TWI737649B - Resin composition - Google Patents

Abstract

The subject of the present invention is to provide a resin composition that can reduce the roughness of the insulating layer surface, the peeling strength of the insulating layer and the conductor layer after the roughening treatment, the plating penetration depth, the part embedding property, and the flame retardant resin composition; The sheet-like laminated material of the resin composition, a printed wiring board including an insulating layer formed by a cured product of the resin composition, and a semiconductor device.

The solution of the present invention is a resin composition containing (A) epoxy resin, (B) hardener, (C) alkoxysilane compound containing fluorine atoms, and (D) inorganic filler.

Description

Resin composition

The present invention relates to a resin composition. Furthermore, it relates to a sheet-like laminated material containing the resin composition, a printed wiring board containing an insulating layer formed by a cured product of the resin composition, and a semiconductor device.

As a manufacturing technology of a printed wiring board, a build-up manufacturing method in which insulating layers and conductor layers are alternately stacked on an inner substrate is known. The insulating layer is generally formed by curing the resin composition.

For example, Patent Document 1 discloses a resin composition containing an epoxy resin, a curing agent, and an inorganic filler surface-treated with an alkoxysilane compound. The average particle diameter of the inorganic filler is 0.01 μm to 5 μm, and when the non-volatile content in the resin composition is 100% by mass, the content of the inorganic filler is 30% to 90% by mass.

In addition, Patent Document 2 discloses a resin composition containing an epoxy resin, a curing agent, and an inorganic filler. The inorganic filler is surface-treated with an aminoalkylsilane to form a resin composition. When the non-volatile content in the substance is set at 100% by mass, the content of the inorganic filler is 55% by mass to 90% by mass.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2014-12763 A

[Patent Document 2] JP 2014-28880 A

In recent years, the miniaturization and high performance of electronic devices have evolved. In printed wiring boards, multilayer accumulation, fine wiring, and high density are expected. By using the resin composition disclosed in Citation 1 and Citation 2, although the arithmetic average roughness of the insulating layer surface can be reduced in the wet roughening step, a conductor layer with sufficient peeling strength can be formed, but it can be used for plating. Depth, part embedding, and flame retardancy are expected to be further enhanced.

The subject of the present invention is to provide a resin composition that can reduce the roughness of the insulating layer surface, the peeling strength of the insulating layer and the conductor layer after the roughening treatment, the plating penetration depth, the part embedding property, and the flame retardant resin composition; The sheet-like laminated material of the resin composition, a printed wiring board including an insulating layer formed by a cured product of the resin composition, and a semiconductor device.

As a result of diligent research on the above-mentioned subject, the inventors found that the above-mentioned subject can be solved by using an alkoxysilane compound containing a fluorine atom, and finally 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, (C) an alkoxysilane compound containing a fluorine atom, and (D) an inorganic filler.

[2] The resin composition according to [1], wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (D) is 60% by mass or more.

[3] The resin composition according to [1] or [2], wherein the average particle size of the component (D) is 0.01 μm to 2 μm.

[4] The resin composition according to any one of [1] to [3], wherein the component (D) is silica or alumina.

[5] The resin composition according to any one of [1] to [4], wherein the number of fluorine atoms in one molecule of the component (C) is 1-10.

[6] The resin composition according to any one of [1] to [5], wherein the number of alkoxy groups in one molecule of the component (C) is 1 to 5.

[7] The resin composition according to any one of [1] to [6], wherein the component (C) is 3,3,3-trifluoropropyltrimethoxysilane.

[8] The resin composition according to any one of [1] to [7], wherein the component (D) is surface-treated with the component (C).

[9] The resin composition of any one of [1] to [8], which is used for forming an insulating layer of a printed wiring board.

[10] The resin composition of any one of [1] to [9], which is used for the accumulation layer of a printed wiring board.

[11] A sheet-like laminate material comprising the resin composition as described in any one of [1] to [10].

[12] A sheet-like laminate material comprising a resin composition layer formed of the resin composition of any one of [1] to [10].

[13] The sheet-like laminate material according to [12], wherein the thickness of the resin composition layer is 10 μm or less.

[14] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition as described in any one of [1] to [10].

[15] A semiconductor device comprising the printed wiring board as in [14].

According to the present invention, it is possible to provide a resin composition that can reduce the roughness of the insulating layer surface, the peeling strength of the insulating layer and the conductor layer after the roughening treatment, the plating penetration depth, the part embedding property, and the good flame retardancy; The sheet-like laminated material of the resin composition, a printed wiring board including an insulating layer formed by a cured product of the resin composition, and a semiconductor device.

1‧‧‧Inner substrate

1a‧‧‧Hole

2‧‧‧Materials attached temporarily

3‧‧‧Parts

4‧‧‧Circuit wiring

11‧‧‧The first main surface

12‧‧‧Second main surface

100‧‧‧Inner substrate (hole substrate) temporarily equipped with parts

[Fig. 1] Fig. 1 is a schematic view showing an example of a cross-section of an inner substrate to which parts are temporarily attached.

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

[Resin composition]

The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, (C) an alkoxysilane compound containing a fluorine atom, and (D) an inorganic filler.

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

<(A) Epoxy resin>

As the epoxy resin, 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, ginseng Phenolic epoxy resin, naphthol novolak epoxy resin, phenol novolak epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, Onion type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear Aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane dimethanol type epoxy resin, naphthyl ether Type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, bixylenol type epoxy resin, etc. An epoxy resin may be used individually by 1 type, or may be used in combination of 2 or more types. (A) The component is preferably one or more selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, and biphenyl type epoxy resin.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile content of the epoxy resin is set to 100% by mass, it is preferable that at least 50% by mass is an epoxy resin having two or more epoxy groups in one molecule. Among them, it is preferable to include an epoxy resin that has two or more epoxy groups in a molecule and is liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin"), and that contains 3 or more epoxy groups in a molecule. A solid epoxy resin with more than one epoxy group at a temperature of 20°C (hereinafter referred to as "solid epoxy resin"). As the epoxy resin, by using a liquid epoxy resin and a solid epoxy resin in combination, a resin composition having excellent flexibility is obtained. In addition, the breaking strength of the cured product of the resin composition is also improved.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidol are preferred. Amine type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and those with a butadiene structure Epoxy resin, more preferably glycidylamine epoxy resin Grease, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, and "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation. (Bisphenol A epoxy resin), "jER807" (bisphenol F epoxy resin), "jER152" (phenol novolac epoxy resin), "630", "630LSD" (glycidylamine epoxy resin) Resin), "ZX1059" (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "EX-721" manufactured by Nagase ChemteX (Stock) Glycidyl ester type epoxy resin), "Celoxide2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel, "PB-3600" (epoxy resin with butadiene structure), New Japan "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Ferrochemical Co., Ltd., "630LSD" (glycidylamine epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., etc. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

As the solid epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, ginseng phenol type epoxy resin, naphthol type epoxy resin, Biphenyl type epoxy resin, naphthalene ether type epoxy resin, onion type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin, more preferably naphthalene type tetrafunctional epoxy resin, naphthalene Phenolic epoxy resin and biphenyl epoxy resin. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type 4 Functional epoxy resin), "N-690" (cresol novolac epoxy resin), "N-695" (cresol novolac epoxy resin), "HP-7200" (dicyclopentadiene epoxy resin) Oxy resin), "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" ( Naphthyl ether type epoxy resin), "EPPN-502H" (ginseng phenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000 ", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., "ESN485" (naphthol novolak type epoxy resin) Resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (onion ring) manufactured by Mitsubishi Chemical Corporation Oxygen resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., and "YL7800" (茀 type) Epoxy resin), "jER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane epoxy resin), etc. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used together as an epoxy resin, the quantity ratio (liquid epoxy resin: solid epoxy resin) is preferably 0:0.1~1:15 in terms of mass ratio. Scope. By setting the ratio of the liquid epoxy resin to the solid epoxy resin in this range, it is obtained i) When used in the form of a resin sheet, it brings moderate adhesiveness, ii) When used in the form of a resin sheet, it has sufficient flexibility to improve handling, and iii) a cured product with sufficient breaking strength can be obtained. Effect. From the viewpoint of the effects of i) to iii) above, the mass ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1:0.3 The range of ~1:10 is more preferably the range of 1:0.6~1:8.

The content of the epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3 from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. Above mass%. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, but it is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.

In the present invention, the content of each component in the resin composition, unless otherwise specified, is the value when the non-volatile component in the resin layer is set to 100% by mass.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and still more preferably 110 to 1000. By setting it in this range, it is possible to provide an insulating layer in which the crosslinking density of the cured product becomes sufficient and the surface roughness is small. Furthermore, the epoxy equivalent can be measured in accordance with JIS K7236, which is the mass of a resin containing 1 equivalent of epoxy groups.

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 epoxy resin is determined by gel permeation chromatography (GPC) The weight average molecular weight in terms of polystyrene measured by the method.

<(B) Hardener>

The curing agent is not particularly limited as long as it has the function of curing epoxy resin. Examples include phenolic curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, and cyanate ester curing agents. Hardener, and carbodiimide hardener, etc. The curing agent may be used singly, or two or more of them may be used in combination. (B) The component is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent.

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

Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395", DIC (stock) system "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc.

