JP2018044133A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which is hardly affected by thickness of an insulating layer when micro wiring is formed, and can impart an insulating layer excellent in peel strength.SOLUTION: A resin composition contains (A) an epoxy resin and (B) a curing agent, where an etching rate (E1) in a first roughening test of immersing a surface of a first layer with a thickness of 30 μm which is formed of a cured product obtained by thermal curing the resin composition at 100°C for 30 minutes and at 180°C for 30 minutes in a swollen liquid at 60°C for 10 minutes, in an oxidant solution at 80°C for 20 minutes, in a neutralization liquid at 40°C for 5 minutes is 0.8≤E1≤2, and an etching rate (E2) in a second roughening test of immersing a surface of a second layer with a thickness of 10 μm which is formed of a cured product obtained by similarly thermal curing the resin composition, in a swollen liquid at 60°C for 10 minutes, in an oxidant solution at 80°C for 20 minutes, in a neutralization liquid at 40°C for 5 minutes is 1≤E2≤2.5.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. Furthermore, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device containing the resin composition.

  In recent years, in order to achieve miniaturization of electronic devices, the printed wiring board has been further reduced in thickness, and accordingly, the wiring circuit on the inner layer substrate has been miniaturized. For example, Patent Document 1 describes an adhesive film (resin sheet) that can handle fine wiring.

JP 2014-36051 A

  The inventors of the present invention have studied to apply a conventional resin sheet to an insulating layer of a printed wiring board in order to achieve downsizing of electronic equipment, and found that the etching rate is increased. It has been found that increasing the etching rate makes it easier to cause a short circuit and it is difficult to apply a conventional resin sheet as it is. In particular, when a thin resin composition layer is applied to build-up applications, the etching rate tends to be different due to the difference in the insulating layer thickness between the part with wiring and the part without wiring, making it difficult to form stable fine wiring. Tend to be. In addition, when only the etching rate at the time of the thin film is focused and the components contained in the resin composition are adjusted, it becomes difficult to form fine wiring when forming an insulating layer having a conventional thickness, which makes it versatile. There is a possibility that the material will be missing.

  An object of the present invention is to provide a resin composition that is less affected by the thickness of the insulating layer when forming fine wiring and can provide an insulating layer having excellent peel strength; a resin sheet containing the resin composition; It is providing a printed wiring board provided with the insulating layer formed using the composition, and a semiconductor device.

  As described above, the present inventors have found that when a thin film is applied to the insulating layer, the etching rate increases, and it becomes difficult to miniaturize the wiring circuit on the inner layer substrate. As a result of intensive studies to solve the above problems, the inventors of the present invention roughened the cured resin compositions having thicknesses of 10 μm and 30 μm respectively under predetermined conditions, and etched each of the roughened surfaces. By adjusting each component contained in the resin composition so that the rate satisfies a predetermined relationship, an insulating layer that is less affected by the thickness of the insulating layer when forming fine wiring and has excellent peel strength is provided. The inventors have found that this is possible and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition comprising (A) an epoxy resin and (B) a curing agent,
The surface of the first layer having a thickness of 30 μm composed of a cured product obtained by thermally curing the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes is applied to the swelling liquid at 60 ° C. for 10 minutes. Etching rate (E1) in the first roughening test in which the sample is immersed in the solution at 80 ° C. for 20 minutes and in the neutralizing solution at 40 ° C. for 5 minutes, 0.8 ≦ E1 ≦ 2,
The surface of the second layer having a thickness of 10 μm consisting of a cured product obtained by thermally curing the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes is applied to the swelling liquid at 60 ° C. for 10 minutes. A resin composition in which an etching rate (E2) in a second roughening test in which a solution is immersed in a solution at 80 ° C. for 20 minutes and in a neutralizing solution at 40 ° C. for 5 minutes is 1 ≦ E2 ≦ 2.5.
[2] The resin composition according to [1], which is for forming a wiring having a wiring pitch of 10 μm or less.
[3] The resin composition according to [1] or [2], which is for wiring formation by a semi-additive construction method.
[4] The resin composition according to any one of [1] to [3], which is used for forming an insulating layer of a printed wiring board.
[5] The resin composition according to any one of [1] to [4], which is for an interlayer insulating layer of a printed wiring board.
[6] The resin composition according to any one of [1] to [5], which contains an inorganic filler (C).
[7] The resin composition according to [6], 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.
[8] The resin composition according to [6] or [7], wherein the average particle size of the component (C) is 0.05 μm to 0.35 μm.
[9] The resin composition according to any one of [1] to [8], which contains a fluorine compound.
[10] The resin composition according to [9], wherein the fluorine compound is a fluorine-containing epoxy resin.
[11] A support and a resin composition layer formed on the support and formed from the resin composition according to any one of [1] to [10], wherein the thickness of the resin composition layer is The resin sheet which is 30 micrometers or less.
[12] For forming an insulating layer of a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer The resin sheet according to [11].
[13] A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
The insulating layer is a printed wiring board which is a cured product of the resin composition according to any one of [1] to [10].
[14] A semiconductor device including the printed wiring board according to [13].

  According to the present invention, a resin composition that is less affected by the thickness of the insulating layer when forming fine wiring and can provide an insulating layer having excellent peel strength; a resin sheet containing the resin composition; A printed wiring board including an insulating layer formed using the composition and a semiconductor device can be provided.

FIG. 1 is a partial cross-sectional view schematically showing an example of a printed wiring board.

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

  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.

[Resin composition]
The resin composition of the present invention is a resin composition containing (A) an epoxy resin and (B) a curing agent, and the resin composition is thermally cured at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes. First, the surface of the first layer having a thickness of 30 μm made of the obtained cured product is immersed in the swelling solution at 60 ° C. for 10 minutes, in the oxidizing agent solution at 80 ° C. for 20 minutes, and in the neutralizing solution at 40 ° C. for 5 minutes. The etching rate (E1) in the roughening test is 0.8 ≦ E1 ≦ 2, and the cured product is obtained by thermally curing the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes. Etching rate in the second roughening test in which the surface of the second layer having a thickness of 10 μm is immersed in the swelling solution at 60 ° C. for 10 minutes, in the oxidizing solution at 80 ° C. for 20 minutes, and in the neutralizing solution at 40 ° C. for 5 minutes. (E2) is 1 ≦ E2 ≦ 2.5. Thereby, when forming fine wiring, it becomes difficult to receive the influence of the thickness of an insulating layer, and it becomes possible to provide the insulating layer excellent in peel strength.

  In the present invention, the etching rate (E1) indicates a ratio (%) of mass lost by conducting the first roughening test on the surface of the first layer of the cured product having a thickness of 30 μm. Moreover, an etching rate (E2) shows the ratio (%) of the defect | deletion by performing a 2nd roughening test on the surface of the 2nd layer of 10 micrometers in thickness cured | curing material. Details of the first and second roughening tests will be described later.

