JP6776577B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions. Further, the present invention relates to an adhesive film, a printed wiring board, and a semiconductor device.

As a manufacturing technique for a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately stacked on an inner layer substrate is known. The insulating layer is generally formed by curing the resin composition. For example, Patent Document 1 describes a resin composition containing a specific epoxy resin and a curing agent, which has low dielectric constant and high heat resistance.

JP-A-2015-57465

In recent years, the miniaturization and high performance of electronic devices have progressed, and in multi-layer printed wiring boards, the build-up layer has been made into multiple layers, and there is a demand for miniaturization and high density of wiring. In order to achieve further miniaturization and high density of wiring, a resin composition having good compatibility and melt viscosity, which provides an insulating layer having low dielectric loss tangent and excellent plating adhesion and substrate adhesion, is required. However, the current situation is that all of these have not been met.

An object of the present invention is to provide a resin composition having good compatibility and melt viscosity, which provides an insulating layer having low dielectric loss tangent and excellent plating adhesion and substrate adhesion.

As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by using a resin having a vinyl group in combination with a predetermined amount of indene marron resin, and have completed the present invention. It was.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a resin having a vinyl group, and (D) an indene marron resin.
A resin composition in which the content of the component (D) is 5% by mass to 20% by mass when the resin component is 100% by mass.
[2] The resin composition according to [1], wherein at least one of the components (C) has an aromatic ring.
[3] The resin composition according to [1] or [2], wherein the content of the component (C) is 5% by mass to 20% by mass when the resin component is 100% by mass.
[4] The resin composition according to any one of [1] to [3], wherein at least one of the components (B) is an active ester-based curing agent.
[5] The resin composition according to any one of [1] to [4], further comprising (E) an inorganic filler.
[6] The resin composition according to [5], wherein the content of the component (E) is 50% by mass or more when the non-volatile component of the resin composition is 100% by mass.
[7] The resin composition according to any one of [1] to [6], wherein the component (D) is a copolymer of indene, kumaron, and styrene.
[8] The resin composition according to any one of [1] to [7], which is used for forming an insulating layer of a printed wiring board.
[9] An adhesive film comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [8].
[10] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [8].
[11] A semiconductor device including the printed wiring board according to [10].

According to the present invention, it is possible to provide a resin composition having good compatibility and melt viscosity, which provides an insulating layer having a low dielectric loss tangent and excellent plating adhesion and substrate adhesion.

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

[Resin composition]
The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, (C) a resin having a vinyl group, and (D) an indenkumaron resin, and the content of the component (D) is a resin. When the component is 100% by mass, it is 5% by mass to 20% by mass. In the present invention, the “resin component” refers to a component of the non-volatile components constituting the resin composition, excluding the (E) inorganic filler described later. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) Epoxy resin>
The resin composition of the present invention contains (A) an epoxy resin. Examples of the epoxy resin include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy resin. Naftor novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene Examples thereof include ether type epoxy resin, trimethylol type epoxy resin, and tetraphenylethane type epoxy resin. One type of epoxy resin may be used alone, or two or more types may be used in combination. The component (A) is preferably an aromatic skeleton-containing epoxy resin from the viewpoint of reducing the average linear thermal expansion rate, and is preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a diphenyl type epoxy resin. It is more preferably one or more selected from the cyclopentadiene type epoxy resin, and the biphenyl type epoxy resin is further preferable. The aromatic skeleton is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles.

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

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. The alicyclic epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure are preferable, and glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and 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 Co., Ltd., "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. , "Epicoat 828EL" (bisphenol A type epoxy resin), "jER807", "1750" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine) Type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type) Epoxy resin), "Selokiside 2021P" manufactured by Daicel Co., Ltd. (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "Selokiside 2021P" manufactured by Nippon Steel Chemical Co., Ltd. Examples thereof include "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane), and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid epoxy resin 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, and 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), and "N-690" manufactured by DIC Co., Ltd. (Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA" -7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN "manufactured by Nippon Kayaku Co., Ltd. -502H "(Trisphenol type epoxy resin)," NC7000L "(Naftor novolac type epoxy resin)," NC3000H "," NC3000 "," NC3000L "," NC3100 "(biphenyl type epoxy resin), Nippon Steel & Sumitomo Metal Corporation "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), Mitsubishi Chemical Co., Ltd. "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (Bixilenoll type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" manufactured by Mitsubishi Chemical Co., Ltd. ( Bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. Can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their quantity ratio (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:15 in terms of mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) appropriate adhesiveness is provided when used in the form of an adhesive film, and ii) when used in the form of an adhesive film. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.5 to 1:10 in terms of mass ratio. Is more preferable, and the range of 1: 1 to 1: 8 is even more preferable.

