JP2014156515A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition excellent in fracture elongation, low in not only arithmetic average roughness of an insulator layer surface in a wet type roughening process but also square root-mean-square roughness, capable of forming a plated conductor layer having enough peel strength, and low in linear thermal expansion coefficient.SOLUTION: There is provided a curable resin composition containing (A) a phenoxy resin having a fluorene structure, (B) an epoxy resin and (C) a curing agent, in which (C) the curing agent contains one or more kind selected from among a phenol curing agent, a cyanate ester curing agent and an active ester curing agent, and (A) the phenoxy resin is at 1 to 20 mass% based on the 100 mass% of total of (A) the phenoxy resin, (B) the epoxy resin and (C) the curing agent.

Description

  The present invention relates to a curable resin composition. Furthermore, this invention relates to the curable resin composition for insulating layers, the sheet-like laminated material, the multilayer printed wiring board, and a semiconductor device containing the said curable resin composition.

  2. Description of the Related Art In recent years, electronic devices have been reduced in size and performance, and in multilayer printed wiring boards, build-up layers have been multilayered, and miniaturization and high density of wiring have been demanded.

  Various approaches have been made against this. For example, Patent Document 1 uses a polymer epoxy resin having a specific structure as a resin composition for a printed wiring board, and has heat resistance, low water absorption, electrical characteristics, moldability, flexibility, impact resistance and adhesion. To improve the performance (claims and paragraph number 0003 and the like). However, the resin composition of Patent Document 1 is a specific curing agent selected from a phenol curing agent, a cyanate ester curing agent, and an active ester curing agent by combining a phenoxy resin having a specific fluorene structure and an epoxy resin in a specific ratio. There is no description of a curable resin composition characterized by containing any of the above.

JP 2003-252951 A

  The problem to be solved by the present invention has a specific strength (breaking elongation), and not only the arithmetic average roughness of the insulating layer surface is low in the wet roughening process, but also the root mean square roughness is low (low roughness) And providing a curable resin composition that can form a plated conductor layer having a sufficient peel strength and has a low linear thermal expansion coefficient.

As a result of intensive studies to solve the above problems, the present inventors have obtained a resin composition containing (A) a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a curing agent, C) The curing agent includes one or more selected from a phenol curing agent, a cyanate ester curing agent, and an active ester curing agent, and the total of (A) phenoxy resin, (B) epoxy resin, and (C) curing agent is 100 masses. %, The curable resin composition characterized in that (A) the phenoxy resin is 1 to 20% by mass has the above-described excellent strength, low roughness, high peel strength, and low linear thermal expansion coefficient. The inventors have found that this can be achieved and have completed the present invention.
That is, the present invention includes the following aspects.
[1]
(A) A resin composition containing a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a curing agent,
(C) The curing agent includes one or more selected from a phenol curing agent, a cyanate ester curing agent, and an active ester curing agent,
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 20% by mass. Curable resin composition.
[2]
The curable resin composition according to [1], wherein the (A) phenoxy resin has a weight average molecular weight of 8000 to 100,000.
[3]
The curable resin composition according to [1] or [2], wherein the (A) phenoxy resin has an unsubstituted bisphenol fluorene structure or a biscresol fluorene structure.
[4]
The (B) epoxy resin is selected from the group consisting of a bisphenol type epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a mixture of these epoxy resins. The curable resin composition according to any one of [1] to [3].
[5]
When the nonvolatile 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 5%. The curable resin composition according to any one of [1] to [4], which is 30% by mass and the content of the (C) curing agent is 3 to 20% by mass.
[6]
Furthermore, (D) The curable resin composition of any one of [1]-[5] containing an inorganic filler.
[7]
The curable resin composition according to [6], wherein the average particle diameter of the (D) inorganic filler is 0.01 to 5 μm.
[8]
The curable resin composition according to [6] or [7], wherein the content of the inorganic filler (D) is 30 to 90% by mass when the nonvolatile component in the curable resin composition is 100% by mass. object.
[9]
The curable resin composition according to any one of [6] to [8], wherein the (D) inorganic filler is silica.
[10]
A curable resin composition for an insulating layer of a multilayer printed wiring board, comprising 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, comprising the curable resin composition according to any one of [1] to [10].
[12]
[1] A sheet-like laminate material comprising the curable resin composition according to any one of [11].
[13]
A multilayer print comprising an insulating layer obtained by thermosetting the curable resin composition according to any one of [1] to [11] or the sheet-like laminated material according to [12] Wiring board.
[14]
[13] A semiconductor device comprising the multilayer printed wiring board according to [13].

The present invention preferably includes the following aspects.
[A] (A) a phenoxy resin having a weight average molecular weight of 8000 to 100,000, an unsubstituted bisphenol fluorene structure or a biscresol fluorene structure, and a bixylenol structure or a bisphenol acetophenone structure;
(B) an epoxy resin selected from the group consisting of a bisphenol type epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a mixture of these epoxy resins,
(C) a curing agent containing at least one selected from a phenol curing agent, a cyanate ester curing agent, and an active ester curing agent, and (D) an inorganic filler that is silica having an average particle diameter of 0.01 to 5 μm. A resin composition comprising:
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 20% by mass,
When 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%. A curable resin composition, wherein the content of the curing agent (C) is 3 to 20% by mass and the content of the (D) inorganic filler is 30 to 90% by mass.

The insulating layer of the multilayer printed wiring board produced by thermosetting the curable resin composition of the present invention has excellent strength (breaking elongation) and the arithmetic average roughness of the insulating layer surface in the wet roughening step. Not only low, but also the root mean square roughness is low, a plated conductor layer having a sufficient peel strength can be formed thereon, and the linear thermal expansion coefficient is also low.
In particular, in the present invention, the low roughness and high peel strength can be achieved by using a phenoxy resin having a fluorene structure as component (A). In addition, the epoxy resin composition usually containing a relatively large amount of an inorganic filler is inferior in resin flow in a thin film, and voids may be generated between laminated conductors, and the peel strength is likely to decrease. Thus, it is possible to improve a peel strength by using a component (A).

[Curable resin composition]
A curable resin composition which is one embodiment of the present invention is a resin composition containing (A) a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a curing agent, wherein (C ) The curing agent includes one or more selected from a phenol curing agent, a cyanate ester curing agent, and an active ester curing agent, and the total of the (A) phenoxy resin, the (B) epoxy resin, and the (C) curing agent. When the content is 100% by mass, the curable resin composition is characterized in that the (A) phenoxy resin is 1 to 20% by mass. Hereinafter, the curable resin composition of the present invention will be described in detail.

フルオレン構造として好ましくは、ビスフェノールフルオレン構造である。当該フェノキシ樹脂は、フルオレン構造の他、任意にビキシレノール構造及びビスフェノールアセトフェノン構造を少なくとも１種以上有していてもよい。各構造は以下の式（１）〜（３）で表すことができる。 (A) Phenoxy resin having a fluorene structure As the phenoxy resin having a fluorene structure that can be used in the present invention, any phenoxy resin can be used as long as it has at least one fluorene structure shown below. .
Fluorene structure:

The fluorene structure is preferably a bisphenol fluorene structure. The phenoxy resin may optionally have at least one bixylenol structure and bisphenolacetophenone structure in addition to the fluorene structure. Each structure can be represented by the following formulas (1) to (3).