  The resin composition contains (A) an epoxy resin and (B) a curing agent, and if necessary, (C) an inorganic filler, (D) a thermoplastic resin, (E) a curing accelerator, (F) Additives such as flame retardants and (G) organic fillers may be included. Moreover, it is preferable that the resin composition of this invention contains a fluorine compound from a viewpoint with which an etching rate (E1) and an etching rate (E2) satisfy | fill the said relationship. A fluorine compound is a compound containing one or more fluorine atoms per molecule and is a concept including an organic compound and an inorganic compound. Moreover, the weight average molecular weight of a fluorine compound is 100-5000 normally. The fluorine compound is preferably contained as any one of the components (A) to (G), and the fluorine compound is preferably contained as the component (A). A fluorine compound may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, when a fluorine compound contains as (A) component, you may use (A) component combining (A) component which is not a fluorine compound and a fluorine compound. 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. Examples of (A) epoxy resins include fluorine-containing epoxy resins such as bisphenol AF type epoxy resins and perfluoroalkyl type epoxy resins; bisphenol A type epoxy resins; bisphenol F type epoxy resins; bisphenol S type epoxy resins; Type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; naphthol novolac type epoxy resin; phenol novolac type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; naphthol type epoxy resin; Epoxy resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Epoxy resin having butadiene structure; alicyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexane dimethanol type epoxy resin; naphthylene ether type epoxy resin; trimethylol type epoxy resin; Examples include ethane type epoxy resins. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  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 the epoxy resin, the epoxy resin has excellent flexibility and the breaking strength of the cured product is 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, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are cycloaliphatic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure. Glycidylamine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF Type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC, “828US”, “jER828EL” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. "JER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" (bisphenol A) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Type epoxy resin and bisphenol F type epoxy resin), “YD-8125G” (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation , Daicel "Celoxide 2021P" (an alicyclic epoxy resin having an ester skeleton), "PB-3600" (an epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1, 4) manufactured by Nippon Steel Chemical Co., Ltd. -Glycidylcyclohexane), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "E-7432", "E-7632" (perfluoroalkyl type epoxy resin) manufactured by Daikin Industries, Ltd., 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) Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311 ”,“ EXA-7311-G3 ”,“ EXA-7311-G4 ”,“ EXA-7311-G4S ”,“ HP6000 ”(naphthylene ether type epoxy resin),“ EPPN-502H ”(manufactured by Nippon Kayaku Co., Ltd.) Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy) Fat), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin), “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ), “YX4000H”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “PG” manufactured by Osaka Gas Chemical Co., Ltd. -100 "," CG-500 "," YL7800 "(fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation," jER1010 "manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type epoxy resin)," jER1031S "(tetraphenyl) Ethane type epoxy tree ) "YL7760" (bisphenol AF type epoxy resin) and the like.

  The component (A) is preferably a fluorine-containing epoxy resin that is a fluorine compound from the viewpoint of satisfying the above formulas (1) and (2).

  When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:15 in terms of mass ratio. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility is obtained, handling properties are improved, and iii) a cured product of the resin composition layer 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: 0.1 to 1:10 by mass ratio. Is more preferable, and the range of 1: 0.3 to 1: 3 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 20% by mass from the viewpoint of obtaining an insulating layer exhibiting good tensile fracture strength and insulation reliability. % Or more. 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 40 mass% or less.

When the resin composition of the present invention contains a combination of a fluorine-containing epoxy resin and an epoxy resin other than the fluorine-containing epoxy resin, the mass of the fluorine-containing epoxy resin in the resin composition is W _A , and the fluorine-containing epoxy in the resin composition when the mass of the epoxy resin other than the resin was _{W B,} it is preferable that the W B / _{W a} 1 to 10, more preferably from 1 to 5, 1 to 3, or 1 to 2 Is more preferable. When W _B / W _A is in the above range, the wiring circuit can be miniaturized.

  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 being in this range, the crosslinked density of the cured product of the resin composition layer is sufficient, and an insulating layer having a small surface roughness can be provided. 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. The curing agent is not particularly limited as long as it has a function of curing an epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester Examples thereof include a curing agent and a carbodiimide curing agent. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  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.

  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., “NHN” manufactured by Nippon Kayaku Co., Ltd. “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375”, “SN395” manufactured by Nippon Steel & Sumikin Co., Ltd. “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” manufactured by DIC, and the like can be mentioned.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally 1 molecule of ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of a heterocyclic hydroxy compound, are carried out. A compound having two or more thereof 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 having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM "," EXB-8000L-65TM "(manufactured by DIC)," EXB9416-70BK "(manufactured by DIC) as an active ester compound containing a naphthalene structure, and" DC808 "as an active ester compound containing an acetylated product of phenol novolac ( Mitsubishi Chemical Co., Ltd.), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent which is an acetylated product of phenol novolac, "YLH1026" as an active ester-based curing agent is benzoyl product of E Nord novolac (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and the like.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd. and “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” (phenol novolac type polyfunctional cyanate ester resin), “ULL-950S” (polyfunctional cyanate ester resin), and “BA230” manufactured by Lonza Japan. , “BA230S75” (a prepolymer in which part or all of bisphenol A dicyanate is triazine-modified into a trimer), and the like.

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

  The amount ratio of 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: 0.01 to 1: 2. 1: 0.015 to 1: 1.5 are more preferable, and 1: 0.02 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 making the quantity ratio of an epoxy resin and a hardening | curing agent into such a range, the heat resistance of the hardened | cured material of a resin composition layer improves more.

  In one embodiment, the resin composition includes the aforementioned epoxy resin and a curing agent. The resin composition is a mixture of a liquid epoxy resin and a solid epoxy resin (A) as an epoxy resin (mass ratio of liquid epoxy resin: solid epoxy resin is preferably 1: 0.1 to 1:15, more preferably 1: 0.3-1: 10, more preferably 1: 0.3-1: 3), (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.

In the present invention, as the (B) curing agent, it is preferable that the etching rates (E1) and (E2) satisfy at least the above relationship and include at least an active ester curing agent from the viewpoint of improving peel strength. When the total content of the resin components excluding the component (C) is W _c and the content of the active ester curing agent is W _d , (W _d / W _c ) × 100 satisfies 5 or more. Preferably, it satisfies 8 or more, more preferably 10 or more. The upper limit is preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less.

  Although content of the hardening | curing agent in a resin composition is not specifically limited, Preferably it is 20 mass% or less from the viewpoint of etching rate (E1) and (E2) satisfy | filling the said relationship, and improving peel strength, More preferably, it is 15 It is 10 mass% or less, More preferably, it is 10 mass% or less. The lower limit is not particularly limited but is preferably 2% by mass or more.

