JP2017036403A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition exhibiting high adhesive force (peel strength) to a conductive layer even with low roughness and capable of achieving an insulation layer exhibiting low dielectric tangent.SOLUTION: There is provided a resin composition containing (A) a compound having a constitutional unit represented by the formula (1), (B) an epoxy resin and (C) a curing agent. (1), where X represents a residue removing 2 epoxy groups from bifunctional epoxy compound, Y represents a residue removing 2 phenolic hydroxyl group from a bifunctional phenolic compound, Rand Rrepresent a hydrogen atom or Rand Rmay be integrated to form a ring, Rrepresents a monovalent aliphatic hydrocarbon group, a monovalent alicyclic hydrocarbon or a monovalent aromatic hydrocarbon group.SELECTED DRAWING: None

Description

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

  As a technique for manufacturing a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method by the build-up method, the insulating layer is generally formed by curing a resin composition. As a resin composition for forming such an insulating layer, for example, a resin composition containing an epoxy resin and a predetermined active ester compound as essential components is known (see Patent Document 1).

JP 2009-235165 A

According to the resin composition described in Patent Document 1, it is possible to provide a resin composition having a high heat resistance and a low dielectric loss tangent, but further improvement in performance is desired.
The problem to be solved by the present invention is to provide a resin composition that can achieve an insulating layer exhibiting high adhesion (peel strength) to a conductor layer and low dielectric loss tangent even if the roughness is low. is there.

  As a result of intensive studies on the above problems, the present inventors have combined (A) a compound having a structural unit represented by the following formula (1), (B) an epoxy resin, and (C) a curing agent. The present inventors have found that the problem can be solved and have completed the present invention.

（式中、Ｘは、２官能エポキシ化合物からエポキシ基を２個除いた残基を表し、Ｙは、２官能フェノール化合物からフェノール性水酸基を２個除いた残基を表し、Ｒ^１及びＲ^２は水素原子を表すか、又は、Ｒ^１とＲ^２とが一体となって環を形成していてもよく、Ｒ^３は１価の脂肪族炭化水素基、脂肪族環を有する１価の炭化水素基、又は芳香族環を有する１価の炭化水素基を表す。）
［２］ （Ａ）化合物の重量平均分子量が、８０００〜１０００００である、[１]に記載の樹脂組成物。
［３］ （Ａ）化合物の末端がエステル基である［１］又は［２］に記載の樹脂組成物。
［４］ Ｒ^３が芳香族環を有する１価の炭化水素基を表す、［１］〜［３］のいずれかに記載の樹脂組成物。
［５］ 樹脂組成物中の不揮発成分を１００％とした場合の（Ａ）化合物の含有量が、０．５質量％〜１５質量％である［１］〜［４］のいずれかに記載の樹脂組成物。
［６］ （Ｂ）エポキシ樹脂が、ビスフェノール型エポキシ樹脂、フッ素含有エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂及びこれらのエポキシ樹脂の混合物からなる群から選択される、１種または２種以上である、［１］〜［５］のいずれかに記載の樹脂組成物。
［７］ （Ｃ）硬化剤が、フェノール系硬化剤、シアネートエステル系硬化剤及び活性エステル系硬化剤から選択される１種以上を含む［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ （Ｃ）硬化剤が、トリアジン構造含有フェノール系樹脂、トリアジン構造含有アルキルフェノール系樹脂、シアネートエステル系硬化剤及び活性エステル系硬化剤から選択される１種以上を含む、［１］〜［７］のいずれかに記載の樹脂組成物。
［９］ さらに、（Ｄ）無機充填材を含む、［１］〜［８］のいずれかに記載の樹脂組成物。
［１０］ （Ｄ）無機充填材の平均粒子径が、０．０１μｍ〜５μｍである、［９］に記載の樹脂組成物。
［１１］ 樹脂組成物中の不揮発成分を１００質量％とした場合の（Ｄ）無機充填材の含有量が３０〜９０質量％である、［９］又は［１０］に記載の樹脂組成物。
［１２］ （Ｄ）無機充填材がシリカである、［９］〜［１１］のいずれかに記載の樹脂組成物。
［１３］ プリント配線板の絶縁層用である［１］〜［１２］のいずれかに記載の樹脂組成物。
［１４］ プリント配線板のビルドアップ層用である［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有する、シート状積層材料。
［１６］ ［１］〜［１４］のいずれかに記載の樹脂組成物若しくは［１５］に記載のシート状積層材料を熱硬化して得られた絶縁層を含む、プリント配線板。
［１７］ ［１６］に記載のプリント配線板を含む、半導体装置。 That is, the present invention includes the following contents.
[1] (A) a compound having a structural unit represented by the following formula (1),
A resin composition containing (B) an epoxy resin and (C) a curing agent.

