JP2018090708A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition of excellent compatibility, which forms an insulating layer having a low dielectric loss tangent, good plating adhesion and good adhesion to a base, and good smear removability.SOLUTION: A resin composition contains (A) an epoxy resin, (B) a curing agent, and (C) a compound having a cyclic ether structure with a 5 or more membered ring, where the content of (C) component is 1 mass%-50 mass% when the resin component is 100 mass%.SELECTED DRAWING: None

Description

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

  As a printed wiring board manufacturing technique, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer circuit board is known. The insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 describes a resin composition comprising (A) a radical polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component. .

JP 2014-034580 A

  Many proposals of an epoxy resin composition suitable for forming an insulating layer of an inner circuit board have been made including the resin composition described in Patent Document 1, but in recent years, an insulating layer excellent in low dielectric loss tangent has been proposed. There is an increasing demand for resin compositions that can be formed. In addition, as electronic devices become smaller and higher in performance, in multilayer printed wiring boards, the build-up layer is multilayered, and miniaturization and higher density of wiring are required.

  In order to achieve further miniaturization and higher density of wiring, resin composition with good compatibility that provides an insulating layer with low dielectric loss tangent, good plating adhesion and base adhesion, and excellent smear removability Things are required, but not all of these are met.

  An object of the present invention is to provide a resin composition having a good compatibility, which provides an insulating layer having a low dielectric loss tangent, good plating adhesion and base adhesion, and excellent smear removability; a sheet containing the resin composition An object of the present invention is to provide a printed circuit board including an insulating layer formed using the resin composition, and a semiconductor device.

  The present inventors have found that conventional general resin compositions have poor smear removability when the dielectric loss tangent is lowered, that is, the dielectric loss tangent and smear removability are in a trade-off relationship. As a result of intensive studies to solve the above problems, the present inventors have (A) an epoxy resin, (B) a curing agent, and a predetermined amount of (C) a cyclic ether structure having a 5-membered ring or more. It has been found that by containing a compound, an insulating layer having a low dielectric loss tangent, good plating adhesion and base adhesion, and excellent smear removability can be obtained, and the present invention has been completed.

［１３］ プリント配線板の絶縁層形成用である、［１］〜［１２］のいずれかに記載の樹脂組成物。
［１４］ プリント配線板の層間絶縁層形成用である、［１］〜［１２］のいずれかに記載の樹脂組成物。
［１５］ ［１］〜［１４］のいずれかに記載の樹脂組成物を含む、シート状基材。
［１６］ 支持体と、該支持体上に設けられた、［１］〜［１４］のいずれかに記載の樹脂組成物で形成された樹脂組成物層とを含む、接着フィルム。
［１７］ 第１の導体層、第２の導体層、及び、第１の導体層と第２の導体層との間に形成された絶縁層を含むプリント配線板であって、
該絶縁層は、［１］〜［１４］のいずれかに記載の樹脂組成物の硬化物である、プリント配線板。
［１８］ ［１７］に記載のプリント配線板を備える、半導体装置。 That is, the present invention includes the following contents.
[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) a compound having a cyclic ether structure of five or more members,
(C) The resin composition whose content of a component is 1 mass%-50 mass% when a resin component is 100 mass%.
[2] The resin composition according to [1], wherein the content of the component (A) is 5% by mass to 50% by mass when the resin component is 100% by mass.
[3] The resin composition according to [1] or [2], wherein the content of the component (B) is 5% by mass to 60% by mass when the resin component is 100% by mass.
[4] The resin composition according to any one of [1] to [3], wherein the component (B) is an active ester curing agent.
[5] The resin composition according to any one of [1] to [4], comprising (D) an inorganic filler.
[6] The resin composition according to [5], wherein the content of the component (D) is 50% by mass or more when the nonvolatile component of the resin composition is 100% by mass.
[7] The resin composition according to any one of [1] to [6], wherein the component (C) includes a dioxane structure.
[8] The resin composition according to any one of [1] to [7], wherein the component (C) has a carbon-carbon unsaturated bond.
[9] The resin composition according to any one of [1] to [8], wherein the component (C) has a carbon-carbon double bond.
[10] The component (C) has one or more functional groups selected from the group consisting of vinyl group, methacryl group, acrylic group, allyl group, styryl group, and propenyl group, [1] to [9] The resin composition in any one of.
[11] The resin composition according to any one of [1] to [10], wherein the component (C) has a vinyl group.
[12] The resin composition according to any one of [1] to [11], wherein the component (C) is the following compound.

[13] The resin composition according to any one of [1] to [12], which is used for forming an insulating layer of a printed wiring board.
[14] The resin composition according to any one of [1] to [12], which is for forming an interlayer insulating layer of a printed wiring board.
[15] A sheet-like substrate comprising the resin composition according to any one of [1] to [14].
[16] An adhesive film comprising a support and a resin composition layer formed on the support and formed from the resin composition according to any one of [1] to [14].
[17] 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 [14].
[18] A semiconductor device comprising the printed wiring board according to [17].

