the sheet-like laminate may be laminated on one or both sides of the circuit board using a vacuum press. The laminating step of heating and pressurizing under reduced pressure can be carried out using a general vacuum pressure-resistant machine. For example, it is carried out by pressurizing a metal plate such as a heated SUS plate to the side of the support. The pressurization condition is preferably 70 to 250 ° C, preferably 100 to 230 ° C, and the degree of pressure reduction is generally 0.01 MPa or less, preferably 0.001 MPa or less under reduced pressure, and the pressure is 0.5 °. The range of 4 MPa is carried out under the conditions of a press time of 30 to 150 minutes. Heating and pressurization can be carried out in one stage, but it is preferable to carry out the conditions of two or more stages from the viewpoint of controlling the blooming of the resin. For example, it is preferable that the first-stage pressurization condition is a pressurization pressure of 0.1 to 1.5 MPa at a temperature of 70 to 150 ° C, and a second-stage pressurization condition of a temperature of 150 to 200 ° C at a pressurization pressure of 0.5 to 4 MPa. . The time of each stage is preferably carried out for 20 to 120 minutes. The insulating layer can be formed on the circuit substrate by thermally hardening the resin composition layer. Commercially available vacuum hot presses, such as MNPC-V-750-5-200 (made by Nihon Seiki Co., Ltd.) and VH1-1603 (made by Kitagawa Seiki Co., Ltd.).

Next, the insulating layer formed on the circuit substrate is subjected to a hole punching process to form a via hole and a via hole. The hole punching process can be performed by a known method such as a cobalt head, a laser, a plasma, or the like if necessary, and the most common method is a hole punching process using a laser such as a carbon dioxide gas laser or a YAG laser. . When the support is not peeled off before the hole punching, it will peel off at this time.

Next, the surface of the insulating layer is subjected to the above-mentioned roughening treatment, and then a conductor layer is formed on the insulating layer by dry plating or wet plating. Dry plating can be carried out by a known method such as vapor deposition, sputtering, or ion plating. Wet electroplating, for example, a method of forming a conductor layer by electroless plating and electrolytic plating, or a method of forming a conductor layer by electroless plating when a conductor layer forms an electroplated photoresist of an inverse pattern. Thereafter, a method of forming a pattern may be carried out by repeating the above-described series of steps several times by a subtractive method, an additive method, or the like known to those skilled in the art, and a multilayer printed wiring board of a multi-layer laminated layer may be laminated. The invention is suitable for the layering of a multilayer printed wiring board because of its low roughness and high tearing degree.

[semiconductor device]

A semiconductor device can be manufactured using the multilayer printed wiring board produced above. The conductive portion of the multilayer printed wiring board used in the present invention can be manufactured by mounting a semiconductor wafer. “Conduit” means “where the electrical signal is transmitted in a multilayer printed wiring board”, which can be disposed on the surface or in landfill. Moreover, the conductive portion of the partial conductor layer or other connectors can be turned on. The "semiconductor wafer" may be an electrical circuit component made of a semiconductor material, and is not particularly limited.

The mounting method of the semiconductor wafer in the manufacture of the semiconductor device of the present invention is not particularly limited as long as the function of the semiconductor wafer is effective, for example, the wire bonding mounting method, the trigger wafer mounting method, and the use of the non-bumping. A method of mounting a build-up layer (BBUL), a method of mounting an anisotropic conductive film (ACF), a method of mounting using a non-conductive film (NCF), and the like.

Example

The invention will be specifically described below by way of examples, but the invention is not limited to the examples. In addition, the "parts" described below are not specifically indicated as "mass parts", and "%" means "% by mass" unless otherwise specified.

<Measurement method, evaluation method>

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

[Preparation of peeling strength, arithmetic mean roughness (Ra value), and self-centered average square root roughness (Rq value)] (1) Underlayer treatment of laminate

A copper cloth substrate epoxy resin double-sided copper laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Co., Ltd. R5715ES) was double-etched by 1 μm on a copper surface by CZ8100 manufactured by Meike Co., Ltd. Coarse processing.