<(C) Inorganic filler>
In one embodiment, the resin composition may contain an inorganic filler. 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. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferable as the silica. 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 preferably 0.35 μm or less, more preferably 0.32 μm or less, still more preferably 0.3 μm or less, and even more preferably 0.29 μm or less from the viewpoint of improving the ability to form a fine circuit. preferable. From the viewpoint of improving dispersibility in the resin composition layer, the lower limit of the average particle diameter is preferably 0.05 μm or more, more preferably 0.06 μm or more, and further preferably 0.07 μm or more. Examples of commercially available inorganic fillers having such an average particle diameter include “UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd. and “SPH516-05” manufactured by Nippon Steel & Sumikin Materials.

  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 methyl ethyl ketone by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring device, “LA-500” manufactured by Horiba, Ltd., “SALD-2200” manufactured by Shimadzu Corporation, etc. can be used.

  Inorganic fillers are fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, and silane-based cups that are fluorine compounds from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents such as a ring agent, an organosilazane compound, and a titanate coupling agent, and more preferably treated with a fluorine-containing silane coupling agent. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-” manufactured by Shin-Etsu Chemical Co., Ltd. 7103 "(3,3,3-trifluoropropyltrimethoxysilane) and the like.

  The degree of the surface treatment with the surface treatment agent is 0.2 to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the component (C) from the viewpoint of improving the dispersibility of the inorganic filler. It is preferable that the surface treatment is performed at 0.2 to 3 parts by mass, and the surface treatment is preferably performed at 0.3 to 2 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. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 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 suppressing the increase in melt viscosity of the resin varnish and 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.

  From the viewpoint of improving the thickness stability of the resin composition layer, the content of the inorganic filler in the resin composition is preferably 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass. Preferably it is 53 mass% or more, More preferably, it is 55 mass% or more. The upper limit of the content of the inorganic filler in the resin composition is preferably 85% by mass or less, from the viewpoint of improving the fine circuit forming ability and the tensile fracture strength of the insulating layer (cured product of the resin composition layer). Preferably it is 80 mass% or less, More preferably, it is 75 mass% or less.

<(D) Thermoplastic resin>
In one embodiment, the resin composition of the present invention may contain (D) a thermoplastic resin.

  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 polystyrene-converted weight average molecular weight of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 40,000 or more. Although an upper limit is not specifically limited, Preferably it is 70,000 or less, More preferably, it is 60,000 or less. 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-converted 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-804L / K- manufactured by Showa Denko KK as a column. 804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as the 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” (bisphenolacetophenone) manufactured by Mitsubishi Chemical Corporation. In addition, “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YL7500BH30”, “YX6954BH30”, “YX7553”, “YX7553BH30”, “YL7769BH30” manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. ”,“ 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”, “Electrical butyral 6000-EP”, and Sekisui. Examples include ESREC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Chemical Industries.

  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 polyamideimide resin include “Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin also include modified polyamide-imides 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 polyphenylene ether resin include oligophenylene ether / styrene resin “OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Company.

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

  Of these, phenoxy resin and polyvinyl acetal resin are preferable as the thermoplastic resin. Accordingly, in a preferred embodiment, the thermoplastic resin includes one or more selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin. Among these, as the thermoplastic resin, a phenoxy resin is preferable, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable. By using a phenoxy resin having a weight average molecular weight of 40,000 or more, the wiring circuit can be miniaturized.

  When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.1% by mass to 10% by mass, more preferably 0.2% by mass to 5% by mass, and still more preferably 0.8%. 3% by mass to 1% by mass.

<(E) Curing accelerator>
In one embodiment, the resin composition of the present invention may further contain (E) a curing accelerator.

  Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. A curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal 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- Phenylimidazole 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.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  When the resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass to 3% by mass, more preferably 0.01% by mass to 3% by mass, and 0.01% by mass. More preferably, ˜1% by mass.

<(F) Flame retardant>
In one embodiment, the resin composition of the present invention may contain (F) a flame retardant. 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, such as “HCA-HQ” manufactured by Sanko Co., Ltd., “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd., and the like. As the flame retardant, those which are difficult to hydrolyze are preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

  When the resin composition contains a flame retardant, the content of the flame retardant is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and 0.5% by mass to 10% by mass. More preferred is mass%.

<(G) Organic filler>
In one embodiment, the resin composition of the present invention may contain (G) an organic filler. (G) By containing a component, the tensile fracture strength of the hardened | cured material of the resin composition layer of a resin sheet can be improved. As the organic filler, any organic filler that can be used in forming the insulating layer of the 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, and examples thereof include “EXL2655” manufactured by Dow Chemical Japan, “AC3401N” and “AC3816N” manufactured by Aika Industry.

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

<(H) Optional additive>
In one embodiment, the resin composition of the present invention may further contain other additives as necessary. Examples of such other additives include organic copper compounds, organic zinc compounds, and organic compounds. Examples include organometallic compounds such as cobalt compounds, and resin additives such as thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and coloring agents.

<Physical properties and uses of resin composition>
The surface of the first layer having a thickness of 30 μm consisting of a cured product obtained by thermally curing the resin composition of the present invention at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes is applied to the swelling liquid at 60 ° C. for 10 minutes. The etching rate (E1) is 0.8 ≦ E1 ≦ 2 when a first roughening test is performed in which the sample is immersed in an oxidizing agent solution at 80 ° C. for 20 minutes and in a neutralizing solution at 40 ° C. for 5 minutes.
In addition, the surface of the second layer having a thickness of 10 μm made of a cured product obtained by thermally curing the resin composition of the present invention at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes is used as a swelling liquid at 60 ° C. Etching rate (E2) is 1 ≦ E2 ≦ 2.5 when a second roughening test is performed by immersing in an oxidant solution at 80 ° C. for 10 minutes and in a neutralizing solution at 40 ° C. for 5 minutes for 10 minutes. .
By adjusting each component contained in the resin composition so that the etching rate (E1) and the etching rate (E2) satisfy the above relationship, it is difficult to be affected by the thickness of the insulating layer when forming fine wiring, An insulating layer having excellent peel strength can be provided.

  The etching rate (E1) satisfies 0.8 ≦ E1 ≦ 2, preferably satisfies 0.9 ≦ E1 ≦ 1.8, and more preferably satisfies 1 ≦ E1 ≦ 1.5. Fine circuit peeling can be suppressed by setting the etching rate (E1) to 0.8 or more, and electroless copper residue can be suppressed by setting the etching rate (E1) to 2 or less. The etching rate (E1) can be measured according to the method described in <Measurement of etching rate> described later.

  The etching rate (E2) satisfies 1 ≦ E2 ≦ 2.5, preferably satisfies 1 ≦ E2 ≦ 2, and more preferably satisfies 1.2 ≦ E2 ≦ 1.8. Fine circuit peeling can be suppressed by setting the etching rate (E2) to 1 or more, and electroless copper residue can be suppressed by setting the etching rate (E1) to 2.5 or less. The etching rate (E2) can be measured according to the method described in <Measurement of etching rate> described later.

