KR102600199B1 - Resin composition - Google Patents

Abstract

[Problem] Provision of a resin composition that produces a printed wiring board that exhibits good reflow behavior in the component mounting process even if the printed wiring board is thin, a sheet-like laminate material containing the resin composition, a printed wiring board, and a semiconductor device.
[Solution] Contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and (C) the inorganic filler is a compound represented by the following formula (1), and a compound represented by the following formula (2) A resin composition whose surface has been treated with at least one surface treatment agent selected from the group consisting of compounds. X shows a vinyl group, y is an alkylene group of 4 or more carbon atoms, r ¹ to R ³ represents an alkyl group of carbon atoms 1 to 6, and z is an alkylene group.
Chemical formula (1)
XY-Si(OR ¹ ) ₃
Chemical formula (2)
(R ² O) ₃ Si-Z-Si(OR ³ ) ₃

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to resin compositions. It also relates to sheet-like laminated materials, printed wiring boards, and semiconductor devices containing the resin composition.

As a manufacturing technology for printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately overlapped on an inner layer substrate is known. In the manufacturing method using the build-up method, the insulating layer is generally formed by curing the resin composition.

For example, Patent Document 1 contains an epoxy resin, a curing agent, and an inorganic filler, and the inorganic filler is surface-treated with aminoalkylsilane, and when the non-volatile component in the resin composition is 100% by mass, the inorganic filler A resin composition having a content of 55 to 90% by mass is described.

[Patent Document 1] Japanese Patent Publication No. 2014-28880

However, with the recent replacement of lead-containing solder with lead-free solder, the temperature of solder reflow in the component mounting process by solder reflow is increasing. Additionally, in order to achieve miniaturization of electronic devices in recent years, printed wiring boards are becoming thinner, and the thickness of inner substrates and insulating layers tends to gradually become thinner. As printed wiring boards become thinner, stabilizing reflow behavior tends to become more difficult.

The object of the present invention is to provide a resin composition that produces a printed wiring board that exhibits good reflow behavior in the component mounting process even if the printed wiring board is thin, a sheet-like laminate material containing the resin composition, a printed wiring board, and a semiconductor device. It's in doing.

As a result of intensive study of the above-described problem, the present inventors have found that the above-described problem can be solved by using an inorganic filler surface-treated with a specific surface treatment agent, and have completed the present invention.

That is, the present invention includes the following contents.

[1] A resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,

(C) A resin composition in which the inorganic filler is surface-treated with at least one surface treatment agent selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2).

Chemical formula (1)

XY-Si(OR ¹ ) ₃

(In Formula (1) _, CH ₂ ) _m -, Ar-(CH ₂ ) _m -(NR) _n -, or NH ₂ -(CH ₂ ) _m -(NR) _n -, Ar represents a phenyl group which may have a substituent, and R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 6, n represents an integer of 0 or 1, and Y represents an alkylene group having 4 or more carbon atoms that may have a substituent. , or represents an alkenylene group having 4 or more carbon atoms which may have a substituent, R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ¹ may be the same or different.)

Chemical formula (2)

(R ² O) ₃ Si-Z-Si(OR ³ ) ₃

(Z represents an alkylene group that may have a substituent, -NR-, an oxygen atom, a sulfur atom, or a group consisting of a combination of two or more thereof, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² and R ³ each independently represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ² and R ³ may be the same or different.)

[2] The resin composition according to claim 1, wherein Y in the general formula (1) represents an alkylene group having 6 or more carbon atoms which may have a substituent.

[3] The method of claim 1 or 2, wherein Z in the formula (2) represents an alkylene group having 6 or more carbon atoms which may have a substituent, or a group consisting of a combination of an alkylene group which may have a substituent and -NR-. Representing a resin composition.

[4] The resin composition according to any one of claims 1 to 3, wherein R ¹ in the formula (1), R ² and R ³ in the formula (2) represent a methyl group or an ethyl group.

[5] The compound according to any one of items 1 to 4, wherein the compound represented by formula (1) is 8-glycidoxyoctyl trimethoxysilane, N-2-(aminoethyl)-8-aminooctyl Trimethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane, 3-(2-glycidylphenyl)propyl trimethoxysilane, 6-vinylhexyl trimethoxysilane, and 8-methacrylo. It is any one of 1oxyoctyl trimethoxysilane, and the compound represented by formula (2) is any one of bistrimethoxysilylhexane, bistrimethoxysilyloctane, and bis(trimethoxysilylpropyl)ethylenediamine. , resin composition.

[6] The resin composition according to any one of claims 1 to 5, wherein the average particle diameter of component (C) is 0.01 μm to 5 μm.

[7] The resin composition according to any one of claims 1 to 6, wherein component (C) is silica.

[8] The resin composition according to any one of claims 1 to 7, wherein the content of component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.

[9] The resin composition according to any one of claims 1 to 8, wherein component (C) is surface treated with a surface treatment agent in an amount of 0.2 parts by mass to 2 parts by mass based on 100 parts by mass of component (C).

[10] The resin composition according to any one of claims 1 to 9, wherein the amount of carbon per unit surface area of component (C) is 0.05 mg/m ² to 1 mg/m ² .

[11] The resin composition according to any one of claims 1 to 10, wherein component (A) is at least one selected from bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and biphenyl-type epoxy resin.

[12] The resin composition according to any one of claims 1 to 11, wherein component (B) is at least one selected from phenol-based curing agents, naphthol-based curing agents, activated ester-based curing agents, and cyanate ester-based curing agents.

[13] The resin composition according to any one of claims 1 to 12, which is used for forming an insulating layer of a printed wiring board.

[14] The resin composition according to any one of claims 1 to 13, which is used for forming a build-up layer of a printed wiring board.

[15] A sheet-like laminated material comprising a resin composition layer formed of the resin composition according to any one of claims 1 to 14.

[16] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 14.

[17] The printed wiring board according to item 16, wherein the amount of deflection of the insulating layer is 350 μm or less.

[18] A semiconductor device comprising the printed wiring board according to item 16 or 17.

According to the present invention, it is possible to provide a resin composition that produces a printed wiring board that exhibits good reflow behavior in the component mounting process even if the printed wiring board is thin, a sheet-like laminate material containing the resin composition, a printed wiring board, and a semiconductor device. It came to be.

Hereinafter, the resin composition of the present invention, a sheet-like laminated material containing the resin composition, a printed wiring board, and a semiconductor device will be described in detail.

In this specification, the term “may have a substituent” written immediately before a group refers to the case where the hydrogen atom of the group is not substituted with a substituent, and some or all of the hydrogen atoms of the group are substituents. It means both sides when replaced with .

In this specification, the term “C _p to C _q ” (p and q are positive integers, satisfying p < q) indicates that the number of carbon atoms of the organic group described immediately after this term is p to q. . For example, “C ₁ to C ₁₀ The expression “alkyl group” refers to an alkyl group having 1 to 10 carbon atoms, and “C ₁ to C ₁₀ The expression “alkyl ester” refers to an ester of an alkyl group having 1 to 10 carbon atoms.

[Resin composition]

The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein (C) the inorganic filler is a compound represented by the following formula (1), and the following formula ( It is characterized in that the surface is treated with at least one surface treatment agent selected from the group consisting of compounds represented by 2).

Chemical formula (1)

XY-Si(OR ¹ ) ₃

(In Formula (1) _, CH ₂ ) _m -, Ar-(CH ₂ ) _m -(NR) _n -, or NH ₂ -(CH ₂ ) _m -(NR) _n -, Ar represents a phenyl group which may have a substituent, and R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 6, n represents an integer of 0 or 1, and Y represents an alkylene group having 4 or more carbon atoms that may have a substituent. , or represents an alkenylene group having 4 or more carbon atoms which may have a substituent, R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ¹ may be the same or different.)

Chemical formula (2)

(R ² O) ₃ Si-Z-Si(OR ³ ) ₃

(Z represents an alkylene group that may have a substituent, -NR-, an oxygen atom, a sulfur atom, or a group consisting of a combination of two or more thereof, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² and R ³ each independently represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ² and R ³ may be the same or different.)

Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) Epoxy resin>

The resin composition of the present invention contains (A) epoxy resin (hereinafter also referred to as (A) component).