The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10 when the resin component is 100% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. By mass or more, more preferably 20% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by 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. Within this range, the crosslink density of the cured product becomes 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 the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<(B) Hardener>
The resin composition of the present invention contains (B) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a curing agent. Examples include carbodiimide-based curing agents. The curing agent may be used alone or in combination of two or more. The component (B) is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a carbodiimide-based curing agent, and a cyanate ester-based curing agent, and is preferably an active ester-based 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. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851", "MEH-7851H" manufactured by Meiwa Kasei Co., Ltd. "NHN", "CBN", "GPH" manufactured by Yakuhin Co., Ltd., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN495" manufactured by Nippon Steel & Sumitomo Metal Corporation "SN375", "SN395", "TD-2090", "LA-7052", "LA-7554", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC Corporation. And so on.

An active ester-based curing agent is preferable from the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer. The active ester-based curing agent is not particularly limited, but generally contains one molecule of an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. A compound having two or more of them is preferably used. The active ester-based 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-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based 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, pyromellitic acid and the like. 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, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

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 phenol novolac, and an active ester compound containing a benzoyl product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

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

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Chemicals Corporation.

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), 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 Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (bisphenol A disicanate) manufactured by Ronza Japan Co., Ltd. Prepolymers in which some or all of them are triazined to form a trimer) and the like.

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

The amount ratio of the epoxy resin to the curing agent is a ratio of [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the curing agent], preferably in the range of 1: 0.1 to 1:10. 1: 0.5 to 1: 5 is more preferable, and 1: 1 to 1: 3 is even more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is The value obtained by dividing the solid content mass of each curing agent by the reaction group equivalent is the total value for all the curing agents. By setting the amount ratio of the epoxy resin and the curing agent within such a range, the heat resistance of the cured product of the resin composition is further improved.

The content of the curing agent in the resin composition is not particularly limited, but when the resin component is 100% by mass, it is preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less. .. The lower limit is not particularly limited, but is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more.

<(C) Resin having a vinyl group>
The resin composition of the present invention contains (C) a resin having a vinyl group. By containing the component (C) in combination with the component (D) described later, a resin composition having good compatibility and melt viscosity, which provides an insulating layer having low dielectric loss tangent and excellent plating adhesion and substrate adhesion, can be obtained. be able to. The component (C) may be used alone or in combination of two or more.

（式（１）中、Ｒ^１〜Ｒ^６はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基を表し、Ａは、下記式（２）又は下記式（３）で表される基を表す。）

（式（２）中、Ｅは下記式（Ｅ−１）、（Ｅ−２）又は（Ｅ−３）を表す。）

（式（３）中、Ｒ^７〜Ｒ^１４はそれぞれ独立に水素原子、炭素原子数６以下のアルキル基又はフェニル基を表し、Ｅは下記式（Ｅ−１）、（Ｅ−２）又は（Ｅ−３）を表す。ａ、ｂは、少なくとも一方が０でない０〜１００の整数を表す。）

（式（Ｅ−１）〜（Ｅ−３）中、Ｒ^１５〜Ｒ^３４はそれぞれ独立に水素原子、炭素原子数６以下のアルキル基、又はフェニル基を表す。Ｇは、炭素原子数２０以下の直鎖状、分岐状又は環状の２価の炭化水素基を表す。） The component (C) is not particularly limited as long as it has a vinyl group, but preferably has an aromatic ring, and above all, a resin represented by the following formula (1) is preferable from the viewpoint of storage stability. ..

(In the formula (1), R ^{1 to} R ⁶ independently represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, respectively, and A is a group represented by the following formula (2) or the following formula (3). Represents.)

(In the formula (2), E represents the following formula (E-1), (E-2) or (E-3))

(In the formula (3), R ^{7 to} R ¹⁴ independently represent a hydrogen atom and an alkyl group or a phenyl group having 6 or less carbon atoms, respectively, and E represents the following formula (E-1), (E-2) or ( Represents E-3). A and b represent integers from 0 to 100 in which at least one of them is not 0.)

(In formulas (E-1) to (E-3), R ^{15 to} R ³⁴ independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. G has 20 or less carbon atoms. Represents a linear, branched or cyclic divalent hydrocarbon group.

In the formula (1), R ^{1 to} R ⁶ independently represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and are preferably hydrogen atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group and the like.