  The procedure of the thermosetting of the resin composition and the first and second roughening treatment tests will be described later. It can be performed according to the methods described in “Curing” and “(4) Step of roughening treatment”.

  The swelling liquid used in the first and second roughening tests is preferably an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide. Commercially available products may be used as the swelling liquid, for example, Swelling Dip Securigant P manufactured by Atotech Japan.

  The oxidizing agent solution used in the first and second roughening tests is preferably an aqueous solution having a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%. A commercial item may be used for an oxidizing agent solution, for example, Atotech Japan Inc. concentrate compact CP etc. are mentioned.

  The neutralizing solution used in the first and second roughening tests is preferably an aqueous sulfuric acid solution. A commercially available product may be used as the neutralizing solution, and examples thereof include Reduction Solution Securigant P manufactured by Atotech Japan.

  The arithmetic average roughness Ra of the surface of the first layer after the roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, and still more preferably 100 nm or less from the viewpoint of the ability to form a fine circuit. Although it does not specifically limit about a minimum, Preferably it is 0 nm or more, More preferably, it is 30 nm or more, More preferably, it is 50 nm or more. When the arithmetic average roughness Ra of the surface of the first layer after the roughening treatment is within the above range, the peel strength can be effectively increased. The arithmetic average roughness Ra can be measured according to the method described in <Measurement of arithmetic average roughness (Ra) and root mean square roughness (Rq)> described later.

  The root mean square roughness Rq of the surface of the first layer after the roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less from the viewpoint of fine circuit forming ability. Although it does not specifically limit about a minimum, Preferably it is 0 nm or more, More preferably, it is 30 nm or more, More preferably, it is 50 nm or more. When the root mean square roughness Rq of the surface of the first layer after the roughening treatment is within the above range, the peel strength can be effectively increased. The root mean square roughness Rq can be measured according to the method described in <Measurement of arithmetic mean roughness (Ra) and root mean square roughness (Rq)> described later.

  The arithmetic average roughness Ra of the surface of the second layer after the roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less from the viewpoint of fine circuit forming ability. Although it does not specifically limit about a minimum, Preferably it is 0 nm or more, More preferably, it is 30 nm or more, More preferably, it is 50 nm or more. When the arithmetic average roughness Ra of the surface of the second layer after the roughening treatment is within the above range, the peel strength can be effectively increased. The arithmetic average roughness Ra can be measured according to the method described in <Measurement of arithmetic average roughness (Ra) and root mean square roughness (Rq)> described later.

  The root mean square roughness Rq of the surface of the second layer after the roughening treatment is preferably 200 nm or less, more preferably 150 nm or less, and still more preferably 100 nm or less from the viewpoint of the ability to form a fine circuit. Although it does not specifically limit about a minimum, Preferably it is 0 nm or more, More preferably, it is 30 nm or more, More preferably, it is 50 nm or more. When the root mean square roughness Rq of the surface of the second layer after the roughening treatment is within the above range, the peel strength can be effectively increased. The root mean square roughness Rq can be measured according to the method described in <Measurement of arithmetic mean roughness (Ra) and root mean square roughness (Rq)> described later.

  A cured product obtained by thermally curing the resin composition of the present invention at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes exhibits a characteristic of excellent peel strength with a conductor layer made of plating or the like. For details, after conducting the first roughening test or the second roughening test on the surface of the cured product obtained by thermally curing the resin composition of the present invention at 100 ° C for 30 minutes and further at 180 ° C for 30 minutes, the conductor When the layer is formed, the peel strength between the cured product and the conductor layer is excellent. The peel strength is preferably 0.3 kgf / cm or more, more preferably 0.4 kgf / cm or more, and further preferably 0.45 kgf / cm or more when the thickness of the insulating layer is 10 μm. On the other hand, the upper limit value of the peel strength is not particularly limited, but may be 1.5 kgf / cm or less, 1 kgf / cm or less, or the like. When the thickness of the insulating layer is 30 μm, it is preferably 0.3 kgf / cm or more, more preferably 0.4 kgf / cm or more, and further preferably 0.45 kgf / cm or more. On the other hand, the upper limit value of the peel strength is not particularly limited, but may be 1.5 kgf / cm or less, 1 kgf / cm or less, or the like. The peel strength can be evaluated according to the method described in <Measurement of plating adhesion (plating peel strength)> described later.

  The resin composition of the present invention is less affected by the thickness of the insulating layer when forming fine wiring, and provides an insulating layer having excellent peel strength. For this reason, the cured product obtained by thermosetting the resin composition of the present invention at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes exhibits the property that the circuit is difficult to peel off.

  The resin composition of the present invention has a characteristic that a residue when a pattern electroless copper plating layer is formed on a cured product obtained by thermosetting at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes is suppressed. Show.

  The resin composition of the present invention is hardly affected by the thickness of the insulating layer when forming fine wiring. That is, the insulating layer formed using the resin composition of the present invention can form fine wiring without being affected by the thickness.

  The resin composition of the present invention is less affected by the thickness of the insulating layer when forming fine wiring, and provides an insulating layer having excellent peel strength. Therefore, in the resin composition of the present invention, the ratio (L / S) of the circuit width (L (μm)) to the width (S (μm)) between circuits is, for example, 5 μm / 5 μm or less (wiring pitch is 10 μm or less). Can be suitably used as a resin composition (for forming a wiring having (L / S) of 5 μm / 5 μm or less). Further, it can be suitably used as a resin composition (for wiring formation by a semi-additive method) for forming fine wiring by a semi-additive method, and for forming an insulating layer of a printed wiring board (printed-wiring board) Can be suitably used as a resin composition (for forming an insulating layer) and more suitable as a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for an interlayer insulating layer of a printed wiring board). Can be used for The ratio (L / S) is preferably 5 μm / 5 μm or less (wiring pitch is 10 μm or less), more preferably 4 μm / 4 μm or less (wiring pitch is 8 μm or less), and 3 μm / 3 μm or less (wiring pitch is 6 μm or less). More preferably, it is 2 μm / 2 μm or less (wiring pitch is 4 μm or less) or 1 μm / 1 μm or less (wiring pitch is 2 μm or less).

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer provided on the support. The resin composition layer is formed from the resin composition of the present invention, and the thickness of the resin composition layer is 30 μm. It is as follows.

  From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the resin composition layer is 30 μm or less, preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 1.5 micrometers or more, 2 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, corona treatment, and antistatic 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”, “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 T60” manufactured by Toray Industries, Inc., “Purex” manufactured by Teijin Limited, “Unipeel” manufactured by Unitika, 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.

