JP2017036377A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which provides a printed wiring board exhibiting good reflow behavior in a component mounting process even when the printed wiring board is thin, and to provide a sheet-like laminated material, a printed wiring board, and a semiconductor device containing the resin composition.SOLUTION: A resin composition contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler. The inorganic filler (C) has been surface-treated with at least one surface treatment agent selected from the group consisting of compounds represented by general formula (1): X-Y-Si(OR)and compounds represented by general formula (2): (RO)Si-Z-Si(OR). X represents a vinyl group or the like; Y represents a ≥4C alkylene group or the like; Rto Reach represent a 1-6C alkyl group or the like; and Z represents an alkylene group or the like.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. Furthermore, it is related with the sheet-like laminated material, the printed wiring board, and semiconductor device containing the said resin composition.

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

  For example, Patent Document 1 contains an epoxy resin, a curing agent, and an inorganic filler, the inorganic filler is surface-treated with aminoalkylsilane, and the nonvolatile component in the resin composition is 100% by mass The resin composition whose content of this inorganic filler is 55-90 mass% is described.

JP 2014-28880 A

  By the way, with the recent replacement from lead-containing solder to lead-free solder, the solder reflow temperature in the component mounting process by solder reflow is increasing. In recent years, the printed wiring board has been further reduced in thickness in order to achieve miniaturization of electronic devices, and the thickness of the inner substrate and the insulating layer tends to be gradually reduced. As the printed wiring board becomes thinner, it tends to be difficult to stabilize the reflow behavior.

  An object of the present invention is to provide a resin composition that provides a printed wiring board exhibiting good reflow behavior in a component mounting process even when the printed wiring board is thin, a sheet-like laminated material containing the resin composition, and a printed material An object is to provide a wiring board and a semiconductor device.

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

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
(C) The inorganic filler is surface-treated with at least one surface treatment agent selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). Resin composition.
X—Y—Si (OR ¹ ) ₃ (1)
(In general formula (1), X is a vinyl group, an epoxy group, a glycidyl ether group, a methacryloyl group, a methacryloyloxy group, an acryloyl group, an acryloyloxy group, an amino group, Ar— (NR) _n — (CH ₂ ) _{m. -, Ar- (CH 2) m} - (NR) n -, or _{NH 2 - (CH 2) m} - (NR) n - represents, Ar represents a phenyl group which may have a substituent, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 6, n represents an integer of 0 or 1, and Y may have a substituent. Represents an alkylene group having 4 or more carbon atoms, or an alkenylene group having 4 or more carbon atoms which may have a substituent, and R ¹ represents 1 to 6 carbon atoms which may have a substituent. A plurality of R ¹ may be the same And may be different.)
(R ² O) ₃ Si—Z—Si (OR ³ ) ₃ (2)
(Z represents an alkylene group which may have a substituent, —NR—, an oxygen atom, a sulfur atom, or a group consisting of a combination of two or more thereof, and R is a hydrogen atom or a carbon atom having 1 carbon atom. Represents an alkyl group of ˜3, R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ² and R ³ are the same. Or it may be different.)
[2] The resin composition according to [1], wherein Y in the general formula (1) represents an alkylene group having 6 or more carbon atoms which may have a substituent.
[3] Z in General Formula (2) is an alkylene group having 6 or more carbon atoms which may have a substituent, or a combination of an alkylene group which may have a substituent and —NR—. The resin composition according to [1] or [2], which represents a group consisting of:
[4] The resin composition according to any one of [1] to [3], wherein R ^{1 in} the general formula (1), R ² and R ³ in the general formula (2) each represents a methyl group or an ethyl group. object.
[5] The compound represented by the general formula (1) is 8-glycidoxyoctyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, N-phenyl-8-aminooctyl- One of trimethoxysilane, 3- (2-glycidylphenyl) propyltrimethoxysilane, 6-vinylhexyltrimethoxysilane, and 8-methacryloyloxyoctyltrimethoxysilane, which is represented by the general formula (2) The resin composition according to any one of [1] to [4], wherein is any one of bistrimethoxysilylhexane, bistrimethoxysilyloctane, and bis (trimethoxysilylpropyl) ethylenediamine.
[6] The resin composition according to any one of [1] to [5], wherein the average particle size of the component (C) is 0.01 μm to 5 μm.
[7] The resin composition according to any one of [1] to [6], wherein the component (C) is silica.
[8] The resin composition according to any one of [1] to [7], wherein the content of the component (C) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass. .
[9] The component (C) is surface-treated with 0.2 to 2 parts by mass of a surface treatment agent with respect to 100 parts by mass of the component (C), according to any one of [1] to [8] The resin composition as described.
[10] (C) a carbon amount per unit surface area of the component is at ^{0.05mg / m 2 ~1mg / m 2} , [1] ~ resin composition according to any one of [9].
[11] The resin according to any one of [1] to [10], wherein the component (A) is at least one selected from a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a biphenyl type epoxy resin. Composition.
[12] Any of [1] to [11], wherein the component (B) is at least one selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent, and a cyanate ester curing agent. The resin composition described in 1.
[13] The resin composition according to any one of [1] to [12], which is used for forming an insulating layer of a printed wiring board.
[14] The resin composition according to any one of [1] to [13], which is for forming a buildup layer of a printed wiring board.
[15] A sheet-shaped laminated material including a resin composition layer formed of the resin composition according to any one of [1] to [14].
[16] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [14].
[17] The printed wiring board according to [16], wherein the amount of warping of the insulating layer is 350 μm or less.
[18] A semiconductor device comprising the printed wiring board according to [16] or [17].