R ^{7 to} R ^{14 in} the formula (3) and R ^{15 to} R ³⁴ in the formulas (E-1) to (E-3) are independently hydrogen atoms, alkyl groups having 6 or less carbon atoms, or phenyl. Represents a group. Examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group and the like. As R ^{7 to} R ¹⁴ , a hydrogen atom and a methyl group are preferable.

At least one of a and b represents an integer of 0 to 100 which is not 0, an integer of 0 to 50 is preferable, and an integer of 0 to 10 is more preferable.

G represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. Examples of the divalent hydrocarbon group include an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, and an alkynylene group having 2 to 20 carbon atoms. Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group and a butylene group. Examples of the alkenylene group having 2 to 20 carbon atoms include a vinylene group, a propenylene group, and a butenylene group. Examples of the alkynylene group having 2 to 20 carbon atoms include an ethynylene group, a propynylene group, and a butynylene group.

The vinyl group in the resin having a vinyl group may have a substituent. Further, the above-mentioned alkyl group, phenyl group, and divalent hydrocarbon group may also have a substituent.

The substituent is not particularly limited, and is, for example, a halogen atom, -OH, -OC _1-6 alkyl group, -N (C _1-6 alkyl group) ₂ , C _1-6 alkyl group, C _6-. Examples thereof include 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 _p-q " (p and q are positive integers and satisfy p <q) is described immediately after this term and the number of carbon atoms of the organic group is p to q. Indicates that there is. For example, the expression "C _1-6 alkyl group" indicates an alkyl group having 1 to 6 carbon atoms.

The above-mentioned substituent may further have a substituent (hereinafter, may be referred to as a "secondary substituent"). Unless otherwise specified, the same as the above-mentioned substituent may be used as the secondary substituent.

（式中、Ｒ^１〜Ｒ^６、Ｅ、ａ、ｂは、式（１）又は式（３）中の符号のものと同じであり、好ましい範囲も同様である。）

Hereinafter, specific examples of the component (C) will be illustrated, but the present invention is not limited thereto.

(In the formula, R ^{1 to} R ⁶ , E, a, and b are the same as those with the symbols in the formula (1) or the formula (3), and the preferable range is also the same.)

As the component (C), a commercially available product may be used, and specific examples of the commercially available product include "OPE-2St 2200 (number average molecular weight 2200)" and "OPE-2St 1200" manufactured by Mitsubishi Gas Chemicals Corporation. "Number average molecular weight 2200)" (styrene-modified polyphenylene ether resin), "YL7776 (number average molecular weight 331)" manufactured by Mitsubishi Chemical Corporation, (bixylenol diallyl ether resin) and the like can be mentioned.

The number average molecular weight of the component (C) is preferably in the range of 100 to 10000, preferably from 200 to 3000, from the viewpoint of preventing volatilization during drying of the resin varnish and preventing the melt viscosity of the resin composition from increasing too much. It is more preferable that the range is. The number average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method is obtained by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K- by Showa Denko Corporation as a column. 804L can be measured using chloroform or the like as a mobile phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.

For the details of the component (C), the description in paragraphs 0010 to 0022 of JP2014-34580A can be referred to, and the content thereof is incorporated in the present specification.

From the viewpoint of obtaining a resin composition having good compatibility, the content of the component (C) is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably, when the resin component is 100% by mass. It is 20% by mass or less, or 15% by mass or less. The lower limit of the content of the component (C) is preferably 1% by mass or more, more preferably 1% by mass or more, when the resin component is 100% by mass from the viewpoint of achieving the desired effect in combination with the component (D) described later. Is 3% by mass or more, more preferably 5% by mass or more.

<(D) Indene marron resin>
The resin composition of the present invention contains a predetermined amount of the (D) indenkumaron resin. By containing a predetermined amount of the component (D), the compatibility is improved, and a resin composition having a good balance of physical properties can be obtained. The kumaron skeleton contained in the component (D) has good compatibility with a highly polar epoxy resin or a curing agent, and the indene skeleton and the kumaron skeleton have good compatibility with a vinyl resin having low polarity. Therefore, it is considered that the resin acts as a compatibilizer between the resin having high polarity and the resin having low polarity, and the compatibility of the entire resin composition is improved.

Examples of the component (D) include a copolymer of indene and kumaron, a copolymer of inden, kumaron and styrene, and the like.

The content ratio of the marron component in the indene marron resin is preferably 5 mol% or more, more preferably 8 mol% or more, still more 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 marron resin is preferably 30 mol% or more, more preferably 35 mol% or more, still more preferably 40 mol% or more. The upper limit is preferably 80 mol% or less, more preferably 75 mol% or less, still more preferably 70 mol% or less.