  The resin sheet is prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further drying 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 resin sheet, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not bonded 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 resin sheet can be stored in a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

  The resin sheet of the present invention is less affected by the thickness of the insulating layer when forming fine wiring, and provides an insulating layer (cured product of the resin composition layer) having excellent peel strength. Therefore, the resin sheet of the present invention can be suitably used as a resin sheet (for forming an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, and forms an interlayer insulating layer of the printed wiring board. Therefore, it can be used more suitably as a resin sheet (resin sheet for an interlayer insulating layer of a printed wiring board). In addition, the resin sheet of the present invention has a ratio (L / S) of a circuit width (L (μm)) to a width (S (μm)) between circuits, for example, for forming a wiring having 5 μm / 5 μm or less ( (L / S) can be suitably used as a resin sheet (for wiring formation with a wiring pitch of 10 μm or less) of 5 μm / 5 μm or less (wiring pitch is 10 μm or less), and for forming fine wiring by a semi-additive method (by a semi-additive method) It can also be suitably used as a resin sheet (for wiring formation). The ratio (L / S) is preferably 5 μm / 5 μm or less (wiring pitch is 10 μm or less), more preferably 4 μm / 4 μm or less (wiring pitch is 8 μm or less), 3 μm / 3 μm or less (wiring pitch is 6 μm or less), 2 μm / 2 μm or less (wiring pitch is 4 μm or less) or 1 μm / 1 μm or less (wiring pitch is 2 μm or less) is more preferable. Moreover, for example, in a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, By forming the insulating layer with a resin sheet, the insulating performance can be improved.

[Printed wiring board, printed wiring board manufacturing method]
The printed wiring board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed of a cured product of the resin composition of the present invention. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer from the second conductor layer (the conductor layer is referred to as a wiring layer). is there). Since the insulating layer formed of the cured product of the resin composition of the present invention is excellent in thin film insulating properties, the distance between the first conductor layer and the second conductor layer (the insulating layer between the first and second conductor layers). Even if the thickness is 6 μm or less, the insulation is excellent.

  The thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, and even more preferably 5 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. The distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers) is the main surface of the first conductor layer 1 as shown in FIG. 11 and the thickness t 1 of the insulating layer 3 between the main surface 21 of the second conductor layer 2. The first and second conductor layers are conductor layers adjacent to each other via an insulating layer, and the main surface 11 and the main surface 21 face each other. The thickness of the insulating layer between the first and second conductor layers can be measured according to the method described in <Measurement of distance between conductor layers (thickness of insulating layer between conductor layers)>.

  Note that the thickness t2 of the entire insulating layer is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 15 μm or less, or 10 μm or less. Although it does not specifically limit about a minimum, Usually, it can be set as 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

The printed wiring board of this invention can be manufactured by the method including the process of following (I) and (II) using the above-mentioned resin sheet.
(I) The process of laminating | stacking so that the resin composition layer of a resin sheet may join to an inner layer board | substrate on an inner layer board | substrate (II) The process of thermosetting a resin composition layer and forming 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 circuit board with a built-in component, an inner layer board with a built-in component can be used.

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

  Lamination of the inner layer substrate and the resin sheet 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 pressurizing laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurizing laminator.

  After lamination, the laminated resin sheets 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). Moreover, if necessary, the multilayer wiring board may be formed by repeatedly forming the insulating layer and the conductor layer in the steps (II) to (V). In this case, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1) is preferably within the above range.

  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. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. 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 in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer 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 used for a roughening process, 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 oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan. Moreover, as a neutralization liquid used for a roughening process, acidic aqueous solution is preferable, As a commercial item, "Reduction Solution Securigant P" by Atotech Japan is mentioned, for example. 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.

  The roughening treatment in the step (IV) may adopt the same procedure and conditions as those in the first or second roughening test.

  In one embodiment, the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is the arithmetic average roughness Ra of the surface of the first layer after the roughening treatment and the arithmetic average roughness Ra of the surface of the second layer after the roughening treatment. The average roughness Ra is the same, and the preferable range is also the same.

  In one embodiment, the root mean square roughness Rq of the surface of the insulating layer after the roughening treatment is the root mean square roughness Rq of the surface of the first layer after the roughening treatment and the second layer after the roughening treatment. This is the same as the root mean square roughness Rq of the surface, and the preferred range is also the same.

  Step (V) is a step of forming a conductor layer. When the conductor layer is not formed on the inner layer substrate, the step (V) is a step of forming the first conductor layer. When the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer. Step (V) is a step of forming the second 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.

  Since an insulating layer uses the hardened | cured material of the resin composition of this invention, when forming fine wiring, it is hard to receive to the influence of the thickness of an insulating layer. Therefore, as a wiring pattern, for example, a wiring pattern in which a ratio (L / S) of a circuit width (line; L) to a width (space; S) between circuits is 5 μm / 5 μm or less (that is, a wiring pitch is 10 μm or less). Can be used. Furthermore, L / S = 4 μm / 4 μm or less (wiring pitch 8 μm or less), L / S = 3 μm / 3 μm or less (wiring pitch 6 μm or less), L / S = 2 μm / 2 μm or less (wiring pitch 4 μm or less), L / S A wiring pattern of S = 1 μm / 1 μm or less (wiring pitch of 2 μm or less) can be used. Note that the wiring pitch need not be the same throughout the circuit board.

  Since the resin sheet of the present invention provides an insulating layer having a good component embedding property, it can be suitably used even when the printed wiring board is a component built-in circuit board. The component built-in circuit board can be manufactured by a known manufacturing method.

  A printed wiring board manufactured using the resin sheet of the present invention includes an insulating layer that is a cured product of the resin composition layer of the resin sheet of the present invention, and an embedded wiring layer embedded in the insulating layer. It may be.

[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

  Examples of 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.

  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples. In the following, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

<Measurement of average particle size of inorganic filler>
100 mg of an inorganic filler, 0.1 g of a dispersant (“SN9228” manufactured by San Nopco) and 10 g of methyl ethyl ketone were weighed in a vial and dispersed with an ultrasonic wave for 20 minutes. Using a laser diffraction type particle size distribution measuring device (“SALD-2200” manufactured by Shimadzu Corporation), the particle size distribution was measured by a batch cell method, and the average particle size by the median diameter was calculated.

<Measurement of specific surface area of inorganic filler>
The specific surface area of the inorganic filler was measured using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.).