From the viewpoint of obtaining an insulating layer excellent in adhesion to the conductor layer, an active ester-based curing agent is also preferable. Although there are no particular restrictions on the active ester curing agent, it is generally preferable to use phenolic esters, thiophenolic esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds having two or more compounds in one molecule. The esters are highly reactive ester groups. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent derived from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent derived from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. hardener. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, and methylated bisphenol F. Methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1 ,6-Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type Diphenol compounds, phenol novolacs, etc. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, it is preferably an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, and an active ester compound containing a phenol structure. The active ester compound of the acetylated compound of novolak, the active ester compound of the benzyl compound containing the phenol novolak, and the active ester compound containing the naphthalene structure is more preferable, and the active ester containing the dicyclopentadiene type diphenol structure is more preferable. Compound. The so-called "dicyclopentadiene-type diphenol structure" refers to a bivalent structural unit formed by phenylene-bicyclopentylene-phenylene.

As a commercially available product of an active ester curing agent, as an active ester compound containing a dicyclopentadiene-type diphenol structure, examples include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC -8000H-65TM" and "EXB-8000L-65TM" (manufactured by DIC Co., Ltd.). Examples of the active ester compound containing naphthalene structure include "EXB9416-70BK" (manufactured by DIC Co., Ltd.), which contains novolac The active ester compound of the acetylated compound can include "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.), and the active ester compound of the benzoyl compound containing phenol novolak can include "YLH1026" (Mitsubishi Chemical Co., Ltd.) As the active ester hardener of the acetate of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) can be cited, and the active ester compound of the benzoate of phenol novolak includes "DC808" (manufactured by Mitsubishi Chemical Corporation). "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

Specific examples of benzoxazine-based hardeners include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd..

As the cyanate ester curing agent, for example, bisphenol A two Cyanate ester, polyphenol cyanate ester, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis(2,6-dimethylbenzonitrile) Acid ester), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenyl propane, 1,1- Bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methyl) Ethylene)) benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether, etc. are made of bifunctional cyanate resin, phenol novolac and cresol phenol Multifunctional cyanate resins derived from varnishes, prepolymers of these cyanate resins with a part of triazine, etc. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate resin) manufactured by Lonza Japan (Stock), "BA230", and "BA230S75" (becomes Part or all of the bisphenol A dicyanate is a prepolymer of the trimer of triazine), etc.

Specific examples of the carbodiimide-based hardener include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd., and the like.

The ratio of the amount of epoxy resin to hardener is based on the ratio of [total number of epoxy groups in epoxy resin]: [total number of reactive groups in hardener], preferably in the range of 1:0.01 to 1:2, more Preferably, it is 1:0.015~1:1.5, and even more preferably is 1:0.02~1:1. Here, the so-called reactive groups of the hardener refer to active hydroxyl groups, active ester groups, etc., which vary depending on the type of hardener. In addition, the so-called total number of epoxy groups of epoxy resin refers to the value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins. The so-called total of the reactive groups of the hardener The number refers to the value obtained by dividing the solid content of each hardener by the equivalent of the reactive base, and totaling it for all hardeners The value. By setting the ratio of the amount of the epoxy resin to the curing agent within this range, the heat resistance of the cured product of the resin composition can be further improved.

In one embodiment, the resin composition includes the aforementioned (A) epoxy resin and (B) hardener. The resin composition preferably contains: (A) a mixture of a liquid epoxy resin and a solid epoxy resin as the epoxy resin (liquid epoxy resin: the mass ratio of the solid epoxy resin is preferably 1:0.1 ~1:15, more preferably 1:0.3~1:10, and even more preferably 1:0.6~1:8), and as (B) the hardener is selected from phenolic hardeners, naphthol hardeners, One or more of the group consisting of active ester hardeners and cyanate ester hardeners (preferably selected from the group consisting of phenol hardeners, naphthol hardeners, and active ester hardeners One or more of them).

Although the content of the hardener in the resin composition is not particularly limited, it is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and still more preferably 15% by mass or less . In addition, the lower limit is not particularly limited, but is preferably 0.5% by mass or more.

<(C) Alkoxysilane compound containing fluorine atom>

The resin composition of the present invention contains the component (C). As a result of diligent research, the inventors found that by including the component (C), the surface roughness of the insulating layer can be reduced, and a conductor layer with sufficient peel strength can be formed. At the same time, the plating penetration depth, part embedding property, and flame retardancy Become good. (C) The ingredients are chemically stable. Therefore, the resistance to oxidants (Desmear liquid) is improved, and the roughness and plating can be reduced. Apply the depth of penetration, which can increase the peel strength. In addition, since the component (C) has flame retardancy, flame retardancy can be imparted even if the flame retardant described later is not included.

From the viewpoint of reducing the resistance to the oxidizing agent used in the roughening treatment and the plating penetration depth of the component (C), the number of fluorine atoms in one molecule of the component (C) is preferably 1 to 10, and more preferably fluorine The number of atoms is 1 to 5, and more preferably the number of fluorine atoms is 1 to 3.

The component (C) preferably has a fluorinated alkyl group, and the fluorinated alkyl group preferably has a fluorine atom at the end, from the viewpoint of reducing the resistance to the oxidizing agent used in the roughening treatment and the plating penetration depth. The fluorinated alkyl group is preferably a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably a fluorinated alkyl group having 1 to 10 carbon atoms, and still more preferably a fluorinated alkyl group having 1 to 6 carbon atoms. Examples of such fluorinated alkyl groups include -CF ₃ , -CH ₂ CF ₃ , -CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₃ , -CH(CF ₃ ) ₂ , and -CH ₂ CH ₂ CH ₂ CF ₃ , -CH ₂ CH(CF ₃ ) ₂ , -C(CF ₃ ) _3, etc., preferably -CH ₂ CH ₂ CF ₃ .

In addition, from the viewpoint of improving the reactivity of the component (C), the number of alkoxy groups in one molecule of the component (C) is preferably 1 to 5, and more preferably the number of alkoxy groups is 1 to 3. More preferably, the number of alkoxy groups is 2 to 3.

As the alkoxy group in the component (C), from the viewpoint of improving reactivity, an alkoxy group having 1 to 20 carbon atoms is preferred, an alkoxy group having 1 to 10 carbon atoms is more preferred, and even more Preferably, it is an alkoxy group having 1 to 6 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, isobutoxy, t-butoxy, and pentoxy. Group, hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy, preferably methoxy.

The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include halogen atoms, -OH, -OC _1-6 alkyl, -N(C _1-6 alkyl) ₂ , C _1-6 alkyl, and C _6-10 aryl. , -NH ₂ , -CN, -C(O)OC _1-6 alkyl, -COOH, -C(O)H, -NO ₂ and so on.

Here, the term "C _pq "(p and q are positive integers and satisfy p<q) means that only the number of carbon atoms of the organic group described in this term is p~q. For example _{, the expression of "C 1-6} alkyl" means an alkyl group with 1 to 6 carbon atoms.

The above-mentioned substituent may further have a substituent (hereinafter, it may be referred to as a "secondary substituent"). As the secondary substituent, unless otherwise specified, the same ones as the above-mentioned substituents can be used.

As the molecular weight of the component (C), from the viewpoint of improving compatibility, it is preferably 50 to 2000, more preferably 75 to 100, and still more preferably 100 to 500.

Among these, as the component (C), 3,3,3-trifluoropropyltrimethoxysilane, perfluoro(poly)ether group-containing alkoxysilane compounds, and the like can be cited. These can be used individually by 1 type, and can also be used in combination of 2 or more types. Among them, as the component (C), 3,3,3-trifluoropropyltrimethoxysilane is preferred. For the component (C), commercially available products can be used. Examples include "KBM-7103" and "OPTOOLDSX" manufactured by Shin-Etsu Chemical Co., Ltd.

Although the aspect of the component (C) contained in the resin composition of the present invention is not particularly limited, it is preferably contained in the resin composition in the following aspects (i) to (iii), more preferably The form of (i) or (iii) is contained in the resin composition, and more preferably the form of (i) is contained in the resin composition Chengzhong. That is, the component (C) as the surface treatment agent of the component (D) is preferably contained in the resin composition.

(i) (C) component is contained as a surface treatment agent of (D) component

(ii) Component (C) is separately contained in the resin composition

(iii) Component (C) can be included as a surface treatment agent for component (D), and component (C) can be contained in the resin composition alone

"The component (C) is contained as a surface treatment agent of the component (D)" means that the component (D) is surface-treated with the component (C). In this case, the component (C) is usually on the surface of the component (D). In addition, the phrase "the component (C) is contained in the resin composition alone" means that the component (C) is not contained as the surface treatment agent of the component (D). However, when the component (C) is not contained as the surface treatment agent of the component (D), the component (D) is released in the resin composition and is effective for reducing the surface roughness of the insulating layer.

When the content of the component (C) is contained in the resin composition as the component (C) alone, it is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and still more preferably 0.2% by mass or more. Although the upper limit is not particularly limited, it is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6% by mass or less.

When the (C) component is contained as the surface treatment agent of the (D) component, the degree of the surface treatment of the (C) component will reduce the surface roughness of the insulating layer and the plating penetration depth. 100 parts by mass of (D) component, preferably 0.2 parts by mass to 5 parts by mass of (C) component for surface treatment, more preferably 0.3 parts by mass to 3 parts by mass Part (C) component is surface treated, and more preferably 0.5 to 2.5 parts by mass (C) component is surface treated.

<(D) Inorganic filler>

Although the material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silica, 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, titanic acid Magnesium, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silica and alumina are particularly suitable. As the silica, spherical silica is preferred. The inorganic filler may be used singly or in combination of two or more kinds.