  According to the present invention, a resin composition having a low compatibility, a good dielectric compatibility, a good plating adhesion and base adhesion, and an insulating layer excellent in smear removal; a sheet containing the resin composition An adhesive film containing the resin composition; a printed wiring board including an insulating layer formed using the resin 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, sheet-like substrate, adhesive film, printed wiring board, and semiconductor device of the present invention will be described in detail.

[Resin composition]
The resin composition of the present invention is a resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) a compound having a cyclic ether structure of a 5-membered ring or more, and containing (C) component When the amount is 100% by mass of the resin component, the amount is 1% by mass to 50% by mass. As a result, it is possible to provide a resin composition with good compatibility that has an insulating layer with a low dielectric loss tangent, good plating adhesion and base adhesion, and excellent smear removability.

  The “resin component” refers to a component excluding the inorganic filler (D) described later among the non-volatile components constituting the resin composition. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Epoxy resin>
The resin composition 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. The epoxy resin has two or more epoxy groups in one molecule and is a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and / or three or more epoxy groups in one molecule. It is preferably a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. As the epoxy resin, a liquid epoxy resin and a solid epoxy resin may be used in combination.

  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.

  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. The range of 1: 0.1 to 1:10 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, when the resin component is 100% by mass from the viewpoint of obtaining an insulating layer showing good tensile fracture strength and insulation reliability. It is 10 mass% or more, More preferably, it is 20 mass% 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.

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

  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” and the like manufactured by DIC.

  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 between the epoxy resin and the curing agent is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] in the range of 1: 0.01 to 1: 3. 1: 0.015 to 1: 2 are more preferable, and 1: 0.02 to 1: 1.5 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.

  Although content of a hardening | curing agent is not specifically limited, When a resin component is 100 mass%, Preferably it is 60 mass% or less, More preferably, it is 55 mass% or less, More preferably, it is 50 mass% or less. The lower limit is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. By setting the content of the curing agent to 5% by mass or more, it is possible to improve plating adhesion and base adhesion. Further, when the amount is 60% by mass or less, the smear removability is improved in the active ester curing agent, and the dielectric loss tangent can be lowered in the phenol curing agent and the naphthol curing agent.

<(C) Compound having a cyclic ether structure of 5 or more member ring>
When the resin component is 100% by mass, the resin composition contains 1% by mass to 50% by mass of (C) a compound having a cyclic ether structure of five or more members.

  As described above, conventionally, there has been a trade-off relationship between dielectric loss tangent and smear removability, but (C) the dielectric loss tangent is lowered by containing a predetermined amount of a compound having a cyclic ether structure of five or more members. In addition, it is possible to improve the smear removability. A cyclic ether having 5 or more members has a property of low dielectric loss tangent because the movement of molecules is restricted. In addition, since cyclic ethers having 5 or more members are polar, they have a certain degree of hydrophilicity. The hydrophilic property facilitates removal of smear and improves smear removability. Furthermore, it is thought that compatibility, plating adhesion, and substrate adhesion are improved by having polarity and hydrophilicity. However, the technical scope of the present invention is not limited by the description of the mechanism that can obtain the effects described here.

  The number of oxygen atoms contained in the cyclic ether structure is preferably 1 or more, more preferably 2 or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. Although a minimum is not specifically limited, Preferably it is 5 or less, More preferably, it is 4 or less, More preferably, it is 3 or less.

  The cyclic ether structure having 5 or more members is not particularly limited as long as it has 5 or more members, and may be a monocyclic, polycyclic or condensed ring. Moreover, (C) component may have a some cyclic ether structure. The cyclic ether structure is preferably a 5- to 10-membered ring, more preferably a 5- to 8-membered ring, and even more preferably a 5- to 6-membered ring. Specific examples of the cyclic ether structure having five or more members include a furan structure, a tetrahydrofuran structure, a dioxolane structure, a pyran structure, a dihydropyran structure, a tetrahydropyran structure, a dioxane structure, etc. Among them, from the viewpoint of improving compatibility. The compound having a cyclic ether structure having a 5-membered ring or more preferably contains a dioxane structure. The dioxane structure is a concept including a 1,2-dioxane structure, a 1,3-dioxane structure and a 1,4-dioxane structure, and a 1,3-dioxane structure is preferable.

  Moreover, substituents, such as an alkyl group and an alkoxy group, may couple | bond with the cyclic ether structure 5 or more membered. These substituents usually have 1 to 6 carbon atoms (preferably 1 to 3).

  The component (C) preferably has a carbon-carbon unsaturated bond and more preferably has a carbon-carbon double bond from the viewpoint of lowering the dielectric loss tangent. The carbon-carbon unsaturated bond may be included in the cyclic ether structure or may be included outside the cyclic ether structure, but among them, it is preferable to have the functional group described later. A plurality of carbon-carbon unsaturated bonds may be contained in the component (C).