(2) lamination followed by film

Using a batch type vacuum press laminating machine MVLP-500 (manufactured by Nago Seisakusho Co., Ltd., the adhesive film produced in the examples and the comparative examples was laminated on the above-mentioned double-treated epoxy double-sided copper-clad laminate) In the lamination, the pressure was reduced to 30 h after the pressure was 30 seconds, and then press-bonded under the conditions of 30 seconds, 100 ° C, and a pressure of 0.74 MPa.

(3) hardened resin composition

After peeling the support film of the polyethylene terephthalate (PET) film, the resin composition was cured at 100 ° C for 30 minutes and then hardened at 180 ° C for 30 minutes to form an insulating layer. .

(4) roughening treatment

The laminate in which the insulating layer was formed was immersed in Swelling Dip Securiganth P (glycol ether, aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether as a swelling liquid at 60 ° C. 5 minutes (Example 1, Comparative Example 1, 4, 5), 10 minutes (Examples 2, 3, Comparative Examples 2, 3). Secondly, immersed in Atte Iron Japan as a roughening solution at 80 ° C 15 minutes in Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) (Example 1, Comparative Examples 1, 4, 5), 20 minutes (Examples 2, 3, Comparative Example 2) 3), immersed in a dosing solution Securiganth P (aqueous solution of sulfuric acid) as a neutralizing solution for 4 minutes at 40 ° C. After drying at 80 ° C for 30 minutes, the obtained substrate was used as the evaluation substrate A. .

(5) Plating using the addition method

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

[Measurement of arithmetic mean roughness (Ra value) after roughening, self-sufficient average square root roughness (Rq value)]

Using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Pico Co., Ltd.), the Ra value and the Rq value were obtained by a value in a measurement range of 121 μm × 92 μm obtained from a 50-fold lens in a VSI contact mode. Further, the measurement was performed by the average of 10 points obtained by each.

[Determination of the peeling strength (peeling strength) of the electroplated conductor layer]

After the conductor layer of the evaluation substrate B was cut out to a portion having a width of 10 mm and a length of 100 mm, one end thereof was smashed with a peeling fixture (TSEO AG, automatic glue type tester AC-50C-SL), and the room temperature (25 ° C) was measured. The load (kgf/cm (N/cm)) when peeling 35 mm was pulled in the vertical direction at a speed of 50 mm/min.

[Measurement Line Thermal Expansion Coefficient (CTE)]

The film obtained in the examples and the comparative examples was heated at 200 ° C for 90 minutes to be thermally cured, and then peeled off from the support PET film to obtain a flaky cured product. A test piece having a width of 5 mm, a length of 15 mm, and a thickness of 30 mm was cut out from the cured product, and then subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Riga Co., Ltd.). Will test After the sheet device was placed in the above apparatus, the sheet was continuously measured twice 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.

[Evaluation of resin landfill] (1) Underlying processing of the substrate

IPC MULTI-PURPOSE TEST BOARD NO.IPC B-25 is formed on the glass cloth substrate epoxy double-sided copper laminate [copper foil thickness 35μm, substrate thickness 0.3mm, Matsushita Electric Co., Ltd. R5715ES] Type (line/space = 175/175 μm comb pattern (50% residual copper)), and double-sided impregnation of the CZ8100 made by Meike Co., Ltd. to roughen the copper surface.

(2) lamination followed by film

The batch film produced by the examples and the comparative examples was laminated in such a manner as to contact the resin composition surface using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by a famous machine). At the time of lamination, the pressure was reduced to a pressure of 13 hPa or less in 30 seconds, and then press-bonded at 30 seconds, 120 ° C, and a pressure of 0.74 MPa. Next, preheating was carried out for 60 seconds under conditions of 120 ° C and a pressure of 0.5 MPa.

(3) hardened resin composition

After lamination, the support PET film was peeled off, and the resin composition was thermally cured to form an insulating layer at a curing condition of 100 ° C for 30 minutes and thereafter at 180 ° C for 30 minutes.

(4) Evaluation of the landfill of the resin surface

Use a micro optical microscope to observe the line/space = 175/ The insulating layer on the 175 μm comb-tooth pattern (50% residual copper ratio) was “○” in the case of a well-filled material, and the resin was smothered with a “x”.