（式（１）中、Ｒ₁は、互いに同一であっても異なっていてもよく、水素原子、Ｃ_1~10の炭化水素基及びハロゲン元素からなる群から選ばれる基であり、Ｒ₂は、互いに同一であっても異なっていてもよく、水素原子、Ｃ_1~10の炭化水素基又はハロゲン元素から選ばれる基であり、ｎは、互いに同一であっても異なっていてもよく、０〜４の整数である。） Bisphenol fluorene structure (see JP2003-252951)

(In the formula (1), R ₁ is a group selected from the group consisting of hydrocarbon radicals and halogen elements was to or different, a hydrogen atom, C 1 _{~ 10} are identical to each other, R ₂ is May be the same or different from each other, and is a hydrogen atom, a C _1-10 hydrocarbon group or a halogen element, and n may be the same or different from each other, and It is an integer of ~ 4.)

ビスクレゾールフルオレン構造

As the bisphenolfluorene structure, the following structures are particularly preferable.

Unsubstituted bisphenol fluorene structure

Biscresol fluorene structure

Bixylenol structure

（式（３）中、Ｒ₃は、互いに同一であっても異なっていてもよく、水素原子、Ｃ_1~10の炭化水素基及びハロゲン元素からなる群から選ばれる基であり、Ｒ₄は、水素原子、Ｃ_1~10の炭化水素基及びハロゲン元素からなる群から選ばれる基であり、Ｒ₅は、水素原子又はＣ_1~10の炭化水素基であり、ｍは０〜５の整数である。） Bisphenol acetophenone structure (see JP2003-252951)

(In the formula (3), R ₃ is a group selected from the group consisting of hydrocarbon radicals and halogen elements was to or different, a hydrogen atom, C 1 _{~ 10} are identical to each other, R ₄ is , A hydrogen atom, a group selected from the group consisting of a C _1-10 hydrocarbon group and a halogen element, R ₅ is a hydrogen atom or a C _1-10 hydrocarbon group, and m is an integer of 0-5. .)

In a more preferred embodiment, in the formula (1), R _{1 s} 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 C _1-6. An alkyl group, more preferably a hydrogen atom or a methyl group, and R _{2 s} 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 C _{1 to 6} alkyl groups, more preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, and n may be the same or different from each other, and may be 0 to 3, more preferably 1 to 2. It is an integer.
Further, in formula (3), R ₃ may be the being the same or different, a hydrogen atom or a hydrocarbon group of C _{1 ~ 8,} and more preferably a hydrogen atom or an alkyl group of C _{1 ~ 6,} more preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, R ₄ is a hydrogen atom or a hydrocarbon group of C _{1 ~ 8,} and more preferably hydrogen atom or an alkyl group C _{1 ~ 6,} more preferably hydrogen atom or a methyl group, particularly preferably a hydrogen atom, R ₅ is a hydrogen atom or a hydrocarbon group of C _{1 ~ 8,} and more 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 an integer of 0 to 3, more preferably 1 to 2.

The phenoxy resin having a fluorene structure is preferably a phenoxy resin having at least one or more fluorene structures and any structure other than at least one or more fluorene structures. Specifically, a phenoxy resin having a bixylenol structure and a substituted or unsubstituted bisphenolfluorene structure, or a phenoxy resin having a bixylenol structure, a bisphenolacetophenone structure, and a biscresol fluorene structure is preferable. More specifically, in the bisphenol fluorene structure, in formula (1), R ₁ has a hydrogen atom and a methyl group, and R ₂ is a hydrogen atom (that is, biscresol fluorene structure (1-2)). Is preferred. In the bisphenol acetophenone structure, in formula (3), R ₃ is preferably a hydrogen atom, R ₄ is a hydrogen atom, and R ₅ is a methyl group.

  As an example of the manufacturing method of the phenoxy resin which has a fluorene structure, it can manufacture by making the epoxy group of a bixylenol type epoxy resin react with the phenol group of a bisphenol fluorene derivative. Specifically, the ratio of the number of epoxy groups of the bixylenol type epoxy resin to the number of phenol groups derived from the bisphenolfluorene derivative is preferably 1: 1 to 1.3: 1, more preferably 1: 1 to 1.2: 1. 1.01-1 to 1.1: 1 are more preferable. Furthermore, in the case of a phenoxy resin having a bisphenol acetophenone structure and a biscresol fluorene structure, the ratio of the number of phenol groups derived from the bisphenol acetophenone derivative to the number of phenol groups derived from the biscresol fluorene derivative is preferably 1: 5 to 1:15. : 7 to 1:11 is more preferable. Thereby, the linear thermal expansion coefficient of the epoxy resin A can be lowered.

The content of the phenoxy resin having a fluorene structure is as follows: (A) phenoxy resin when the total of (A) phenoxy resin, (B) epoxy resin described later, and (C) curing agent described later is 100% by mass. Is 1 to 20% by mass, preferably 2 to 15% by mass, and more preferably 5 to 12% by mass. If the content of the phenoxy resin is 1% by mass or more, low arithmetic average roughness and low root-mean-square roughness are obtained, and if it is 20% by mass or less, the cross-linked site can be sufficiently maintained, so that low arithmetic average roughness and Low root mean square roughness and low coefficient of linear thermal expansion can be maintained.
Moreover, when the sum total of (A) phenoxy resin and the (B) epoxy resin mentioned later is 100 mass%, (A) phenoxy resin becomes like this. Preferably it is 2-30 mass%, More preferably, 4- 20% by mass.
The epoxy equivalent of the phenoxy resin having a fluorene structure (the mass of the resin containing 1 equivalent of an epoxy group) is preferably 5000 to 30000 (g / equivalent), more preferably 7000 to 20000 (g / equivalent), and still more preferably 9000. ˜15000 (g / equivalent) is suitable. If the epoxy equivalent of the phenoxy resin having a fluorene structure is 5000 or more, it has excellent elongation at break, and if it is 30000 or less, the cross-linked site can be kept sufficiently, so that low arithmetic average roughness and low root mean square roughness are obtained. And a low linear thermal expansion coefficient can be maintained. The epoxy equivalent can be measured according to JIS K7236 (2001).
The weight average molecular weight of the phenoxy resin having a fluorene structure is, for example, 8000 to 100,000, preferably 15000 to 80000, more preferably 20000 to 60000, and further preferably 25000 to 40000. If the weight average molecular weight of the phenoxy resin is 8000 or more, it has excellent breaking elongation, and if it is 100,000 or less, compatibility with the resin composition is improved, and low arithmetic average roughness and low root mean square are obtained. It can be roughness. The weight average molecular weight of the phenoxy resin can be measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  When the non-volatile component in the said curable resin composition is 100 mass%, content of (A) phenoxy resin which has a fluorene structure becomes like this. Preferably it is 0.3-10 mass%, More preferably, it is 0.5- It is suitable that it is 7 mass%, More preferably, it is 0.7-5 mass%.