  The component (C) is selected from the group consisting of a vinyl group, a methacryl group, an acrylic group, an allyl group, a styryl group, and a propenyl group from the viewpoint of lowering the dielectric loss tangent and facilitating reaction with the component (A). It preferably has at least one kind of functional group, and more preferably has a vinyl group. The functional group may be contained in any of the components (C), may be contained in the cyclic ether structure, or may be contained outside the cyclic ether structure. You may have two or more functional groups.

（式（１）中、環Ａは５員環以上の環状エーテル構造を有する２価の基を表し、Ｂ^１及びＢ^２はそれぞれ独立に単結合又は２価の連結基を表し、Ｃ^１及びＣ^２はそれぞれ独立に官能基を表す。） The compound having a cyclic ether structure having 5 or more members is preferably represented by the following general formula (1).

(In formula (1), ring A represents a divalent group having a cyclic ether structure of 5 or more members, B ¹ and B ² each independently represents a single bond or a divalent linking group, and C ¹ and C ² each independently represents a functional group.)

  Ring A represents a divalent group having a cyclic ether structure of five or more members. The cyclic ether structure having 5 or more members is the same as the above cyclic ether structure having 5 or more members, and the preferred range is also the same.

  Specific examples of the divalent group having a cyclic ether structure of 5 or more members include a furan-2,5-diyl group, a tetrahydrofuran-2,5-diyl group, a dioxolane-2,5-diyl group, and a pyran- 2,5-diyl group, dihydropyran-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,2-dioxane-3,6-diyl group, 1,3-dioxane-2,5- Examples include diyl group, 1,4-dioxane-2,5-diyl group, 5-ethyl-1,3-dioxane-2,5-diyl group, and the like. 5-ethyl-1,3-dioxane-2,5 -Diyl groups are preferred.

B ¹ and B ² each independently represent a single bond or a divalent linking group, and a divalent linking group is preferred. Examples of the divalent linking group include an alkylene group that may have a substituent, an alkynylene group that may have a substituent, an arylene group that may have a substituent, and a substituent. A heteroarylene group, an ester bond, an ether bond, an amide bond, a urea bond, a urethane bond, a group represented by —C (═O) —, —S—, —SO—, —NH—, etc. A group obtained by combining a plurality of these groups.

  The alkylene group which may have a substituent is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or An alkylene group having 1 to 3 carbon atoms is more preferable. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a 1,1-dimethylethylene group. -A dimethylethylene group is preferred.

The alkylene group may have a substituent. The substituent is not particularly limited, for example, a halogen atom, -OH, _{-O-C 1-6} alkyl group, -N _{(C 1-6 alkyl) 2, C 1-6 alkyl, C 6- A 10} aryl group, —NH ₂ , —CN, —C (O) O—C _1-6 alkyl group, —COOH, —C (O) H, —NO _{2 and the} like.

Here, the term “C _pq ” (p and q are positive integers, satisfying p <q) means that the number of carbon atoms of the organic group described immediately after this term is p to q. Represents something. For example, the expression “C _1-6 alkyl group” refers to an alkyl group having 1 to 6 carbon atoms.

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

  The alkynylene group which may have a substituent is preferably an alkynylene group having 2 to 10 carbon atoms, more preferably an alkynylene group having 2 to 6 carbon atoms, and further an alkynylene group having 2 to 5 carbon atoms. preferable. Examples of the alkynylene group include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, and a hexynylene group. The substituent that the alkynylene group may have is the same as the substituent that the alkylene group may have.

  As the arylene group which may have a substituent, an arylene group having 6 to 14 carbon atoms is preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group. The substituent that the arylene group may have is the same as the substituent that the alkylene group may have.

  The heteroarylene group which may have a substituent is preferably a heteroarylene group having 3 to 15 carbon atoms, more preferably a heteroarylene group having 3 to 9 carbon atoms, and a heteroarylene group having 3 to 6 carbon atoms. More preferred is an arylene group. Examples of the heteroarylene group include a flangyl group, a pyridinediyl group, a thiophenediyl group, and the like. The substituent that the heteroarylene group may have is the same as the substituent that the alkylene group may have.

Among these, B ¹ and B ² are groups in which one or more are selected from an alkylene group which may have a substituent, an alkynylene group which may have a substituent, an ester bond and an ether bond. The alkylene group which may have a substituent and the group which selected 1 or more from the ester bond and combined are more preferable.

C ¹ and C ² each independently represent a functional group. Examples of the functional group include a vinyl group, a methacryl group, an acrylic group, an allyl group, a styryl group, a propenyl group, and an epoxy group, and a vinyl group is more preferable.

Hereinafter, although the specific example (exemplary compound) of (C) component is shown, (C) component is not limited to these.