<Used inorganic filler>
Inorganic filler 1: N-phenyl-3-amino with respect to 100 parts of spherical silica (manufactured by Nippon Steel & Sumikin Materials, “SPH516-05”, average particle size 0.29 μm, specific surface area 16.3 m ² / g) Surface treated with 1 part of propyltrimethoxysilane (“KBM573”, manufactured by Shin-Etsu Chemical Co., Ltd.).
Inorganic filler 2: N-phenyl-3-aminopropyl with respect to 100 parts of spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., “UFP-30”, average particle size 0.078 μm, specific surface area 30.7 m ² / g) Surface treated with 2 parts of trimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.).
Inorganic filler 3: N-phenyl-3-aminopropyltrimethoxysilane with respect to 100 parts of spherical silica (manufactured by Admatechs, “SC2500SQ”, average particle size 0.63 μm, specific surface area 11.2 m ² / g) (Shin-Etsu Chemical Co., Ltd., “KBM573”) surface treated with 1 part.

[Preparation of resin composition]
<Preparation of Resin Composition 1>
6 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 5 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Corporation “YL7760”, epoxy equivalent of about 238) 15 parts, bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., epoxy equivalent of about 169, bisphenol A type and bisphenol F type 1: 1 mixture) 4 2 parts of phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Chemical Corporation, cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution having a solid content of 30% by mass, Mw = 44000), mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone Dissolve by heating with stirring It was. After cooling to room temperature, there are 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%), active ester system 7 parts of curing agent (“EXB-8000L-65M” manufactured by DIC, MEK solution with active group equivalent of about 220, 65% by mass of non-volatile component), 80 parts of inorganic filler 1, amine-based curing accelerator (4-dimethylamino) 0.05 part of pyridine (DMAP) was mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare Resin Composition 1.

<Preparation of resin composition 2>
6 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 5 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238) 15 parts, cyclohexane type epoxy resin (Mitsubishi Chemical Corporation "ZX1658GS", epoxy equivalent of about 135), phenoxy resin (Mitsubishi Chemical Corporation "YL7500BH30", solid content 2 parts of a 30 mass% cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution, Mw = 44000) was dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. After cooling to room temperature, there are 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%), active ester system 7 parts of curing agent (“EXB-8000L-65M” manufactured by DIC, MEK solution having an active group equivalent of about 220, 65% by mass of non-volatile components), 50 parts of inorganic filler 2, amine-based curing accelerator (4-dimethylamino) 0.05 part of pyridine (DMAP) was mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare Resin Composition 2.

<Preparation of resin composition 3>
6 parts of bixylenol type epoxy resin (Mitsubishi Chemical "YX4000HK", epoxy equivalent of about 185), 15 parts of naphthalene type epoxy resin (Nippon Steel & Sumikin Chemicals "ESN475V", epoxy equivalent of about 332), bisphenol type epoxy resin (Nippon Steel) "ZX1059" manufactured by Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 4 parts of a 1: 1 mixture of bisphenol A type and bisphenol F type), naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC, epoxy equivalent) About 213) 2 parts, 2 parts of phenoxy resin (YX7553BH30 manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass), mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone The solution was heated and dissolved with stirring. After cooling to room temperature, there were 3 parts of a triazine skeleton-containing novolak curing agent (“LA7054” manufactured by DIC, MEK solution having a hydroxyl equivalent weight of about 125 and a solid content of 60%), and a naphthol curing agent (manufactured by DIC “ SN-495V ", hydroxyl equivalent of about 231) 6 parts, inorganic filler 3 70 parts, amine curing accelerator (4-dimethylaminopyridine (DMAP)) 0.05 part, and uniformly mixed with a high-speed rotary mixer After the dispersion, the resin composition 3 was prepared by filtering with a cartridge filter (“SHP020” manufactured by ROKITECHNO).

<Preparation of resin composition 4>
6 parts of bixylenol type epoxy resin (Mitsubishi Chemical "YX4000HK", epoxy equivalent of about 185), 10 parts of naphthalene type epoxy resin (Nippon Steel Sumikin Chemical Co., Ltd. "ESN475V", epoxy equivalent of about 332), cyclohexane type epoxy resin (Mitsubishi) 4 parts of “ZX1658GS” manufactured by Kagaku Co., Ltd., about 135 parts of epoxy equivalent, 2 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) are mixed with solvent naphtha. The mixture was dissolved by heating in a mixed solvent of 20 parts and 10 parts of cyclohexanone with stirring. After cooling to room temperature, there are 2 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%), active ester system 20 parts of curing agent (“EXB-8000L-65M” manufactured by DIC, MEK solution having an active group equivalent of about 220 and 65% by mass of non-volatile components), 70 parts of inorganic filler 3, amine-based curing accelerator (4-dimethylamino) 0.05 parts of pyridine (DMAP) was mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare Resin Composition 4.

The components used for the preparation of the resin compositions 1 to 4 and their blending amounts (parts by mass) are shown in the following table. The abbreviations in the table below are as follows.
YX4000HK: Boxylenol type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185
ESN475V: Naphthalene type epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 332
EXA-7311-G4: naphthylene ether type epoxy resin, manufactured by DIC, epoxy equivalent of about 213
YL7760: Bisphenol AF type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238
ZX1059: bisphenol type epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1: 1 mixture of bisphenol A type and bisphenol F type ZX1658GS: cyclohexane type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 135
LA-3018-50P: Triazine skeleton-containing cresol novolac curing agent, manufactured by DIC, 2-methoxypropanol solution having a hydroxyl group equivalent of about 151 and a solid content of 50% LA-7054: Triazine skeleton-containing novolac curing agent, manufactured by DIC, MEK solution SN-495V having a hydroxyl group equivalent of about 125 and a solid content of 60%: naphthol-based curing agent, manufactured by DIC, hydroxyl group equivalent of about 231
EXB-8000L-65M: Active ester type curing agent, manufactured by DIC, active group equivalent of about 220, MEK solution YX7553BH30 with 65% by mass of non-volatile components: Phenoxy resin, manufactured by Mitsubishi Chemical Co., Ltd., cyclohexanone with a solid content of 30% by mass: methyl ethyl ketone ( 1: 1 solution of MEK) YL7500BH30: Phenoxy resin, manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass, Mw = 44000
DMAP: amine curing accelerator, 4-dimethylaminopyridine

[Preparation of resin sheet A]
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., having a thickness of 38 μm, a softening point of 130 ° C., hereinafter referred to as “release PET”, which has been release-treated with an alkyd resin release agent (“AL-5” manufactured by Lintec) I prepared.)

  Each resin composition was uniformly applied with a die coater so that the thickness of the resin composition layer after drying was 10 μm on the release PET, and the mold was released by drying at 70 ° C. to 95 ° C. for 2 minutes. A resin composition layer was obtained on PET. Next, a rough surface of a polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is bonded to the surface of the resin composition layer not bonded to the support. Laminated so that. Thereby, the resin sheet A which consists of order of mold release PET (support body), a resin composition layer, and a protective film was obtained.

[Preparation of resin sheet B]
In the production of the resin sheet A, the resin composition layer after drying was uniformly applied with a die coater so that the thickness of the resin composition layer was 30 μm. A resin sheet B was obtained in the same manner as the resin sheet A except for the above items.