Although the average particle size of the inorganic filler is not particularly limited, it is preferably 2 μm or less, more preferably 1.5 μm or less, from the viewpoint of obtaining an insulating layer with small surface roughness or improving the formation of fine wiring. It is 1μm or less. Although the lower limit of the average particle diameter is not particularly limited, it is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 0.3 μm or more. Commercial products of inorganic fillers having such an average particle size include, for example, "YC100C", "YA050C", "YA050C-MJE", "YA010C", and "UFP-30" manufactured by Admatechs Corporation. , Tokuyama made "Sifil NSS-3N", "Sifil NSS-4N", "Sifil NSS-5N", (stock) Admatechs system "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", etc.

The average particle size of the inorganic filler can be measured by the laser diffraction and scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis by a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured as the average particle size. It is preferable to use an inorganic filler dispersed in water by ultrasonic waves as the measurement sample. As a laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

The inorganic filler is preferably surface-treated with a surface treatment agent. Examples of the surface treatment agent include (C) component and surface treatment agents other than (C) component (hereinafter also referred to as "other surface treatment agents"). The inorganic filler may be surface-treated with the component (C), or may be surface-treated with other surface treatment agents. From the viewpoint of improving moisture resistance and dispersibility, as well as reducing the surface roughness of the insulating layer and the depth of plating penetration, it is preferable to use the (C) component for surface treatment, and other surfaces other than the (C) component may be used. The treatment agent performs surface treatment.

Examples of other surface treatment agents include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanate-based coupling agents, and the like. These can be used individually by 1 type, and can also be used in combination of 2 or more types. Commercial products of such other surface treatment agents include, for example, "KBM-403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBM-803" (3-mercaptopropyl Trimethoxysilane), "KBE-903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-573" (N-phenyl-) manufactured by Shin-Etsu Chemical Co., Ltd. 3-aminopropyltrimethoxysilane), "SZ-31" (hexamethylsilazane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-103" (phenyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Base silane), "KBM-4803" (long-chain epoxy silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of each inorganic filler. The amount of carbon per unit surface area of each inorganic filler, from the viewpoint of improving the dispersibility of the inorganic filler, is preferably 0.05 mg/m ² or more, more preferably 0.1 mg/m ² or more, and still more preferably 0.2 mg/m ² or more. In addition, from the viewpoint of preventing the melt viscosity of the resin varnish or the melt viscosity in the form of a sheet from increasing, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg/m ² the following. The amount of carbon per unit surface area of each inorganic filler can be measured according to the method described in <Calculation of the amount of carbon per unit surface area> described later.

The content of the inorganic filler in the resin composition is preferably 60% by mass or more, more preferably 65% by mass or more, and still more preferably 70% by mass or more from the viewpoint of obtaining an insulating layer with a low thermal expansion rate. 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, and still more preferably 85% by mass or less. When the component (D) is surface-treated with the component (C), the content of the above-mentioned inorganic filler includes (C) Content of ingredients.

<(E) Thermoplastic resin>

The resin composition of the present invention may contain (E) thermoplastic resin in addition to the components (A) to (D).

Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyimide resins, polyetherimide resins, and polyimide resins. The ash resin, polyether ash resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, preferably phenoxy resin. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more types.

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 still 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 the gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured using LC-9A/RID-6A manufactured by Shimadzu Corporation and Shodex K-800P/K-804L manufactured by Showa Denko Corporation. /K-804L is used as the column, and chloroform is used as the moving equivalent. It is measured at the column temperature of 40°C and can be calculated using the calibration curve of standard polystyrene.

Examples of phenoxy resins include those having a skeleton selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, stilbene skeleton, and dicyclopentadiene skeleton. A phenoxy resin with at least one type of skeleton in the group consisting of a framework, a norbornene skeleton, a naphthalene skeleton, an onion skeleton, adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The end of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types. As specific examples of phenoxy resins, "1256" and "4250" (both phenoxy resins containing bisphenol A skeleton) manufactured by Mitsubishi Chemical Co., Ltd., and "YX8100" (containing bisphenol S skeleton) Phenoxy resin), and "YX6954BH30" (phenoxy resin containing bisphenol acetophenone skeleton), among others, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Mitsubishi "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794BH30", "YL7213BH30", "YL7290BH30", "YL7482BH30", etc. manufactured by Chemical Corporation.

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include "Electrochemical Butyral 4000-2", "Electrochemical Butyral 5000-A", "Electrochemical Butyral 6000-C" manufactured by Denki Chemical Industry Co., Ltd. "Electrochemical Butyral 6000-EP", S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series manufactured by Sekisui Chemical Industry Co., Ltd.

Specific examples of polyimide resins include "RIKACOAT SN20" and "RIKACOAT PN20". In addition, as a specific example of the polyimide resin, a linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (Japanese Patent Laid-Open No. 2006-37083) The modification of polyimide in the bulletin), polyimide containing a polysiloxane skeleton (polyimide described in JP 2002-12667 and JP 2000-319386, etc.), etc. Polyimide.

Specific examples of polyimide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. As specific examples of polyimide resins, modified polyimide resins such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyimide imide) manufactured by Hitachi Chemical Co., Ltd. can also be cited. Amide imine.

As a specific example of the polyether sulfite resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like can be cited.

As a specific example of polyphenylene ether resin, oligophenylene ether manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited. Styrene resin "OPE-2St 1200", etc.

As a specific example of the polyimide resin, the polyimide "P1700" and "P3500" manufactured by Solvay Advanced Polymers (stocks) can be cited.

Among them, as the thermoplastic resin, phenoxy resin and polyvinyl acetal resin are preferred. According to this, in a suitable embodiment, the thermoplastic resin system includes one or more of the group consisting of phenoxy resin and polyvinyl acetal resin.

When the resin composition contains a thermoplastic resin, the thermoplastic The content of the sexual resin is preferably 0.5% by mass to 10% by mass, more preferably 0.6% by mass to 5% by mass, and still more preferably 0.7% by mass to 3% by mass.

<(F) Hardening accelerator>

The resin composition of the present invention may contain (F) a hardening accelerator in addition to the components (A) to (D).

Examples of the hardening accelerator include phosphorus hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, metal hardening accelerators, etc., preferably phosphorus hardening accelerators, amine hardening accelerators, etc. The hardening accelerator, the imidazole-based hardening accelerator, and the metal-based hardening accelerator are more preferably an amine-based hardening accelerator, an imidazole-based hardening accelerator, or a metal-based hardening accelerator. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of phosphorus-based hardening accelerators include triphenyl phosphine, phosphonium borate compounds, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, and tetrabutyl phosphonium decanoic acid. Salt, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc., preferably triphenyl phosphine, tetrabutyl Base phosphonium caprate.

Examples of amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, and (Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8- Diazabicyclo(5,4,0)-undecene.

Examples of imidazole-based hardening accelerators include 2-methyl Imidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl 4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyano Ethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenyl Imidazole, 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'-Undecylimidazolyl-(1')]- Ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4 -Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole[1,2-a]benzene Imidazole compounds such as bisimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. and the addition of imidazole compounds and epoxy resin The compound is preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

Commercially available products can be used as the imidazole-based hardening accelerator, and examples include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

As the guanidine-based hardening accelerator, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, metformin Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl bis Guanidine, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide , 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., preferably dicyandiamide, 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Examples of the metal-based hardening 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) acetylpyruvate, cobalt (III) acetylpyruvate, and copper (II) acetylpyruvate. Organocopper complexes, organic zinc complexes such as zinc (II) acetopyruvate, organic iron complexes such as iron (III) acetopyruvate, nickel (II) acetylpyruvate, etc. The organic nickel complexes, manganese (II) acetopyruvate and other organic manganese complexes. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

Although the content of the hardening accelerator in the resin composition is not particularly limited, it is preferably 0.01 to 9% by mass when the total amount of the non-volatile components of the epoxy resin and the hardener is 100% by mass.

<(G) Flame Retardant>

Even if the resin composition of the present invention does not contain a flame retardant, it has excellent flame retardancy, but it may contain (G) a flame retardant. Examples of flame retardants include organic phosphorus flame retardants, phosphorus compounds containing organic nitrogen, nitrogen compounds, metal hydroxides, and the like. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

Commercially available products can be used as the flame retardant, and examples include "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Dahachi Chemical Industry Co., Ltd., and the like.

When the resin composition contains a flame retardant, although the content of the flame retardant is not particularly limited, it is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and still more preferably It is more preferably 0.5% by mass to 10% by mass.

<(H) Organic Filling Material>

The resin composition may contain (H) an organic filler from the viewpoint of improving stretching. As the organic filler, any organic filler that can be used when forming the insulating layer of a printed wiring board can be used, and examples thereof include rubber particles, polyamide fine particles, and silica particles.

As the rubber particles, commercially available products can be used. For example, "EXL2655" manufactured by Dow Chemical Japan Co., Ltd., "AC3816N" manufactured by Ganz Chemicals Co., Ltd., and the like can be cited.

When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and still more preferably 0.3% by mass to 5% by mass, Or 0.5% by mass to 3% by mass.

<(I) Any additives>

The resin composition may contain other additives if necessary. Examples of the other additives include organic copper compounds, organic zinc compounds, and organic Organometallic compounds such as cobalt compounds, and resin additives such as tackifiers, defoamers, levelers, adhesion imparting agents, and coloring agents.