<Synthesis Example 1>

Synthesis of epoxy resin a _{1 with} a bixylenol structure, a bisphenol acetonitrile structure and a bisphenol oxime structure

222 g of a bixylenol type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), 15 g of bisphenol acetonitrile (phenolic hydroxyl equivalent 145), and biscresol oxime (JFE Chemical Co., Ltd.) 170 g of phenolic hydroxyl equivalent 190) and 150 g of cyclohexanone were placed in a reaction vessel and stirred to dissolve. Next, 0.5 g of a tetramethylammonium chloride solution was added dropwise, and the mixture was reacted at 180 ° C for 5 hours under a nitrogen atmosphere. As a result, the reaction was filtered using a filter cloth, and then diluted with a solvent to obtain an epoxy resin a ₁ .

‧Epoxy equivalent: 2120

‧Solid component 40% by mass of 1:1 solution of MEK and cyclohexanone

Further, the epoxy resin a ₁ is formed of a skeleton having the following three structures.

<Synthesis Example 2>

Synthesis of epoxy resin a ₂ having a bixylenol structure, a bisphenol acetonitrile structure and a bisphenol oxime structure

203 g of a bixylenol type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), 15 g of bisphenol acetonitrile (phenolic hydroxyl equivalent 145), and biscresol oxime (JFE 芴) 170 g of phenolic hydroxyl equivalent 190) and 150 g of cyclohexanone were placed in a reaction vessel and stirred to dissolve. Next, 0.5 g of a tetramethylammonium chloride solution was added dropwise, and the mixture was reacted at 180 ° C for 5 hours under a nitrogen atmosphere. After the reaction was completed, it was filtered using a filter cloth, and then diluted with a solvent to obtain an epoxy resin a ₂ .

‧Epoxy equivalent: 4120

‧ Solid solution of 35% by mass of 1:1 solution of MEK and cyclohexanone

Further, the epoxy resin a ₂ is formed of a skeleton having the following three structures.

<Synthesis Example 3>

Synthesis of epoxy resin a ₃ having a biphenyl structure, a bixylenol structure, a bisphenol acetonitrile structure and a bisphenol oxime structure

1:1 mixture of biphenyl type epoxy resin and dixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. YL6121H, epoxy equivalent 175) 192g, bisphenol acetophenone (phenolic hydroxyl equivalent 145) 15g 157 g of bisphenol hydrazine (phenolic hydroxyl equivalent 175) and 150 g of cyclohexanone were placed in a reaction vessel and stirred to dissolve. Next, 0.5 g of a tetramethylammonium chloride solution was added dropwise, and the mixture was reacted at 180 ° C for 5 hours under a nitrogen atmosphere. After the reaction was completed, it was filtered using a filter cloth, and then diluted with a solvent to obtain an epoxy resin a ₃ .

‧Epoxy equivalent: 3980

‧ solid component 35 mass% cyclohexanone solution

Further, the epoxy resin a ₃ is formed of a skeleton having the following four structures.