  According to the present invention, even when the printed wiring board is thin, a resin composition that provides a printed wiring board that exhibits good reflow behavior in a component mounting process, a sheet-like laminated material containing the resin composition, and a print A wiring board and a semiconductor device can be provided.

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

  In the present specification, the term “which may have a substituent” attached immediately before a group means that the hydrogen atom of the group is not substituted with a substituent, and the hydrogen atom of the group It means both when a part or all of is substituted with a substituent.

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

[Resin composition]
The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and (C) the inorganic filler is represented by the following general formula (1) ) And at least one surface treatment agent selected from the group consisting of compounds represented by the following general formula (2).
X—Y—Si (OR ¹ ) ₃ (1)
(In general formula (1), X is a vinyl group, an epoxy group, a glycidyl ether group, a methacryloyl group, a methacryloyloxy group, an acryloyl group, an acryloyloxy group, an amino group, Ar— (NR) _n — (CH ₂ ) _{m. -, Ar- (CH 2) m} - (NR) n -, or _{NH 2 - (CH 2) m} - (NR) n - represents, Ar represents a phenyl group which may have a substituent, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 6, n represents an integer of 0 or 1, and Y may have a substituent. Represents an alkylene group having 4 or more carbon atoms, or an alkenylene group having 4 or more carbon atoms which may have a substituent, and R ¹ represents 1 to 6 carbon atoms which may have a substituent. A plurality of R ¹ may be the same And may be different.)
(R ² O) ₃ Si—Z—Si (OR ³ ) ₃ (2)
(Z represents an alkylene group which may have a substituent, —NR—, an oxygen atom, a sulfur atom, or a group consisting of a combination of two or more thereof, and R is a hydrogen atom or a carbon atom having 1 carbon atom. Represents an alkyl group of ˜3, R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ² and R ³ are the same. Or it may be different.)

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

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

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, Phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring Epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. The component (A) is preferably at least one selected from bisphenol A type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, phenol novolac type epoxy resins, and alicyclic epoxy resins having an ester skeleton. And epoxy resins having a butadiene structure are preferred, and bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins and naphthalene type epoxy resins are more preferred. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL” (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), “jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “YL7760” (bisphenol AF type epoxy resin), “ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ( Bisphenol A type epoxy resin and bisphenol F type epoxy resin mixture), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” (ester structure) manufactured by Daicel Corporation Alicyclic Epoxy with Resin), "PB-3600" (epoxy resin having a butadiene structure), Nippon Steel Chemical Co., Ltd. "ZX1658", "ZX1658GS" (liquid 1,4 glycidyl cyclohexane) and the like. These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” manufactured by DIC Corporation. "(Cresol novolac type epoxy resin)", "N-695" (Cresol novolac type epoxy resin), "HP-7200" (Dicyclopentadiene type epoxy resin), "HP-7200HH", "EXA7311", "EXA7311-G3 ”,“ EXA7311-G4 ”,“ EXA7311-G4S ”,“ HP6000 ”(naphthylene ether type epoxy resin),“ EPPN-502H ”(trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.,“ NC7000L ” (Naphthol novolac type epoxy resin), “NC3000 ”,“ NC3000 ”,“ NC3000L ”,“ NC3100 ”(biphenyl type epoxy resin),“ ESN475V ”(naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.,“ ESN485 ”(naphthol novolak type epoxy resin), Mitsubishi “YX4000H”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin) manufactured by Kagaku Co., Ltd., “ “PG-100”, “CG-500”, “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1010” (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “jER1031S” (Tetraphenylethane type epoxy resin) And the like.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 6 by mass ratio. preferable. By making the quantitative ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is provided when used in the form of an adhesive film, ii) when used in the form of an adhesive film Sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1: 5 by mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 4 is more preferable.

  The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. That's it. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

  In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and can provide an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

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

  The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and Examples thereof include carbodiimide curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. The component (B) is preferably at least one selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent and a cyanate ester curing agent.

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

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” manufactured by Nippon Steel & Sumikin Co., Ltd. “LA7052”, “LA7054”, “LA3018”, “EXB-9500” manufactured by DIC Corporation, and the like.

  From the viewpoint of obtaining an insulating layer having a small surface roughness after the roughening treatment and obtaining an insulating layer having excellent adhesion to the conductor layer, an active ester curing agent is also preferred. Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between 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 obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. 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 the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  As a commercial product of an active ester type curing agent, as an active ester compound containing a dicyclopentadiene type diphenol structure, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (manufactured by DIC Corporation) ), “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, and benzoyl of phenol novolac Examples of the active ester compound containing a compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins), “BA230”, “BA230S75” (bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. For example, a prepolymer partially or wholly converted into a trimer).