As epoxy resins, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type. Epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naph. Tylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and bixylenol type epoxy resin. Epoxy resins may be used individually, or two or more types may be used in combination. The component (A) is preferably at least one selected from bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and biphenyl-type epoxy resin.

It is preferable that the epoxy resin contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Among these, an epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20°C (hereinafter referred to as “liquid epoxy resin”) and an epoxy resin that has three or more epoxy groups in one molecule and is in a solid state at a temperature of 20°C (hereinafter referred to as “liquid epoxy resin”). It is preferable to include (hereinafter referred to as “solid epoxy resin”). As an epoxy resin, a resin composition with excellent flexibility is obtained by using a liquid epoxy resin and a solid epoxy resin in combination. Additionally, the breaking strength of the cured product of the resin composition is also improved.

Liquid epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin, phenol novolac-type epoxy resin, and alicyclic epoxy resin with an ester skeleton. , and epoxy resins having a butadiene structure are preferable, and bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol AF-type epoxy resins, and naphthalene-type epoxy resins are more preferable. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, and "828US" and "jER828EL" (bisphenol A type) manufactured by Mitsubishi Chemical Corporation. epoxy resin), “jER807” (bisphenol F-type epoxy resin), “jER152” (phenol novolak-type epoxy resin), “ZX1059” (bisphenol A-type epoxy resin and bisphenol F-type) manufactured by Nippon-Steel Sumiking Chemical Co., Ltd. mixture of epoxy resins), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Co., Ltd., “Celoxide 2021P” manufactured by Daicel Co., Ltd. (alicyclic epoxy with an ester skeleton) resin), "PB-3600" (epoxy resin having a butadiene structure), and "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane) manufactured by Nippon Chemical Co., Ltd. These may be used individually, or two or more types may be used in combination.

Solid epoxy resins include naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, Anthracene-type epoxy resin, bisphenol A-type epoxy resin, and tetraphenylethane-type epoxy resin are preferable, and naphthalene-type tetrafunctional epoxy resin, naphthol-type epoxy resin, and biphenyl-type epoxy resin are more preferable. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), and "N-690" (cresolanoic acid) manufactured by DIC Co., Ltd. rockfish type epoxy resin), “N-695” (cresol novolac type epoxy resin), “HP-7200” (dicyclopentadiene type epoxy resin), “HP-7200HH”, “EXA7311”, “EXA7311-G3” , “EXA7311-G4”, “EXA7311-G4S”, “HP6000” (naphthylene ether type epoxy resin), “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., “NC7000L” ( Naphthol novolac type epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthol type epoxy resin) manufactured by Nippon Tetsu Sumiking Chemical Co., Ltd. , “ESN485” (naphthol novolac type epoxy resin), “YX4000H” manufactured by Mitsubishi Chemical Corporation, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), and “YX8800”. (Anthracene type epoxy resin), “PG-100” and “CG-500” manufactured by Osaka Gas Chemicals Co., Ltd., “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. ( Examples include “jER1010” (solid bisphenol A-type epoxy resin), “jER1031S” (tetraphenylethane-type epoxy resin), and “YL7760” (bisphenol AF-type epoxy resin) manufactured by Note).

When using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, their ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:6 in mass ratio. By keeping the ratio of the liquid epoxy resin and the solid epoxy resin within this range, i) appropriate adhesion is achieved when used in the form of an adhesive film, and ii) sufficient flexibility is obtained when used in the form of an adhesive film, thereby improving handleability. This is improved, and iii) a cured product with sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1:0.3 to 1:5 in mass ratio, and 1:0.6. to 1:4 is more preferable.

The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is achieved, but is preferably 50 mass% or less, more preferably 30 mass% or less, and still more preferably 20 mass% or less.

In addition, in the present invention, unless otherwise specified, the content of each component in the resin composition is a value assuming that the nonvolatile component in the resin composition is 100% by mass.

The epoxy equivalent weight of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, and even more preferably 110 to 1000. By falling within this range, the crosslinking density of the cured product becomes sufficient and an insulating layer with small surface roughness can be produced. In addition, the epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

<(B) Hardener>

The resin composition of the present invention contains (B) a curing agent (hereinafter also referred to as (B) component).

The curing agent is not particularly limited as long as it has the function of curing the epoxy resin, and examples include phenol-based curing agents, naphthol-based curing agents, activated ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. etc. can be mentioned. One type of hardening agent may be used individually, or two or more types may be used together. The component (B) is preferably at least one selected from phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, and cyanate ester-based curing agents.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. Furthermore, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among these, a phenol novolak curing agent containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, “MEH-7700,” “MEH-7810,” and “MEH-7851” manufactured by Meiwa Kasei Co., Ltd. and “MEH-7851” manufactured by Nippon Kayaku Co., Ltd. NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" manufactured by Nippon Tetsu Sumikin Co., Ltd. ", "LA7052", "LA7054", "LA3018", and "EXB-9500" manufactured by DIC Corporation.

An active ester-based curing agent is also preferable from the viewpoint of obtaining an insulating layer with small surface roughness after roughening treatment and from the viewpoint of obtaining an insulating layer with excellent adhesion to the conductor layer. There are no particular restrictions on the active ester-based curing agent, but generally, it has two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Compounds are preferably used. The active ester-based curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester-based curing agents obtained from carboxylic acid compounds and hydroxy compounds are preferable, and active ester-based curing agents obtained from carboxylic acid compounds, phenol compounds, and/or naphthol compounds are more preferable. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, 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, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolak, etc. are mentioned. Here, “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylate of phenol novolak, and a benzoylate of phenol novolac. Active ester compounds are preferred, and among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferred. “Dicyclopentadiene-type diphenol structure” refers to a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" (manufactured by DIC Co., Ltd.) , "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylate of phenol novolac, and phenol Examples of the active ester compound containing the benzoylate of novolak include "YLH1026" (manufactured by Mitsubishi Chemical Corporation).

Specific examples of benzoxazine-based curing agents include "HFB2006M" manufactured by Showa Kobunshi Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Seiko Co., Ltd.

Examples of cyanate ester-based curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylenecyanate), and 4,4'-methylenebis(2,6- dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolac, etc., some of these cyanate resins are triazinated. Prepolymers, etc. can be mentioned. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both phenol novolak-type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (bisphenol A dicyanate) manufactured by Ronza Japan Co., Ltd. and prepolymers in which part or all of the polymer is triazylated to form a trimer.

Specific examples of carbodiimide-based curing agents include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

The ratio of the epoxy resin and the curing agent is preferably in the range of 1:0.1 to 1:2 in the ratio of [total number of epoxy groups of the epoxy resin]:[total number of reactive groups of the curing agent], and 1:0.15 to 1:1.5. It is more preferable, and 1:0.2 to 1:1 is even more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, etc., and varies depending on the type of the curing agent. In addition, the total number of epoxy groups of an epoxy resin is the solid mass of each epoxy resin divided by the epoxy equivalent, which is the sum of all epoxy resins, and the total number of reactive groups of the curing agent is the solid mass of each curing agent divided by the reactor equivalent. The value divided by is the sum of all hardeners. By keeping the amount ratio of the epoxy resin and the curing agent within this range, the heat resistance of the cured product of the resin composition is further improved.

In one embodiment, the resin composition includes (A) the epoxy resin and (B) the curing agent described above. The resin composition is (A) an epoxy resin, which is a mixture of a liquid epoxy resin and a solid epoxy resin (the mass ratio of liquid epoxy resin:solid epoxy resin is preferably 1:0.1 to 1:8, more preferably 1:0.3 to 1: 7, more preferably 1:0.6 to 1:6), (B) as a curing agent, at least one selected from the group consisting of phenol-based curing agents, naphthol-based curing agents, activated ester-based curing agents, and cyanate ester-based curing agents (preferably Specifically, it is preferable to each include at least one selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, and an active ester-based curing agent.

The content of the curing agent in the resin composition is not particularly limited, but is preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 20 mass% or less, and even more preferably 18 mass% or less. Additionally, the lower limit is not particularly limited, but is preferably 3% by mass or more.