  As the component (C), commercially available products may be used. For example, “A-DOG” (compound of the above specific example) manufactured by Shin-Nakamura Chemical Co., Ltd., “KAYARAD R-604” manufactured by Nippon Kayaku Co., Ltd. Compounds of specific examples) and the like.

  The content of the component (C) is 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more when the resin component is 100% by mass. The upper limit is 50% by mass or less, preferably 48% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less. By setting the content to 1% by mass or more, the dielectric loss tangent can be lowered and further the smear removability can be improved. By setting the content to 50% by mass or less, the plating adhesion and the base adhesion can be improved. it can.

  The mass ratio of the epoxy resin to the component (C) (epoxy resin: mass of the component (C)) is preferably in the range of 1: 0.01 to 1: 100, and in the range of 1: 0.1 to 1:90. More preferably, the range of 1: 0.1 to 1:80 is more preferable. By making it in such a range, compatibility can be improved.

<(D) Inorganic filler>
The resin composition may contain an inorganic filler (D) in addition to the components (A) to (C) from the viewpoint of reducing the dielectric loss tangent and improving the smear removability.

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

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in 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 alkoxysilane, 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 surface-treated with 0.2 to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the inorganic filler from the viewpoint of improving 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 an increase in the 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.

  When the resin composition contains an inorganic filler, the content of the inorganic filler is from the viewpoint of lowering the dielectric loss tangent and improving smear removability, when the nonvolatile component in the resin composition is 100% by mass, Preferably it is 50 mass% or more, More preferably, it is 55 mass% or more, More preferably, it is 60 mass% or more, 65 mass% or more, or 70 mass% or more. The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, or 75% by mass from the viewpoint of the mechanical strength of the insulating layer. % Or less.

<(E) Curing accelerator>
In one embodiment, the resin composition may contain (E) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and organic peroxide-based curing accelerators. A phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an imidazole curing accelerator and an organic peroxide 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-me Examples thereof include imidazole compounds such as ru-3-benzylimidazolium chloride, 2-methylimidazoline, 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.

  Examples of organic peroxide curing accelerators include dicumyl peroxide, cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, and di-tert-butyl. Examples thereof include peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide and the like. A commercially available product may be used as the organic peroxide curing accelerator, and examples thereof include “Park Mill D” manufactured by NOF Corporation.

  When the resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass to 1% by mass when the nonvolatile component in the resin composition is 100% by mass. The mass% is more preferably 0.5% by mass, and more preferably 0.01% by mass to 0.1% by mass.

<(F) Indencoumarone resin>
In one embodiment, the resin composition may contain (F) indene coumarone resin. Examples of the indene coumarone resin include a copolymer of indene and coumarone, a copolymer of indene, coumarone and styrene, and the like.

  The content ratio of the coumarone component in the indene coumarone resin is preferably 5 mol% or more, more preferably 8 mol% or more, and further preferably 10 mol% or more. The upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, still more preferably 30 mol% or less.

  The content ratio of the indene component in the indene coumarone resin is preferably 30 mol% or more, more preferably 35 mol% or more, and further preferably 40 mol% or more. The upper limit is preferably 80 mol% or less, more preferably 75 mol% or less, and still more preferably 70 mol% or less.

  When the indencoumarone resin is a copolymer of indene, coumarone and styrene, the content ratio of the styrene component is preferably 20 mol% or more, more preferably 25 mol% or more, and further preferably 30 mol% or more. The upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and still more preferably 60 mol% or less.

  Specific examples of indene coumarone resins include “H-100”, “V-120S”, “V-120”, etc., manufactured by Nikko Chemical.

  When the resin composition contains an indencoumarone resin, from the viewpoint of improving compatibility, the content of the indencoumarone resin is 0.1 to 3 when the nonvolatile component in the resin composition is 100% by mass. % By mass is preferred, 0.3-2% by mass is more preferred, and 0.5-1.5% by mass is more preferred.

<(G) Thermoplastic resin>
In one embodiment, the resin composition may contain (G) 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 NS ”,“ 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 an oligophenylene ether / styrene resin “OPE-2St 1200” having a vinyl group 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 1 to 10% by mass, and preferably 1.5 to 5% by mass when the nonvolatile component in the resin composition is 100% by mass. Is more preferable, and 2% by mass to 5% by mass is more preferable.

<(H) Flame retardant>
In one embodiment, the resin composition may contain (H) 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 to 20% by mass, and preferably 0.5 to 15% by mass when the nonvolatile component in the resin composition is 100% by mass. Is more preferable, and 0.5-10 mass% is further more preferable.

<(I) Organic filler>
In one embodiment, the resin composition may contain (I) an organic filler. (I) By containing a component, the tensile fracture strength of the hardened | cured material of the resin composition layer of an adhesive film 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 to 20% by mass, and preferably 0.2 to 10% when the nonvolatile component in the resin composition is 100% by mass. The mass% is more preferable, and 0.3 to 5 mass%, or 0.5 to 3 mass% is more preferable.