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

  The amount ratio between the epoxy resin and the curing agent is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] in the range of 1: 0.1 to 1: 2. 1: 0.15 to 1: 1.5 are more preferable, and 1: 0.2 to 1: 1 are more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

  In one embodiment, the resin composition includes the aforementioned (A) epoxy resin and (B) a curing agent. The resin composition is a mixture of a liquid epoxy resin and a solid epoxy resin (A) as an epoxy resin (the mass ratio of liquid epoxy resin: solid epoxy resin is preferably 1: 0.1 to 1: 8, more preferably 1: 0.3-1: 7, more preferably 1: 0.6-1: 6), (B) a phenolic curing agent, a naphthol curing agent, an active ester curing agent and a cyanate ester One or more selected from the group consisting of curing agents (preferably one or more selected from the group consisting of phenolic curing agents, naphthol curing agents and active ester curing agents) are preferably included.

  Although content of the hardening | curing agent in a resin composition is not specifically limited, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 18 mass% or less. The lower limit is not particularly limited but is preferably 3% by mass or more.

<(C) Inorganic filler>
The resin composition of the present invention contains (C) an inorganic filler (hereinafter also referred to as (C) component), wherein the (C) component is a compound represented by the following general formula (1), and the following general formula: Surface treatment is performed with at least one surface treatment agent selected from the group consisting of compounds represented by (2).
X—Y—Si (OR ¹ ) ₃ (1)
(In general formula (1), X is a vinyl group, an epoxy group, a glycidyl ether group, a methacryloyl group, a methacryloyloxy group, an acryloyl group, an acryloyloxy group, an amino group, Ar— (NR) _n — (CH ₂ ) _{m. -, Ar- (CH 2) m} - (NR) n -, or _{NH 2 - (CH 2) m} - (NR) n - represents, Ar represents a phenyl group which may have a substituent, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 6, n represents an integer of 0 or 1, and Y may have a substituent. Represents an alkylene group having 4 or more carbon atoms, or an alkenylene group having 4 or more carbon atoms which may have a substituent, and R ¹ represents 1 to 6 carbon atoms which may have a substituent. A plurality of R ¹ may be the same And may be different.)
(R ² O) ₃ Si—Z—Si (OR ³ ) ₃ (2)
(Z represents an alkylene group which may have a substituent, —NR—, an oxygen atom, a sulfur atom, or a group consisting of a combination of two or more thereof, and R is a hydrogen atom or a carbon atom having 1 carbon atom. Represents an alkyl group of ˜3, R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ² and R ³ are the same. Or it may be different.)

  The component (C) in the present invention is surface-treated with at least one surface treatment agent selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2). Yes. As a result of diligent research by the present inventors, a divalent group (general) that bonds a silicon atom and a functional group site (X in the general formula (1)) as in the compound represented by the general formula (1). When the inorganic filler is surface-treated with a compound in which the main chain of Y) in formula (1) is a long chain, the amount of warpage during reflow of the insulating layer formed by the cured product of the resin composition (maximum variation in reflow behavior) It was found that can be reduced. Further, it has been found that by subjecting the inorganic filler to the surface treatment with the above compound, the minimum melt viscosity is lowered and good circuit embedding property is obtained. In addition, the inventors of the present invention have a divalent group (Z in the general formula (2) which is bonded to each silicon atom in a compound having silicon atoms at both ends, such as a compound represented by the general formula (2). It has been found that the same effect can be obtained even when the inorganic filler is surface-treated with a compound having a long chain as the main chain.

  In the present specification, unless otherwise specified, the component (C) represents an inorganic filler surface-treated with a surface treatment agent.

  The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less, from the viewpoint of obtaining an insulating layer having a small surface roughness and improving the fine wiring formability. Or it is 1 micrometer or less. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.1 micrometer or more, More preferably, it is 0.3 micrometer or more. Examples of commercially available inorganic fillers having such an average particle size include, for example, “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C” manufactured by Admatechs, manufactured by Denki Kagaku Kogyo Co., Ltd. “UFP-30”, “Silfil NSS-3N”, “Silfil NSS-4N”, “Sylfil NSS-5N” manufactured by Tokuyama Corporation, “SC2500SQ”, “SO-C2”, “SO-C2” manufactured by Admatechs Co., Ltd. -C1 "and the like.

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. or the like can be used.

  As the surface treatment agent, the compound represented by the general formula (1) or the compound represented by the general formula (2) may be used alone, the compound represented by the general formula (1), and the general You may use combining the compound represented by Formula (2).

The compound represented by the general formula (1) has the following structure.
X—Y—Si (OR ¹ ) ₃ (1)
(In general formula (1), X is a vinyl group, an epoxy group, a glycidyl ether group, a methacryloyl group, a methacryloyloxy group, an acryloyl group, an acryloyloxy group, an amino group, Ar— (NR) _n — (CH ₂ ) _{m. -, Ar- (CH 2) m} - (NR) n -, or _{NH 2 - (CH 2) m} - (NR) n - represents, Ar represents a phenyl group which may have a substituent, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 6, n represents an integer of 0 or 1, and Y may have a substituent. Represents an alkylene group having 4 or more carbon atoms, or an alkenylene group having 4 or more carbon atoms which may have a substituent, and R ¹ represents 1 to 6 carbon atoms which may have a substituent. A plurality of R ¹ may be the same And may be different.)