<(C) Inorganic filler>

The resin composition of the present invention contains (C) an inorganic filler (hereinafter also referred to as component (C)), and component (C) is a compound represented by the following formula (1), and a compound represented by the following formula (2) The surface is treated with at least one surface treatment agent selected from the group consisting of.

Chemical formula (1)

XY-Si(OR ¹ ) ₃

(In Formula (1) _, CH ₂ ) _m -, Ar-(CH ₂ ) _m -(NR) _n -, or NH ₂ -(CH ₂ ) _m -(NR) _n -, Ar represents a phenyl group which may have a substituent, and R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 6, n represents an integer of 0 or 1, and Y represents an alkylene group having 4 or more carbon atoms that may have a substituent. , or represents an alkenylene group having 4 or more carbon atoms which may have a substituent, R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ¹ may be the same or different.)

Chemical formula (2)

(R ² O) ₃ Si-Z-Si(OR ³ ) ₃

(Z represents an alkylene group that may have a substituent, -NR-, an oxygen atom, a sulfur atom, or a group consisting of a combination of two or more thereof, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² and R ³ each independently represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ² and R ³ may be the same or different.)

Component (C) in the present invention is surface treated with at least one surface treatment agent selected from the group consisting of a compound represented by the formula (1) and a compound represented by the formula (2). As a result of intensive research by the present inventors, like the compound represented by the formula (1), the main chain of the divalent group (Y in the formula (1)) connecting the silicon atom and the functional group moiety (X in the formula (1)) is a long chain. It was discovered that by surface-treating an inorganic filler with a phosphorus compound, the amount of deflection (maximum variation in reflow behavior) of the insulating layer formed from the cured resin composition during reflow can be reduced. Additionally, it was found that by surface treating the inorganic filler with the above compound, the minimum melt viscosity was lowered and good circuit embedding properties were obtained. In addition, the present inventors propose a compound having silicon atoms at both ends, such as the compound represented by the formula (2), each of which has a long main chain of the divalent group (Z in the formula (2)) that bonds to the silicon atom, and is used as an inorganic filler. It was discovered that the same effect could be obtained even if the surface was treated.

In this specification, unless otherwise specified, component (C) shall represent an inorganic filler that has been surface treated with a surface treatment agent.

The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon compounds, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate. , barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Additionally, spherical silica is preferred as the silica. One type of inorganic filler may be used alone, or two or more types may be used in combination.

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, from the viewpoint of obtaining an insulating layer with small surface roughness and improving fine wiring formability. is 2㎛ or less, or 1㎛ or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, and even more preferably 0.3 μm or more. Commercially available inorganic fillers having such an average particle diameter include, for example, “YC100C”, “YA050C”, “YA050C-MJE”, and “YA010C” manufactured by Adomatex Co., Ltd., and “UFP” manufactured by Denki Chemical Co., Ltd. -30”, “Silfil NSS-3N”, “Silfil NSS-4N”, “Silfil NSS-5N” manufactured by Tokuyama Co., Ltd., “SC2500SQ”, “SO-C2”, “SO” manufactured by Adomatex Co., Ltd. -C1” and the like.

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 created on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. The measurement sample can preferably be one in which an inorganic filler is dispersed in water by ultrasonic waves. As a laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba Chemical Co., Ltd., etc. can be used.

As a surface treatment agent, the compound represented by the formula (1) or the compound represented by the formula (2) may be used alone, or the compound represented by the formula (1) and the compound represented by the formula (2) may be used in combination. It's also good.

The compound represented by formula (1) has the following structure.

Chemical formula (1)

XY-Si(OR ¹ ) ₃

(In Formula (1) _, CH ₂ ) _m -, Ar-(CH ₂ ) _m -(NR) _n -, or NH ₂ -(CH ₂ ) _m -(NR) _n -, Ar represents a phenyl group which may have a substituent, and R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 6, n represents an integer of 0 or 1, and Y represents an alkylene group having 4 or more carbon atoms that may have a substituent. , or represents an alkenylene group having 4 or more carbon atoms which may have a substituent, R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ¹ may be the same or different.)

X is a vinyl group, epoxy, glycidyl ether, methacryloy jade, methacryloy jade, acrylo diary, acrylic ilocytes, amino group, ar- (NR) _N- (Ch ₂ ) _m- -(CH ₂ ) _m -(NR) _n -, or NH ₂ -(CH ₂ ) _m -(NR) _n -.

Ar represents a phenyl group which may have a substituent. The substituents that the phenyl group may have will be described later.

m represents an integer of 0 to 6, an integer of 1 to 4 is preferable, and an integer of 1 to 3 is more preferable. n represents an integer of 0 or 1, and 1 is preferable.

R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group, and propyl group. R is preferably a hydrogen atom.

Ar-(NR) _n -(CH ₂ ) _m -, Ar-(CH ₂ ) _m -(NR) _n -, or NH ₂ -(CH ₂ ) _m -(NR) _n - is, for example, aminoethylene. Amino group, benzylamino group, phenylamino group, etc. are mentioned.

Among these, preferred examples of A phenylamino group is more preferable.

Y represents an alkylene group having 4 or more carbon atoms which may have a substituent, or an alkenylene group having 4 or more carbon atoms which may have a substituent. The number of carbon atoms of the alkylene group and the alkenylene group is 4 or more, preferably 5 or more, more preferably 6 or more, and still more preferably 7 or more. The upper limit is not particularly limited, but is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. If the number of carbon atoms is less than 4, the bond distance between the silicon atom and the functional group site is short, the amount of warping of the insulating layer formed by the cured resin composition increases during reflow, the minimum melt viscosity increases, and the circuit embedding property is poor. .

The alkylene group having 4 or more carbon atoms, which may have a substituent, may be either linear or branched. Examples of alkylene groups having 4 or more carbon atoms that may have substituents include butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dodecylene group, etc., and pentyl group. A lene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group are preferable, a hexylene group, a heptylene group, an octylene group, and a nonylene group are more preferable, and an octylene group is still more preferable.

The alkenylene group having 4 or more carbon atoms, which may have a substituent, may be either linear or branched. Examples of alkenylene groups having 4 or more carbon atoms that may have substituents include 1-butenylene group, 1-pentenylene group, 1-hexenylene group, 1-heptenylene group, and 1-octenylene group. You can. Among these, 1-butenylene group, 1-pentenylene group, 1-hexenylene group, 1-heptynylene group, and 1-octynylene group are preferable, and 1-pentenylene group is more preferable.

The phenyl group represented by Ar, the alkylene group with 4 or more carbon atoms and the alkenylene group with 4 or more carbon atoms represented by Y may have a substituent. There is no particular limitation on the substituent, and examples include halogen atom, alkyl group, cycloalkyl group, alkenyl group, alkoxy group, cycloalkyloxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, monovalent heterocyclic group, alkyl Liden group, amino group, silyl group, acyl group, acyloxy group, carboxyl group, sulfo group, cyano group, nitro group, hydroxy group, mercapto group, oxo group, etc. Additionally, the substituents may have multiple substituents, and the multiple substituents may be bonded to each other to form a ring.

Halogen atoms used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and urea atoms.

The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 3. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl group.

The number of carbon atoms of the cycloalkyl group used as a substituent is preferably 3 to 12, more preferably 3 to 6. Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.

The number of carbon atoms of the alkenyl group used as a substituent is preferably 2 to 12, more preferably 2 to 6. Examples of the alkenyl group include vinyl group, propenyl group (aryl group), 1-butenyl group, and 1-hexenyl group. When there is a plurality of alkenyl groups as substituents, the plurality of alkenyl groups may be bonded to each other to form a ring. For example, when the ethylene portion of an alkenylene group having 4 or more carbon atoms contains two vinyl groups as substituents, the vinyl groups may be bonded to each other to form a 1,2-phenylene group.

The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 6. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, s-butoxy group, isobutoxy group, t-butoxy group, pentyloxy group, hexyloxy group, and heptyloxy group. group, octyloxy group, nonyloxy group, and decyloxy group.

The number of carbon atoms of the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. Examples of the cycloalkyloxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, and cyclohexyloxy group.

An aryl group used as a substituent is an aromatic hydrocarbon with one hydrogen atom on the aromatic ring removed. The number of carbon atoms of the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryl group include phenyl group, naphthyl group, and anthracenyl group.