<Example 1>

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, crystalline 2 functional ring Oxygen equivalent (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 heating Dissolved in 40 parts of solvent oil. After cooling to room temperature (25 ° C), epoxy resin a ₁ , 12 parts, and a phenol resin containing a triazine skeleton (hardening agent, DIC (manufactured by DIC), "LA-7054", hydroxyl equivalent of 125% solid content 60%) MEK solvent) 12 parts, naphthalene type hardener ("SK-485"SN-485" hydroxyl equivalent: 215 solid content 60% MEK solution) 15 parts, hardening accelerator (4-dimethylamino group) Pyridine (DMAP), 2% by mass of MEK solution of solid content) 3 parts, flame retardant (HCA-HQ, manufactured by Sanguang Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydrogen-9 - Oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts, phenylamino decane-based coupling agent ("SKM573" manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") 225 parts of 矽 (average particle diameter: 0.5 μm, "SOC 2" manufactured by Aideman) was uniformly dispersed in a high-speed rotary mixer to prepare a resin paint. Next, the resin paint was uniformly applied to a polyethylene terephthalate film (Lylon, manufactured by Lintik Co., Ltd.), which was 38 μm thick, and was used for the measurement of the coefficient of thermal expansion (CTE). On the release surface of the cured product "PET501010" (thickness: 50 μm), the thickness of the dried resin composition layer was 30 μm, and then 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.) and a crystalline bifunctional epoxy resin (YX4000HK, manufactured by Mitsubishi Chemical Corporation) with an epoxy equivalent of 185. 5 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269) 12 parts were heated and dissolved in 30 parts of solvent oil. After cooling to room temperature (25 deg.] C), epoxy resin mixed with a ₂ 4 parts of bisphenol A type cyanate resin (Longzha Japan (shares) manufactured by "BA230S75" cyanate equivalent 232, non-volatile content 75 mass 20 parts of MEK solution) 20 parts, phenol novolac type polyfunctional cyanate resin ("3030" made by Lonza Japan Co., Ltd., glycerine ester equivalent 133, MEK solution of 85% by mass of nonvolatile matter) 6 parts, hardened Promoter (4-dimethylaminopyridine, MEK solution of solid content 2% by mass) 1 part, hardening accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetoacetate (Co(III)Ac) ), 3 parts by weight of MEK solution of solid content: 3 parts, 2 parts of rubber particles (manufactured by Ganzi Co., Ltd., Staf non-AC3816N), flame retardant (HCA-HQ, manufactured by Sanguang Co., Ltd., 10-( 2,5-Dihydroxyphenyl)-10-hydrogen-9-oxo-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts, phenylamino decane-based coupling agent (Shin-Etsu Chemical Industry) (KBM573), 100 parts of spherical cerium oxide (average particle diameter: 0.5 μm, "SOC 2" manufactured by Aideman), which was surface-treated, was uniformly dispersed by a high-speed rotary mixer to prepare a resin paint. Next, in the same manner as in Example 1, a film was formed.

<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, dicyclopentadiene A 12-part epoxy resin ("HP-7200H" manufactured by DIC Co., Ltd., epoxy equivalent 275) was dissolved in 30 parts of solvent oil by heating. After cooling to room temperature (25 ° C), an epoxy resin a ₃ 15 parts, an active ester compound ("HPC8000-65T" manufactured by DIC), a weight average molecular weight of about 2700, and a nonvolatile content of the active group equivalent of 223 were mixed. 35 parts of a toluene solution), a hardening accelerator (4-dimethylaminopyridine, a solid content of 2% by mass in a MEK solution), 6 parts, and a flame retardant ("Hica-HQ" manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl)-10-hydrogen-9-oxo-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 2 parts, phenylamino decane-based coupling agent (Shin-Etsu Chemical) Industrial Co., Ltd., "KBM573") 150 parts of spherical cerium oxide (average particle size: 0.5 μm, "SOC2" manufactured by Aideman Co., Ltd.)), and then uniformly dispersed in a high-speed rotary mixer to prepare a resin coating. paint. Next, in the same manner as in Example 1, a film was formed.

<Comparative Example 1>

In addition, the epoxy resin a ₁ 12 parts of the first embodiment was changed to a phenoxy resin (YX6954BH30 manufactured by Mitsubishi Chemical Corporation), and the bisphenol acetonitrile structure was contained, and the solid content of 30% by mass of MEK and cyclohexanone was 1 A film was prepared in the same manner as in Example 1 except that the solution was an epoxy equivalent of 13,000 (15 parts).

<Comparative Example 2>

In addition, the epoxy resin a ₂ 4 parts of the second embodiment was changed to a phenoxy resin (YX6954BH30 manufactured by Mitsubishi Chemical Corporation), and the bisphenol acetonitrile structure was contained, and the solid content of 30% by mass of MEK and cyclohexanone was 1 A film was prepared in the same manner as in Example 2 except that the solution was an epoxy equivalent of 13,000 (5 parts).