X is a vinyl group, an epoxy group, a glycidyl ether group, a methacryloyl group, a methacryloyloxy group, an acryloyl group, an acryloyloxy group, an amino group, Ar— (NR) _n — (CH ₂ ) _m —, Ar— (CH ₂ ). _m - _{(NR) n} -, or _{NH 2 - (CH 2) m} - (NR) n - represents a.

Ar represents a phenyl group which may have a substituent. The substituent which the phenyl group may have will be described later.
m represents an integer of 0 to 6, an integer of 1 to 4 is preferable, and an integer of 1 to 3 is more preferable. n represents an integer of 0 or 1, and 1 is preferable.

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

Ar— (NR) _n — (CH ₂ ) _m —, Ar— (CH ₂ ) _m — (NR) _n —, or NH ₂ — (CH ₂ ) _m — (NR) _n — includes, for example, aminoethylene An amino group, a benzylamino group, a phenylamino group, etc. are mentioned.

  Among these, X is preferably a vinyl group, an epoxy group, a glycidyl ether group, a methacryloyloxy group, an aminoethyleneamino group, or a phenylamino group, and an epoxy group, a glycidyl ether group, a methacryloyloxy group, an aminoethyleneamino group, phenyl. An amino group is more preferable.

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

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

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

  The phenyl group represented by Ar, the alkylene group having 4 or more carbon atoms and the alkenylene group having 4 or more carbon atoms represented by Y may have a substituent. The substituent is not particularly limited, and examples thereof include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, alkoxy groups, cycloalkyloxy groups, aryl groups, aryloxy groups, arylalkyl groups, arylalkoxy groups, monovalent groups. And heterocyclic groups, alkylidene groups, amino groups, silyl groups, acyl groups, acyloxy groups, carboxy groups, sulfo groups, cyano groups, nitro groups, hydroxy groups, mercapto groups, oxo groups, and the like. A plurality of substituents may be present, and the plurality of substituents may be bonded to each other to form a ring.

  Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

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

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

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

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

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

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

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

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

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

  The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from a heterocyclic ring of a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3-21, more preferably 3-15, and still more preferably 3-9. The monovalent heterocyclic group includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocyclic ring include thienyl group, pyrrolyl group, furanyl group, furyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, quinolyl group, and isoquinolyl group. Is mentioned.

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

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

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

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

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

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

  Specific examples of the compound represented by the general formula (1) include 8-glycidoxyoctyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, and N-phenyl-8-amino. Examples include octyl-trimethoxysilane, 3- (2-glycidylphenyl) propyltrimethoxysilane, 6-vinylhexyltrimethoxysilane, and 8-methacryloyloxyoctyltrimethoxysilane, but the present invention is not limited to these. It is not something.

The compound represented by the general formula (2) has the following structure.
(R ² O) ₃ Si—Z—Si (OR ³ ) ₃ (2)
(Z represents an alkylene group which may have a substituent, —NR—, an oxygen atom, a sulfur atom, or a group consisting of a combination of two or more thereof, and R is a hydrogen atom or a carbon atom having 1 carbon atom. Represents an alkyl group of ˜3, R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ² and R ³ are the same. Or it may be different.)

  Z represents an alkylene group which may have a substituent, -NR-, an oxygen atom, a sulfur atom, or a group consisting of a combination of two or more thereof, and R represents a hydrogen atom or a carbon atom number of 1 to Represents an alkyl group of 3; The main chain of Z is preferably a long chain, and the number of atoms constituting the main chain (the number of main chain atoms between silicon atoms at both ends) is preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more. Although it does not specifically limit about an upper limit, Preferably it is 20 or less, More preferably, it is 15 or less, More preferably, it is 10 or less, or 9 or less. When the number of atoms constituting the main chain is less than 4, the amount of warping of the insulating layer formed by the cured product of the resin composition becomes large at the time of reflow, the minimum melt viscosity becomes high, and the circuit embedding property becomes poor. There is a case. The atom constituting the main chain of Z represents a carbon atom of the main chain of the alkylene group, a nitrogen atom of -NR-, an oxygen atom, and a sulfur atom.

  When Z represents an alkylene group which may have a substituent, the number of carbon atoms of the alkylene group which may have a substituent is preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more. Although it does not specifically limit about an upper limit, Preferably it is 20 or less, More preferably, it is 15 or less, More preferably, it is 10 or less, or 9 or less. Specific examples and preferred ranges of the alkylene group are the same as those of the alkylene group having 4 or more carbon atoms represented by Y in the general formula (1).

  When Z represents a group consisting of the above two or more combinations, the number of carbon atoms of the alkylene group constituting the group consisting of two or more combinations is preferably 1 to 10, more preferably 1 to 6, and even more preferably. 1-3. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. A methylene group, an ethylene group, and a propylene group are preferable, and an ethylene group and a propylene group are preferable. . The alkylene group which may have a substituent may be linear or branched.

＊は結合手を表す。 Examples of the group consisting of two or more combinations include those in which an alkylene group which may have a substituent and -NR- are bonded, an alkylene group which may have a plurality of substituents, and a plurality of -NR-. In which an alkylene group which may have a substituent and an oxygen atom are bonded, an alkylene group which may have a substituent and a sulfur atom are bonded, etc. An alkylene group which may have a group and -NR- are bonded, or an alkylene group which may have a plurality of substituents and a plurality of -NR- are bonded alternately, that is, has a substituent. The group which consists of the combination of the alkylene group which may be made, and -NR- is preferable. Specific examples of the group consisting of the above two or more combinations include the following groups, but the present invention is not limited thereto.