(B) Epoxy Resin The (B) component epoxy resin is an epoxy resin different from the (A) component phenoxy resin. The (B) component epoxy resin preferably has an epoxy equivalent that is different from the (A) component phenoxy resin. The epoxy equivalent of the component (B) epoxy resin (the mass of the resin containing 1 equivalent of an epoxy group) is preferably 50 to 3000 (g / equivalent), more preferably 100 to 2000 (g / equivalent), and still more preferably. It is suitable that it is 150-1000 (g / equivalent), Most preferably, it is 200-500 (g / equivalent). Thereby, the crosslinking density of the insulating layer obtained from the curable resin composition becomes sufficient, which is advantageous for low roughness. The epoxy equivalent can be measured according to JIS K7236 (2001). Preferably, the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule.
Specific epoxy resins include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol type epoxy resins such as bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and phenol novolacs. Type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, anthracene epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, Ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, trimethylol type epoxy resins, halogenated epoxy resins, and crystalline bifunctional epoxy resin. More preferably, the (B) epoxy resin is selected from the group consisting of a bisphenol type epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, and a mixture of these epoxy resins. These may be used alone or in combination of two or more.

  Among these epoxy resins, from the viewpoint of improving heat resistance, bisphenol A type epoxy resin, bisphenol F type epoxy resin, crystalline bifunctional epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin and two or more of these Is preferred. Specifically, for example, mixed epoxy resin of bisphenol A type and F type (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd.), bisphenol A type epoxy resin (“Epicoat 828EL” manufactured by Mitsubishi Chemical Corporation), “YL980” ”,“ JER1009 ”), bisphenol F type epoxy resin (“ jER806H ”,“ YL983U ”manufactured by Mitsubishi Chemical Corporation), naphthalene type bifunctional epoxy resin (“ HP4032 ”,“ HP4032D ”,“ HP4032SS ”manufactured by DIC Corporation). , “EXA4032SS”), naphthalene type tetrafunctional epoxy resin (“HP4700”, “HP4710” manufactured by DIC Corporation), naphthol type epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd.), butadiene structure Epoxy resin ("PB-3600" manufactured by Daicel Chemical Industries, Ltd.) Epoxy resins having a biphenyl structure (“NC3000H”, “NC3000L”, “NC3100” manufactured by Nippon Kayaku Co., Ltd.), bixylenol type epoxy resins (“YX4000”, “YX4000H”, “YX4000HK” manufactured by Mitsubishi Chemical Corporation) , “YL6121”), anthracene type epoxy resin (“YX8800” manufactured by Mitsubishi Chemical Corporation), naphthylene ether type epoxy resin (“EXA-7310”, “EXA-7311”, “EXA-7311L manufactured by DIC Corporation) ”,“ EXA7311-G3 ”), glycidyl ester type epoxy resin (“ EX711 ”,“ EX721 ”manufactured by Nagase ChemteX Corporation,“ R540 ”manufactured by Printec Co., Ltd.), dicyclopentadiene type epoxy resin (DIC ( "HP-7200H") manufactured by Co., Ltd.

The structural formula of the main component of HP4032SS is as follows.

（式中、Ｇｒはグリシジル基。） The structural formula of YX4000HK is as follows.

(In the formula, Gr is a glycidyl group.)

（式中、ｎは１〜２０までの整数。） The structural formula of HP-7200H is as follows.

(In the formula, n is an integer from 1 to 20.)

（式中、ｎは１〜２０までの整数。） The structural formula of NC3000L is as follows.

(In the formula, n is an integer from 1 to 20.)

The structural formula of jER1009 is as follows.

The content of the (B) epoxy resin is preferably 30 to 80% by mass, more preferably 100% by mass when the total of the (A) phenoxy resin, the (B) epoxy resin and the (C) curing agent is 100% by mass. It is 35-75 mass%, More preferably, it is 40-70 mass%.
The content of the (B) epoxy resin in the curable resin composition of the present invention is not particularly limited, but from the viewpoint of achieving both low roughness of the insulating layer and high peel strength, the curing is performed. When the non-volatile component in a resin composition is 100 mass%, 5-30 mass% is preferable, 7-25 mass% is more preferable, and 10-20 mass% is still more preferable.

(C) Curing agent The curing agent used in the present invention can be cured by crosslinking the phenoxy resin and the epoxy resin, and is selected from a phenol curing agent, a cyanate ester curing agent, and an active ester curing agent. 1 or more types. The phenol resin, cyanate ester resin, and active ester resin that constitute these phenol curing agent, cyanate ester curing agent, and active ester curing agent, respectively, can significantly reduce the surface roughness of the insulating layer.

  Although there is no restriction | limiting in particular as a phenol resin, A biphenyl type phenol resin, a naphthalene type phenol resin, a phenol novolak resin, a naphthylene ether type phenol resin, and a triazine skeleton containing phenol resin are preferable. Specifically, MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei Co., Ltd.) of biphenyl type phenol resin, NHN, CBN, GPH (Nippon Kayaku Co., Ltd.) of naphthalene type phenol resin, SN-170, SN-180, SN-190, SN-475, SN-485, SN-495, SN-375, SN-395 (manufactured by Nippon Steel Chemical Co., Ltd.), EXB9500 (manufactured by DIC Corporation) , Phenol novolac resin TD2090 (manufactured by DIC Corporation), naphthylene ether type phenol resin EXB-6000 (manufactured by DIC Corporation), triazine skeleton-containing phenol resins LA-3018, LA-7052, LA-7054, LA-1356 (manufactured by DIC Corporation), and the like. These may be used alone or in combination of two or more.

（ｎは１〜２０までの整数。） The structural formula of SN-485 is as shown in the following formula (4).

(N is an integer from 1 to 20.)

（ｎは１〜２０までの整数。） 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 novolak-type cyanate ester resins, dicyclopentadiene-type cyanate ester resins, bisphenol-type cyanate ester resins, and prepolymers in which these are partially triazine. Specifically, a phenol novolak polyfunctional cyanate ester resin represented by the following formula (6) (manufactured by Lonza Japan KK, PT30S: number average molecular weight 380, PT60: number average molecular weight 560), the following formula (7) A bisphenol A type cyanate ester resin (BA230S75, manufactured by Lonza Japan Co., Ltd.), which is a prepolymer in which a part or all of the bisphenol A type cyanate ester resin represented by the above formula is triazine is converted into a trimer, ) Dicyclopentadiene type cyanate ester resin (Lonza Japan Co., Ltd., DT-4000, DT-7000), and the like. Specifically, the number average molecular weight is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as a column. Using chloroform or the like as a mobile phase, the measurement can be made at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve. These may be used alone or in combination of two or more.

［式中、ｎは平均値として任意の数（好ましくは０〜２０、より好ましくは１〜１０）を示す。］

[In formula, n shows arbitrary numbers (preferably 0-20, more preferably 1-10) as an average value. ]

（式中、ｎは平均値として０〜５の数を表す。）

(In formula, n represents the number of 0-5 as an average value.)

  The active ester resin that 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 that reacts with an epoxy resin. The active ester resin can react with the epoxy resin, and a resin compound having two or more active ester groups in one molecule is preferable. Generally, a resin compound selected from the group consisting of phenol ester, thiophenol ester, N-hydroxyamine ester and heterocyclic hydroxy compound ester, having two or more ester groups with high reaction activity in one molecule, It is preferably used as an active ester resin. The active ester resin may be used alone or in combination of two or more.

  From the viewpoint of improving heat resistance, an active ester resin obtained from a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound is more preferable. An active ester resin obtained from a product obtained by reacting one or more selected from a phenol compound, a naphthol compound and a thiol compound with a carboxylic acid compound is more preferable. 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 even more preferable. An aromatic resin compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and in one molecule of the aromatic resin compound Particularly preferred are aromatic resin compounds having two or more active ester groups. The active ester resin may be linear or hyperbranched. In addition, if the compound having at least two carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring, it is heat resistant. Sexuality can be increased.