<Comparative Example 3>

In addition, 15 parts of the epoxy resin a _{3 of} Example 3 was changed to a phenoxy resin (YX6954BH30 manufactured by Mitsubishi Chemical Corporation), and a bisphenol acetonitrile structure was contained, and a solid component of 30% by mass of MEK and cyclohexanone was used. A film was prepared in the same manner as in Example 3 except that the solution was an epoxy equivalent of 13,000 (10 parts).

<Comparative Example 4>

In addition, the epoxy resin a ₁ 12 parts of Example 1 was changed to a bisphenol A type epoxy resin ("JER1009" manufactured by Mitsubishi Chemical Corporation, an epoxy equivalent of 2740, a solid content of 40% by mass of MEK and cyclohexanone. The film was prepared in the same manner as in Example 1 except that the 1:1 solution was 12 parts.

<Comparative Example 5>

A film was formed in the same manner as in Example 1 except that the amount of the epoxy resin a ₁ of Example 1 was changed from 12 parts to 50 parts.

The results are shown in Tables 1 and 2.

From the results of Tables 1 and 2, Examples 1 to 3 using the curable resin composition of the present invention have good low roughness, sufficient tear strength, low coefficient of thermal expansion, and resin landfill. Sex. On the other hand, in Comparative Examples 1 to 5, since the curable resin composition of the present invention was not used, the arithmetic mean roughness and the self-centered average square root roughness were large, and the tear strength was small and the coefficient of linear thermal expansion was large.

Claims (16)

A curable resin composition characterized by containing (1) containing (1-A) having a structure selected from a biphenyl structure, a bixylenol structure, a bisphenol acetophenone structure, and a bisphenol fluorene structure. In the epoxy resin mixture of the two or more types of the epoxy resin A and the epoxy resin B other than the epoxy resin A (1-B), the ring is 100% by mass of the epoxy resin mixture. The content of the oxygen resin A is 3 to 30% by mass, the epoxy resin equivalent of the epoxy resin A is an epoxy resin mixture of 1,500 to 4,800, (2) a curing agent, and (3) an inorganic filler. The curable resin composition of claim 1, wherein the content of the epoxy resin A in the case where the nonvolatile content in the curable resin composition is 100% by mass is 0.5 to 10% by mass. The hardenable resin composition of claim 1 or 2, wherein the (1-B) epoxy resin B is a bisphenol type epoxy resin, a crystalline bifunctional epoxy resin, or a dicyclopentadiene type epoxy resin. A resin, a naphthalene type epoxy resin, and a mixture of such epoxy resins are selected in the group. The curable resin composition according to claim 1 or 2, wherein the epoxy resin equivalent of the above (1) epoxy resin mixture is from 50 to 3,000. The curable resin composition according to claim 1 or 2, wherein the curing agent (2) is one or more selected from the group consisting of a phenol resin, a cyanate resin, and an active ester resin. The curable resin composition of claim 1 or 2, wherein the aforementioned (3) The inorganic filler has an average particle diameter of 0.01 to 5 μm. The curable resin composition of claim 1 or 2, wherein the aforementioned (3) inorganic filler is surface-treated with a surface treatment agent. The curable resin composition of claim 1 or 2, wherein the (3) inorganic filler is cerium oxide. The curable resin composition of claim 1 or 2, wherein the content of the hardener (2) is from 1 to 30% by mass, and the amount of the hardening agent in the curable resin composition is 100% by mass. 3) The content of the inorganic filler is 30 to 90% by mass. A curable resin composition for an insulating layer of a multilayer printed wiring board, which comprises the curable resin composition according to claim 1 or 2. A curable resin composition for a build-up layer of a multilayer printed wiring board, which comprises the curable resin composition according to claim 1 or 2. A sheet-like laminate comprising a curable resin composition as claimed in claim 1 or 2. The lamella laminate of claim 12, wherein the thickness is 5 to 30 μm. A multilayer printed wiring board characterized by comprising an insulating layer obtained by thermally hardening a curable resin composition as claimed in claim 1 or 2. A multilayer printed wiring board characterized by comprising an insulating layer obtained by thermally hardening a sheet-like laminate of claim 12. A semiconductor device characterized by comprising the multilayer printed wiring board of claim 15.