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

<Physical properties and uses of resin composition>
The resin composition of the present invention has a low dielectric loss tangent, good plating adhesion and base adhesion, can provide an insulating layer with excellent smear removability, and good compatibility. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and interlayer insulation of the printed wiring board. It can be more suitably used as a resin composition for forming a layer (a resin composition for an interlayer insulating layer of a printed wiring board). Moreover, since the resin composition of this invention brings about an insulating layer favorable for component embedding property, it can be used conveniently also when a printed wiring board is a component built-in circuit board.

  A cured product obtained by thermally curing the resin composition at 190 ° C. for 90 minutes exhibits a characteristic that the dielectric loss tangent is low. That is, an insulating layer having a low dielectric loss tangent is provided. The dielectric loss tangent is preferably 0.005 or less, more preferably 0.0045 or less, and still more preferably 0.004 or less. The lower limit is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in <Measurement of dielectric loss tangent> described later.

  A cured product obtained by thermosetting the resin composition at 190 ° C. for 90 minutes exhibits a property of excellent adhesion (plating adhesion) with a conductor layer made of plating or the like. That is, an insulating layer showing good plating adhesion is provided. The plating adhesion is preferably more than 0.3 kgf / cm, more preferably 0.31 kgf / cm or more, and still more preferably 0.32 kgf / cm or more. The upper limit is not particularly limited, but may be 10 kgf / cm or less, 1 kgf / cm or less, or the like. The plating adhesion can be measured according to the method described in <Measurement of plating adhesion> described later.

  A cured product obtained by thermally curing the resin composition at 190 ° C. for 90 minutes exhibits the property of being excellent in adhesiveness (base adhesiveness) with a copper foil or the like. That is, an insulating layer showing good base adhesion is provided. The substrate adhesion is preferably more than 0.3 kgf / cm, more preferably 0.31 kgf / cm or more, and still more preferably 0.32 kgf / cm or more. The upper limit is not particularly limited, but may be 10 kgf / cm or less, 1 kgf / cm or less, or the like. The base adhesion can be measured according to the method described in <Measurement of base adhesion> described later.

  A cured product obtained by thermally curing the resin composition at 190 ° C. for 90 minutes exhibits a characteristic that smears generated during via hole formation are easily removed (excellent smear removability). That is, an insulating layer exhibiting good smear removability is provided. Since the smear removal property is excellent, the maximum smear length measured from the wall surface side of the bottom of the via hole is preferably less than 3 μm, more preferably 2.5 μm or less, and even more preferably 2 μm or less. The lower limit is not particularly limited, but may be 0.01 μm or more. The smear removability can be measured according to the method described in <Evaluation of smear removability at the bottom of via hole> described later.

  Since the resin composition contains a predetermined amount of the component (C), the resin composition exhibits excellent compatibility. Since the resin composition is excellent in compatibility, the resin composition is preferably observed with no precipitation of coarse particles and oil droplets of 30 μm or more (more preferably 40 μm or more, more preferably 50 μm or more).

[Sheet substrate]
The resin composition of the present invention can be used by being applied in a varnish state, but industrially, it is generally preferable to use it in the form of a sheet-like substrate containing the resin composition. As the sheet-like substrate, the following adhesive film and prepreg are preferable.

<Adhesive film>
In one embodiment, the adhesive film includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

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

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

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

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

  The support may be subjected to mat treatment, 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.

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

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

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

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

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

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

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

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

[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).

  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.

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

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

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurizing laminator.

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

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

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

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

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

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

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

  In one embodiment, the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it is 1 nm or more. The root mean square roughness Rq of the insulating layer surface after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it is 1 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact type surface roughness meter.

  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 the adhesive film of the present invention provides an insulating layer with good component embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board. The component built-in circuit board can be manufactured by a known manufacturing method.

  A printed wiring board manufactured using the adhesive film of the present invention is an aspect including an insulating layer that is a cured product of the resin composition layer of the adhesive film, and an embedded wiring layer embedded in the insulating layer. Also good.

  In other embodiments, the printed wiring board can be manufactured using the prepreg described above. The manufacturing method is basically the same as when an adhesive film is used.

[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 is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the wire bonding mounting method, the flip chip mounting method, and the bumpless buildup layer are used. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. 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.

<Example 1>
40 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was dissolved in 30 parts of solvent naphtha with stirring and then cooled to room temperature. 330 parts of an inorganic filler (“SO-C2” manufactured by Admatechs Co., Ltd., average particle diameter of 0.5 μm, carbon amount per unit surface area of 0.38 mg / m ² ) were mixed, and kneaded and dispersed with three rolls. Thereto, 92.3 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC, 65% non-volatile toluene solution having an active group equivalent of about 223), a compound having a cyclic ether structure of 5 or more members. ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.) 15 parts, 5 parts of indencoumarone resin ("H-100" manufactured by Nikkaku Chemical Co., Ltd.), 5% of 4-dimethylaminopyridine (DMAP) as a curing accelerator 2 parts of MEK solution and 0.13 part of dicumyl peroxide (“PARK Mill D” manufactured by NOF Corporation) were mixed and dispersed uniformly with a rotary mixer to prepare Resin Varnish 1.