The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. Examples of aryloxy groups used as substituents include phenoxy group, 1-naphthyloxy group, and 2-naphthyloxy group.

The number of carbon atoms of the arylalkyl group used as a substituent is preferably 7 to 25, more preferably 7 to 19, further preferably 7 to 15, and even more preferably 7 to 11. Examples of the arylalkyl group include phenyl-C ₁ to C ₁₂ alkyl group, naphthyl-C ₁ to C ₁₂ alkyl group, and anthracenyl-C ₁ to C ₁₂ alkyl group.

The number of carbon atoms of the arylalkoxy group used as a substituent is preferably 7 to 25, more preferably 7 to 19, further preferably 7 to 15, and even more preferably 7 to 11. Examples of the arylalkoxy group include phenyl-C ₁ to C ₁₂ alkoxy group and naphthyl-C ₁ to C ₁₂ alkoxy group.

A monovalent heterocyclic group used as a substituent refers to a group in which one hydrogen atom has been removed from the heterocyclic ring of a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3 to 21, more preferably 3 to 15, and still more preferably 3 to 9. The monovalent heterocyclic group also includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocycle include thienyl group, pyrrolyl group, furanyl group, furyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, Quinolyl group and isoquinolyl group can be mentioned.

An alkylidene group used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms of the alkylidene group is preferably 1 to 20, more preferably 1 to 14, further preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkylidene group include methylidene group, ethylidene group, propylidene group, isopropylidene group, butylidene group, s-butylidene group, isobutylidene group, t-butylidene group, pentylidene group, Hexylidene group, heptylidene group, octylidene group, nonylidene group, and decylidene group.

The acyl group used as a substituent has the formula: -C(=0)-R ⁴ A group represented by (in the formula, R ⁴ refers to an alkyl group or an aryl group). R ⁴ The alkyl group represented by may be either linear or branched. Examples of the aryl group represented by R include phenyl group, naphthyl group, and anthracenyl group. The number of carbon atoms of the acyl group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. Examples of the acyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, and benzoyl group.

The acyloxy group used as a substituent has the formula: -OC(=0)-R ⁵ refers to a group represented by (wherein R ⁵ is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R ⁵ include phenyl group, naphthyl group, and anthracenyl group. The number of carbon atoms of the acyloxy group is preferably 2 to 20, more preferably 2 to 13, and still more preferably 2 to 7. Examples of the acyloxy group include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, and benzoyloxy group.

The above substituent may further have a substituent (hereinafter sometimes referred to as a “secondary substituent”). As the secondary substituent, unless otherwise specified, the same substituent as above may be used.

R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and plural R ¹ may be the same or different. The alkyl group having 1 to 6 carbon atoms, which may have a substituent, may be either linear or branched. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is more preferable. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, and n-hexyl, and include methyl, ethyl, and propyl groups. , n-butyl group is preferable, methyl group, ethyl group, and propyl group are more preferable, and methyl group and ethyl group are still more preferable.

The alkyl group having 1 to 6 carbon atoms represented by R ¹ may have a substituent. The substituent is the same as the substituent that the alkylene group with 4 or more carbon atoms represented by Y may have, and the preferable range is also the same.

Specific examples of the compound represented by formula (1) include 8-glycidoxyoctyl trimethoxysilane, N-2-(aminoethyl)-8-aminooctyl trimethoxysilane, and N-phenyl-8-aminooctyl- Trimethoxysilane, 3-(2-glycidylphenyl)propyl trimethoxysilane, 6-vinylhexyl trimethoxysilane, 8-methacryloyloxyoctyl trimethoxysilane, etc., but the present invention is not limited to these.

The compound represented by formula (2) has the following structure.

Chemical formula (2)

(R ² O) ₃ Si-Z-Si(OR ³ ) ₃

(Z represents an alkylene group that may have a substituent, -NR-, an oxygen atom, a sulfur atom, or a group consisting of a combination of two or more thereof, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² and R ³ each independently represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ² and R ³ may be the same or different.)

Z represents an alkylene group that may have a substituent, -NR-, an oxygen atom, a sulfur atom, or a group consisting of a combination of two or more thereof, and R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The main chain of Z is preferably a long chain, and the number of atoms constituting the main chain (the number of atoms in the main chain between silicon atoms at both ends) is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. . The upper limit is not particularly limited, but is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, or 9 or less. If the number of atoms constituting the main chain is less than 4, the amount of warping of the insulating layer formed by the cured product of the resin composition increases upon reflow, the minimum melt viscosity increases, and circuit embedding properties may be poor. The atoms constituting the main chain of Z refer to the carbon atom of the main chain of the alkylene group, the nitrogen atom of -NR-, the oxygen atom, and the sulfur atom.

When Z represents an alkylene group that may have a substituent, the number of carbon atoms of the alkylene group that may have a substituent is preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more. The upper limit is not particularly limited, but is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, or 9 or less. Specific examples and preferred ranges of the alkylene group are the same as the alkylene group having 4 or more carbon atoms represented by Y in the formula (1).

When Z represents a group consisting of a combination of two or more of the above, the number of carbon atoms of the alkylene group constituting the group consisting of a combination of two or more is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3. . Examples of such alkylene groups include methylene group, ethylene group, propylene group, butylene group, pentylene group, and hexylene group, with methylene group, ethylene group, and propylene group being preferred, and ethylene group and propylene group being preferred. do. The alkylene group, which may have a substituent, may be either linear or branched.

Groups consisting of combinations of the above two or more include those in which an alkylene group that may have a substituent is bonded to -NR-, an alkylene group that may have multiple substituents bonded alternately to a plurality of -NR-, and alkyl that may have a substituent. Examples include a bond between a lene group and an oxygen atom, a bond between an alkylene group that may have a substituent and a sulfur atom, a bond between an alkylene group that may have a substituent and -NR-, and an alkylene group that may have multiple substituents. A group consisting of a plurality of -NR- bonded alternately, that is, a group consisting of a combination of an alkylene group that may have a substituent and -NR- is preferable. Specific examples of groups consisting of a combination of two or more of the above include the following groups, but the present invention is not limited to these.

＊ indicates the number of bonds.

R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R is the same as R in the formula (1), and the preferable range is also the same.

R ² and R ³ each independently represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ² and R ³ may be the same or different. R ² and R ³ are the same as R ¹ in Formula (1), and their preferred ranges are also the same.

Specific examples of the compound represented by formula (2) include bistrimethoxysilylhexane, bistrimethoxysilyloctane, and bis(trimethoxysilylpropyl)ethylenediamine, but the present invention is not limited to these. no.

The compound represented by the formula (1) and the compound represented by the formula (2) may be commercially available or may be synthesized using a known synthetic method.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably 0.2 to 2 parts by mass of the surface treatment agent, based on 100 parts by mass of component (C), and 0.2 parts by mass. It is preferable that the surface is treated in an amount of 1 to 1 part by mass, and it is preferable that the surface is treated in an amount of 0.3 to 0.8 parts by mass.

The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.05 mg/m ² or more, more preferably 0.1 mg/m ² or more, and even more preferably 0.2 mg/m ² or more. . On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the melt viscosity in sheet form, 1 mg/m ² or less is preferable, 0.8 mg/m ² or less is more preferable, and 0.5 mg/m ² or less is even more preferable. desirable.

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, “EMIA-320V” manufactured by Horiba Chemical Co., Ltd., etc. can be used.

The inorganic filler may be added to a surface treatment agent selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2), and may be surface treated with another surface treatment agent. Other surface treatment agents include, for example, amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, alkoxysilane compounds, and pentasilane coupling agents. Nosilazane compounds, etc. can be mentioned. Commercially available products of these other surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and "KBM803" (3-mer) manufactured by Shin-Etsu Chemical Co., Ltd. Captopropyltrimethoxysilane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyl) manufactured by Shin-Etsu Chemical Co., Ltd. trimethoxysilane), “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. .

The content of the inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more from the viewpoint of obtaining an insulating layer with a low coefficient of thermal expansion. From the viewpoint of the mechanical strength of the insulating layer, the upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, 80% by mass or less, Or it is 75% by mass or less.