* Represents a bond.

  R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R is synonymous with R of General formula (1), and its preferable range is also the same.

R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms that may have a substituent, and a plurality of R ² and R ³ may be the same or different. Good. R ² and R ³ have the same meaning as R ^{1 in the} general formula (1), and the preferred range is also the same.

  Specific examples of the compound represented by the general formula (2) include bistrimethoxysilylhexane, bistrimethoxysilyloctane, and bis (trimethoxysilylpropyl) ethylenediamine, but the present invention is limited to these. It is not a thing.

  A commercial item may be used for the compound represented by General formula (1), and the compound represented by General formula (2), and you may synthesize | combine using a well-known synthesis method.

  The degree of the surface treatment with the surface treatment agent is 0.2 to 2 parts by mass of the surface treatment agent with respect to 100 parts by mass of component (C) from the viewpoint of improving the dispersibility of the inorganic filler. The surface treatment is preferably performed at 0.2 parts by mass to 1 part by mass, and preferably at 0.3 parts by mass to 0.8 parts by mass.

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

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

  In addition to the surface treatment agent selected from the group consisting of the compound represented by the general formula (1) and the compound represented by the general formula (2), the inorganic filler is further surface-treated with another surface treatment agent. It may be. Examples of other surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, and titanate coupling agents. Examples of such commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM803” (3 manufactured by Shin-Etsu Chemical Co., Ltd.). -Mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBE903” (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) ), “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  The content of the inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more from the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion. 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, still more preferably 85% by mass or less, and 80% by mass from the viewpoint of the mechanical strength of the insulating layer. Or 75% by mass or less.

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

  Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resins and polyester resins, and phenoxy resins are preferred. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

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

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, “YL7769BH30”, “YL6794”, “YL7213”, “YL7290”, “YL7482” and the like.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, and “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd. Sekisui Chemical Co., Ltd.'s S-REC BH series, BX series, KS series, BL series, BM series and the like.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

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

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  Of these, phenoxy resin and polyvinyl acetal resin are preferable as the thermoplastic resin. Therefore, in one suitable embodiment, (D) component contains 1 or more types selected from the group which consists of a phenoxy resin and polyvinyl acetal resin.

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

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

  Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, phosphorus-based curing accelerators, amine-based curing accelerators, and imidazole-based accelerators. A curing accelerator is preferable, and an amine-based curing accelerator and an imidazole-based curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

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

  Examples of the imidazole curing accelerator include 2-methylimidazole, 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-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-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-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Examples include imidazole compounds such as 3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2-phenyl. Imidazole is preferred.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 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- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  The content of the curing accelerator in the resin composition is not particularly limited, but when the total amount of the nonvolatile components of the epoxy resin and the curing agent is 100% by mass, it should be used in the range of 0.05% by mass to 3% by mass. Is preferred.

<(F) Flame retardant>
The resin composition of the present invention may contain a flame retardant (hereinafter also referred to as component (F)). Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  Commercially available products may be used as the flame retardant, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd.

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

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

  As the rubber particles, commercially available products may be used. Examples thereof include “EXL-2655” manufactured by Dow Chemical Japan Co., Ltd., “AC3816N” manufactured by Ganz Kasei Co., Ltd., and the like.

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

  The resin composition may further contain other additives as necessary. Examples of such other additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, Acrylate resin (for example, (ACA) Z251 manufactured by Daicel Ornex Co., Ltd., light acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.), phosphine oxide compound (for example, I819 manufactured by BASF Japan Ltd.), etc. Examples thereof include resin additives such as a sticking agent, an antifoaming agent, a leveling agent, an adhesion imparting agent, and a coloring agent.

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

[Sheet laminated material]
The resin composition of the present invention can be used by being applied in a varnish state, but industrially generally, it is used in the form of a sheet-like laminate material including a resin composition layer formed of the resin composition. Is preferred.

  As the sheet-like laminated material, the following adhesive films and prepregs are preferable.

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

  The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and even more preferably 50 μm or less or 40 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more, etc.

  Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

  The support may be subjected to mat treatment or corona treatment on the surface to be bonded to the resin composition layer.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. , “AL-5”, “AL-7”, “Lumirror T6AM” manufactured by Toray Industries, Inc., and the like.

  Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  For the adhesive film, for example, a resin varnish obtained by dissolving a resin composition in an organic solvent is prepared, and this resin varnish is applied onto a support using a die coater or the like, and further dried to form a resin composition layer. Can be manufactured.

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

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

  In the adhesive film, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can be stored in a roll. When an adhesive film has a protective film, it can be used by peeling off the protective film.

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

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and even more preferably 20 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it is 10 micrometers or more.

  The prepreg can be produced by a known method such as a hot melt method or a solvent method.

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

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

  The minimum melt viscosity of the resin composition layer refers to the minimum viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, the melt viscosity decreases in the initial stage as the temperature rises, and then exceeds a certain level, the melt viscosity increases as the temperature rises. To do. The minimum melt viscosity refers to the melt viscosity at such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method, and can be measured, for example, according to the method described in <Measurement of minimum melt viscosity> described later.