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

Specific examples of the indene marron resin include "H-100", "V-120S", and "V-120" manufactured by Nikko Kagaku Co., Ltd.

The content of the component (D) is 5% by mass or more, preferably 8% by mass or more, and more preferably 10 when the resin component is 100% by mass from the viewpoint of obtaining a resin composition having good compatibility. It is mass% or more. The upper limit of the content of the component (D) is 20% by mass or less, preferably 18% by mass or less, from the viewpoint of obtaining a resin composition having a good melt viscosity and obtaining an insulating layer having excellent substrate adhesion. It is preferably 16% by mass or less or 15% by mass or less.

<(E) Inorganic filler>
The resin composition of the present invention may further contain (E) an inorganic filler. The material of the inorganic filler is not particularly limited, but 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 , Zirconate oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconate titanate, zirconate titnate phosphate and the like. Of these, silica is particularly suitable. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, still more preferably 2 μm or less, more preferably 2 μm or less, from the viewpoint of improving circuit embedding property and obtaining an insulating layer having low surface roughness. It is 1.5 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, 0.5 μm or more, or 1 μm or more. Examples of commercially available inorganic fillers having such an average particle size include "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., and "YC100C" and "YC100C" manufactured by Admatex Co., Ltd. "YA050C", "YA050C-MJE", "YA010C", "UFP-30" manufactured by Denka Co., Ltd., "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N", manufactured by Tokuyama Co., Ltd. Examples thereof include "SC2500SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Admatex Co., Ltd.

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd. or the like can be used.

Inorganic fillers include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanate-based coupling agents, etc. from the viewpoint of enhancing moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and "KBM803" (3-mercaptopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long chain) manufactured by Shin-Etsu Chemical Co., Ltd. (Epoxy type silane coupling agent) and the like.

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, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further preferable. 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 a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. or the like can be used.

The content of the inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 50% by mass or more, when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion. It is 55% by mass or more, more preferably 60% by mass or more, or 65% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, or 80% by mass or less from the viewpoint of mechanical strength of the insulating layer, particularly elongation.

<(F) Curing accelerator>
The resin composition of the present invention may contain (F) 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 the like, and phosphorus-based curing accelerators and amine-based curing accelerators. Curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 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 trimerite, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biganide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

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

The content of the curing accelerator in the resin composition is not particularly limited, but when the resin component is 100% by mass, it is preferably 0.01% by mass to 3% by mass.

<(G) Thermoplastic resin>
The resin composition of the present invention 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, polycarbonate resin, polyetheretherketone resin, and the like. Examples thereof include polyester resin, and phenoxy resin is preferable. The thermoplastic resin may be used alone or in combination of two or more.

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

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen. Examples thereof include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" manufactured by Mitsubishi Chemical Corporation. Bisphenol acetophenone skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation, "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, Examples thereof include "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482".

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "Electrified Butyral 4000-2", "Electrified Butyral 5000-A", "Electrified Butyral 6000-C", and "Electrified Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd. , Sekisui Chemical Co., Ltd.'s Eslek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series and the like.

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by New Japan Chemical Co., Ltd. Specific examples of the polyimide resin include a 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), and a polysiloxane skeleton. Examples thereof include modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

Specific examples of the polyamide-imide resin include "Vilomax HR11NN" and "Vilomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Industries, Ltd.

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

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

Among them, as the thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Therefore, in one preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins.

When the resin composition of the present invention contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.5% by mass to 15% by mass, more preferably 0% by mass, when the resin component is 100% by mass. It is 6% by mass to 12% by mass, more preferably 0.7% by mass to 10% by mass.

<(H) Flame Retardant>
The resin composition of the present invention 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. The flame retardant may be used alone or in combination of two or more.

As the flame retardant, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd.

When the resin composition of the present invention contains a flame retardant, the content of the flame retardant is not particularly limited, but when the resin component is 100% by mass, it is preferably 0.5% by mass to 20% by mass, more preferably. It is more preferably 0.5% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass.

<(I) Organic filler>
The resin composition of the present invention may contain (I) an organic filler. As the organic filler, any organic filler that can be used when forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

Commercially available products may be used as the rubber particles, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan Co., Ltd. and "AC3816N" manufactured by Aica Kogyo Co., Ltd.

When the resin composition of the present invention contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0% by mass, when the resin component is 100% by mass. It is 2% by mass to 10% by mass, more preferably 0.3% by mass to 5% by mass, or 0.5% by mass to 3% by mass.