  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. Of these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred from the viewpoint of heat resistance. Specific examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.

  Specific examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxy Examples include benzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac. Among them, from the viewpoint of improving heat resistance and 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, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac are preferred, catechol, 1 , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophene Non-tetrahydrobenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolak are more preferable. 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxy More preferred are hydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, phenol novolac, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadienyl diphenol, Phenol novolac is even more preferred, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthal Emissions, dicyclopentadienyl diphenol especially preferred, dicyclopentadienyl diphenol is particularly preferred. Specific examples of the thiol compound include benzenedithiol and triazinedithiol.

  Specifically, the active ester resin includes an active ester resin containing a dicyclopentadienyl diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. An active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadienyl diphenol structure are more preferable. Commercially available products include EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation) as active ester resins containing a dicyclopentadienyl diphenol structure, and EXB9416-70BK as an active ester resin containing a naphthalene structure. (Manufactured by DIC Corporation), DC808 (manufactured by Mitsubishi Chemical Corporation) as an active ester resin containing an acetylated product of phenol novolac, YLH1026 (manufactured by Mitsubishi Chemical Corporation) as an active ester resin containing a benzoylated product of phenol novolac, Etc.

（式中、ｍは０又は１であり、ｎが平均値として０．２５〜１．５、好ましくは、０．４〜１．２である）で表されるジシクロペンタジエニルジフェノール構造を含み、末端にＸ−基及びＸＯ−基（ここでＸは置換基を有していてもよいフェニル基又はナフチル基である）を有する樹脂化合物である。当該活性エステル樹脂の重量平均分子量は、好ましくは１５００〜４０００であり、より好ましくは２０００〜３０００である。
殊更好ましい活性エステル樹脂は、以下の式（１０）で表されるジシクロペンタジエニルジフェノール構造を有し、末端にＸ−基及びＸＯ−基（ここでＸは置換基を有していてもよいナフチル基である）を有し、重量平均分子量が約２７００の活性エステル樹脂であるＨＰＣ−８０００−６５Ｔである。 Particularly preferred active ester resins are those represented by the following general formula (9):

(Wherein m is 0 or 1 and n is 0.25 to 1.5 as an average value, preferably 0.4 to 1.2), and a dicyclopentadienyl diphenol structure represented by And a terminal compound having an X-group and an XO-group (wherein X is an optionally substituted phenyl group or naphthyl group). The weight average molecular weight of the active ester resin is preferably 1500 to 4000, and more preferably 2000 to 3000.
A particularly preferred active ester resin has a dicyclopentadienyl diphenol structure represented by the following formula (10), and has an X-group and an XO-group (where X has a substituent). HPC-8000-65T, which is an active ester resin having a weight average molecular weight of about 2700.

（式中、ｍは０又は１であり、ｎが平均値として０．４〜１．２である）

(In the formula, m is 0 or 1, and n is 0.4 to 1.2 as an average value)

  The content of the curing agent (C) in the curable resin composition of the present invention is not particularly limited, but from the viewpoint of achieving both low roughness of the insulating layer and high peel strength, the curing is performed. When the non-volatile component in a resin composition is 100 mass%, 3-20 mass% is preferable, 5-18 mass% is more preferable, and 7-15 mass% is still more preferable.

  Moreover, when the epoxy group number of the whole epoxy resin is set to 1, 0.2-2 are preferable, as for the reactive group number of a hardening | curing agent, 0.3-1.5 are more preferable, and 0.4-1 are still more preferable. Here, the “number of epoxy groups in the entire epoxy resin” is a value obtained by adding the values obtained by dividing the solid mass of each epoxy resin present in the curable resin composition by the epoxy equivalent for all epoxy resins. Further, “reactive group” means a functional group capable of reacting with an epoxy group, and “reactive group number” means the solid content mass of the curing agent present in the resin composition divided by the reactive group equivalent. This is the total value of all the values.

(D) Inorganic filler Examples of the inorganic filler that can be used in the present invention include silica, alumina, mica, mica, silicate, barium sulfate, magnesium hydroxide, and titanium oxide. Silica and alumina are preferable. In particular, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and spherical silica is preferable, and spherical silica and fused silica are more preferable. Spherical fused silica is more preferable from the viewpoint of improving the filling property of the inorganic filler with respect to the sheet-shaped laminated material of the present invention containing the curable resin composition. One or more inorganic fillers can be used. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 1 μm or less, from the viewpoint of forming fine wiring on the insulating layer. 8 μm or less is even more preferable, and 0.6 μm or less is particularly preferable. 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, from the viewpoint of preventing the viscosity of the varnish from increasing and handleability from decreasing. 0.07 μm or more is more preferable, and 0.1 μm or more is even more preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, LA-950 manufactured by Horiba, Ltd. or the like can be used.

    Although content in particular of an inorganic filler is not restrict | limited, From a viewpoint of preventing that the flexibility of the sheet | seat form of a sheet-like laminated material falls, the non-volatile component in curable resin composition was 100 mass%. In this case, the amount of the inorganic filler is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and still more preferably 50 to 85% by mass. In particular, in the present invention, it is possible to improve the peel strength even in a curable resin composition containing 50% by mass or more of an inorganic filler.

  The inorganic filler is preferably subjected to surface treatment (coating) with a coupling agent or the like in order to improve moisture resistance and dispersibility. The surface treatment agent (coupling agent) is selected from an epoxysilane coupling agent, an aminosilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, and a titanate coupling agent. One or more are preferred. Among these, aminosilane coupling agents are preferable because they are excellent in moisture resistance, dispersibility, and properties of cured products, and phenylaminosilane coupling agents are more preferable. Commercially available products include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. ”(Phenyltrimethoxysilane),“ SZ-31 ”(hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[Other ingredients]
In addition to the components described above, the curable resin composition of the present invention includes, as other components, a curing accelerator; a thermoplastic resin; a thermosetting resin such as a vinylbenzyl compound, an acrylic compound, a maleimide compound, and a blocked isocyanate compound. Flame retardants such as phosphorus compounds and metal hydroxides; Organic fillers such as silicon powder, nylon powder, fluorine powder, and rubber particles; Organic solvents; Thickeners such as Orben and Benton; Silicone, fluorine, and high Molecular antifoaming agents; adhesion-imparting agents such as imidazole, thiazole, triazole and silane coupling agents; coloring agents such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow and carbon black; added An agent or the like can be appropriately blended.

  As the curing accelerator, any curing accelerator can be used as long as it can accelerate the crosslinking and curing of the epoxy resin by the curing agent. For example, an amine compound, a guanidine compound, an imidazole compound, Examples thereof include phosphonium compounds and metal curing accelerators. These may be used alone or in combination of two or more.

  The amine compound that can be used in the present invention is not particularly limited, but trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6,- And amine compounds such as tris (dimethylaminomethyl) phenol and 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU). You may use these 1 type or in combination of 2 or more types. These may be used alone or in combination of two or more.