<(D) Thermoplastic resin>

The resin composition of the present invention preferably contains (D) a thermoplastic resin (hereinafter also referred to as (D) component) in addition to components (A) to (C).

Thermoplastic resins include, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamidoimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, and polyphenylene. Examples include ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin, and phenoxy resin is preferred. Thermoplastic resins may be used individually, or two or more types may be used in combination.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene was measured using LC-9A/RID-6A manufactured by Shimadzu Sesakusho Co., Ltd. as a measuring device and Shodex K-800P/K- manufactured by Showa Denko Co., Ltd. as a column. 804L/K-804L can be calculated using chloroform or the like as a mobile phase, measuring the column temperature at 40°C, and using a standard polystyrene calibration curve.

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, and naphthalene skeleton. , a phenoxy resin having at least one skeleton selected from the group consisting of anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be a functional group such as a phenolic hydroxyl group or an epoxy group. One type of phenoxy resin may be used alone, or two or more types may be used in combination. Specific examples of phenoxy resins include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton), "YX8100" (phenoxy resins containing a bisphenol S skeleton), and "YX6954" manufactured by Mitsubishi Chemical Corporation. (Phenoxy resin containing bisphenol acetophenone skeleton); In addition, "FX280" and "FX293" manufactured by Nippon-Steel Chemicals Co., Ltd., and "YX6954BH30" and "YX7553" manufactured by Mitsubishi Chemical Corporation. ", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30", and "YL7482".

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include, for example, Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-C, manufactured by Denki Chemical Co., Ltd. Butyral 6000-EP”, S-Rec BH series, BX series, KS series, BL series, BM series manufactured by Sekisui Chemical Co., Ltd.

Specific examples of polyimide resins include “Ricca Coat SN20” and “Ricca Coat PN20” manufactured by Shinnihon Rika Co., Ltd. Specific examples of polyimide resins include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides (polyimides described in Japanese Patent Application Laid-Open No. 2006-37083); and modified polyimides such as polysiloxane skeleton-containing polyimides (polyimides described in Japanese Patent Application Laid-Open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386, etc.).

Specific examples of polyamide-imide resin include “Viromax HR11NN” and “Viromax HR16NN” manufactured by Toyobo Seki Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Tsumitomo Chemical Co., Ltd.

Specific examples of polysulfone resins include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

Specific examples of the polyphenylene ether resin include the oligophenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi Chemical Corporation.

Among them, phenoxy resin and polyvinyl acetal resin are preferable as thermoplastic resins. Therefore, in one suitable embodiment, component (D) includes at least one selected from the group consisting of phenoxy resin and polyvinylacetal resin.

The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and still more preferably 1% by mass to 5% by mass.

<(E) Curing accelerator>

The resin composition of the present invention preferably contains (E) a curing accelerator (hereinafter referred to as (E) component) in addition to components (A) to (C).

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. An accelerator is preferable, and an amine-based curing accelerator and an imidazole-based curing accelerator are more preferable. The curing accelerator may be used individually, or two or more types may be used in combination.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, and (4-methylphenyl)triphenyl. Examples include phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tris(dimethylaminomethyl)phenol, 1, Examples include 8-diazabicyclo(5,4,0)-undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 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'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenyl imidazoleisocyanuric acid adduct, 2 -Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benz Imidazole compounds such as imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. Examples include 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As an imidazole-based curing accelerator, a commercial product may be used, for example, “P200-H50” manufactured by Mitsubishi Chemical Corporation.

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., dicyandiamide, 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonato and cobalt (III) acetylacetonato, organic copper complexes such as copper (II) acetylacetonato, and organic metal complexes such as zinc (II) acetylacetonato. Examples include zinc complexes, organic iron complexes such as iron(III) acetylacetonato, organic nickel complexes such as nickel(II) acetylacetonato, and organic manganese complexes such as manganese(II) acetylacetonato. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

The content of the curing accelerator in the resin composition is not particularly limited, but is preferably used in the range of 0.05% by mass to 3% by mass when the total amount of non-volatile components of the epoxy resin and the curing agent is 100% by mass.

<(F) Flame retardant>

The resin composition of the present invention may contain a flame retardant (hereinafter also referred to as component (F)). Examples of flame retardants include organophosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. Flame retardants may be used individually, or two or more types may be used in combination.

As a flame retardant, a commercially available product may be used, for example, "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Daihachi Chemical Co., Ltd., etc.

The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and even more preferably 0.5% by mass to 10% by mass. .

<(G) Organic filler>

The resin composition may further contain an organic filler (hereinafter also referred to as (G) component) from the viewpoint of improving elongation. As the component (G), any organic filler that can be used in forming the insulating layer of a printed wiring board may be used, and examples include rubber particles, polyamide fine particles, and silicon particles.

As the rubber particles, commercially available products may be used, for example, "EXL-2655" manufactured by Dow Chemical Nippon Co., Ltd., "AC3816N" manufactured by Gantz Chemical Co., Ltd., etc.

The content of component (G) in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, further preferably 0.3% by mass to 5% by mass, or 0.5% by mass. to 3% by mass.

The resin composition may also contain other additives as needed. Examples of such other additives include organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and acrylate resins (e.g., Daicel - (ACA)Z251 manufactured by Allnex Co., Ltd., light acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd., etc.), phosphine oxide compounds (for example, I819 manufactured by BASF Japan Co., Ltd., etc.) , resin additives such as thickeners, anti-foaming agents, leveling agents, adhesion imparting agents, and colorants.

The resin composition of the present invention results in an insulating layer exhibiting good reflow behavior. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for forming an interlayer insulating layer of a printed wiring board) It can be more suitably used as a resin composition for an interlayer insulating layer.

[Sheet-like laminated material]

Although the resin composition of the present invention can be used by applying it in a varnish state, it is generally suitable for use industrially in the form of a sheet-like laminated material containing a resin composition layer formed from the resin composition.

As sheet-like laminated materials, adhesive films and prepregs shown below are preferable.

In one embodiment, the adhesive film includes a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is formed from the resin composition of the present invention.

From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, further preferably 60 μm or less, and even more preferably 50 μm or less or 40 μm or less. . The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 1 μm or more, 5 μm or more, or 10 μm or more.

Examples of the support include films, metal foils, and release papers made of plastic materials, and films and metal foils made of plastic materials are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PEN"), etc. polyester, polycarbonate (hereinafter abbreviated as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), polyether sulfide (PES), and polyether ketone. , polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using a metal foil as a support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferable. As the copper foil, a foil made of a simple metal of copper may be used, or a foil made of an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. It's also good.

The support may be matted or corona treated on the surface bonded to the resin composition layer.

Additionally, as the support, you may use a support with a mold release layer that has a mold release layer on the surface bonded to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more types of release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. The support with the release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL" manufactured by Lintech Co., Ltd., which are PET films having a release layer containing an alkyd resin-based release agent as a main component. -7”, “Lumira T6AM” manufactured by Toray Co., Ltd., etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using a support body with a release layer, it is preferable that the entire thickness of the support body with a release layer is within the above range.

The adhesive film can be produced, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish on a support using a die coater or the like, and then drying it to form a resin composition layer.

Organic solvents include, for example, ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, Carbitols such as cellosolve and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. Organic solvents may be used individually, or two or more types may be used in combination.

Drying may be performed by known methods such as heating or hot air spraying. Drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, the resin composition is dried at 50°C to 150°C for 3 to 10 minutes. Layers can be formed.

In the adhesive film, a protective film similar to the support can also be laminated on the side of the resin composition layer that is not bonded to the support (that is, the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating a protective film, adhesion of dust or the like and scratches on the surface of the resin composition layer can be prevented. The adhesive film can be wound into a roll and stored. When the adhesive film has a protective film, it becomes usable by peeling off the protective film.

In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

The sheet-like fiber base material used for the prepreg is not particularly limited, and commonly used prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and even more preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited, but is usually 10 μm or more.

Prepreg can be manufactured by known methods such as hot melt method and solvent method.

The thickness of the prepreg can be within the same range as that of the resin composition layer in the adhesive film.