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

For example, the printed wiring board of the present invention can be produced by a method including the following steps (I) and (II) using the above-mentioned adhesive film.
(I) A step of laminating an adhesive film on an inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate (II) A step of thermosetting the resin composition layer to form an insulating layer

  The “inner layer substrate” used in step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is further formed is also included in the “inner layer board” in the present invention. When the printed wiring board is a component built-in circuit board, an inner layer board with built-in components may be used.

  Lamination | stacking of an inner layer board | substrate and an adhesive film can be performed by heat-pressing an adhesive film to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the adhesive film to the inner layer substrate (hereinafter also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll). In addition, it is preferable not to press the thermocompression bonding member directly on the adhesive film but to press it through an elastic material such as heat resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the inner layer substrate.

  Lamination of the inner layer substrate and the adhesive film may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

  After lamination, the laminated adhesive film may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

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

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

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

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

  When manufacturing a printed wiring board, you may further implement (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V).

  Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  In one embodiment, the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, further preferably 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less. It is. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments is cited.

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

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

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

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.

  In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

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

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

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

[Semiconductor device]
A 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 the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified. In the structural formula, Me represents a methyl group.

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

[Measurement of maximum reflow behavior variation]
(1) Preparation of measurement substrate sample Glass cloth base epoxy resin double-sided copper-clad laminate with inner layer circuit (copper foil thickness 3 μm, substrate thickness 0.1 mm, manufactured by Hitachi Chemical Co., Ltd., MCL-E- 770G) on one side of the adhesive film (film thickness 40 μm) produced in the examples and comparative examples, using a batch type vacuum pressure laminator (manufactured by Meiki Seisakusho, product name MLVP-500), an inner layer circuit board Laminated on both sides. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at 100 ° C. and a pressure of 0.74 MPa.

(2) Curing of sample A glass cloth base epoxy resin double-sided copper-clad laminate obtained by pressing the adhesive films prepared in Examples and Comparative Examples on one side was fixed at the four sides with a jig for 90 minutes at 200 ° C. in an oven. Cured and removed.

(3) Measurement of reflow behavior maximum variation (μm) A sample adjusted for measurement was cut into a 2 cm square, and a warp measurement analysis system (AKMORITRIX, Thermoray AXP) was used with an inner center 1.0 cm square as the measurement range. The maximum reflow behavior variation was measured. The heating rate is 0.67 ° C./sec. After the temperature is raised from 30 ° C. to 260 ° C., the process of releasing heat and returning to 30 ° C. is performed twice, and the maximum value of the warping behavior of the sample during the second measurement The difference between the minimum values was calculated and expressed as the maximum reflow behavior variation (μm).

[Measurement of minimum melt viscosity]
The thermosetting resin composition layers of the adhesive films prepared in Examples and Comparative Examples were subjected to dynamic viscoelasticity using a dynamic viscoelasticity measuring apparatus (“Rhesol-G3000” manufactured by UBM). It was measured. The measurement was performed from a starting temperature of 60 ° C. at a heating rate of 5 ° C./minute, a measurement interval temperature of 2.5 ° C., and a frequency of 1 Hz / deg.

[Calculation of carbon amount per unit surface area]
3 g of each of the following inorganic fillers was used as a sample. The sample and 30 g of MEK (methyl ethyl ketone) were placed in a centrifuge tube, stirred to suspend the solid content, and irradiated with 500 W ultrasonic waves for 5 minutes. Thereafter, solid-liquid separation was performed by centrifugation, and 20 g of the supernatant was removed. Furthermore, 20 g of MEK was added, the solid content was suspended by stirring, and 500 W ultrasonic waves were irradiated for 5 minutes. Thereafter, solid-liquid separation was performed by centrifugation, and 26 g of the supernatant was removed. The remaining suspension was dried at 160 ° C. for 30 minutes. 0.3 g of this dried sample was accurately weighed in a measuring crucible, and a combustion aid (3.0 g of tungsten and 0.3 g of tin) was further placed in the measuring crucible. The measuring crucible was set in a carbon analyzer (“EMIA-321V2” manufactured by Horiba, Ltd.), and the amount of carbon was measured. The amount of carbon per unit surface area was calculated by dividing the measured amount of carbon by the specific surface area of the inorganic filler used.

<Used inorganic filler>
Inorganic filler 1: 8-glycidoxyoctyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) represented by the following structural formula with respect to 100 parts of spherical silica (“SC2500SQ” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) The product surface-treated with 0.6 part by molecular weight 306.2. The amount of carbon per unit area was 0.33 mg / m ² .

Inorganic filler 2: N-2- (aminoethyl) -8-aminooctyl represented by the following structural formula with respect to 100 parts of spherical silica (“SC2500SQ” manufactured by Admatechs Co., Ltd., average particle size: 0.5 μm) Surface treatment with 0.6 parts of trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 291.2). The amount of carbon per unit area was 0.27 mg / m ² .

Inorganic filler 3: bistrimethoxysilylhexane (manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following structural formula with respect to 100 parts of spherical silica (“SC2500SQ” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm), Molecular weight 326.2) Surface-treated with 0.6 part. The amount of carbon per unit area was 0.28 mg / m ² .