（式中、Ｒ₆〜Ｒ₉は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、シアノ基、ニトロ基、ホルミル基、Ｃ_1~20アルキル基、Ｃ_2~20アルケニル基、Ｃ_2~20アルキニル基、Ｃ_3~20アリル基、Ｃ_4~20アルキルジエニル基、Ｃ_4~20ポリエニル基、Ｃ_6~20アリール基、Ｃ_6~20アルキルアリール基、Ｃ_6~20アリールアルキル基、Ｃ_4~20シクロアルキル基、Ｃ_4~20シクロアルケニル基、（Ｃ_5~10シクロアルキル）Ｃ_1~10アルキル基、Ｃ_1~10炭化水素基を有していてもよいシリル基、エポキシ樹脂に由来するヒドロキシエチル基である）で表される化合物であってもよい。 As an imidazole compound that can be used in the present invention, the following general formula (11)

(Wherein, R ₆ to R ₉ may be the same as or different from each other, a hydrogen atom, a halogen atom, a cyano group, a nitro group, formyl groups, C 1 _{~ 20} alkyl groups, C 2 _{~ 20} alkenyl groups, C _2-20 alkynyl group, C 3 _{~ 20} aryl group, C 4 _{~ 20} alkyldienyl group, C 4 _{~ 20} polyenyl group, C 6 _{~ 20} aryl group, C 6 _{~ 20} alkylaryl group, C 6 _{~ 20} arylalkyl group, C 4 _{~ 20} cycloalkyl group, C 4 _{~ 20} cycloalkenyl group, (C 5 _{~ 10} cycloalkyl) C 1 _{~ 10} alkyl group, C 1 _{~ 10} hydrocarbon group a silyl group, which may have a It may be a compound represented by a hydroxyethyl group derived from an epoxy resin.

  More specifically, imidazole compounds are 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'-un Decylimidazolyl- (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 isocyanuric acid adduct, 2-phenylimidazole Cyanuric acid 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 It may be a compound selected from the group consisting of 2,4-diamino-6-vinyl-S-triazine. These may be used alone or in combination of two or more.

  Although it does not specifically limit as a metal type hardening accelerator which can be used by this invention, The organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and tin, is mentioned. It is done. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

  The content of the curing accelerator is preferably used in the range of 0.005 to 3% by mass, when the total of nonvolatile components in the curable resin composition is 100% by mass, 0.01 to 1% by mass It is more preferable to use in the range.

  As the thermoplastic resin, for example, (A) a phenoxy resin other than a phenoxy resin having a fluorene structure, a polyvinyl acetal resin, a polyimide resin, a polyamideimide resin, a polyethersulfone resin, a cycloolefin, to the extent that the effects of the present invention are not impaired. Examples thereof include a polymer and a polysulfone resin, and a polyvinyl acetal resin is preferable. These may be used alone or in combination of two or more.

  The polystyrene-reduced weight average molecular weight of the thermoplastic resin is preferably in the range of 8000 to 70000, more preferably in the range of 10,000 to 60000, and still more preferably in the range of 20000 to 60000. The polystyrene-reduced weight average molecular weight of the thermoplastic resin can be measured by gel permeation chromatography (GPC) as in the method of measuring the weight average molecular weight of (A) phenoxy resin.

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

[Preparation of curable resin composition]
The curable resin composition of the present invention is appropriately mixed with the above components, and if necessary, a kneading means such as a three roll, ball mill, bead mill, sand mill, or a high-speed rotating mixer, a super mixer, a planetary mixer, etc. It can be prepared by kneading or mixing with stirring means. Moreover, it can also prepare as a resin varnish by adding the organic solvent mentioned above.

  In the curable resin composition of the present invention, not only the arithmetic average roughness of the insulating layer surface is low, but also the root mean square roughness is low, and a plated conductor layer having sufficient peel strength can be formed thereon. Therefore, in manufacture of a multilayer printed wiring board, it can use suitably as a curable resin composition for insulating layers of a multilayer printed wiring board. Furthermore, it can be suitably used as a curable resin composition for forming a conductor layer by plating (resin composition for an insulating layer of a multilayer printed wiring board in which a conductor layer is formed by plating), and further a multilayer printed wiring board It is suitable as a curable resin composition for a buildup layer.

  Although it does not specifically limit as a form of the curable resin composition of this invention, It can apply to sheet-like laminated materials, such as an adhesive film and a prepreg, and a circuit board (a laminated board use, a multilayer printed wiring board use, etc.). The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but in general, it is preferably used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. . The softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminate property of the sheet-like laminated material.

[Multilayer printed wiring board]
The curable resin composition of the present invention can be used as a curable resin composition for an insulating layer of a multilayer printed wiring board. The multilayer printed wiring board which can be used by this invention is a multilayer printed wiring board containing the insulating layer obtained by thermosetting the curable resin composition and sheet-like laminated material of this invention.
Here, the thermosetting conditions may be appropriately selected according to 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 to 210 ° C. The curing time is 10 minutes to 180 minutes, preferably 20 to 120 minutes. In addition, thermosetting may be performed in two stages.
Here, the linear thermal expansion coefficient (CTE) (JIS K7197) of the insulating layer is preferably 20 ppm / ° C. or less, preferably 19 ppm / ° C. or less, as measured by an average linear thermal expansion coefficient of 25 to 150 ° C. Is more preferable. The lower limit is not particularly limited, but is generally 4 ppm / ° C. Thereby, distortion with an insulating layer (build-up layer) and a conductor layer (wiring) can be prevented, and a highly reliable multilayer printed wiring board can be obtained.

The surface of the insulating layer may be roughened. Examples of the dry roughening treatment include plasma treatment. The wet roughening treatment is performed, for example, by applying various treatment liquids. The method of performing the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralization liquid in this order is mentioned. Therefore, the treatment liquid may be a kit of these swelling liquid, oxidizing agent, and neutralizing liquid. The wet roughening treatment is preferable in that a large area or a plurality of sheets can be processed at a time, and the productivity is high.
The swelling treatment with the swelling liquid is performed by immersing 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). Examples of the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include sodium hydroxide solution and potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Securiganth P (Swelling Dip Securiganth P) and Swelling Dip Securiganth SBU manufactured by Atotech Japan Co., Ltd. be able to.
The roughening treatment with 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). Examples of the oxidizing agent include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can. Moreover, it is preferable that the density | concentration of the permanganate in an alkaline permanganic acid solution shall be 5-10 mass%. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP, Dosing Solution Securigant P manufactured by Atotech Japan Co., Ltd.
Neutralization treatment with a neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C for 3 to 10 minutes (preferably at 35 to 45 ° C for 3 to 8 minutes). As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant 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 at 60 to 100 ° C. for 20 to 40 minutes).

  The surface roughness of the surface of the insulating layer after the roughening treatment is preferably such that the arithmetic average roughness (Ra) is 350 nm or less, more preferably 300 nm or less, and 200 nm or less in order to improve fine wiring formation. More preferably, it is more preferably 100 nm or less. Although there is no restriction | limiting in the lower limit of arithmetic mean roughness (Ra), Generally it will be 10 nm or more, 40 nm or more, 70 nm or more, etc. The root mean square 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. Although there is no restriction | limiting in the lower limit of root mean square roughness (Rq), Generally it will be 20 nm or more, 50 nm or more, 90 nm or more. In addition, since the root mean square roughness (Rq) reflects the local state of the insulating layer surface, it can be confirmed by grasping Rq that the surface of the insulating layer is denser and smoother, and the peel strength is stable. Turn into. This corresponds to the surface roughness of the insulating layer after the curable resin composition is thermally cured and roughened.