The minimum melt viscosity of the resin composition layer in the sheet-like laminated material is preferably 6000 poise (600 Pa·s) or less, more preferably 5000 poise (500 Pa·s) or less, and 4000 poise (400 Pa) from the viewpoint of obtaining good circuit embedding properties. ·s) or less, 3500 poise (350 Pa·s) or less, or 3000 poise (300 Pa·s) or less is more preferable. The lower limit of the minimum melt viscosity is preferably 100 poise (10 Pa·s) or more, more preferably 200 poise (20 Pa·s) or more, and still more preferably 250 poise (25 Pa·s) or more.

The minimum melt viscosity of the resin composition layer refers to the minimum viscosity that the resin composition layer exhibits when the resin of the resin composition layer is melted. In detail, when the resin composition layer is heated at a certain temperature increase rate to melt the resin, the melt viscosity decreases with the temperature increase in the initial stage, and then, beyond a certain level, the melt viscosity increases with the temperature increase. Minimum melt viscosity refers to the melt viscosity at this minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method, for example, by the method described in <Measurement of minimum melt viscosity> described later.

[Printed wiring board]

The printed wiring board of the present invention is characterized by including an insulating layer formed of a cured product of the resin composition of the present invention.

For example, the printed wiring board of the present invention can be manufactured by a method including the steps (I) and (II) below using the adhesive film described above.

(I) A process of laminating an adhesive film on an inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate.

(II) Process of forming an insulating layer by heat curing the resin composition layer

The “inner layer substrate” used in step (I) is mainly a substrate such as a glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, or thermosetting polyphenylene ether substrate, or one side of the substrate. Alternatively, it refers to a circuit board with conductor layers (circuits) patterned on both sides. In addition, when manufacturing a printed wiring board, an inner layer circuit board of an intermediate product on which an insulating layer and/or a conductor layer must be additionally formed is also included in the "inner layer substrate" referred to in the present invention. If the printed wiring board is a circuit board with embedded components, it is good to use an inner layer board with embedded components.

Lamination of the inner layer substrate and the adhesive film can be performed, for example, by heat-pressing the adhesive film to the inner layer substrate from the support side. Examples of members for heat-pressing the adhesive film to the inner layer substrate (hereinafter referred to as “heat-pressing members”) include heated metal plates (SUS head plates, etc.) or metal rolls (SUS rolls). In addition, it is preferable not to press the heat-pressed member directly onto the adhesive film, but to press it through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the inner layer substrate.

Lamination of the inner layer substrate and the adhesive film may be performed by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C. The compression pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. . Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd. and a vacuum applicator manufactured by Nichigo Morton Co., Ltd.

After lamination, the laminated adhesive film may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a heat-pressing member from the support side. The press conditions for the smoothing treatment can be the same as the heat-pressing conditions for the above-described lamination. Smoothing treatment can be performed using a commercially available laminator. Additionally, the lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator.

The support may be removed between step (I) and step (II), or may be removed after step (II).

In step (II), the resin composition layer is thermoset to form an insulating layer.

The heat curing conditions of the resin composition layer are not particularly limited, and conditions normally employed when forming the insulating layer of a printed wiring board may be used.

For example, the heat curing conditions of the resin composition layer vary depending on the type of resin composition, etc., but the curing temperature is in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 200°C). °C range), and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before thermally curing the resin composition layer, the resin composition layer may be preheated to a temperature lower than the curing temperature. For example, prior to heat curing the resin composition layer, the resin composition layer is cured at a temperature of 50°C or higher and less than 120°C (preferably 60°C or higher and 110°C or lower, more preferably 70°C or higher and 100°C or lower). You may preheat for more than a minute (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

When manufacturing a printed wiring board, (III) a step of making holes in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be additionally performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that can be used in the production of printed wiring boards. Additionally, when the support is removed after step (II), the support may be removed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). ) may be carried out in between.

Process (III) is a process of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, laser, or plasma, depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole may be appropriately determined depending on the design of the printed wiring board.

Process (IV) is a process of roughening the insulating layer. The procedures and conditions of the roughening process are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. The swelling liquid is not particularly limited, and includes an alkaline solution and a surfactant solution, and is preferably an alkaline solution. As the alkaline solution, a sodium hydroxide solution or a potassium hydroxide solution is more preferable. Examples of commercially available swelling liquids include "Swelling Deep Securiganth P" and "Swelling Deep Securiganth SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment using the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid of 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing swelling of the insulating layer resin to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40°C to 80°C for 5 to 15 minutes. The oxidizing agent is not particularly limited, but examples include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Additionally, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. In addition, as the neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. Treatment with a neutralizing liquid can be performed by immersing the treated surface, which has been roughened with an oxidizing agent, in a neutralizing liquid at 30°C to 80°C for 5 to 30 minutes. In terms of workability, etc., a method of immersing the object roughened with an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness Ra of the surface of the insulating layer after roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, even more preferably 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm. It is as follows. The arithmetic average roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. A specific example of a non-contact surface roughness meter is "WYKO NT3300" manufactured by BCO Instruments.

Step (V) is a step of forming a conductor layer.

The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (e.g., nickel/chromium alloy, copper/nickel alloy, and copper/titanium alloy) ) can include a layer formed of. Among these, from the viewpoint of versatility of forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy or copper-nickel alloy , an alloy layer of a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper is more preferable. This is more preferable.

The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semiadditive method or a fulladditive method. Below, an example of forming a conductor layer by the semiadditive method will be shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern is formed to expose a portion of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Afterwards, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer with a desired wiring pattern.

The insulating layer formed using the resin composition of the present invention exhibits good reflow behavior. In one embodiment, the maximum variation in reflow behavior (bending amount) of the insulating layer is preferably 350 μm or less, more preferably 330 μm or less, even more preferably 320 μm or less, 310 μm or less, or 300 μm or less. . The lower limit of the maximum variation in reflow behavior is not particularly limited, but can be 0.5 μm or more, 1 μm or more, etc. The maximum variation in reflow behavior of the insulating layer can be measured, for example, according to the method described in <Measurement of maximum variation in reflow behavior> described later.

Since the insulating layer in the printed wiring board of the present invention is formed of a cured product of the resin composition of the present invention, it exhibits good reflow behavior even if the printed wiring board is thin. The thickness of the printed wiring board of the present invention is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 40 μm or less. The lower limit is not particularly limited, but is 5 μm or more.

In another embodiment, the printed wiring board of the present invention can be manufactured using the above prepreg. The manufacturing method is basically the same as when using an adhesive film.

[Semiconductor device]

The semiconductor device of the present invention is characterized by comprising the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Semiconductor devices include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trams, ships, aircraft, etc.). there is.

The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) at conductive points on a printed wiring board. A “continuity point” is a “point where an electric signal is transmitted on a printed wiring board,” and the location may be on the surface or buried. Additionally, 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 when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically includes a wire bonding mounting method, a flip chip mounting method, and a bump-free build-up layer (BBUL). ), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), etc. Here, the “mounting method using a bump-less build-up layer (BBUL)” refers to a “mounting method in which a semiconductor chip is directly embedded in a recessed portion of a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board.”

[Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, in the following description, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified. In addition, Me in the structural formula represents a methyl group.

First, various measurement and evaluation methods will be explained.

[Measurement of maximum variation in reflow behavior]

(1) Adjustment of substrate sample for measurement

Fabricated in the Examples and Comparative Examples on one side of a glass fiber-based epoxy resin double-sided copper clad laminate (copper foil thickness 3 μm, substrate thickness 0.1 mm, manufactured by Hitachi Kasei Co., Ltd., MCL-E-770G) forming an inner layer circuit. One adhesive film (film thickness: 40 μm) was laminated on both sides of the inner layer circuit board using a batch vacuum pressure laminator (product name: MLVP-500, manufactured by Meiki Seisakusho Co., Ltd.). The laminate was performed by depressurizing for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then compressing for 30 seconds at 100°C and a pressure of 0.74 MPa.

(2) Curing of the sample

The glass fiber-based epoxy resin double-sided copper-clad laminate, in which the adhesive film produced in Examples and Comparative Examples was pressed on one side, was fixed on four sides with a jig, cured in an oven at 200°C for 90 minutes, and taken out.