In addition, from the viewpoint of manufacturing a flexible printed wiring board, the resin composition preferably further contains a polybutadiene structure, a urethane structure, an amide structure, and a molecular end having a polybutadiene structure in the molecule. Phenolic structure of polyimide resin. When the polyimide resin is contained, the content is preferably 10% by mass to 85% by mass, more preferably 15% by mass to 50% by mass, and still more preferably 20% by mass to 30% by mass.

The details of the polyimide can refer to the record of International Publication No. 2008/153208, and this content is incorporated into this specification.

The resin composition of the present invention provides an insulating layer with good surface roughness, peel strength, plating penetration depth, part embedding properties, and flame retardancy of the thermoset surface. Accordingly, 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 is more suitable for use as an interlayer for forming a printed wiring board The resin composition of the insulating layer (the resin composition for the interlayer insulating layer of a printed wiring board) is used. In addition, since the resin composition of the present invention provides an insulating layer with good parts embedding, it can be suitably used even when the printed wiring board is a circuit board with a built-in part.

[Flake Laminated Material]

Although the resin composition of the present invention can be applied and used in a varnish state, it is generally industrially suitable for use in the form of a sheet-like laminate containing the resin composition.

As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

In one embodiment, the resin sheet already includes a support and a resin composition layer bonded to the support, and the resin composition layer is formed of the resin composition of the present invention.

The thickness of the resin composition layer is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and still more preferably 600 μm or less. In particular, in the present invention, since the plating penetration depth can be suppressed to be small, it is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can usually be 1 μm or more, 1.5 μm or more, 2 μm or more.

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

When a film made of a plastic material is used as the support, as the plastic material, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter Sometimes abbreviated as "PEN") such as polyester, polycarbonate (hereinafter sometimes referred to as "PC"), polymethylmethacrylate (PMMA) and other acryl, cyclic polyolefin, triacetin Base cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using metal foil as a support, as a metal Examples of the foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil made of a single metal of copper can be used, and a foil made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can also be used.

The support may be frosted or corona treated on the surface joined with the resin composition layer.

In addition, as the support, a support with a mold release layer having a mold release layer on the surface to be bonded to the resin composition layer can be used. As the mold release agent used for the mold release layer of the support with the mold release layer, for example, it may be selected from the group consisting of alcohol resins, polyolefin resins, urethane resins, and silicone resins. One or more release agents. Commercial products can be used for the support with a release layer. Examples include PET film with a release layer based on an acid-alcohol resin-based release agent, namely "SK-1" and "AL" made by Lintec. -5", "AL-7", Toray's "LumirrorT6AM", etc.

Although the thickness of the support is not particularly limited, it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In the case of using a support with a release layer, it is preferable that the thickness of the entire support with a release layer is in the above-mentioned range.

The resin sheet, for example, a resin varnish in which a resin composition is dissolved in an organic solvent can be prepared by coating the resin varnish on a support using a die coater or the like, and then drying it to form a resin composition layer.

As the organic solvent, for example, acetone, methyl ethyl Ketones such as ketones (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate and other acetates, solvents Carbitols such as fiber and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone And other amide-based solvents. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

Drying can be performed by a well-known drying method such as heating and blowing hot air. Although the drying conditions are not particularly limited, the content of the organic solvent in the resin composition layer is 10% by mass or less, and drying is preferably performed so that it is 5% by mass or less. Although it differs depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% to 60% by mass of organic solvent is used, it can be dried at 50°C to 150°C for 3 minutes to 10 minutes. A resin composition layer is formed.

In the resin sheet, on the surface not bonded to the support of the resin composition layer (that is, the surface on the opposite side to the support), a protective film corresponding to the support may be further laminated. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent adhesion or scratches of dust and the like on the surface of the resin composition layer. The resin sheet can be wound into a roll for storage. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

The sheet-like fibrous substrate used for the prepreg is not particularly limited. It can be used as glass cloth, aromatic polyamide (Aramid) Users of substrates for prepregs such as woven fabrics and liquid crystal polymer non-woven fabrics. From the viewpoint of thinning of the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and still more preferably 600 μm or less. In particular, because the present invention can suppress the plating penetration depth to be small, it is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. Although the lower limit of the thickness of the sheet-like fibrous base material is not particularly limited, it can usually be 1 μm or more, 1.5 μm or more, 2 μm or more.

The prepreg can be manufactured by a well-known method such as a hot melt method and a solvent method.

The thickness of the prepreg may be in the same range as the resin composition layer of the above-mentioned resin sheet.

The lowest melt viscosity of the sheet-like laminate resin composition layer (in the case of a prepreg, the resin composition impregnated in the sheet-like fiber substrate) is preferably from the viewpoint of obtaining good part embedding properties 12000poise (1200Pa.s) or less, more preferably 10000poise (1000Pa.s) or less, still more preferably 8000poise (800Pa.s) or less, 5000poise (500Pa.s) or less, or 4000poise (400Pa.s) or less. 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 from the viewpoint of stably maintaining the thinness and thickness of the resin composition layer. (25Pa.s) or more.

The so-called minimum melt viscosity of the resin composition layer means that when the resin of the resin composition layer is melted, the resin composition layer exhibits the lowest viscosity. Spend. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, the melt viscosity decreases with the temperature rise in the initial stage, and then when the temperature exceeds a certain level, the melt viscosity increases together with the temperature rise. The so-called minimum melt viscosity refers to the minimum melt viscosity. The minimum melt viscosity of the resin composition layer can be measured using the dynamic viscoelastic method, for example, it can be measured according to the method described in the below-mentioned "Measuring the minimum melt viscosity of the resin composition layer".

The cured product of the resin composition (or resin composition layer) of the present invention (for example, the resin composition is thermally cured at 190°C for 90 minutes) exhibits excellent flame retardancy characteristics. The flame retardancy is preferably V-0 according to UL-94V standard or better than V-0. The evaluation of flame retardancy can be measured according to the method described in <Evaluation of flame retardancy> described later.

[Printed Wiring Board]

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

For example, the printed wiring board of the present invention uses the above-mentioned resin sheet, and can be manufactured by a method including the following steps (I) and (II).

(I) The step of laminating the resin sheet on the inner substrate by bonding the resin composition layer of the resin sheet to the inner substrate

(II) Steps of forming insulating layer from thermosetting resin composition layer

The "inner substrate" used in step (I) mainly refers to substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. Or form A circuit substrate with a conductor layer (circuit) on one or both sides of the substrate is patterned. When a printed wiring board is manufactured, an inner layer circuit board in which an insulating layer and/or a conductor layer is to be formed as an intermediate product is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in parts, it is sufficient to use an inner-layer substrate with built-in parts (the conductor layer is also referred to as a wiring layer).

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet against the inner layer substrate from the support side. As a member for heat-pressing the resin sheet to the inner layer substrate (hereinafter also referred to as "heating and pressing member"), for example, a heated metal plate (SUS mirror plate, etc.) or metal roller (SUS roller) can be cited. However, it is preferable not to directly press the heating and pressing member on the resin sheet, but to press through an elastic material such as heat-resistant rubber so that the surface irregularities of the inner substrate are fully followed by the resin sheet.

The lamination of the inner substrate and the resin sheet can be implemented by a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa The heating and pressing time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure at a pressure of 26.7 hPa or less.

The lamination process can be implemented using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressure laminator manufactured by Meiji Seisakusho Co., Ltd., and a vacuum applicator manufactured by Nichigo-Morton Co., Ltd. can be cited.

After lamination, under normal pressure (atmospheric pressure), for example, by pressing the heating and pressing member from the support side, smoothing treatment of the laminated resin sheet can be performed. The pressing conditions of the smoothing treatment can be the same conditions as the heating and pressing conditions of the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. Still, the lamination and smoothing process can be continuously performed using a commercially available vacuum laminator.

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

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

The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions generally used when forming the insulating layer of a printed wiring board can be used.

For example, although the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, etc., the curing temperature can be in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably 170 ℃~200℃), 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 thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before the thermosetting resin composition layer, the resin composition layer can be prepared at a temperature above 50°C but less than 120°C (preferably 60°C or more and 110°C or less, more preferably 70°C or more and 100°C or less). Heating for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

When manufacturing a printed wiring board, (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer can be further implemented. These steps (III) to (V) can be implemented in various methods known to those with ordinary knowledge in the field of the invention in the manufacture of printed wiring boards. Still, in the case of removing the support after step (II), it can be done between step (II) and step (III), between step (III) and step (IV), or between step ((IV) and step (IV)). (V) Implemented in between.