<(J) Arbitrary additive>
The resin composition of the present invention may further contain other additives, if necessary, and such other additives include, for example, organic copper compounds, organic zinc compounds, organic cobalt compounds and the like. Examples thereof include metal compounds, thickeners, defoaming agents, leveling agents, adhesion-imparting agents, resin additives such as colorants, and the like.

The resin composition of the present invention can provide an insulating layer having a low dielectric loss tangent and excellent plating adhesion and substrate adhesion, and also has good compatibility and melt viscosity. 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 preferably used as a resin composition for forming a layer (resin composition for an interlayer insulating layer of a printed wiring board). Further, since the resin composition of the present invention provides an insulating layer having good component embedding property, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

[Adhesive film]
The adhesive film of the present invention has a support and a resin composition layer containing the resin composition of the present invention provided on the support.

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

Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, 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, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyethylene. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and 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.) may be used. You may use it.

The surface of the support to be joined to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" manufactured by Lintec Co., Ltd., which is a PET film having a release layer containing an alkyd resin-based release agent as a main component. , "AL-5", "AL-7", "Lumilar T6AM" manufactured by Toray Industries, Inc., and the like.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

For the adhesive film, for example, a resin varnish in which a resin composition is dissolved 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. It can be manufactured by.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

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

In the adhesive film, a protective film similar to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. The adhesive film can be rolled up and stored. If the adhesive film has a protective film, it can be used by peeling off the protective film.

The minimum melt viscosity of the resin composition layer (or resin composition) in the adhesive film is preferably 1000 poise or more, more preferably 1500 poise or more, and 2000 poise or more from the viewpoint of stably maintaining the thickness even if the resin composition layer is thin. Is even more preferable. The upper limit of the minimum melt viscosity is preferably 12000 poise or less, more preferably 10000 poise or less, still more preferably 8000 poise or less, and 5000 poise or less from the viewpoint of obtaining good circuit embedding property.

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

The resin composition layer (or resin composition) in the adhesive film of the present invention exhibits excellent compatibility. That is, in the resin composition layer (or resin composition) in the adhesive film of the present invention, coarse particles of 50 μm or more do not precipitate. The compatibility can be measured according to the method described in <Evaluation of compatibility> described later.

The insulating layer formed using the adhesive film (or resin composition) of the present invention exhibits low dielectric loss tangent. From the viewpoint of preventing heat generation at high frequencies, reducing signal delay and signal noise, the dielectric loss tangent is preferably 0.010 or less, more preferably 0.009 or less, 0.008 or less, 0.007 or less, 0.006 or less, Or 0.005 or less is more preferable. The lower limit of the dielectric loss tangent is preferably as low as possible, but it can usually be 0.001 or more. The dielectric loss tangent can be measured according to the method described in <Evaluation of dielectric loss tangent> described later.

The insulating layer formed by using the adhesive film (or resin composition) of the present invention exhibits good plating adhesion. That is, it provides an insulating layer showing good plating peel strength. The plating peel strength is preferably 1.5 kgf / cm or less, more preferably 1 kgf / cm or less, still more preferably 0.5 kgf / cm or less. The upper limit may be 0.1 kgf / cm or more. The evaluation of the plating peel strength can be performed according to the method described in [Measurement of Plating Adhesion] described later.

The insulating layer formed by using the adhesive film (or resin composition) of the present invention exhibits good substrate adhesion. That is, it provides an insulating layer showing good base peel strength. The base peel strength is preferably 1.5 kgf / cm or less, more preferably 1 kgf / cm or less, still more preferably 0.5 kgf / cm or less. The upper limit may be 0.1 kgf / cm or more. The evaluation of the base adhesion can be performed according to the method described in [Measurement of base adhesion] described later.

A prepreg may be formed using the resin composition of the present invention. A prepreg can be formed by impregnating a sheet-shaped fiber base material with the resin composition of the present invention. Therefore, in one embodiment, the prepreg of the present invention comprises a sheet-like fiber substrate and the resin composition of the present invention impregnated in the sheet-like fiber substrate.

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for the prepreg such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-shaped fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, still more preferably 600 μm or less. In particular, since the plating depth can be suppressed to be small in the present invention, it is preferably 30 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

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 above-mentioned adhesive film.

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

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

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

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

The inner layer substrate and the adhesive film may be laminated by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 26.7 hPa or less.

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

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

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

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

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

For example, the thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but the curing temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C., more preferably 170 ° C. to 170 ° C. 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 heated 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 longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

When manufacturing a printed wiring board, at least one of (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer is further carried out. May be good. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When the support is removed after the step (II), the removal of the support is performed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out between IV) and step (V).