(3) Measurement of maximum variation in reflow behavior (㎛)

The sample adjusted for measurement was cut into 2 cm angles, the 1.0 cm angle of the inner center was set as the measurement range, and the maximum variation in reflow behavior was measured using a bending measurement analysis system (Samorey AXP, manufactured by AKROMETRIX). . After raising the temperature from 30℃ to 260℃ at a temperature increase rate of 0.67℃/sec, the process of dissipating heat and returning to 30℃ was performed twice, and the difference between the maximum and minimum values of the bending behavior of the sample during the second measurement was calculated. and the reflow behavior was expressed as the maximum variation (㎛).

[Measurement of lowest melt viscosity]

The dynamic viscoelasticity of the thermosetting resin composition layer of the adhesive film produced in Examples and Comparative Examples was measured using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by U·B·M Co., Ltd.). Measurements were made from a starting temperature of 60°C, a temperature increase rate of 5°C/min, a measurement interval temperature of 2.5°C, and a frequency of 1Hz/deg.

[Calculation of carbon amount per unit surface area]

3g of each of the following inorganic fillers was used as a sample. The sample and 30 g of MEK (methyl ethyl ketone) were placed in the centrifuge tube of the centrifuge, stirred to suspend the solid content, and 500 W of ultrasonic waves were applied for 5 minutes. Afterwards, solid and liquid were separated by centrifugation, and 20 g of supernatant was removed. Additionally, 20 g of MEK was added, stirred to suspend the solid content, and 500 W of ultrasonic waves were applied for 5 minutes. Afterwards, solid and liquid were separated by centrifugation, and 26 g of supernatant was removed. The remaining suspension was dried at 160°C for 30 minutes. 0.3 g of this dried sample was accurately weighed into a measuring crucible, and an auxiliary agent (3.0 g of tungsten and 0.3 g of tin) was added to the measuring crucible. The crucible for measurement was set in a carbon analyzer (“EMIA-321V2” manufactured by Horiba Seisakusho Co., Ltd.), and the amount of carbon was measured. The carbon amount per unit surface area was calculated by dividing the measured carbon amount by the specific surface area of the inorganic filler used.

<Weapon filler used>

Inorganic filler 1: 8-glycidoxyoctyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) represented by the following structural formula for 100 parts of spherical silica (“SC2500SQ” manufactured by Adomatex Co., Ltd., average particle diameter: 0.5 μm). Note) Manufactured, molecular weight 306.2) Surface treated with 0.6 parts. The amount of carbon per unit area was 0.33 mg/m ² .

Inorganic filler 2: N-2-(aminoethyl)-8-aminooctyltrimethoxy represented by the following structural formula, based on 100 parts of spherical silica (“SC2500SQ” manufactured by Adomatex Co., Ltd., average particle diameter: 0.5 μm) Surface treated with 0.6 parts of silane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 291.2). The amount of carbon per unit area was 0.27 mg/m ² .

Inorganic filler 3: Bistrimethoxysilylhexane (manufactured by Shin-Etsu Chemical Co., Ltd., Molecular weight 326.2) Surface treated with 0.6 parts. The amount of carbon per unit area was 0.28 mg/m ² .

Inorganic filler 4: Bistrimethoxysilyloctane (manufactured by Shin-Etsu Chemical Co., Ltd., Molecular weight 354.2) Surface treated with 0.6 parts. The amount of carbon per unit area was 0.28 mg/m ² .

Inorganic filler 5: Bis(trimethoxysilylpropyl)ethylenediamine (Shin-Etsu Chemical Co., Ltd.) represented by the following structural formula for 100 parts of spherical silica (“SC2500SQ” manufactured by Adomatex Co., Ltd., average particle diameter: 0.5 μm) Note) Manufactured, molecular weight 384.2) Surface treated with 0.6 parts. The amount of carbon per unit area was 0.28 mg/m ² .

Inorganic filler 6: N-phenyl-8-aminooctyl-trimethoxysilane (Shin-Etsu Co., Ltd.) represented by the following structural formula for 100 parts of spherical silica (“SC2500SＱ” manufactured by Adomatex Co., Ltd., average particle diameter: 0.5 μm) Manufactured by Kakukogyo Co., Ltd., surface treated with 0.6 parts (molecular weight: 325.2). The amount of carbon per unit area was 0.33 mg/m ² .

Inorganic filler 7: 3-(2-glycidylphenyl)propyltrimethoxysilane (( Manufactured by Shin-Etsu Chemical Co., Ltd., surface treated with 0.6 parts (molecular weight: 312.1). The amount of carbon per unit area was 0.28 mg/m ² .

Inorganic filler 8: 8-methacryloxyoctyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) represented by the following structural formula for 100 parts of spherical silica (“SC2500SQ” manufactured by Adomatex Co., Ltd., average particle diameter: 0.5 μm). Note) Manufactured, molecular weight 318.2) Surface treated with 0.6 parts. The amount of carbon per unit area was 0.28 mg/m ² .

Inorganic filler 9: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “SC2500SQ” manufactured by Adomatex Co., Ltd., average particle diameter 0.5 μm) for 100 parts. KBM403”, molecular weight 236.3) surface treated with 0.6 parts. The amount of carbon per unit area was 0.21 mg/m ² .

Inorganic filler 10: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical) for 100 parts of spherical silica (“SC2500SQ” manufactured by Adomatex Co., Ltd., average particle diameter 0.5 μm) “KBM603” manufactured by Kogyo Co., Ltd., molecular weight 222.4), surface treated with 0.6 parts. The amount of carbon per unit area was 0.22 mg/m ² .

Inorganic filler 11: N-phenyl-3-aminopropyl-trimethoxysilane (Shin-Etsu Chemical Co., Ltd.) for 100 parts of spherical silica (“SC2500SＱ” manufactured by Adomatex Co., Ltd., average particle diameter 0.5 μm) Manufactured as “KBM573”, molecular weight 255.4) surface treated with 0.6 parts. The amount of carbon per unit area was 0.24 mg/m ² .

Inorganic filler 12: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “SC2500SQ” manufactured by Adomatex Co., Ltd., average particle diameter 0.5 μm) for 100 parts. KBM503”, molecular weight 248.4) surface treated with 0.6 parts. The amount of carbon per unit area was 0.22 mg/m ² .

[Example 1]

14 parts of bixylenol type epoxy resin (epoxy equivalent 190, “YX4000HK” manufactured by Mitsubishi Chemical Corporation), 14 parts of liquid bisphenol type epoxy resin (epoxy equivalent weight approximately 165, “ZX1059” manufactured by Nippon-Steel Chemicals Co., Ltd., bisphenol A 12 parts of biphenyl type epoxy resin (epoxy equivalent weight 269, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.) are heated and dissolved with stirring in 30 parts of solvent naphtha, Then it was cooled to room temperature. Into the mixed solution, 0.5 parts of rubber particles (AC3816N, manufactured by Gantz Kasei Co., Ltd.), swelled in 6 parts of solvent naphtha for 12 hours at 20°C, and 150 parts of inorganic filler (1) were mixed, and a flame retardant (Sanko) was added to the mixed solution. “HCA-HQ” manufactured by Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 1㎛) 2 parts It was added, mixed with three rolls and dispersed. In addition, 14 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Co., Ltd., a toluene solution with a non-volatile content of 65% by mass with an active group equivalent of about 223), and a phenol novolak-based curing agent containing a triazine skeleton (DIC (DIC) Note) 10 parts of 2-methoxypropanol solution with a solid content of 50% of the product “LA3018-50P” (hydroxyl equivalent weight approximately 151), phenoxy resin (weight average molecular weight 35000, “YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 30 parts by mass of non-volatile content) 15 parts of 1:1 solution of MEK and cyclohexanone) and 2 parts of 5% by mass of MEK solution of 4-dimethylaminopyridine (DMAP) as a curing accelerator were mixed and uniformly dispersed with a rotary mixer to make a resin varnish. Produced. Next, this resin varnish was spread on the release surface of a polyethylene terephthalate film (“AL-5” manufactured by Lintech Co., Ltd., thickness 38 μm) with alkyd release treatment, and die so that the thickness of the dried resin composition layer was 40 μm. It was applied uniformly with a coater and dried at 80 to 110°C (average 95°C) for 5 minutes to obtain an adhesive film.