Inorganic filler 4: bistrimethoxysilyloctane (Shin-Etsu Chemical Co., Ltd.) represented by the following structural formula with respect to 100 parts of spherical silica (“SC2500SQ” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) Molecular weight 354.2) Surface-treated with 0.6 part. The amount of carbon per unit area was 0.28 mg / m ² .

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

Inorganic filler 6: N-phenyl-8-aminooctyl-trimethoxysilane represented by the following structural formula with respect to 100 parts of spherical silica (“SC2500SQ” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) ( Surface treatment with 0.6 part of Shin-Etsu Chemical Co., Ltd., molecular weight 325.2). The amount of carbon per unit area was 0.33 mg / m ² .

Inorganic filler 7: 3- (2-glycidylphenyl) propyltrimethoxysilane represented by the following structural formula with respect to 100 parts of spherical silica (“SC2500SQ” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) ( Surface treatment with 0.6 part manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 312.1). The amount of carbon per unit area was 0.28 mg / m ² .

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

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

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

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

Inorganic filler 12: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM503” with respect to 100 parts of spherical silica (“SC2500SQ” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm)) “Surface treatment with a molecular weight of 248.4) 0.6 parts. The amount of carbon per unit area was 0.22 mg / m ² .

[Example 1]
14 parts of bixylenol type epoxy resin (epoxy equivalent 190, “YX4000HK” manufactured by Mitsubishi Chemical Corporation), liquid bisphenol type epoxy resin (epoxy equivalent of about 165, “ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), bisphenol A type and bisphenol F type 1: 1 mixed product) 12 parts, biphenyl type epoxy resin (epoxy equivalent 269, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.) is dissolved in 30 parts of solvent naphtha with stirring, and then brought to room temperature. Until cooled. Into the mixed solution, 0.5 part of rubber particles (manufactured by Ganz Kasei Co., Ltd., AC3816N) was mixed in 6 parts of solvent naphtha for 12 hours at 20 ° C., and 150 parts of inorganic filler 1 were mixed. Flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 1 μm) Two parts were added and kneaded and dispersed with three rolls. Thereto, 14 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution having a non-volatile content of 65% by mass with an active group equivalent of about 223), a phenol novolac curing agent containing a triazine skeleton (DIC) 10 parts 2-methoxypropanol solution of 50% solid content of “LA3018-50P” (hydroxyl equivalent: 151) manufactured by Co., Ltd., phenoxy resin (weight average molecular weight: 35000, “YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd .: 30% by mass 15 parts of MEK and cyclohexanone (1: 1 solution) and 2 parts of a 5% by weight MEK solution of 4-dimethylaminopyridine (DMAP) as a curing accelerator are mixed and uniformly dispersed with a rotary mixer to obtain a resin varnish. Produced. Next, the resin composition layer after drying the resin varnish on the release surface of a polyethylene terephthalate film with an alkyd release treatment (“AL-5” manufactured by Lintec Corporation, thickness 38 μm) has a thickness of 40 μm. Then, it was uniformly coated with a die coater so as to be dried at 80 to 110 ° C. (average 95 ° C.) for 5 minutes to obtain an adhesive film.

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

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

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

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

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

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

[Example 8]
10 parts of naphthalene type epoxy resin (“HP4032SS” manufactured by DIC Corporation), liquid bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type) 10 Parts, 20 parts of naphthol type epoxy resin (“ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd.), phenoxy resin (weight average molecular weight 35000, “YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd.), MEK with 30% by mass of nonvolatile components, 15 parts of a cyclohexanone (1: 1 solution) was dissolved in 50 parts of solvent naphtha with stirring and then cooled to room temperature. Next, 12 parts of active ester compound (DIC Corporation "HPC8000-65T", active ester equivalent 223, solid content 65% toluene solution), bisphenol A dicyanate prepolymer (Lonza Japan Co., Ltd. "BA230S75", 12 parts of a cyanate equivalent of about 232, a MEK solution having a nonvolatile content of 75% by mass), a phenol novolac type polyfunctional cyanate ester resin (“PT30S” manufactured by Lonza Japan Co., Ltd., a cyanate equivalent of about 133%, a MEK solution having a nonvolatile content of 85% by mass) 6 parts, 0.5 parts of rubber particles (manufactured by Ganz Kasei Co., Ltd., Staphyloid AC3816N) swollen in 5 parts of solvent naphtha at room temperature for 12 hours, 150 parts of inorganic filler 7, flame retardant (Sanko "HCA-HQ", 10- (2,5-dihydroxyphenyl) -1 manufactured by 2 parts of hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 1 μm) and 2 parts of a curing accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 5% by mass) were added. The resin varnish was prepared by uniformly dispersing with a rotary mixer. Next, an adhesive film was obtained in the same manner as in Example 1.