  The resin varnish 1 is placed on the release surface of a polyethylene terephthalate film with an alkyd release treatment (PET film, “AL-5” manufactured by Lintec Corporation, thickness 38 μm), and the thickness of the resin composition layer after drying is 40 μm Then, it was uniformly coated with a die coater and dried at 80 to 110 ° C. (average 95 ° C.) for 5 minutes to prepare an adhesive film 1.

<Example 2>
In Example 1, the bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was changed from 40 parts to 25 parts, and an inorganic filler (“SO-C2” manufactured by Admatechs Co., Ltd.) The diameter was changed to 0.5 μm and the carbon amount per unit surface area of 0.38 mg / m ² was changed from 330 parts to 320 parts, and an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, active group equivalent of about 223). 15% of a compound (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) having a cyclic ether structure of 5 or more members is changed from 92.3 parts to 61.5 parts. To 40 parts. Except for the above, a resin varnish 2 and an adhesive film 2 were produced in the same manner as in Example 1.

<Example 3>
In Example 1, a compound having a cyclic ether structure having a 5-membered ring or more (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) was changed from 15 parts to 1.5 parts, and a bixylenol type epoxy resin (Mitsubishi Chemical Corporation) was changed. “YX4000HK”, epoxy equivalent of about 185) was changed from 40 parts to 45 parts, and an active ester curing agent (“HPC-8000-65T” manufactured by DIC, toluene solution of 65% non-volatile content of active group equivalent of about 223) ) Was changed from 92.3 parts to 84.6 parts, and further, 22.5 parts of a thermoplastic resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Inc., toluene solution with a nonvolatile content of 60%) was mixed. Except for the above, a resin varnish 3 and an adhesive film 3 were produced in the same manner as in Example 1.

<Example 4>
In Example 1, the xylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was changed from 40 parts to 20 parts, and an inorganic filler (“SO-C2” manufactured by Admatechs Co., Ltd.) The diameter of 0.5 μm and the amount of carbon per unit surface area of 0.38 mg / m ² was changed from 330 parts to 310 parts, and an active ester curing agent (“HPC-8000-65T” manufactured by DIC, active group equivalent of about 223) 15% of a compound (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) having a cyclic ether structure of 5 or more members is changed from 92.3 parts to 46.2 parts. To 50 parts. Except for the above, a resin varnish 4 and an adhesive film 4 were produced in the same manner as in Example 1.

<Comparative Example 1>
In Example 1, the xylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was changed from 40 parts to 20 parts, and an inorganic filler (“SO-C2” manufactured by Admatechs Co., Ltd.) The diameter of 0.5 μm and the amount of carbon per unit surface area of 0.38 mg / m ² was changed from 330 parts to 310 parts, and an active ester curing agent (“HPC-8000-65T” manufactured by DIC, active group equivalent of about 223) 15% of a compound (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) having a cyclic ether structure of 5 or more members is changed from 92.3 parts to 46.2 parts. To 60 parts. Except for the above, a resin varnish 5 and an adhesive film 5 were produced in the same manner as in Example 1.

<Comparative example 2>
In Example 3, a compound having a cyclic ether structure of 5 or more members (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) was changed from 1.5 parts to 0.5 parts, and a thermoplastic resin (Mitsubishi Gas Chemical Co., Ltd.) was used. “OPE-2St 1200” (a toluene solution with a nonvolatile content of 60%) was changed from 22.5 parts to 24.2 parts. Except for the above, a resin varnish 6 and an adhesive film 6 were produced in the same manner as in Example 3.

<Comparative Example 3>
In Example 1, 15 parts of a compound having a cyclic ether structure of 5 or more members (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) is added to a resin having a vinyl group (“23G” manufactured by Shin-Nakamura Chemical Co., Ltd.) 15 Changed to the department. Except for the above, a resin varnish 7 and an adhesive film 7 were produced in the same manner as in Example 1.

<Comparative Example 4>
In Example 1, 15 parts of a compound having a cyclic ether structure having a 5-membered ring or more (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) is added to a resin having a vinyl group (“A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.). ) Changed to 15 copies. Except for the above, a resin varnish 8 and an adhesive film 8 were produced in the same manner as in Example 1.

<Comparative Example 5>
In Example 1, 15 parts of a compound having a cyclic ether structure of 5 or more members (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to a thermoplastic resin (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Co., Inc.). Min. 60% toluene solution). Except for the above, a resin varnish 9 and an adhesive film 9 were produced in the same manner as in Example 1.