  The peel strength is preferably 0.45 kgf / cm (4.41 N / cm) or more, and 0.50 kgf / cm (4. 4 N / cm) in order to keep the insulating layer and a layer adjacent thereto, for example, a conductor layer sufficiently adhered. 90 N / cm) or more is more preferable. The upper limit of peel strength is preferably as high as possible and is not particularly limited, but is generally 1.5 kgf / cm (14.7 N / cm) or less, 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, and the like.

  The elongation at break is measured in accordance with JIS K7127, the tensile strength of a cured product obtained by thermosetting the curable resin composition. Specifically, a test piece cut out in a dumbbell shape from this cured product can be prepared, the PET film can be peeled off, and measurement can be performed using an orientec tensile tester RTC-1250A. The elongation at break is preferably 1.5%, more preferably 1.7% or more.

[Sheet laminated material]
The sheet-like laminated material used in the present invention is a sheet-like material before curing, in which the curable resin composition is layered. The sheet-like laminated material is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which the resin composition is dissolved in the organic solvent described above, and applying the resin varnish to a support using a die coater or the like. Further, the organic solvent is further dried by heating or hot air blowing to form a resin composition layer (sheet-like laminate material) on the support, whereby a sheet-like laminate material with a support can be produced. Moreover, a sheet-like laminated material can also be made into a prepreg by impregnating and drying a resin varnish on a sheet-like reinforcing base material such as glass cloth by a hot melt method or a solvent method. In addition, a sheet-like laminated material with a support may be referred to as an adhesive film.

The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, a resin composition layer is formed by drying a varnish containing 30 to 60% by mass of an organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. can do.
Although the thickness of the obtained sheet-like laminated material is not particularly limited, for example, a range of 1 to 150 μm is preferable, a range of 2 to 100 μm is more preferable, a range of 3 to 50 μm is further preferable, and a range of 5 to 30 μm is particularly preferable. preferable.

  The sheet-like laminated material may have a plurality of resin composition layers, may have a support on one side of the resin composition layer, and have a protective film on the other side. Also good.

[Support]
Examples of the support that can be used in the present invention include plastic films and metal foils. Specifically, as a plastic film, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, acrylic, cyclic polyolefin, triacetyl cellulose, polyether sulfide , Polyether ketone, polyimide and the like. Among these, a polyethylene terephthalate film and a polyethylene naphthalate film are preferable, and a polyethylene terephthalate film that is inexpensive and easily available is particularly preferable.
Examples of the metal foil include copper foil and aluminum foil.

From the viewpoint of versatility, a plastic film is preferable. When a plastic film is used, in order to improve peelability, it is necessary to use a support whose surface in contact with the layer containing the curable resin composition is subjected to a release treatment. preferable. The release agent used for the release treatment is not particularly limited as long as the layer containing the curable resin composition can be peeled from the support, and examples thereof include silicon release agents, alkyd resin release agents, and polyolefins. Resins, urethane resins, fluororesins and the like can be mentioned. In addition, you may use the plastic film with a release layer marketed as a support body by which the mold release process was carried out, As a preferable thing, for example, it has a release layer which has an alkyd resin type release agent as a main component. Examples of the PET film include SK-1, AL-5, and AL-7 (manufactured by Lintec Corporation). The plastic film may be subjected to mat treatment or corona treatment, and a release layer may be formed on the treated surface. On the other hand, the metal foil can be removed by an etching solution, or the metal foil may be used as a conductor layer without being removed.
Although the thickness of a support body is not specifically limited, The range of 10-150 micrometers is preferable, The range of 20-50 micrometers is more preferable, The range of 25-45 micrometers is further more preferable.

  The protective film that can be used in the present invention may be provided for the purpose of preventing adhesion of dust and the like to the layer containing the curable resin composition. As the protective film, a plastic film similar to the support can be used. The protective film may be subjected to a surface treatment such as a mud treatment or a corona treatment, or may be subjected to a mold release treatment similar to the above. 3-30 micrometers is preferable and, as for the thickness of a protective film, 5-20 micrometers is more preferable.

[Multilayer printed wiring board using sheet-like laminated material]
Next, an example of a method for producing a multilayer printed wiring board using the sheet-like laminated material produced as described above will be described.
First, a sheet-like laminated material is laminated (laminated) on one side or both sides of a circuit board using a vacuum laminator. Examples of the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards. Also, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board. The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

In the above laminate, when the sheet-like laminate material has a protective film, after removing the protective film, the sheet-like laminate material and the circuit board are preheated as necessary, and the sheet-like laminate material is pressurized and Laminate to circuit board while heating. In the sheet-like laminated material of the present invention, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is suitably used. Lamination conditions are not particularly limited. For example, the pressure is reduced to an air pressure of 20 mmHg (26.7 hPa) or less for about 10 to 120 seconds, and then the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., pressure bonding pressure. (Lamination pressure) is preferably 0.1 to 1.5 MPa, more preferably 0.5 to 1.2 MPa, and pressure bonding time (laminating time) is preferably 5 to 180 seconds. The laminating method may be a batch method or a continuous method using a roll. The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.
Thereafter, after cooling to near room temperature, the support is peeled off, and the resin composition is heat-cured to form a cured product, whereby an insulating layer can be formed on the circuit board. The heat curing conditions may be appropriately selected according to the type 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 curing time. Is carried out by heating for 20 to 180 minutes, preferably 30 to 120 minutes. In addition, thermosetting may be performed in two stages. After the insulating layer is formed, if the support is not peeled before curing, it can be peeled off here if necessary.

  Moreover, a sheet-like laminated material can also be laminated | stacked on the single side | surface or both surfaces of a circuit board using a vacuum press machine. The lamination process for heating and pressurizing under reduced pressure can be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support side. The pressing conditions are 70 to 250 ° C., preferably 100 to 230 ° C., and the degree of vacuum is usually 0.01 MPa or less, preferably 0.001 MPa or less, and the pressing pressure is in the range of 0.5 to 4 MPa. The pressing time is preferably 30 to 150 minutes. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the bleeding of the resin. For example, the first stage press has a temperature in the range of 70 to 150 ° C. and the press pressure is in the range of 0.1 to 1.5 MPa. The second stage press has a temperature in the range of 150 to 200 ° C. and the pressure is 0.5 to 4 MPa. It is preferable to perform in the range. The time for each stage is preferably 20 to 120 minutes. Thus, an insulating layer can be formed on a circuit board by thermosetting the resin composition layer. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

  Next, a via hole or a through hole may be formed by drilling the insulating layer formed on the circuit board. For example, the drilling can be performed by a known method such as drilling, laser, or plasma, or a combination of these methods if necessary, but drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common. Is the method. If the support is not peeled off before drilling, it will be peeled off here.

  Next, the above-described roughening treatment is performed on the surface of the insulating layer, and a conductor layer can be formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. Examples of wet plating include a method in which a conductive layer is formed by combining electroless plating and electrolytic plating, a method in which a plating resist having a pattern opposite to that of the conductive layer is formed, and a conductive layer is formed only by electroless plating. It is done. As a pattern formation method thereafter, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. By repeating the above-described series of steps a plurality of times, a multilayer in which build-up layers are stacked in multiple stages It becomes a printed wiring board. In the present invention, since it has low roughness and high peel, it can be suitably used as a build-up layer of a multilayer printed wiring board.