Step (III) is a step of drilling holes in the insulating layer, whereby holes such as through holes and through holes can be formed in the insulating layer. Step (III) is carried out in accordance with the composition of the resin composition used in the formation of the insulating layer, for example, using a drill, a laser, or a plasma. The size or shape of the hole can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The order and conditions of the roughening treatment are not particularly limited, and the well-known order and conditions generally used when forming the insulating layer of a printed wiring board can be adopted. For example, the swelling treatment with a swelling solution, the roughening treatment with an oxidizing agent, and the neutralization treatment with a neutralization solution can be performed in this order, and the insulating layer can be roughened. Although it does not specifically limit as a swelling liquid, an alkali solution, a surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As this alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. Examples of commercially available swelling fluids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment by the swelling liquid is not particularly limited, but for example, it can be The insulation layer is immersed in the swelling liquid at ℃ for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to impregnate the hardened body with a swelling solution heated to 40°C to 80°C for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent (roughening liquid), for example, the alkaline permanganic acid solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment by an oxidant such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidant solution heated to 60°C to 80°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate Compact CP", "Concentrate Compact P", and "Dozing Solusion Securiganth P" manufactured by Atotech Japan. In addition, as the neutralizing liquid, an acidic aqueous solution is preferable, and as a commercially available product, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. The treatment by the neutralization solution can be performed by immersing the treated surface that has not been roughened by the oxidizing agent solution in the neutralization solution for 5 minutes to 30 minutes at 30°C to 80°C. From the viewpoint of workability and the like, a method of immersing an object to be roughened by an oxidizing agent in a neutral solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

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

The conductor material used in the conductor layer is not particularly limited. For a suitable embodiment, the conductor layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium Above the metal. The conductor layer can be a single metal layer or a composite The gold layer, as the alloy layer, may be, for example, a layer formed by an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, Or nickel and chromium alloy, copper and nickel alloy, copper and titanium alloy alloy layer, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel and chromium alloy layer The alloy layer is more preferably a single metal layer of copper.

The conductor layer can be a single-layer structure, a single metal layer made of different types of metals or alloys, or a multiple-layer structure composed of two or more alloy layers. 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 and chromium alloy.

Although the thickness of the conductor layer varies depending on the design of the desired printed wiring board, it is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

In one embodiment, the conductive layer can be formed by plating. For example, by plating on the surface of the insulating layer by a well-known technique such as a semi-additive method, a full-additive method, etc., a conductor layer with a desired wiring pattern can be formed. The following shows an example in which the conductor layer is formed by the semi-additive method.

First, on the surface of the insulating layer, a plating seed layer is formed by electroless plating. Secondly, on the formed plating seed layer, corresponding to the desired wiring pattern, a mask pattern is formed that exposes a part of the plating seed layer. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like to form a conductor with the desired wiring pattern. Body layer.

Since the resin composition of the present invention provides an insulating layer with good parts embedding properties, it can be suitably used even when the printed wiring board is a circuit board with a built-in part.

As such a method of manufacturing a circuit board with a built-in part, it includes the steps (i) to (v). (i) is the step of preparing temporarily attached parts, and the inner substrate of the temporarily attached parts has opposing The first and second main surfaces, and include an inner substrate that forms a cavity (cavity) penetrating between the first and second main surfaces, a temporarily attached material that is bonded to the second main surface of the inner substrate, and A part that is temporarily attached to the inside of the cavity of the inner substrate by temporarily attaching the material, (ii) the resin sheet of the present invention is laminated with the resin composition layer and the first main surface of the inner substrate The step of (iii) the step of peeling the temporarily attached material from the second main surface of the inner layer substrate, (iv) the resin sheet is laminated so that the resin composition layer is bonded to the second main surface of the inner layer substrate Step, and (v) Step of thermosetting the resin composition layer.

For example, as shown in Fig. 1, the inner substrate 100 (also referred to as the "hole substrate") for temporarily attaching parts has opposed first and second main surfaces 11, 12, and includes forming through the first and The inner layer substrate 1 of the hole 1a between the second main surfaces, the temporarily attached material 2 that is bonded to the second main surface 12 of the inner layer substrate 1, and the inside of the hole 1a of the inner layer substrate From the temporarily attached material 2 and the temporarily attached part 3. The inner substrate 1 can be prepared with circuit wiring 4 such as via wiring and surface wiring.

The holes formed in the inner layer substrate take into consideration the characteristics of the inner layer substrate, and can be formed, for example, by using a well-known method such as a drill, a laser, a plasma, an etching medium, and the like. The holes can be drilled at predetermined intervals and formed in plural, and the opening shape of the holes is not particularly limited, and can be any shape such as rectangular, circular, slightly rectangular, or slightly circular.

As a material for temporary attachment, in order to temporarily attach the part, it is not particularly limited as long as it has an adhesive surface showing sufficient adhesiveness. When manufacturing a circuit board inside the part, any previously known temporary attachment material can be used. . As a material for temporary attachment, for example, PFDKE-1525TT (polyimide film with adhesive) manufactured by Yusawa Manufacturing Co., Ltd., and UC series (UV tape for wafer dicing) manufactured by Furukawa Electric Co., Ltd. .

The parts are temporarily attached to the exposed adhesive surface of the temporarily attached material through the holes. As the parts, suitable electrical parts can be selected according to the desired characteristics. Examples include passive parts such as capacitors, inductors, resistors, multilayer ceramic capacitors, and current parts such as semiconductor bare chips. The same parts can be used in all holes, and different parts can be used in each hole.

Step (ii) is a step of laminating the resin sheet of the present invention such that the resin composition layer is bonded to the first main surface of the inner substrate. The lamination conditions of the first main surface and the resin sheet are the same as the conditions of the above-mentioned step (I), and the preferred ranges are also the same.

After the resin composition layer is laminated on the first main surface of the inner substrate, the resin composition layer can be thermoset. The conditions of the thermosetting resin composition layer are the same as the conditions of the above-mentioned step (II), and the preferred ranges are also the same.

Step (iii) is a step of peeling the temporarily attached material from the second main surface of the inner substrate. The peeling of temporarily attached materials can be carried out according to the type of temporarily attached materials according to the well-known methods in the past.

Step (iv) is a step of laminating the resin sheet such that the resin composition layer is bonded to the second main surface of the inner substrate. The lamination conditions of the second main surface and the resin sheet are the same as the conditions of the above step (I), and the preferred ranges are also the same. The resin composition layer in step (iv) may be the same resin composition layer as the resin composition layer in step (ii), or a different resin composition layer.

Step (v) is a step of thermosetting the resin composition layer. The conditions of the thermosetting resin composition layer are the same as the conditions of the above-mentioned step (II), and the preferred ranges are also the same.

As a method of manufacturing a circuit board with a built-in part, it may further include a step of drilling a hole in the insulating layer (drilling step), a step of roughening the surface of the insulating layer, and a step of forming a conductor layer on the surface of the roughened insulating layer . These steps are as described above.

The printed wiring board of the present invention may include an insulating layer that is a cured product of the resin composition layer of the resin sheet of the present invention, and an embedded wiring layer in which the insulating layer is embedded.

As a manufacturing method of such a printed wiring board, it includes the steps (1) to (4), (1) A step of preparing a substrate with a wiring layer having an inner substrate and a wiring layer provided on at least one surface of the substrate; (2) The resin sheet of the present invention is embedded in the resin composition with the wiring layer The method of layering is a step of laminating on a substrate with a wiring layer and thermally curing it to form an insulating layer, (3) a step of connecting the wiring layer between layers, and (4) a step of removing the substrate.

On both sides of the inner layer substrate used in this manufacturing method, it is preferable to have a metal layer composed of copper foil or the like, and it is more preferable to have a structure in which the metal layer is laminated with two or more metal layers. The details of step (1) are laminating a dry film (photosensitive photoresist film) on a substrate, and using a photomask to perform exposure and development under predetermined conditions to form a patterned dry film. The developed pattern dry film is used as a plating mask, the wiring layer is formed by electrolytic plating, and the pattern dry film is peeled off.

The lamination conditions of the inner substrate and the dry film are the same as the conditions of the above step (II), and the preferred ranges are also the same.

After the dry film is laminated on the inner substrate, in order to form a desired pattern for the dry film, exposure and development are performed under predetermined conditions using a photomask.

Although the line (circuit width)/space (width between circuits) ratio of the wiring layer is not particularly limited, it is preferably 20/20μm or less (that is, the pitch is 40μm or less), and more preferably 18/18μm or less (the pitch is 36μm or less) ), and more preferably 15/15μm or less (pitch 30μm or less). Although the lower limit of the line/space ratio of the wiring layer is not particularly limited, it is preferably 0.5/0.5μm or more, more preferably 1/1μm or more. The pitch does not have to be the same across the entire wiring layer.

After the pattern of the dry film is formed, the wiring layer is formed, and the dry film is peeled off. Here, the formation of the wiring layer can use a dry film forming a desired pattern as a plating mask, and can be implemented by a plating method.

The conductor material used in the wiring layer is not particularly limited. For a suitable embodiment, the wiring layer includes at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium Above the metal. The wiring layer can be a single metal layer or an alloy layer. As the alloy layer, for example, alloys of two or more metals selected from the above group (such as nickel and chromium alloy, copper and nickel alloy, and copper and titanium Alloy) formed by.

Although the thickness of the wiring layer depends on the design of the desired wiring board, it is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, and still more preferably 10 to 20 μm, or 15 μm.

After the wiring layer is formed, the dry film is peeled off. The peeling of the dry film can be implemented by a well-known method. If necessary, the unnecessary wiring pattern can be removed by etching or the like, and the desired wiring pattern can also be formed.

Step (2) is a step of laminating the resin sheet on the substrate with the wiring layer in such a way that the wiring layer is embedded in the thermosetting resin composition layer, and thermally curing it to form an insulating layer. The lamination conditions of the substrate with the wiring layer and the resin sheet are the same as the conditions of the above step (II), and the preferred ranges are also the same.

Step (3) is not particularly limited if it is an interlayer connection wiring layer However, it is preferably at least one of the steps of forming a through hole in the insulating layer, forming a conductive layer, and grinding or grinding the insulating layer to expose the wiring layer. The steps of forming through holes in the insulating layer and forming the conductor layer are as described above.