<Production of Cured Substrate A, Roughened Substrate A, and Evaluation Substrate A>
(1) Copper-clad laminate As a copper-clad laminate, a glass cloth base epoxy resin double-sided copper-clad laminate with copper foil layers laminated on both sides (copper foil thickness 3 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Company, Inc.) “HL832 NSF LCA” (255 × 340 mm size) was prepared.

(2) Lamination of resin sheet The protective film is peeled off from each of the resin sheets A produced in the examples and comparative examples, and a batch type vacuum pressure laminator (manufactured by Nikko Materials, 2-stage build-up laminator, CVP700) is used. The laminate was laminated on both sides of the copper clad laminate so that the resin composition layer was in contact with the copper clad laminate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and pressing for 45 seconds at 130 ° C. and a pressure of 0.74 MPa. Next, hot pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of resin composition layer The copper-clad laminate on which the resin sheet is laminated is placed in an oven at 100 ° C for 30 minutes, then transferred to an oven at 180 ° C and then thermoset for 30 minutes for insulation. A layer was formed and the release PET was peeled off. This is designated as “cured substrate A”.

(4) Process of performing a roughening process The desmear process as a roughening process was performed to the copper clad laminated board (cured board | substrate A) in which the insulating layer was formed. In addition, as a desmear process, the following wet desmear process was implemented.

Wet desmear treatment:
Swelling solution (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 10 minutes, then oxidant solution (“Concentrate Compact CP” manufactured by Atotech Japan Co., Ltd.) In aqueous solution with potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 ° C for 20 minutes, and finally into neutralization solution (“Reduction Solution Securigant P”, sulfuric acid aqueous solution manufactured by Atotech Japan) Immersion was performed at 40 ° C. for 5 minutes. Then, it dried at 80 degreeC for 15 minutes. This is referred to as “roughened substrate A”.

(5) Step of forming conductor layer (5-1) Electroless plating step In order to form a conductor layer on the surface of the roughened substrate A, a plating step including the following steps 1 to 6 (chemical solution manufactured by Atotech Japan Co., Ltd.) The copper plating process using was performed to form a conductor layer.

1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer with via holes)
The surface of the roughened substrate A was washed at 60 ° C. for 5 minutes using a Cleaning Cleaner Security 902 (trade name).
2. Soft etching (cleaning inside via holes)
The surface of the roughened substrate A was treated with an aqueous solution of acidic sodium peroxodisulfate at 30 ° C. for 1 minute.
3. Pre-dip (adjustment of surface charge of insulating layer for Pd application)
The surface of the roughened substrate A is set to Pre. Using Dip Neoganth B (trade name), it was treated at room temperature for 1 minute.
4). Activator application (Pd application to the surface of the insulating layer)
The surface of the roughened substrate A was treated at 35 ° C. for 5 minutes using Activator Neoganth 834 (trade name).
5. Reduction (reduction of Pd applied to the insulating layer)
The surface of the roughened substrate A is set to Reducer Neoganth WA (trade name) and Reducer Accelerator 810 mod. Using a mixed solution with (trade name), it was treated at 30 ° C. for 5 minutes.
6). Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
Using a mixed solution of basic solution print MSK-DK (trade name), copper solution print MS MS (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name), The surface of A was treated at 35 ° C. for 15 minutes to obtain an electroless copper plating layer. The thickness of the formed electroless copper plating layer was 0.5 μm.

(5-2) Formation of wiring pattern After the electroless plating, the surface of the electroless copper plating layer was treated with a 5% sulfuric acid aqueous solution for 30 seconds. Next, a dry film for pattern formation (“Photech RY-3600”, manufactured by Hitachi Chemical Co., Ltd., thickness 19 μm) is electroless copper using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). It laminated | stacked on both surfaces of the plating layer. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then applying pressure at 70 ° C. and a pressure of 0.1 MPa for 20 seconds.

  Then, the glass mask (photomask) in which the wiring pattern shown below was formed was arrange | positioned on the dry film, and was irradiated with light with the projection exposure machine ("UX-2240" by Ushio Electric Co., Ltd.). Subsequently, a 30% 1% sodium carbonate aqueous solution was sprayed for 30 seconds at an injection pressure of 0.15 MPa. Then, it washed with water, the development (pattern formation) of the dry film was performed, and the pattern electroless copper plating layer was obtained.

Glass mask wiring pattern:
A glass mask having 10 comb tooth patterns of i) to v) below was used.
i) L / S = 1 μm / 1 μm, that is, a comb-tooth pattern with a wiring pitch of 2 μm (wiring length 15 mm, 16 lines)
ii) L / S = 2 [mu] m / 2 [mu] m, that is, a comb tooth pattern with a wiring pitch of 4 [mu] m (wiring length 15 mm, 16 lines)
iii) L / S = 3 μm / 3 μm, that is, a comb tooth pattern with a wiring pitch of 6 μm (wiring length 15 mm, 16 lines)
iv) L / S = 4 μm / 4 μm, that is, a comb tooth pattern with a wiring pitch of 8 μm (wiring length: 15 mm, 16 lines)
v) L / S = 5 μm / 5 μm, that is, a comb-teeth pattern with a wiring pitch of 10 μm (wiring length 15 mm, 16 lines)

(5-3) Electroplating step After development of the dry film, after heat treatment at 150 ° C. for 30 minutes, copper sulfate electroplating was performed to form an electrolytic copper plating layer (conductor layer) having a thickness of 5 μm. . The total thickness of the electroless copper plating layer and the electroplating layer was about 5.5 μm.

  Next, a 3% sodium hydroxide solution at 50 ° C. was sprayed at an injection pressure of 0.2 MPa, and the dry film was peeled off from both sides of the substrate. After performing an annealing treatment by heating at 190 ° C. for 60 minutes, an unnecessary conductor layer (copper layer) is removed by using an etchant for flash etching (an etchant for SAC process manufactured by Ebara Densan). A circuit was formed. The obtained substrate is referred to as “evaluation substrate A”. Hereinafter, the cured substrate A, the roughened substrate A, and the evaluation substrate A may be collectively referred to as “substrate A”.

<Production of Cured Substrate B, Roughened Substrate B, and Evaluation Substrate B>
In <Preparation of Cured Substrate A, Roughened Substrate A, and Evaluation Substrate A>, the resin sheet A used to form the insulating layer was changed to a resin sheet B. Except for the above, a cured substrate B, a roughened substrate B, and an evaluation substrate B were prepared in the same manner as in <Preparation of cured substrate A, roughened substrate A, and evaluation substrate A>. Hereinafter, the cured substrate B, the roughened substrate B, and the evaluation substrate B may be collectively referred to as “substrate B”.