[Example 9]
36 parts of acid group-containing acrylate resin ("(ACA) Z251" manufactured by Daicel Ornex Co., Ltd., weight average molecular weight 14000, resin acid value 66 mgKOH / g, dipropylene glycol monomethyl ether solution having a solid content of 45% by mass), liquid 1, 4-glycidylcyclohexane (“ZX1658GS” manufactured by Nippon Steel Chemical Co., Ltd.), 6 parts of liquid bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Co., Ltd.), dimethylol tricyclodecane diacrylate (Kyoeisha Chemical) 5 parts of “Light Acrylate DCP-A” manufactured by Co., Ltd. was dissolved in 16 parts of solvent naphtha with stirring and then cooled to room temperature. Next, 80 parts of inorganic filler 8 and 5 parts of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide ("I819" manufactured by BASF Japan Ltd., MEK solution with a solid content of 15%) are added and rotated. A resin varnish was prepared by uniformly dispersing with a mixer. Next, an adhesive film was obtained in the same manner as in Example 1.

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

[Comparative Example 2]
A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 10 in Example 1.

[Comparative Example 3]
A resin varnish and an adhesive film were obtained in the same manner as in Example 1 except that the inorganic filler 1 was changed to the inorganic filler 11 in Example 1.

[Comparative Example 4]
A resin varnish and an adhesive film were obtained in the same manner as in Example 8 except that the inorganic filler 6 was changed to the inorganic filler 11 in Example 8.

[Comparative Example 5]
A resin varnish and an adhesive film were obtained in the same manner as in Example 9 except that the inorganic filler 8 was changed to the inorganic filler 12 in Example 9.

Claims (18)

(A) an epoxy resin, (B) a curing agent, and (C) a resin composition containing an inorganic filler,
(C) The inorganic filler is surface-treated with at least one surface treatment agent selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). Resin composition.
X—Y—Si (OR ¹ ) ₃ (1)
(In general formula (1), X is a vinyl group, an epoxy group, a glycidyl ether group, a methacryloyl group, a methacryloyloxy group, an acryloyl group, an acryloyloxy group, an amino group, Ar— (NR) _n — (CH ₂ ) _{m. -, Ar- (CH 2) m} - (NR) n -, or _{NH 2 - (CH 2) m} - (NR) n - represents, Ar represents a phenyl group which may have a substituent, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, m represents an integer of 0 to 6, n represents an integer of 0 or 1, and Y may have a substituent. Represents an alkylene group having 4 or more carbon atoms, or an alkenylene group having 4 or more carbon atoms which may have a substituent, and R ¹ represents 1 to 6 carbon atoms which may have a substituent. A plurality of R ¹ may be the same And may be different.)
(R ² O) ₃ Si—Z—Si (OR ³ ) ₃ (2)
(Z represents an alkylene group which may have a substituent, —NR—, an oxygen atom, a sulfur atom, or a group consisting of a combination of two or more thereof, and R is a hydrogen atom or a carbon atom having 1 carbon atom. Represents an alkyl group of ˜3, R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms which may have a substituent, and a plurality of R ² and R ³ are the same. Or it may be different.)   The resin composition according to claim 1, wherein Y in the general formula (1) represents an alkylene group having 6 or more carbon atoms which may have a substituent.   Z in the general formula (2) is an alkylene group having 6 or more carbon atoms which may have a substituent, or a group consisting of a combination of an alkylene group which may have a substituent and -NR-. The resin composition according to claim 1 or 2, which represents The resin composition according to any one of claims 1 to 3, wherein R ¹ in the general formula (1) and R ² and R ³ in the general formula (2) each represent a methyl group or an ethyl group.   The compound represented by the general formula (1) is 8-glycidoxyoctyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, N-phenyl-8-aminooctyl-trimethoxysilane. , 3- (2-glycidylphenyl) propyltrimethoxysilane, 6-vinylhexyltrimethoxysilane, and 8-methacryloyloxyoctyltrimethoxysilane, and the compound represented by the general formula (2) is bistrimethoxy The resin composition according to any one of claims 1 to 4, which is any one of silylhexane, bistrimethoxysilyloctane, and bis (trimethoxysilylpropyl) ethylenediamine.   (C) The resin composition of any one of Claims 1-5 whose average particle diameter of a component is 0.01 micrometer-5 micrometers.   The resin composition according to claim 1, wherein the component (C) is silica.   (C) The resin composition of any one of Claims 1-7 whose content of a component is 50 mass% or more when the non-volatile component in a resin composition is 100 mass%.   The resin according to any one of claims 1 to 8, wherein the component (C) is surface-treated with 0.2 to 2 parts by mass of a surface treatment agent with respect to 100 parts by mass of the component (C). Composition. (C) carbon content per unit surface area of the component is at ^{0.05mg / m 2 ~1mg / m 2} , the resin composition according to any one of claims 1-9.   The resin composition according to any one of claims 1 to 10, wherein the component (A) is at least one selected from a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a biphenyl type epoxy resin.   The component (B) according to any one of claims 1 to 11, wherein the component is at least one 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. Resin composition.   The resin composition according to any one of claims 1 to 12, which is used for forming an insulating layer of a printed wiring board.   The resin composition according to any one of claims 1 to 13, which is used for forming a buildup layer of a printed wiring board.   The sheet-like laminated material containing the resin composition layer formed with the resin composition of any one of Claims 1-14.   The printed wiring board containing the insulating layer formed with the hardened | cured material of the resin composition of any one of Claims 1-14.   The printed wiring board of Claim 16 whose curvature amount of an insulating layer is 350 micrometers or less.   A semiconductor device comprising the printed wiring board according to claim 16.