As a polishing method or grinding method of the insulating layer, the wiring layer can be exposed. If the polishing or grinding surface is horizontal, it is not particularly limited, and conventionally known polishing methods or grinding methods can be applied. For example, a chemical mechanical polishing device can be used The chemical mechanical grinding method, the mechanical grinding method such as buffing, and the plane grinding method by turning the wheel.

Step (4) is a step of removing the inner substrate to form the printed wiring board of the present invention. The method of removing the inner layer substrate is not particularly limited. In a suitable embodiment, the inner layer substrate is peeled from the printed wiring board at the interface of the metal layer on the inner layer substrate, and the metal layer is etched away, for example, with a copper chloride aqueous solution or the like.

In other embodiments, the printed wiring board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as in the case of using a resin sheet.

The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention. Therefore, it shows that the parts are easy to be embedded. That is, the parts manufactured by using the sheet-like laminated material of the present invention have built-in circuit boards, and all the holes in the parts can be covered with a resin composition. The evaluation of the insertability of parts can be measured according to the method described in <Evaluation of Part Insertion> described later.

The printed wiring board of the present invention includes the The insulating layer formed by the hardened resin composition can reduce the roughness. Specifically, the arithmetic average roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface after the roughening treatment showed good results. The arithmetic average roughness (Ra) is preferably 500 nm or less, more preferably 450 nm or less, and still more preferably 400 nm or less. Although the lower limit is not particularly limited, it may be 100 nm or more. The root mean square roughness (Rq) of the surface of the insulating layer is preferably 600 nm or less, more preferably 550 nm or less, and still more preferably 530 nm or less. Although the lower limit is not particularly limited, it may be 100 nm or more. The evaluation of the arithmetic mean roughness (Ra) and the root mean square roughness (Rq) can be measured according to the method described in (Measurement of the arithmetic mean roughness (Ra) and root mean square roughness (Rq)) described later.

The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention. Therefore, the peel strength (Peel Strength) of the insulating layer and the conductor layer after the roughening treatment shows good results. The peel strength is preferably 0.3 kgf/cm or more, more preferably 0.40 kgf/cm or more, and still more preferably 0.45 kgf/cm or more. Although the upper limit is not particularly limited, it may be 1.2 kgf/cm or less, 0.9 kgf/cm or less. In the present invention, even though the arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer after the roughening treatment are low, it is possible to form a conductive layer exhibiting such a high peel strength, which significantly contributes to Fine wiring of printed wiring boards. The evaluation of peel strength can be measured according to the method described in (Measurement of peel strength) described later.

The insulating layer formed by the resin composition (or resin composition layer) of the present invention shows a good plating penetration depth. The plating The penetration depth is preferably 3.0 μm or less, more preferably 2.5 μm or less, and even more preferably 2.0 μm or less. Although the lower limit is not particularly limited, it may be 0.1 μm or more. As an embodiment, in the present invention, since the plating penetration depth is low, even an insulating layer manufactured using a resin composition layer with a thickness of 10 μm or less has insulating properties, thereby significantly contributing to the printed wiring board Fine wiring and thinning. The evaluation of the plating penetration depth can be measured in accordance with the method described in (Measurement of plating penetration depth) described later.

[Semiconductor device]

The semiconductor device of the present invention includes 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.

Examples of semiconductor devices include various semiconductor devices used in electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trams, ships, and airplanes).

The semiconductor device of the present invention can be manufactured by mounting parts (semiconductor chips) due to the conduction of the printed wiring board. The so-called "conducting point" refers to "the place where the electrical signal is transmitted on the printed wiring board". The place can be a surface or a place where it is embedded. In addition, if the semiconductor wafer is an electrical circuit element using a semiconductor as a material, it is not particularly limited.

The mounting method of the semiconductor wafer when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can effectively perform its functions. Specifically, a wire bonding mounting method and a flip chip mounting method can be cited , By the mounting method of the non-concave accumulation layer (BBUL), by the mounting method of the anisotropic conductive film (ACF), by the non- How to mount conductive film (NCF), etc. Here, the so-called "mounting method by non-convex build-up layer (BBUL)" refers to the "mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board to connect the semiconductor chip to the wiring on the printed wiring board" .

[Example]

Hereinafter, although the present invention will be specifically explained by examples, the present invention is not limited to these examples. However, in the following description, "parts" and "%" mean "parts by mass" and "% by mass" respectively unless otherwise specified.

<Calculation of the amount of carbon per unit surface area>

3 g of each inorganic filler described below was used as a sample. Put the sample and 30g of MEK (methyl ethyl ketone) into the centrifuge tube of the centrifugal separator, stir to suspend the solids, and irradiate 500W ultrasonic waves at 25°C for 5 minutes. Then, solid-liquid separation was performed by centrifugal separation, and 20 g of the supernatant was removed. Furthermore, 20 g of MEK was added, stirring was performed to suspend the solid content, and 500 W ultrasonic waves were irradiated at 25° C. for 5 minutes. Then, solid-liquid separation was performed by centrifugal separation, and 26 g of the supernatant was removed. The remaining suspension was dried at 160°C for 30 minutes. 0.3 g of this dry sample was accurately measured in a crucible for measurement, and a combustion aid (3.0 g of tungsten and 0.3 g of tin) was put in the crucible for measurement. The crucible for measurement was set in a carbon analyzer ("EMIA-321V2" manufactured by Horiba Manufacturing Co., Ltd.), and the carbon content was measured. Divide the measured value of carbon content by the specific surface area of the inorganic filler used to calculate each unit surface The amount of carbon accumulated.

<Used inorganic filler>

Inorganic filler 1: 100 parts to spherical silica ("SC4500SQ" manufactured by Admatechs ("SO-C4" with hexamethyldisilazane surface treatment), average particle size of about 1μm as stated by the manufacturer) 100 parts of spherical silica , With 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7103) 1 part surface treatment. The amount of carbon per unit surface area is 0.25 mg/m ² .

Inorganic filler 2: 100 parts relative to spherical silica ("SC1500SQ" manufactured by Admatechs ("SO-C1" with hexamethyldisilazane surface treatment), average particle size about 0.3μm as stated by the manufacturer) of spherical silica , Surface treated with 2 parts of 3,3,3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7103). The amount of carbon per unit surface area is 0.16 mg/m ² .

Inorganic filler 3: 3,3,3-trifluoropropyltrimethoxysilane ( Shin-Etsu Chemical Co., Ltd., KBM-7103) 1 part of surface treatment. The amount of carbon per unit surface area is 0.12 mg/m ² .

Inorganic filler 4: Relative to 100 parts of spherical silicon dioxide ("SC4500SQ" manufactured by Admatechs ("SO-C4" surface-treated with hexamethyldisilazane), manufacturer’s average particle size of about 1μm), Surface treated with 1 part of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-403"). The amount of carbon per unit surface area is 0.31 mg/m ² .

Inorganic filler 5: 100 parts relative to spherical silica (“SC1500SQ” manufactured by Admatechs (“SO-C1” with hexamethyldisilazane surface treatment), average particle diameter of about 0.3μm according to the manufacturer) , Surface treated with 2 parts of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-903"). The amount of carbon per unit surface area is 0.23 mg/m ² .

Inorganic filler 6: To 100 parts of spherical alumina (Denka Co., Ltd. "DAW-01", manufacturer’s description of average particle size is about 1.5μm), acetoxy aluminum diisopropoxide (Ajinomoto Fine Chemical Technology (Stock) System, "PlainactAL-M") 1 part of surface treatment. The amount of carbon per unit surface area is 0.15 mg/m ² .

Inorganic filler 7: 100 parts of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM- 103) 1 part of surface treatment. The amount of carbon per unit surface area is 0.30 mg/m ² .

[Production of resin sheet]

Using the resin varnish (resin composition) prepared by the following procedure, the resin sheet of the Example and the comparative example was produced.

<Preparation of resin varnish 1>

4 parts of bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1:1 mixture of bisphenol A type and bisphenol F type), dihydroxyxylene (Bixylenol) type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent approximately 185) 6 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent approximately 272 ) 20 parts, heated and dissolved while stirring in a mixed solvent of 15 parts of solvent naphtha and 10 parts of cyclohexanone. After cooling to room temperature, mix it with a cresol novolac hardener containing a triazine skeleton (LA-3018-50P made by DIC), a hydroxyl equivalent of about 151, and a solid content of 50% 2-methoxy Propanol solution) 8 parts, phenolic novolac hardener containing triazine skeleton (LA-7054 made by DIC, a MEK solution with a hydroxyl equivalent of about 125 and a solid content of 60%) 4 parts, naphthol hardening Agent (Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495V", a MEK solution with a hydroxyl equivalent of about 231 and a solid content of 60%) 10 parts, amine hardening accelerator (4-dimethylaminopyridine (DMAP)) , Solid content 5 mass% MEK solution) 1 part, rubber particles (made by Dow Chemical Japan Co., Ltd., EXL2655) 2 parts, inorganic filler 1 190 parts, uniformly dispersed by a high-speed rotary mixer, and then in a cylinder Filter ("SHP050" manufactured by ROKITECHNO) to prepare resin varnish 1.