[Evaluation test]
<Measurement of arithmetic average roughness (Ra), root mean square roughness (Rq)>
Ra value of the insulating layer surface of the roughened substrate A is obtained by using a non-contact type surface roughness meter (WYKO NT3300, manufactured by Beeco Instruments Co., Ltd.) with a VSI contact mode and a numerical value obtained with a measurement range of 121 μm × 92 μm by a 50 × lens. , Rq value was determined. The average value of each 6 points was calculated and shown in the table below.
Further, the same measurement was performed by changing the roughened substrate A to the roughened substrate B, and the results are shown in the following table.

<Measurement of plating adhesion (plating peel strength)>
In the conductor layer of the evaluation substrate A, cut a portion having a width of 10 mm and a length of 100 mm, peel off one end thereof, and use a gripping tool (manufactured by TS E Corp., Autocom type tester AC-50C-SL). Using a Instron universal testing machine, the load (kgf / cm) when 35 mm was peeled in the vertical direction at a speed of 50 mm / min at room temperature was measured, and the peel strength was obtained.
Further, the same measurement was performed by changing the evaluation substrate A to the evaluation substrate B, and the results are shown in the following table.

<Measurement of etching rate>
A sample A of 5 cm × 5 cm was cut out from the cured substrate A, dried at 130 ° C. for 15 minutes, and the mass immediately after the drying was measured. This is sample A, and the mass of sample A is “X1”. Sample A was desmeared (second roughening test) to obtain roughened sample A. The roughened sample A subjected to the second roughening test was washed with water, and the mass immediately after drying at 130 ° C. for 15 minutes was measured. The mass of the roughened sample A immediately after the drying is defined as “X2”. The etching rate (E2) (%) by the roughening process of the hardened | cured material of a resin composition was calculated | required by the following formula.
Etching rate (%) = {(X1-X2) / (X1-Y1)} × 100
Y1: Mass of the copper-clad laminate cut out to 5 cm × 5 cm Further, the cured substrate A was changed to the cured substrate B in the measurement of the etching rate (E2). Except for the above, the etching rate (E1) was measured in the same manner as the etching rate (E2).

<Presence or absence of circuit peeling>
With respect to the comb-tooth patterns i) to v) of the evaluation substrate A, the presence or absence of circuit peeling was confirmed with an optical microscope (manufactured by HIROX, KH-8700 product name). Further, the evaluation substrate A was changed to the evaluation substrate B, and the presence or absence of similar circuit peeling was confirmed. Of the above 10) comb tooth patterns of i) to v), when no circuit peeling was observed for 9 or more pieces, it was judged as “None”, and any one comb tooth pattern resulted in 8 pieces or less. Was evaluated as “Yes”.

<Presence / absence of electroless copper residue>
For the comb patterns of i) to v) of the evaluation substrate A, cross-sectional observation is performed using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.), and unnecessary electroless copper plating layer residues are removed. The presence or absence was confirmed. Further, the evaluation substrate A was changed to the evaluation substrate B, and the presence or absence of an electroless copper residue in a similar circuit was confirmed. When no electroless copper residue is observed for 9 or more of the 10 comb tooth patterns of i) to v) above, it is judged as “No”, and any one comb tooth pattern results in 8 or less. Was evaluated as “Yes”.

<Evaluation of microcircuit formation ability>
In the evaluation board A and the evaluation board B, in the evaluation of the presence / absence of circuit peeling and the presence / absence of the electroless copper residue, if all are “No”, it is determined as “O”, and even one is “Yes” Is “×”.

  In Examples 1 and 2 where the etching rate (E1) is 0.8 to 2.0 and the etching rate (E2) is 1.0 to 2.5, the influence of the thickness of the insulating layer when the fine wiring is formed It is hard to receive and it turns out that it is excellent in peel strength. Moreover, it turns out that circuit peeling and an electroless copper residue are suppressed. From these things, it can be said that Examples 1-2 are excellent in the ability to form a fine circuit. On the other hand, in Comparative Examples 1 and 2 in which the etching rate (E1) is 0.8 to 2.0 and / or the etching rate (E2) is not 1.0 to 2.5, It can be seen that the peel strength is inferior to those of Examples 1 and 2 due to the influence of the thickness. In addition, since the etching rate (E1) and / or the etching rate (E2) is out of the predetermined range, either circuit peeling or electroless copper residue cannot be suppressed. It turns out that it is inferior to microcircuit formation ability compared with Examples 1-2.

  In Examples 1 and 2, it was confirmed that even if the components (C) to (E) were not contained, the results were the same as those in the above examples although there was a difference in the degree.

DESCRIPTION OF SYMBOLS 1 1st conductor layer 11 Main surface 2 of 1st conductor layer 2nd conductor layer 21 Main surface of 2nd conductor layer 3 Insulating layer t1 Space | interval (1st conductor layer and 1st conductor layer) And the thickness of the insulating layer between the second conductor layers)
t2 Total thickness of insulating layer

Claims (14)

A resin composition comprising (A) an epoxy resin and (B) a curing agent,
The surface of the first layer having a thickness of 30 μm composed of a cured product obtained by thermally curing the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes is applied to the swelling liquid at 60 ° C. for 10 minutes. Etching rate (E1) in the first roughening test in which the sample is immersed in the solution at 80 ° C. for 20 minutes and in the neutralizing solution at 40 ° C. for 5 minutes, 0.8 ≦ E1 ≦ 2,
The surface of the second layer having a thickness of 10 μm consisting of a cured product obtained by thermally curing the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes is applied to the swelling liquid at 60 ° C. for 10 minutes. A resin composition in which an etching rate (E2) in a second roughening test in which a solution is immersed in a solution at 80 ° C. for 20 minutes and in a neutralizing solution at 40 ° C. for 5 minutes is 1 ≦ E2 ≦ 2.5.   The resin composition according to claim 1, which is for forming a wiring having a wiring pitch of 10 μm or less.   The resin composition according to claim 1 or 2, which is used for forming a wiring by a semi-additive construction method.   The resin composition according to any one of claims 1 to 3, which is used for forming an insulating layer of a printed wiring board.   The resin composition according to any one of claims 1 to 4, which is used for an interlayer insulating layer of a printed wiring board.   (C) The resin composition of any one of Claims 1-5 containing an inorganic filler.   The resin composition according to claim 6, 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.   (C) The resin composition of Claim 6 or 7 whose average particle diameter of a component is 0.05 micrometer-0.35 micrometer.   The resin composition of any one of Claims 1-8 containing a fluorine compound.   The resin composition according to claim 9, wherein the fluorine compound is a fluorine-containing epoxy resin.   The resin composition layer formed with the support body and the resin composition of any one of Claims 1-10 provided on this support body, The thickness of a resin composition layer is 30 micrometers or less There is a resin sheet.   For forming the insulating layer of a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer. The resin sheet according to claim 11. A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
The printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of claims 1 to 10.   A semiconductor device comprising the printed wiring board according to claim 13.

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