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

The step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be carried out by using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the hole 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 of the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of the printed wiring board can be adopted. 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 solution is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured product in a swelling solution at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan Co., Ltd. Further, the neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Security P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface that has been roughened with an oxidizing agent in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 280 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less, 140 nm or less, 130 nm or less, 120 nm or less, 110 nm. Hereinafter, it is 100 nm or less, 95 nm or less, or 90 nm or less. The lower limit of the Ra value is not particularly limited, but is preferably 0.5 nm or more, and more preferably 1 nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. A specific example of the non-contact type surface roughness meter is "WYKO NT3300" manufactured by B-Coin Sturments.

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

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

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

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

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 of forming the conductor layer by the semi-additive method will be shown.

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

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

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

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 point" is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The mounting method of the semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[Example 1]
40 parts of a biphenyl type epoxy resin (epoxy equivalent 269, "NC3000" manufactured by Nippon Kayaku Co., Ltd.) was dissolved by heating in 25 parts of solvent naphtha with stirring, and then cooled to room temperature. Inorganic filler (“SO-C2” manufactured by Admatex Co., Ltd., average particle size 0.5 μm, carbon amount per unit surface area 0.38 mg / m ² ) 330 parts are mixed and kneaded with 3 rolls to disperse. It was. There, 92.3 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Co., Ltd., a toluene solution having an active group equivalent of about 223 and a non-volatile content of 65% by mass) and a resin having a vinyl group (Mitsubishi Gas). 25 parts of "OPE-2St 2200" manufactured by Kagaku Co., Ltd. (toluene solution with 60% by mass of non-volatile content), 15 parts of indenkumaron resin ("H-100" manufactured by Nikko Kagaku Co., Ltd.), 4-as a curing accelerator Two parts of a 5 mass% MEK solution of dimethylaminopyridine (DMAP) were mixed and uniformly dispersed with a rotary mixer to prepare a resin varnish 1.

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

[Example 2]
In Example 1, a resin having a vinyl group (“OPE-2St 2200” manufactured by Mitsubishi Gas Chemical Company, Inc., a toluene solution having a non-volatile content of 60% by mass) was used as a resin having a vinyl group (“OPE” manufactured by Mitsubishi Gas Chemical Company, Inc.). -2St 1200 "toluene solution with a non-volatile content of 60% by mass) was changed. A resin varnish 2 and an adhesive film 2 were produced in the same manner as in Example 1 except for the above items.

[Example 3]
In Example 1, the indenkumaron resin (“H-100” manufactured by Nikko Kagaku Co., Ltd.) was changed to the indenkumaron resin (“V-120S” manufactured by Nikko Kagaku Co., Ltd.). A resin varnish 3 and an adhesive film 3 were produced in the same manner as in Example 1 except for the above items.

[Example 4]
In Example 1, the indenkumaron resin (“H-100” manufactured by Nikko Kagaku Co., Ltd.) was changed to the indenkumaron resin (“V-120” manufactured by Nikko Kagaku Co., Ltd.). A resin varnish 4 and an adhesive film 4 were produced in the same manner as in Example 1 except for the above items.

[Example 5]
In Example 1,
(1) 25 parts of a resin having a vinyl group ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemicals Co., Ltd., a toluene solution having a non-volatile content of 60% by mass) and a resin having a vinyl group ("OPE" manufactured by Mitsubishi Gas Chemicals Co., Ltd. -2.3 parts of "-2St 2200" non-volatile content 60% by mass toluene solution) and 16.7 parts of resin having a vinyl group (Mitsubishi Gas Chemicals Co., Ltd. "OPE-2St" non-volatile content 60% by mass toluene solution) Change to
(2) 15 parts of indene marron resin (“H-100” manufactured by Nikko Kagaku Co., Ltd.) was changed to 8 parts.
A resin varnish 5 and an adhesive film 5 were produced in the same manner as in Example 1 except for the above items.

[Example 6]
In Example 1,
(1) Change 25 parts of a resin having a vinyl group (toluene solution of "OPE-2St 2200" non-volatile content 60% by mass manufactured by Mitsubishi Gas Chemical Company, Inc.) to 16.7 parts.
(2) 15 parts of indene marron resin (“H-100” manufactured by Nikko Kagaku Co., Ltd.) was changed to 25 parts.
A resin varnish 6 and an adhesive film 6 were produced in the same manner as in Example 1 except for the above items.