[Evaluation method]
<Preparation of sample for evaluation of cured properties>
The adhesive films obtained in Examples and Comparative Examples were thermally cured at 190 ° C. for 90 minutes, and a PET film as a support was peeled off to prepare a sheet-like cured product evaluation sample.

<Measurement of dielectric loss tangent>
A test piece having a width of 2 mm and a length of 80 mm was cut out from the cured product evaluation sample. About the cut-out test piece, the dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using a measuring device “HP8362B” manufactured by Agilent Technologies, Inc. Evaluated by criteria.

<Evaluation of compatibility>
The resin composition layer side of the adhesive films prepared in Examples and Comparative Examples was observed with a microscope (“DIGITAL MICROSCOPE KH-8700” manufactured by Hilox Co., Ltd.) in an area of 1 cm ² to confirm the presence or absence of coarse particles. And evaluated according to the following criteria.
Good: Precipitation of coarse particles of 50 μm or more and oil droplets are not observed in the resin composition layer.
Poor: Precipitation of coarse particles of 50 μm or more and oil droplets are observed in the resin composition layer.

<Preparation of evaluation substrate>
(1) Substrate base treatment A glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic “R1515A”) on which an inner layer circuit was formed was prepared. This laminated board has copper foil as a 1st conductor layer on the surface. Both surfaces of this laminate were immersed in “CZ8101” manufactured by MEC and etched by 1 μm to roughen the copper surface, thereby producing an inner circuit board.

(2) Laminating treatment of adhesive film The adhesive film produced in the examples and comparative examples was prepared by using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Co., Ltd.), and the resin composition layer and the inner circuit board. Lamination was performed on both sides of the inner circuit board so as to be bonded. The laminating process was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Thereafter, the resin composition layer was cured by heating at 190 ° C. for 90 minutes in an oven to obtain an insulating layer.

(3) Via hole formation Using a CO ₂ laser processing machine (LC-2E21B / 1C) manufactured by Hitachi Via Mechanics, mask diameter 1.60 mm, focus offset value 0.050, pulse width 25 μs, power 0.66 W, aperture 13 A part of the insulating layer was irradiated with a laser under the conditions of two shots and a burst mode, and a part of the insulating layer was punched. The top diameter (diameter) of the hole (via hole) formed by drilling was 50 μm. Thereafter, the PET film as the support was peeled off.

(4) Roughening treatment The internal circuit board on which the insulating layer was formed was wet-roughened using a surface treatment agent kit of a swelling liquid, an oxidizing agent, and a neutralizing liquid. Specifically, the interior circuit board on which the insulating layer is formed is added to a swelling liquid, diethylene glycol monobutyl ether-containing swelling dip securigant P (glycol ether, aqueous solution of sodium hydroxide) at 60 ° C., which is a swelling liquid. For 10 minutes, and then as an oxidant, immersed in Atotech Japan's Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally neutralized As a liquid, it was immersed for 5 minutes at 40 ° C. in Reduction Sholysin Securigant P (an aqueous solution of sulfuric acid) manufactured by Atotech Japan, and then dried at 80 ° C. for 30 minutes. The obtained substrate was designated as evaluation substrate A.

(5) Plating by semi-additive method Evaluation substrate A was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. The immersed evaluation substrate A was heated at 150 ° C. for 30 minutes for annealing treatment, and then subjected to copper sulfate electrolytic plating to form a second conductor layer with a thickness of 30 μm. The obtained evaluation substrate A having the second conductor layer was annealed at 190 ° C. for 60 minutes, and the obtained substrate was used as an evaluation substrate B.

<Measurement of plating adhesion>
A notch with a width of 10 mm and a length of 100 mm is made in the second conductor layer of the evaluation board B, and one end thereof is peeled off to grasp the grip (manufactured by TS E Corp., Autocom type tester AC-50C-SL ) And measured the load (kgf / cm) when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature (25 ° C.), and evaluated according to the following criteria.

<Evaluation of smear removability at the bottom of via hole>
The periphery of the via hole bottom of the evaluation substrate A was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface side of the via hole bottom was measured from the obtained image. Here, the “maximum smear length” means the maximum smear length from the circumference of the via bottom to the center of the circle. The evaluation is as follows.
Good: Maximum smear length is less than 3 μm Bad: Maximum smear length is 3 μm or more

<Measurement of substrate adhesion>
(1) Substrate treatment of copper foil The glossy surface of “3EC-III” (electrolytic copper foil, 35 μm) manufactured by Mitsui Kinzoku Mining Co., Ltd. is immersed in Mec etch bond “CZ-8101” manufactured by Mec Co., Ltd. to roughen the copper surface. (Ra value = 1 μm) was performed, and rust prevention treatment (CL8300) was performed. This copper foil is called CZ copper foil. Furthermore, it heat-processed for 30 minutes in 130 degreeC oven.