[Semiconductor device]
A semiconductor device can be manufactured by using the multilayer printed wiring board manufactured as described above. A semiconductor device can be manufactured by mounting a semiconductor chip on a conductive portion of a multilayer printed wiring board that can be used in the present invention. The “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location. Moreover, as long as it conduct | electrically_connects, it may be a part of conductor layers, or other conductive parts, such as a connector. The “semiconductor chip” is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).

 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “part” means “part by mass” unless otherwise specified, and “%” means “% by mass” unless otherwise specified.

<Measurement method / Evaluation method>
First, various measurement methods and evaluation methods will be described.

[Preparation of samples for peel strength, arithmetic average roughness (Ra value), root mean square roughness (Rq value)]
(1) Substrate treatment of laminated board Glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, R5715ES manufactured by Matsushita Electric Works) CZ8100 manufactured by MEC The copper surface was roughened by etching at 1 μm.
(2) Lamination of adhesive film Epoxy resin double-sided copper-clad laminate obtained by roughening the adhesive films prepared in Examples and Comparative Examples using a batch-type vacuum pressure laminator MVLP-500 (manufactured by Meiki Seisakusho). Laminated on both sides. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.

(3) Curing of resin composition After peeling a polyethylene terephthalate (PET) film as a support from a laminated adhesive film, the resin composition is cured under curing conditions of 100 ° C for 30 minutes and 180 ° C for 30 minutes. Thus, an insulating layer was formed.

(4) Roughening treatment The laminated plate on which the insulating layer is formed is a swelling liquid, a swelling ring dip securigant P (glycol ethers, aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. For 5 minutes (Example 1, Comparative Examples 1, 4, 5) or 10 minutes (Examples 2, 3, Comparative Examples 2, 3, 6) at 60 ° C. Next, as a roughening solution, Atotech Japan Co., Ltd. Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 15 minutes (Example 1, Comparative Example 1, 4, 5) for 20 minutes (Examples 2, 3, Comparative Examples 2, 3, 6). Finally, as a neutralizing solution, it was immersed for 5 minutes at 40 ° C. in Reduction Sholysin Securigant P (an aqueous solution of sulfuric acid) of Atotech Japan Co., Ltd. After drying at 80 ° C. for 30 minutes, this substrate was designated as evaluation substrate A.

(5) Plating by semi-additive method Evaluation substrate A was plated to form a conductor layer. Specifically, the evaluation substrate A was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. An annealing treatment was performed by heating at 150 ° C. for 30 minutes, and then an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing treatment was performed at 190 ° C. for 60 minutes. This substrate was designated as evaluation substrate B.

[Measurement of arithmetic average roughness (Ra value) and root mean square roughness (Rq value) after roughening]
Using a non-contact type surface roughness meter (WYKO NT3300, manufactured by Bee Coins Instruments Co., Ltd.), Ra value and Rq value are obtained from numerical values obtained with a measurement range of 121 μm × 92 μm using a 50 × lens. It was. Each was measured by obtaining an average value of 10 points.

[Measurement of peeling strength (peel strength) of plating conductor layer]
Cut the 10mm width and 100mm length into the conductor layer of the evaluation board B, peel off one end and grasp it with a gripping tool (TSE Co., Ltd., Autocom type testing machine AC-50C-SL). The load (kgf / cm (N / cm)) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature (25 ° C.) was measured.

[Measurement of linear thermal expansion coefficient (CTE)]
The adhesive films obtained in the examples and comparative examples were thermally cured by heating at 200 ° C. for 90 minutes, and peeled from the PET film as a support to obtain a sheet-like cured product. The cured product is cut into a test piece having a width of 5 mm, a length of 15 mm, and a thickness of 30 mm, and thermomechanical analysis is performed by a tensile load method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Corporation). It was. After mounting the test piece on the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average linear thermal expansion coefficient (ppm) from 25 ° C. to 150 ° C. in the second measurement was calculated.

(Measurement of fracture elongation)
The adhesive films obtained in Examples and Comparative Examples were thermally cured by heating at 200 ° C. for 90 minutes, the cured product was cut out in a dumbbell shape, and the PET film was peeled off to obtain a test piece. The test piece was measured for tensile strength using an orientec tensile tester RTC-1250A in accordance with JIS K7127, and the elongation at break at 23 ° C. was determined.

<Synthesis Example 1>
Synthesis of phenoxy resin having bixylenol structure and bisphenolfluorene structure In a reaction vessel, 190 g of bixylenol type epoxy resin (Mitsubishi Chemical Corporation YX4000, epoxy equivalent 185), 175 g of bisphenolfluorene (phenolic hydroxyl group equivalent 175), 150 g of cyclohexanone And dissolved by stirring. Next, 0.5 g of a tetramethylammonium chloride solution was added dropwise and reacted at 180 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was filtered using a filter cloth and diluted with a solvent to obtain phenoxy resin A.
Epoxy equivalent: 12200
-Weight average molecular weight: 38000
A 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass The phenoxy resin A had the following structure.

<Synthesis Example 2>
Synthesis of phenoxy resin having bixylenol structure, bisphenolacetophenone structure, and biscresol fluorene structure In a reaction vessel, 190 g of bixylenol type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), bisphenolacetophenone (phenolic hydroxyl group equivalent 145) 14 g, 170 g of biscresol fluorene (manufactured by JFE Chemical Co., Ltd., phenolic hydroxyl group equivalent 190) and 150 g of cyclohexanone were stirred and dissolved. Next, 0.5 g of a tetramethylammonium chloride solution was added dropwise and reacted at 180 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the mixture was filtered using a filter cloth and diluted with a solvent to obtain phenoxy resin B.
Epoxy equivalent: 11000
-Weight average molecular weight: 36000
A 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass The phenoxy resin B had the following structure.

<Synthesis Example 3>
Synthesis of phenoxy resin having bixylenol structure and bisphenolacetophenone structure
In a reaction vessel, 100 g of bixylenol type epoxy resin (“YX4000” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), 80 g of bisphenol acetophenone, and 150 g of cyclohexanone were stirred and dissolved. Next, 0.5 g of a tetramethylammonium chloride solution was added dropwise and reacted at 180 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was filtered using a filter cloth and diluted with a solvent to obtain phenoxy resin C. Note that the phenoxy resin C is a reference example of the present invention because it does not have a fluorene structure.
Epoxy equivalent: 13000
-Weight average molecular weight: 38000
A 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass was used.
The phenoxy resin C had the following structure.

<Example 1>
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 10 parts of crystalline bifunctional epoxy resin (Mitsubishi Chemical Corporation) 10 parts of “YX4000HK”, epoxy equivalent of about 185) and 20 parts of dicyclopentadiene type epoxy resin (“HP-7200H” made by DIC Corporation, epoxy equivalent of 275) are dissolved in 35 parts of solvent naphtha with stirring. It was. After cooling to room temperature, 12 parts of phenoxy resin A, 12 parts of a triazine skeleton-containing phenolic curing agent (“LA-7054” manufactured by DIC Corporation, MEK solution having a 60% solid content of hydroxyl group equivalent of 125), naphthalene Type curing agent (manufactured by Nippon Steel Chemical Co., Ltd. "SN-485" hydroxyl equivalent 215 MEK solution with 60% solid content), curing accelerator (4-dimethylaminopyridine (DMAP), 2% solid content) 3 parts of MEK solution), flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10- 2 parts of oxide, average particle size 2 μm), spherical silica (average particle size 0.24 μm, manufactured by Admatechs Co., Ltd.) surface-treated with a phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) “SOC1” Carbon amount 0.36mg / m ²⁾ 150 parts per unit area, were mixed, and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. Next, a polyethylene terephthalate film with a release treatment (“AL5” manufactured by Lintec Co., Ltd., thickness 38 μm, linear thermal expansion coefficient (CTE), and “PET 501010”, thickness 50 μm for producing a cured product for measuring fracture elongation) A resin varnish is uniformly applied on the mold release surface so that the thickness of the dried resin composition layer is 30 μm, and dried at 80 to 120 ° C. (average 100 ° C.) for 4 minutes to produce an adhesive film. did.