[Comparative Example 1]
In Example 1,
(1) Change 25 parts of a resin having a vinyl group (toluene solution of "OPE-2St 2200" non-volatile content 60% by mass manufactured by Mitsubishi Gas Chemical Company, Inc.) to 50 parts.
(2) 15 parts of indene marron resin (“H-100” manufactured by Nikko Kagaku Co., Ltd.) was changed to 2 parts.
A resin varnish 7 and an adhesive film 7 were produced in the same manner as in Example 1 except for the above items.

[Comparative Example 2]
In Example 1,
(1) Change 25 parts of a resin having a vinyl group (toluene solution of "OPE-2St 2200" non-volatile content 60% by mass manufactured by Mitsubishi Gas Chemical Company, Inc.) to 8.3 parts.
(2) 15 parts of indene marron resin (“H-100” manufactured by Nikko Kagaku Co., Ltd.) was changed to 34 parts.
A resin varnish 8 and an adhesive film 8 were produced in the same manner as in Example 1 except for the above items.

[Evaluation]
<Evaluation of dielectric loss tangent>
The adhesive films produced in Examples and Comparative Examples were heat-cured at 190 ° C. for 90 minutes, and the support was peeled off to obtain a sheet-like cured product. The cured product was cut into a length of 80 mm and a width of 2 mm and used as an evaluation sample. The dielectric positive contact of this evaluation sample was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using an HP8362B device manufactured by Agilent Technologies.

<Measurement of minimum melt viscosity of resin composition layer>
The melt viscosity of the resin composition layer of the adhesive film produced in Examples and Comparative Examples was measured using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM Co., Ltd.). About 1 g of the sample resin composition, using a parallel plate having a diameter of 18 mm, the temperature was raised from a starting temperature of 60 ° C. to 200 ° C. at a heating rate of 5 ° C./min, and the measurement interval temperature was 2.5 ° C. The dynamic viscoelasticity was measured under the measurement condition of strain 1 deg, and the minimum melt viscosity (poise) was calculated.

<Evaluation of compatibility>
The resin composition layer side of the adhesive film produced in Examples and Comparative Examples was observed with a microscope (“DIGITAL MICROSCOPE KH-8700” manufactured by Hirox Co., Ltd.) to confirm the presence or absence of coarse particles, and the following criteria were used. Evaluated in.
-Criteria for compatibility-
◯: Coarse particles of 50 μm or more are not deposited on the resin composition layer of the adhesive film.
X: Coarse particles of 50 μm or more are precipitated on the resin composition layer of the adhesive film.

[Measurement of plating adhesion]
<Preparation of evaluation board>
(1) Base treatment of inner layer circuit board Glass cloth base material with inner layer circuit Epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic Corporation “R1515A”) Both sides of the copper surface were immersed in "CZ8101" manufactured by MEC Co., Ltd. and etched by 1 μm to roughen the copper surface.

(2) Laminating treatment of adhesive film The adhesive film produced in Examples and Comparative Examples is subjected to an inner layer circuit in which the resin composition layer is formed by using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Co., Ltd.). Both sides of the inner layer circuit board were laminated so as to be bonded to the substrate. The laminating treatment was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of Resin Composition Layer The PET film as a support was peeled off from the laminated adhesive film. Then, after preheating at 80 ° C. for 30 minutes, the resin composition layer was thermally cured at 170 ° C. for 30 minutes to form a cured product (insulating layer) on both sides of the inner layer circuit board.

(4) Roughening treatment of cured product The inner layer circuit board on which the cured product was formed on both sides was swelled (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., sodium hydroxide aqueous solution containing diethylene glycol monobutyl ether. ) For 10 minutes at 60 ° C., then a roughening solution (“Concentrate Compact P” manufactured by Attec Japan Co., Ltd., an aqueous solution having a potassium permanganate concentration of about 6% by mass and a sodium hydroxide concentration of about 4% by mass). Was immersed in a neutralizing solution (“Reduction Sholysine Securigant P” manufactured by Atotech Japan Co., Ltd., aqueous solution of hydroxylamine sulfate) at 40 ° C. for 5 minutes. Then, it was dried at 80 ° C. for 30 minutes.

(5) Formation of Conductor Layer A conductor layer was formed on the roughened surface of the cured product according to the semi-additive method.
That is, the roughened substrate 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. Then, after heating at 150 ° C. for 30 minutes to perform annealing treatment, an etching resist was formed and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm. The annealing treatment was carried out at 200 ° C. for 60 minutes to obtain an evaluation substrate.