<Preparation of resin varnish 2>

4 parts of cyclohexanedimethanol type liquid epoxy resin ("ZX1658GS" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent approximately 135), and 4 parts of bisphenol AF type epoxy resin (made by Mitsubishi Chemical Co., Ltd.) YL7760", epoxy resin About 238) 15 parts, naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent: about 330) 15 parts, and phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd.) , 30% solid content of cyclohexanone: methyl ethyl ketone (MEK) 1:1 solution) 10 parts, heated while stirring in a mixed solvent of 15 parts of solvent naphtha and 5 parts of cyclohexanone Dissolve. After cooling to room temperature, mix it with a cresol novolac hardener containing a triazine skeleton ("LA-3018-50P" made by DIC Co., Ltd., a hydroxyl equivalent of about 151, and a solid content of 50% 2-methoxy Propanol solution) 8 parts, active ester curing agent (DIC (stock) "EXB-8000L-65M", active group equivalent of about 220, non-volatile content 65% by mass MEK solution) 12 parts, amine curing accelerator (4-Dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass%) 1.5 parts, 125 parts of inorganic filler 2 are uniformly dispersed with a high-speed rotary mixer, and then a cartridge filter (manufactured by ROKITECHNO" SHP030”) filter to prepare resin varnish 2.

<Preparation of Resin Varnish 3>

50 parts of component (i) prepared as follows, 2 parts of naphthyl ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Co., Ltd., epoxy equivalent of about 213), and bisphenol AF type epoxy resin ( 4 parts of "YL7760" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 238), and 2 parts of flame retardant ("PX-200" manufactured by Dahachi Chemical Industry Co., Ltd.), in 10 parts of solvent naphtha and ring The mixed solvent of 5 parts of hexanone is heated and dissolved while stirring. It is mixed with an active ester-based hardener (DIC Co., Ltd. product "EXB-8000L-65M", 2 parts of MEK solution with active group equivalent of about 220 and 65% by mass of non-volatile content), imidazole-based hardening accelerator (Shikoku Chemical Industry Co., Ltd. "1B2PZ" 1-benzyl-2-phenylimidazole, solid content 5 % MEK solution) and 125 parts of inorganic filler 3 are uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter ("SHP030" manufactured by ROKITECHNO) to prepare resin varnish 3.

((i) Modulation of component)

G-3000 (2-functional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g/eq., solid content 100% by mass, manufactured by Nippon Soda Co., Ltd.) 50g in the reaction vessel , Solvent naphtha (aromatic hydrocarbon-based mixed solvent: "Ipsol150" manufactured by Idemitsu Petrochemical Co., Ltd.) 23.5g, and dibutyltin laurate 0.005g to make it uniformly dissolved. When it became uniform, the temperature was raised to 50°C, and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g/eq.) was added while stirring, and the reaction was performed for about 3 hours. Next, after cooling the reactant to room temperature, 8.96 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylene diamine, and ethyl diglycerol were added here. 40.4 g of alcohol acetate (manufactured by Daicel) was heated to 130°C while stirring, and the reaction was carried out for about 4 hours. It was confirmed by FT-IR that the NCO peak ^{at 2250 cm -1 disappeared.} The confirmation of the disappearance of the NCO peak is regarded as the end of the reaction. After the reactant is cooled to room temperature, it is filtered with a 100-mesh filter cloth to obtain an imide skeleton, an ethyl urethane skeleton, and a butadiene skeleton. Polymer resin (component (i)). The analysis results of this polymer resin (component (i)) are as follows.

Viscosity: 7.5Pa. s(25℃, E-type viscometer)

Acid value: 16.9mgKOH/g

Solid content: 50% by mass

Number average molecular weight: 13723

Glass transition temperature: -10℃

The content of polybutadiene structural part: 50/(50+4.8+8.96)×100=78.4% by mass

<Preparation of Resin Varnish 4>

Except for the preparation of resin varnish 1, 1 190 parts of inorganic filler was changed to 4 190 parts of inorganic filler, and 15 parts of solvent naphtha was changed to 20 parts. Other than the above matters, the resin varnish 4 was prepared in the same manner as the preparation of the resin varnish 1.

<Preparation of Resin Varnish 5>

Except for the preparation of resin varnish 2, 125 parts of inorganic fillers were changed to 5 125 parts of inorganic fillers, and 15 parts of solvent naphtha were changed to 20 parts. Other than the above items, the resin varnish 2 was prepared in the same manner as the resin varnish 2 to prepare the resin varnish 5.

<Preparation of resin varnish 6>

Except for the preparation of resin varnish 3, 3 125 parts of inorganic filler was changed to 6 125 parts of inorganic filler. Other than the above items and resin clear The preparation of the lacquer 3 was carried out in the same manner, and the resin varnish 6 was prepared.

<Preparation of resin varnish 7>

Except for the preparation of resin varnish 1, 1 190 parts of inorganic filler was changed to 7 190 parts of inorganic filler. Other than the above matters, the resin varnish 7 was prepared in the same manner as the preparation of the resin varnish 1.

The materials used in the production of each resin varnish and their blending amounts (mass parts of non-volatile components) are shown in the following table. The content (mass%) of the non-volatile components of the liquid epoxy resin and (C) inorganic filler is also shown together.

<Examples 1 to 3 and Comparative Examples 1 to 4: Production of Resin Sheets>

As a support, prepare a PET film ("Lumirror T6AM" made by Toray Co., Ltd., with a thickness of 38μm, and a softening point of 130°C. , "Release PET").

Put each resin varnish on the release PET, apply it on the die coater so that the thickness of the resin composition layer after drying becomes 25μm, and dry it at 80℃~110℃ for 4 minutes, and then apply it on the release PET The resin composition layer is obtained. Next, on the surface that is not bonded with the release PET of the resin composition layer, as a protective film, a polypropylene film ("ALPHAN MA-430" manufactured by Oji Special Paper Co., Ltd., thickness 20μm) is bonded to the resin composition layer Way to laminate. Thereby, a smooth resin sheet composed of the release PET, the resin composition layer, and the protective film in this order is obtained.

<Measurement of the lowest melt viscosity of the resin composition layer>

The resin composition layer was peeled only from the mold-releasing PET and compressed with a mold to produce measurement pellets (diameter 18 mm, 1.2 g to 1.3 g). Using measurement pellets, using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM (stock)), and using a parallel plate with a diameter of 18 mm for 1 g of the sample resin composition, at a heating rate of 5°C/min from the starting temperature of 60°C The temperature was raised to 200°C, the dynamic viscoelasticity was measured under the measurement conditions of a measurement temperature interval of 2.5°C, a number of vibrations of 1 Hz, and a twist of 1 deg, and the lowest melt viscosity (poise) was calculated. The results are shown in the following table.

<Evaluation of part embedding>

Using the resin sheets produced in the Examples and Comparative Examples, the following procedures were followed to produce a circuit board with temporarily attached parts to evaluate the insertability of the parts.

(1) Preparation of the circuit board (hole board) for temporarily attaching parts

BT resin copper clad laminate on both sides of the glass cloth substrate (the thickness of copper foil is 18μm, the thickness of the substrate is 0.15mm, Mitsubishi Gas Chemical Co., Ltd. "HL832NSF LCA") 255mm×340mm, the overall size is 0.7mm×1.1mm The holes are formed at a pitch of 3mm. Next, both sides are etched with a micro-etching agent ("CZ8100" made by MEC (Stock)) for 1μm, the copper surface is roughened, and then anti-rust treatment ("CL8300" made by MEC (Stock)) is performed, and dried at 180°C. 30 minutes.

(2) Production of circuit board with temporarily attached parts

On one side of the substrate obtained in (1), a 25μm thick polyimide film with adhesive (polyimide 38μm thick, manufactured by Arisawa Manufacturing Co., Ltd., "PFDKE-1525TT") was used in batch vacuum The pressure laminator (Nichigo-Morton Co., Ltd. two-stage accumulation laminator "CVP700") is arranged so that the adhesive is bonded to the substrate and laminated on one side. After the lamination system was depressurized for 30 seconds to reduce the air pressure to 13 hPa or less, it was carried out by pressing it at 80°C and 0.74 MPa for 30 seconds. Secondly, the laminated ceramic capacitor parts (1005=1×0.5mm size, thickness 0.14mm) are temporarily fitted into the holes one by one to make temporary fittings The circuit board of the component (hole board).

(3) Evaluation test of part embedding

A batch-type vacuum pressure laminator (two-stage accumulation laminator "CVP700" manufactured by Nichigo-Morton Co., Ltd.) was used to join the resin composition exposed by peeling the protective film from the resin sheet produced in the Examples and Comparative Examples The material layer is laminated with the surface on the opposite side of the polyimide film arrangement surface of the adhesive-attached circuit substrate (hole substrate) of the temporarily attached parts produced in (2). After the lamination system was depressurized for 30 seconds to reduce the air pressure to 13 hPa or less, it was carried out by pressing it at 120° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was smoothed by hot stamping for 60 seconds under atmospheric pressure, 120° C., and pressure 0.5 MPa. The evaluation substrate A was prepared by peeling off the polyimide film with the adhesive from the circuit board of the temporarily attached part that was cooled to room temperature. From the surface of the polyimide film peeling off the evaluation substrate A, the resin flow in the hole was observed with an optical microscope (150 times) (for 10 holes), the insertability of the part was evaluated by the following criteria, and the results were shown In the following table.

(Assessment criteria)

Judged as

○: All the holes and the outer periphery of the laminated ceramic capacitor parts are coated with resin.

×: Even if there is a hole, a void occurs or the resin is not embedded in the outer periphery of the laminated ceramic capacitor part.