<Example 2>
5 parts of liquid naphthalene type epoxy resin (epoxy equivalent 144, “HP4032SS” manufactured by DIC Corporation), 5 parts of crystalline bifunctional epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), biphenyl type epoxy 12 parts of a resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269) was dissolved by heating in 30 parts of solvent naphtha while stirring. After cooling to room temperature, there are 5 parts of phenoxy resin A, 20 parts of a prepolymer of bisphenol A dicyanate (“BA230S75” manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 232, MEK solution having a nonvolatile content of 75% by mass), 6 parts of phenol novolac type polyfunctional cyanate ester resin ("PT30S" manufactured by Lonza Japan KK, cyanate equivalent of about 133, MEK solution with non-volatile content of 85 mass%), curing accelerator (4-dimethylaminopyridine, solid content of 2 mass) % Of MEK solution), 3 parts of a curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetylacetonate (Co (III) Ac), MEK solution having a solid content of 1% by mass), rubber particles (Gantz) 2 parts by Kasei Co., Ltd., Staphyloid AC3816N, flame retardant (“HCA-HQ” by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -1 Surface treatment with 2 parts of 0-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm, phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts of spherical silica (average particle size 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd., carbon amount 0.39 mg / m ² per unit area) is mixed and dispersed uniformly with a high-speed rotary mixer. A resin varnish was prepared. Next, an adhesive film was produced in the same manner as in Example 1.

<Example 3>
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 10 parts of biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) 12 parts of “NC3000L”, epoxy equivalent 269) were heated and dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 17 parts of phenoxy resin B, active ester compound (“HPC8000-65T” manufactured by DIC Corporation), weight average molecular weight of about 2700, active group equivalent of about 223 with a non-volatile content of 65% by mass 34 parts of toluene solution, 6 parts of curing accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 2% by mass), flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd.), 10- (2,5-dihydroxy Phenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm, 2 parts, phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 150 parts of spherical silica (average particle size 0.5 μm, “SOC2” manufactured by Admatechs Co., Ltd., carbon amount 0.39 mg / m ² per unit area) was mixed with a high-speed rotating mixer. A resin varnish was prepared by dispersing in a single unit. Next, an adhesive film was produced in the same manner as in Example 1.

<Comparative Example 1>
12 parts of phenoxy resin A in Example 1 is changed to 10 parts of bisphenol A type phenoxy resin (“E1256B40” manufactured by Mitsubishi Chemical Corporation, MEK solution having a solid content of 40 mass%, epoxy equivalent 8000, weight average molecular weight of about 50000). Except for this, an adhesive film was produced in the same manner as in Example 1.
<Comparative example 2>
An adhesive film was prepared in exactly the same manner as in Example 2, except that the phenoxy resin A5 part of Example 2 was changed to the phenoxy resin C5 part of Synthesis Example 3.

<Comparative Example 3>
An adhesive film was produced in exactly the same manner as in Example 3, except that the phenoxy resin B17 part of Example 3 was changed to the phenoxy resin C17 part of Synthesis Example 3.
<Comparative example 4>
12 parts of the phenoxy resin of Example 1 is changed to 10 parts of a bisphenol A type epoxy resin ("jER1009" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 2740, 1: 1 solution of MEK and cyclohexanone having a solid content of 40% by mass). Except for this, an adhesive film was produced in the same manner as in Example 1.
<Comparative Example 5>
An adhesive film was produced in exactly the same manner as in Example 1 except that the amount of the epoxy resin A added in Example 1 was changed from 12 parts to 50 parts.
<Comparative Example 6>
12 parts of a triazine skeleton-containing phenolic curing agent of epoxy resin A of Example 1 ("LA-7054" manufactured by DIC Corporation, MEK solution having a solid content of 60% of a hydroxyl group equivalent of 125), naphthalene type curing agent (Nippon Chemical Co., Ltd.) Example except that 15 parts of “SN-485” manufactured by Co., Ltd. and a MEK solution having a solid content of 60% having a hydroxyl group equivalent of 215 are changed to 3 parts of a curing agent (Dicyandiamide, “DICY7” manufactured by Mitsubishi Chemical Corporation). An adhesive film was prepared in exactly the same manner as in Example 1. Since DICY7 is dicyandiamide, it does not fall under any of phenol curing agents, cyanate ester curing agents, and active ester curing agents.
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 low roughness, sufficient peel strength, low linear thermal expansion coefficient, and sufficient breaking elongation. On the other hand, in Comparative Examples 1 to 6, since the curable resin composition of the present invention is not used, the arithmetic mean roughness and root mean square roughness are large, the peel strength is small, and the linear thermal expansion coefficient is large. It was.

Claims (14)

(A) A resin composition containing a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a curing agent,
(C) The curing agent includes one or more selected from a phenol curing agent, a cyanate ester curing agent, and an active ester curing agent,
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 20% by mass. Curable resin composition.   The curable resin composition of Claim 1 whose weight average molecular weights of the said (A) phenoxy resin are 8000-100,000.   The curable resin composition according to claim 1 or 2, wherein the (A) phenoxy resin has an unsubstituted bisphenol fluorene structure or a biscresol fluorene structure.   The (B) epoxy resin is selected from the group consisting of a bisphenol type epoxy resin, a crystalline bifunctional epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a mixture of these epoxy resins. The curable resin composition of any one of Claims 1-3.   When the nonvolatile 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 5%. The curable resin composition according to any one of claims 1 to 4, wherein the content is 30% by mass and the content of the (C) curing agent is 3 to 20% by mass.   Furthermore, (D) Curable resin composition of any one of Claims 1-5 containing an inorganic filler.   The curable resin composition according to claim 6, wherein the average particle diameter of the (D) inorganic filler is 0.01 to 5 μm.   The curable resin composition according to claim 6 or 7, wherein the content of the inorganic filler (D) is 30 to 90% by mass when the nonvolatile component in the curable resin composition is 100% by mass.   The curable resin composition according to any one of claims 6 to 8, wherein the (D) inorganic filler is silica.   A curable resin composition for an insulating layer of a multilayer printed wiring board, comprising the curable resin composition according to claim 1.   A curable resin composition for a buildup layer of a multilayer printed wiring board, comprising the curable resin composition according to any one of claims 1 to 10.   A sheet-like laminated material comprising the curable resin composition according to any one of claims 1 to 11.   A multilayer printed wiring board comprising an insulating layer obtained by thermosetting the curable resin composition according to any one of claims 1 to 11 or the sheet-like laminated material according to claim 12. .   A semiconductor device comprising the multilayer printed wiring board according to claim 13.