<Measurement of peel strength (plating adhesion) between the surface of the cured product and the conductor layer>
Make a notch in the conductor layer of the evaluation substrate with a width of 10 mm and a length of 100 mm, peel off one end of the notch, grasp it with a gripper, and make 35 mm in the vertical direction at a speed of 50 mm / min at room temperature (25 ° C). The load (kgf / cm) at the time of peeling was measured, and the peel strength was determined. A tensile tester (autocom type tester "AC-50C-SL" manufactured by TSE Co., Ltd.) was used for the measurement.

[Measurement of substrate adhesion]
(1) Base treatment of copper foil The glossy surface of 3EC-III (electric field copper foil, 35 μm) manufactured by Mitsui Metal Mine 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 preventive treatment (CL8300) was performed. This copper foil is called CZ copper foil. Further, it was heat-treated in an oven at 130 ° C. for 30 minutes.

(2) Lamination of copper foil and formation of insulating layer A substrate from which the PET film as a support has been peeled off was prepared by performing the same operation as "(2) Laminating treatment of adhesive film" in [Measurement of plating adhesion] above. .. The treated surface of the CZ copper foil of 3EC-III was laminated on the resin composition layer under the same conditions as in "(2) Adhesive film laminating treatment" of the above [Measurement of plating adhesion]. Then, a sample was prepared by curing the resin composition layer under curing conditions of 190 ° C. for 90 minutes to form an insulating layer.

(3) Measurement of Copper Foil Peeling Strength (Adhesion to Base) The prepared sample was cut into small pieces of 150 × 30 mm. Cut a small piece of copper foil with a width of 10 mm and a length of 100 mm using a cutter to peel off one end of the copper foil and use a gripper (manufactured by JIS Co., Ltd., autocom type test). Measured in accordance with JIS C6481 by grasping with a machine, AC-50C-SL) and using an Instron universal testing machine to peel off 35 mm in the vertical direction at a speed of 50 mm / min at room temperature. However, it was defined as "base adhesion".

In the table, the content of the component (A), the content of the component (B), the content of the component (C), and the content of the component (D) are the contents when the resin component is 100% by mass. Represent.

From the table, Examples 1 to 6 containing the component (D) in a predetermined amount and the component (C) have high compatibility, excellent dielectric loss tangent and melt viscosity, and excellent plating adhesion and substrate adhesion. You can see that.

On the other hand, it can be seen that Comparative Example 2 having a large content of the component (D) has a low minimum melt viscosity and is inferior in substrate adhesion as compared with Examples 1 to 6.

Further, in Comparative Example 1 in which the content of the component (D) was low, crystals were precipitated on the adhesive film due to poor compatibility, and the minimum melt viscosity could not be measured. Further, since the compatibility was poor, the insulating layer could not be formed, and the dielectric loss tangent, the plating adhesion, and the substrate adhesion could not be measured.

Claims (11)

A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a resin having a vinyl group, and (D) an indene marron resin.
The content of the component (D) is 5% by mass to 20% by mass when the resin component is 100% by mass.
The content of the component (C) is 1% by mass to 30% by mass when the resin component is 100% by mass.
The component (C) is a resin composition which is a resin represented by the following formula (1).

(In the formula (1), R ^{1 to} R ⁶ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A is represented by the following formula (2) or the following formula (3). Represents a group.)

(In the formula (2), E represents the following formula (E-1), (E-2) or (E-3))

(In the formula (3), R ^{7 to} R ¹⁴ independently represent a hydrogen atom and an alkyl group or a phenyl group having 6 or less carbon atoms, respectively, and E represents the following formula (E-1), (E-2) or ( Represents E-3). A and b represent integers from 0 to 100 in which at least one of them is not 0.)

(In formulas (E-1) to (E-3), R ^{15 to} R ³⁴ independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. G has 20 or less carbon atoms. Represents a linear, branched or cyclic divalent hydrocarbon group. The resin composition according to claim 1, wherein at least one of the components (C) has an aromatic ring. The resin composition according to claim 1 or 2, wherein the content of the component (C) is 5% by mass to 20% by mass when the resin component is 100% by mass. The resin composition according to any one of claims 1 to 3, wherein at least one of the components (B) is an active ester-based curing agent. The resin composition according to any one of claims 1 to 4, further comprising (E) an inorganic filler. The resin composition according to claim 5, wherein the content of the component (E) is 50% by mass or more when the non-volatile component of the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 6, wherein the component (D) is a copolymer of indene, kumaron, and styrene. The resin composition according to any one of claims 1 to 7, which is used for forming an insulating layer of a printed wiring board. An adhesive film having a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 8. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 8. A semiconductor device comprising the printed wiring board according to claim 10.