<Evaluation of the peel strength (peel strength), roughness (arithmetic mean roughness (Ra), root mean square roughness (Rq)), and plating penetration depth of the plated conductor layer>

Using the resin sheets produced in the Examples and Comparative Examples, measurement substrates B and C were produced in the following procedures, and the peel strength, roughness, and plating penetration depth were evaluated.

(1) Substrate treatment of laminates

The glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.3mm, Matsushita Electric Works Co., Ltd. R5715ES) is applied to both sides of the MEC (stock) roughening treatment agent (CZ8100) , Both sides were etched with a micro-etchant ("CZ8100" manufactured by MEC (Stock)) for 1 μm, and the copper surface was roughened.

(2) Laminating of resin flakes

The protective film was peeled off from the resin sheet produced in the Examples and Comparative Examples, and the exposed resin composition layer was used a batch-type vacuum pressure laminator ((stock) Nichigo-Morton two-stage accumulation laminator "CVP700" ), laminated on both sides of the substrate such that the resin composition layer is bonded to the substrate. The lamination is carried out by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing at 110°C and 0.74 MPa for 30 seconds. Next, the laminated resin sheet was smoothed by hot stamping for 60 seconds under atmospheric pressure, 120° C., and pressure 0.5 MPa.

(3) Thermal curing of resin composition layer

After the lamination of the resin sheets, the resin composition layer is thermally cured (at 100°C for 30 minutes, followed by 175°C for 30 minutes) to form insulating layers on both sides of the substrate. At this time, regarding Examples 1, 2 and Comparative Examples 1, 2, and 4, the resin composition layer was thermally cured in a state of mold-releasing PET with a support. Regarding Example 3 and Comparative Example 3, after peeling off the mold release PET that is the support, the resin composition was thermally cured.

(4) Roughening treatment

The laminated board forming the insulating layer is immersed in the swelling liquid Swelling Dip Securiganth P (aqueous solution of glycol ethers and sodium hydroxide) containing Atotech Japan's diethylene glycol monobutyl ether, and immersed at 60°C for 5 minute. Next, as a roughening solution, immerse in Concentrate Compact P (KMnO ₄ : 60g/L, NaOH: 40g/L aqueous solution) of Atotech Japan (stock) at 80°C for 15 minutes (Example 2 and Comparative Example 2 are at 80°C Dipping for 20 minutes). Finally, as a neutralization solution, it was immersed in Reduction solution Securiganth P (aqueous solution of sulfuric acid) of Atotech Japan (stock) at 40°C for 5 minutes. After drying at 80°C for 30 minutes, this substrate is referred to as "evaluation substrate B".

(5) Plating by semi-additive method

The evaluation substrate B prepared in (4) was _{immersed in an electroless plating solution containing PdCl 2} at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. After heating at 150°C for 30 minutes and performing annealing treatment, an etching photoresist is formed. After pattern formation by etching, copper sulfate electrolytic plating is performed to form a conductor layer with a thickness of 30 μm. Next, an annealing treatment was performed at 190°C for 60 minutes, and the obtained substrate was designated as the evaluation substrate C.

(Measurement of Arithmetic Average Roughness (Ra), Root Mean Square Roughness (Rq))

For evaluation substrate B, use a non-contact surface roughness meter (WYKO NT3300 manufactured by Waco Instruments), use VSI contact mode, 50 times lens, and set the measurement range to 121μm×92μm. Calculate the value of Ra and Rq. Calculate the average of 10 points respectively. The results are shown in the following table.

(Measurement of peel strength)

Place a section with a width of 10mm and a length of 100mm on the conductor layer of the evaluation substrate C, peel off this end and hold it with a clamp ((strand) TSE, Autocom type tester AC-50C-SL), and at room temperature ( 25°C) The load (kgf/cm(N/cm)) when peeling 35mm in the vertical direction was measured at a speed of 50mm/min, and the results are shown in the following table.

(Measurement of plating penetration depth)

For evaluation substrate C, cross-sectional observation was performed using a FIB-SEM composite device (SII Nano Technology Co., Ltd. "SMI3050SE"). Detailed and In other words, the cross section in the direction perpendicular to the surface of the evaluation substrate C was cut out by FIB (Clustered Ion Beam), and a cross-sectional SEM image (observation width) near the interface between the plating and the roughened hardened body (insulating layer) 7.5μm, observation magnification×36000). For each sample, randomly selected 10 cross-sectional SEM images were obtained, and the maximum copper plating depth (μm) was measured.

<Evaluation of Flame Retardancy>

(1) Laminating of resin flakes

The resin composition layer exposed by peeling the protective film from the resin sheet produced in the Examples and Comparative Examples was performed using a batch-type vacuum pressure laminator (Nichigo-Morton Co., Ltd. two-stage accumulation laminator "CVP700" ), the resin composition layer and the laminate (no copper foil, substrate thickness 0.2mm, Hitachi Chemical Co., Ltd. 679FG) were bonded on both sides of the laminate. The lamination is carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was smoothed by hot stamping for 60 seconds under atmospheric pressure, 120° C., and pressure 0.5 MPa.

(2) Hardening of the resin composition layer

After the lamination of the resin sheet, the release PET of the support is peeled off, and the resin composition layer is thermally cured (90 minutes at 190°C) to form a cured product on both sides of the laminate.

(3) Flame retardant test

Implemented in accordance with UL-94V specifications. Cut the resulting laminate (thickness about 380μm) into a size of 12.7mm×127mm, cut it so that the edge becomes 1.27mm, and treat it in an oven at 70±1°C for 168 hours, and then cool it in a desiccator for more than 4 hours , And get the test piece.

The furnace was moved directly below the obtained test piece, and the flame was brought into contact with the flame at the center of the lower end of the test piece for 10 seconds, and the burning time after that was measured. Expose the flame again for 10 seconds, and measure the burning time after that. Repeat this 5 times and evaluate according to the following benchmarks.

(Assessment criteria)

V-0: The falling of the burning material does not burn the test piece completely, and the burning time of the test piece is less than 50 seconds

V-1: The falling of the burning material does not burn the test piece completely, and the burning time of the test piece is more than 50 seconds and less than 250 seconds

Not: Falling of the burning material, full burning of the test piece, or burning time of the test piece more than 250 seconds

Using the examples 1 to 3 of the resin composition containing the component (C), it is understood that the part embedding property, arithmetic mean roughness (Ra), root mean square roughness (Rq), peel strength, plating penetration depth, and resistance Excellent flammability.

Compared with Examples 1 to 3 in Comparative Example 1 using a siloxane-based coupling agent (KBM-403) by changing the component (C), it was found that it is easy to agglomerate. As a result, the lowest melt viscosity was increased to improve the embedding of parts. Deterioration, arithmetic average roughness (Ra), root mean square roughness (Rq), plating penetration depth, and flame retardancy are also degraded.

In Comparative Example 2 using an aminosilane coupling agent (KBM-903) for component (C), it is understood that the resin coupling of the amine group with component (A) reduces the plating penetration depth, but it increases the minimum melting point. Viscosity, the embedding of parts deteriorates. In addition, it is understood that the flame retardancy is also deteriorated compared with Examples 1 to 3.

In Comparative Example 3 using aluminum coupling agent (Plainact AL-M) by changing the component (C), it was learned that the arithmetic mean roughness (Ra) and root mean square roughness of the parts are good although the minimum melt viscosity is low. (Rq), plating penetration depth, and deterioration of flame retardancy.

For Comparative Example 4 where the component (C) is changed and the silane compound (KBM-103) is used, it is understood that the silane compound cannot be coupled with the resin such as the component (A) because it does not have a reactive group, thereby increasing the plating penetration depth. In addition, it is understood that compared with Examples 1 to 3, the arithmetic average roughness (Ra), root mean square roughness (Rq), plating penetration depth, and flame retardancy are also deteriorated.

Claims (15)

A resin composition containing (A) an epoxy resin composed of a liquid epoxy resin and a solid epoxy resin, (B) a hardener, (C) an alkoxysilane compound containing fluorine atoms, and ( D) Inorganic filler, the mass ratio of the liquid epoxy resin to the solid epoxy resin is 1:0.1 to 1:15. The resin composition of claim 1, wherein, when the non-volatile content in the resin composition is 100% by mass, the content of the component (D) is 60% by mass or more. The resin composition of claim 1, wherein the average particle size of the component (D) is 0.01 μm to 2 μm. Such as the resin composition of claim 1, wherein the component (D) is silica or alumina. Such as the resin composition of claim 1, wherein the number of fluorine atoms in one molecule of component (C) is 1-10. Such as the resin composition of claim 1, wherein the number of alkoxy groups in one molecule of component (C) is 1 to 5. The resin composition of claim 1, wherein the component (C) is 3,3,3-trifluoropropyltrimethoxysilane. The resin composition of claim 1, wherein the component (D) is surface-treated with the component (C). Such as the resin composition of claim 1, which is used for forming an insulating layer of a printed wiring board. Such as the resin composition of claim 1, which is used for the accumulation layer of a printed wiring board. A sheet-like laminate material, which contains the resin composition according to any one of claims 1 to 10. A sheet-like laminate material comprising a resin composition layer formed of the resin composition according to any one of claims 1 to 10. The sheet-like laminated material of claim 12, wherein the thickness of the resin composition layer is 10 μm or less. A printed wiring board comprising an insulating layer formed by a cured product of a resin composition as claimed in any one of claims 1 to 10. A semiconductor device including the printed wiring board as claimed in claim 14.

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