[Example 2]

A resin varnish and an adhesive film were obtained in the same manner as in Example 1, except that the inorganic filler (1) was changed to the inorganic filler (2).

[Example 3]

A resin varnish and an adhesive film were obtained in the same manner as in Example 1, except that the inorganic filler (1) was changed to the inorganic filler (3).

[Example 4]

A resin varnish and an adhesive film were obtained in the same manner as in Example 1, except that the inorganic filler (1) was changed to the inorganic filler (4).

[Example 5]

A resin varnish and an adhesive film were obtained in the same manner as in Example 1, except that the inorganic filler (1) was changed to the inorganic filler (5).

[Example 6]

A resin varnish and an adhesive film were obtained in the same manner as in Example 1, except that the inorganic filler (1) was changed to the inorganic filler (6).

[Example 7]

A resin varnish and an adhesive film were obtained in the same manner as in Example 1, except that the inorganic filler (1) was changed to the inorganic filler (7).

[Example 8]

10 parts of naphthalene-type epoxy resin (“HP4032SS” manufactured by DIC Corporation), 10 parts of liquid bisphenol-type epoxy resin (“ZX1059” manufactured by Nippon Chemical Co., Ltd., a 1:1 mixture of bisphenol A type and bisphenol F type) 20 parts, naphthol-type epoxy resin (“ESN-475V” manufactured by Nippon Chemical Co., Ltd.), 20 parts, phenoxy resin (weight average molecular weight 35000, “YX7553BH30” manufactured by Mitsubishi Chemical Corporation, non-volatile component 30 mass% 15 parts of a 1:1 solution of MEK and cyclohexanone) were dissolved in 50 parts of solvent naphtha by heating while stirring, and then cooled to room temperature. Next, 12 parts of an active ester compound (“HPC8000-65T” manufactured by DIC Co., Ltd., active ester equivalent weight 223, toluene solution with a solid content of 65%), a prepolymer of bisphenol A dicyanate (“BA230S75” manufactured by Ronza Japan Co., Ltd. ", cyanate equivalent weight about 232, MEK solution with 75% by mass of non-volatile matter) 12 parts, phenol novolac type polyfunctional cyanate ester resin ("PT30S" manufactured by Ronza Japan Co., Ltd., cyanate equivalent weight about 133, non-volatile matter 85 6 parts of MEK solution (% by mass), 0.5 parts of rubber particles (Staphyroid AC3816N, manufactured by Gantz Kasei Co., Ltd.) swollen in 5 parts of solvent naphtha for 12 hours at room temperature, 150 parts of inorganic filler (7), flame retardant. (“HCA-HQ” manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle diameter 1 μm) Two parts of a curing accelerator (4-dimethylaminopyridine, MEK solution with a solid content of 5% by mass) were added and uniformly dispersed with a rotary mixer to prepare a resin varnish. Next, an adhesive film was obtained in the same manner as in Example 1.

[Example 9]

Acrylate resin containing an acid group (“(ACA)Z251” manufactured by Daicel Allnex Co., Ltd., weight average molecular weight 14000, resin acid value 66 mgKOH/g, dipropylene glycol monomethyl ether solution with solid content 45 mass%) 36 parts, liquid 1 , 3 parts of 4-glycidylcyclohexane (“ZX1658GS” manufactured by Nippon Chemical Co., Ltd.), 6 parts of solid bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation), dimethylol tricyclodecane 5 parts of diacrylate (“Light Acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.) was dissolved in 16 parts of solvent naphtha by heating while stirring, and then cooled to room temperature. Next, 80 parts of the inorganic filler (8) and 5 parts of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (“I819” manufactured by BASF Japan Co., Ltd., MEK solution with a solid content of 15%) were added and rotated. It was uniformly dispersed with a mixer to produce a resin varnish. Next, an adhesive film was obtained in the same manner as in Example 1.

[Comparative Example 1]

A resin varnish and an adhesive film were obtained in the same manner as in Example 1, except that the inorganic filler (1) was changed to the inorganic filler (9).

[Comparative Example 2]

A resin varnish and an adhesive film were obtained in the same manner as in Example 1, except that the inorganic filler (1) was changed to the inorganic filler (10).

[Comparative Example 3]

A resin varnish and an adhesive film were obtained in the same manner as in Example 1, except that the inorganic filler (1) was changed to the inorganic filler (11).

[Comparative Example 4]

A resin varnish and an adhesive film were obtained in the same manner as in Example 8, except that the inorganic filler (6) was changed to the inorganic filler (11).

[Comparative Example 5]

A resin varnish and an adhesive film were obtained in the same manner as in Example 9, except that the inorganic filler (8) was changed to the inorganic filler (12).

Claims (19)

A resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
(C) A resin composition in which the inorganic filler is surface-treated with at least one surface treatment agent selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2).
Chemical formula (1)
XY-Si(OR ¹ ) ₃
(In Formula (1) _, CH ₂ ) _m -, Ar-(CH ₂ ) _m -(NR) _n -, or NH ₂ -(CH ₂ ) _m -(NR) _n -, Ar represents a phenyl group which may have a substituent, and R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 6, n represents an integer of 0 or 1, and Y represents an alkylene group having 4 or more carbon atoms that may have a substituent. , or represents an alkenylene group having 4 or more carbon atoms which may have a substituent, R ¹ represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ¹ may be the same or different.)
Chemical formula (2)
(R ² O) ₃ Si-Z-Si(OR ³ ) ₃
(Z is -NR-, which may have a substituent, an oxygen atom, a sulfur atom, an alkylene group which may have multiple substituents, and multiple -NR- groups alternately bonded together, and an oxygen atom bonded to an alkylene group which may have a substituent. represents a group or a group in which a sulfur atom is bonded to an alkylene group that may have a substituent, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² and R ³ each independently represent a carbon atom that may have a substituent. Represents an alkyl group with numbers 1 to 6, and a plurality of R ² and R ³ may be the same or different.) The resin composition according to claim 1, wherein Y in the general formula (1) represents an alkylene group having 6 or more carbon atoms which may have a substituent. The resin composition according to claim 1, wherein Z in the general formula (2) represents a group in which an alkylene group which may have a plurality of substituents and a plurality of -NR- are alternately bonded. The resin composition according to claim 1, wherein R ¹ in the formula (1), R ² and R ³ in the formula (2) represent a methyl group or an ethyl group. The method of claim 1, wherein the compound represented by formula (1) is 8-glycidoxyoctyl trimethoxysilane, N-2-(aminoethyl)-8-aminooctyl trimethoxysilane, N-phenyl-8- Any one of aminooctyl-trimethoxysilane, 3-(2-glycidylphenyl)propyl trimethoxysilane, 6-vinylhexyl trimethoxysilane, and 8-methacryloyloxyoctyl trimethoxysilane. , a resin composition wherein the compound represented by formula (2) is bis(trimethoxysilylpropyl)ethylenediamine. The resin composition according to claim 1, wherein the average particle diameter of component (C) is 0.01 μm to 5 μm. The resin composition according to claim 1, wherein component (C) is silica. The resin composition according to claim 1, wherein the content of component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1, wherein component (C) is surface treated with a surface treatment agent in an amount of 0.2 parts by mass to 2 parts by mass based on 100 parts by mass of component (C). The resin composition according to claim 1, wherein the amount of carbon per unit surface area of component (C) is 0.05 mg/m ² to 1 mg/m ² . The resin composition according to claim 1, wherein the component (A) is at least one selected from bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and biphenyl-type epoxy resin. The resin composition according to claim 1, wherein the component (B) is at least one selected from a phenol-based curing agent, a naphthol-based curing agent, an activated ester-based curing agent, and a cyanate ester-based curing agent. The resin composition according to claim 1, which is used for forming an insulating layer of a printed wiring board. The resin composition according to claim 1, which is used for forming a build-up layer of a printed wiring board. A sheet-like laminated material comprising a resin composition layer formed from the resin composition according to claim 1. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to claim 1. The printed wiring board according to claim 16, wherein the amount of deflection of the insulating layer is 350 μm or less. A semiconductor device comprising the printed wiring board according to claim 16. delete