(2) Lamination of copper foil and formation of an insulating layer Using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Co., Ltd.) Lamination was performed on both sides of the inner circuit board so as to be bonded to the circuit board. The laminating process was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. The PET film as a support was peeled from the laminated adhesive film. The treated surface of the “3EC-III” CZ copper foil was laminated on the resin composition layer from which the support was peeled off under the same conditions as described above. And the sample was produced by hardening | curing a resin composition layer on 190 degreeC and the hardening conditions for 90 minutes, and forming an insulating layer.

(3) Measurement of copper foil peeling strength (adhesion) The prepared sample was cut into small pieces of 150 x 30 mm. Cut the copper foil part of the small piece into a 10 mm wide and 100 mm long part using a cutter, peel off one end of the copper foil and make a gripping tool (manufactured by TS E Corp., Autocom testing machine, AC-50C-SL "), and using an Instron universal testing machine, measure the load when peeling 35 mm vertically at a speed of 50 mm / min in accordance with JIS C6481 at room temperature. The evaluation was based on the following criteria.

The results of the above-described examples and comparative examples are shown in the following table. In the following table, the meanings of the abbreviations are as follows.
YX4000HK: Bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation)
HPC-8000-65T: active ester curing agent (“HPC-8000-65T” manufactured by DIC)
A-DOG: Dioxane acrylic monomer (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-DCP: Dicyclopentane acrylic monomer (“A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.)
23G: Ethylene oxide acrylic monomer (Shin Nakamura Chemical Co., Ltd. “23G”)
OPE-2St 1200: Thermoplastic resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company)
H-100: Indencoumarone resin (“H-100” manufactured by Nikkaku Chemical Co., Ltd.)
SO-C2: Spherical silica ("SO-C2" manufactured by Admatechs)
Park mill D: Dicumyl peroxide (manufactured by NOF Corporation)
DMAP: 4-dimethylaminopyridine In the table, the compounding amount is a solid content conversion value, “content of component (A) (mass%)”, “content of component (B) (mass%)”, And "content (mass%) of (C) component" represents content when a resin component is 100 mass%.

  From the results of Table 1, Examples 1-4 containing the components (A) to (C) and containing the predetermined amount of the component (C) are dielectric loss tangent, compatibility, plating adhesion, base adhesion, and smear. It can be seen that all the removability is excellent.

On the other hand, Comparative Example 1 containing the components (A) to (C), but the content of the component (C) exceeds 50% by mass when the resin component is 100% by mass, the plating adhesion and the base adhesion are carried out. It turns out that it is inferior compared with Examples 1-4.
Comparative Example 2 that contains the components (A) to (C) but the content of the component (C) is less than 1% by mass when the resin component is 100% by mass has a smear removability as in Examples 1 to 4. It turns out that it is inferior compared.
(C) It turns out that the comparative example 3 which does not contain a component is inferior in dielectric loss tangent compared with Examples 1-4.
Further, Comparative Examples 4 to 5 containing no component (C) could not measure the dielectric loss tangent, plating adhesion, base adhesion, and smear removability because of poor compatibility.

  In Examples 1 to 4, it was confirmed that even if the components (D) to (G) were not contained, the results were the same as those in the above examples although there was a difference in 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 (18)

A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) a compound having a cyclic ether structure of five or more members,
(C) The resin composition whose content of a component is 1 mass%-50 mass% when a resin component is 100 mass%.   The resin composition according to claim 1, wherein the content of the component (A) is 5% by mass to 50% by mass when the resin component is 100% by mass.   The resin composition according to claim 1 or 2, wherein the content of the component (B) is 5% by mass to 60% by mass when the resin component is 100% by mass.   The resin composition according to any one of claims 1 to 3, wherein the component (B) is an active ester curing agent.   (D) The resin composition of any one of Claims 1-4 containing an inorganic filler.   (D) The resin composition of Claim 5 whose content of a component is 50 mass% or more when the non-volatile component of a resin composition is 100 mass%.   (C) The resin composition of any one of Claims 1-6 in which a component contains a dioxane structure.   The resin composition according to any one of claims 1 to 7, wherein the component (C) has a carbon-carbon unsaturated bond.   The resin composition according to any one of claims 1 to 8, wherein the component (C) has a carbon-carbon double bond.   The component (C) has one or more functional groups selected from the group consisting of a vinyl group, a methacryl group, an acrylic group, an allyl group, a styryl group, and a propenyl group. The resin composition described in 1.   (C) The resin composition of any one of Claims 1-10 in which a component has a vinyl group. (C) The resin composition of any one of Claims 1-11 whose component is the following compound.

  The resin composition according to any one of claims 1 to 12, which is used for forming an insulating layer of a printed wiring board.   The resin composition according to any one of claims 1 to 12, which is used for forming an interlayer insulating layer of a printed wiring board.   The sheet-like base material containing the resin composition of any one of Claims 1-14.   The adhesive film containing a support body and the resin composition layer formed with the resin composition of any one of Claims 1-14 provided on this support body. 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 14.   A semiconductor device comprising the printed wiring board according to claim 17.

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