(Wherein X represents a residue obtained by removing two epoxy groups from a bifunctional epoxy compound, Y represents a residue obtained by removing two phenolic hydroxyl groups from a bifunctional phenol compound, and R ¹ and R ² Represents a hydrogen atom, or R ¹ and R ² may be combined to form a ring, and R ³ is a monovalent aliphatic hydrocarbon group or a monovalent carbon having an aliphatic ring. Represents a hydrogen group or a monovalent hydrocarbon group having an aromatic ring.)
[2] The resin composition according to [1], wherein the compound (A) has a weight average molecular weight of 8000 to 100,000.
[3] The resin composition according to [1] or [2], wherein the terminal of the compound (A) is an ester group.
[4] The resin composition according to any one of [1] to [3], wherein R ³ represents a monovalent hydrocarbon group having an aromatic ring.
[5] The content of the compound (A) when the nonvolatile component in the resin composition is 100%, according to any one of [1] to [4], which is 0.5% by mass to 15% by mass. Resin composition.
[6] (B) The epoxy resin is selected from the group consisting of a bisphenol type epoxy resin, a fluorine-containing epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a mixture of these epoxy resins. The resin composition according to any one of [1] to [5], which is one type or two or more types.
[7] (C) The resin composition according to any one of [1] to [6], wherein the curing agent includes one or more selected from a phenolic curing agent, a cyanate ester curing agent, and an active ester curing agent. object.
[8] (C) The curing agent includes at least one selected from a triazine structure-containing phenolic resin, a triazine structure-containing alkylphenol resin, a cyanate ester curing agent, and an active ester curing agent. [7] The resin composition according to any one of [7].
[9] The resin composition according to any one of [1] to [8], further comprising (D) an inorganic filler.
[10] The resin composition according to [9], wherein (D) the inorganic filler has an average particle size of 0.01 μm to 5 μm.
[11] The resin composition according to [9] or [10], wherein the content of the inorganic filler (D) is 30 to 90% by mass when the nonvolatile component in the resin composition is 100% by mass.
[12] The resin composition according to any one of [9] to [11], wherein (D) the inorganic filler is silica.
[13] The resin composition according to any one of [1] to [12], which is for an insulating layer of a printed wiring board.
[14] The resin composition according to any one of [1] to [12], which is for a buildup layer of a printed wiring board.
[15] A sheet-shaped laminated material containing the resin composition according to any one of [1] to [14].
[16] A printed wiring board comprising an insulating layer obtained by thermosetting the resin composition according to any one of [1] to [14] or the sheet-like laminated material according to [15].
[17] A semiconductor device comprising the printed wiring board according to [16].

  ADVANTAGE OF THE INVENTION According to this invention, even if roughness is low, while showing the high adhesive force (peel strength) with respect to a conductor layer, the resin composition which can achieve the insulating layer which shows a low dielectric loss tangent can be provided.

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

[Resin composition]
The resin composition of the present invention contains (A) a compound having a structural unit represented by formula (1), (B) an epoxy resin, and (C) a curing agent. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) Compound having a structural unit represented by formula (1)>
The resin composition of the present invention contains (A) a compound having a structural unit represented by the formula (1) (hereinafter also referred to as “(A) compound” or “(A) component”).

In the above formula, X represents a residue obtained by removing two epoxy groups from a bifunctional epoxy compound, Y represents a residue obtained by removing two phenolic hydroxyl groups from a bifunctional phenol compound, and R ¹ and R ² Represents a hydrogen atom, or R ¹ and R ² may be combined to form a ring, and R ³ is a monovalent aliphatic hydrocarbon group or a monovalent alicyclic hydrocarbon group. Or a monovalent aromatic hydrocarbon group.

  X represents a residue obtained by removing two epoxy groups from a bifunctional epoxy compound. As the bifunctional epoxy compound, an epoxy resin having two epoxy groups per molecule is preferable. Examples of such epoxy resins include glycidyl ether type bifunctional epoxy resins, glycidyl ester type bifunctional epoxy resins, bifunctional alicyclic epoxy resins, and the like. In addition, when a bifunctional epoxy compound is a bifunctional alicyclic epoxy resin, the "epoxy group" said about X represents an alicyclic epoxy group.

  The epoxy equivalent of the bifunctional epoxy compound is preferably 50 or more, more preferably 80 or more, and still more preferably 100 or more. The upper limit of the epoxy equivalent is preferably 2000 or less, more preferably 1500 or less, still more preferably 1000 or less, 500 or less, or 350 or less. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a compound containing 1 equivalent of an epoxy group.

The skeleton of the bifunctional epoxy compound is not particularly limited, and may be determined according to the type of terminal group (glycidyl ether group, glycidyl ester group, alicyclic epoxy group) or the like. Examples of the skeleton of the bifunctional epoxy compound include an aromatic skeleton, an aliphatic skeleton, and an alicyclic skeleton. When the terminal group is a glycidyl ether group (that is, when the bifunctional epoxy compound is a glycidyl ether type bifunctional epoxy resin), examples of the aromatic skeleton include a bisphenol skeleton, a naphthalene skeleton, a biphenyl skeleton, and a fluorene skeleton. Examples of the aliphatic skeleton include an alkylene glycol skeleton and the like; Examples of the alicyclic skeleton include a hydrogenated bisphenol skeleton and the like. When the terminal group is a glycidyl ester group (that is, when the bifunctional epoxy compound is a glycidyl ester type bifunctional epoxy resin), examples of the aromatic skeleton include a phthalic acid skeleton; Examples of these include succinic acid skeleton, maleic acid skeleton and the like; examples of alicyclic skeleton include hydrogenated phthalic acid skeleton and the like. When the terminal group is an alicyclic epoxy group (that is, when the bifunctional epoxy compound is a bifunctional alicyclic epoxy resin), the bifunctional epoxy compound has the above-mentioned aromatic skeleton, aliphatic skeleton, alicyclic Any of the skeletons may be included, or a single bond, —O—, —S—, —SO—, or —SO ₂ — may be included as the skeleton.

  Examples of the glycidyl ether type bifunctional epoxy resin include fragrances such as bisphenol A type epoxy resin, tetrabromobisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin. Aliphatic glycidyl ether type bifunctional epoxy resin, ethylene glycol type epoxy resin, propylene glycol type epoxy resin, neopentyl glycol type epoxy resin, hexanediol type epoxy resin, etc., aliphatic glycidyl ether type bifunctional epoxy resin, hydrogenated bisphenol A type Examples include alicyclic glycidyl ether type bifunctional epoxy resins such as epoxy resins.

  Examples of the glycidyl ester type bifunctional epoxy resin include aromatic glycidyl ester type bifunctional epoxy resins such as diglycidyl phthalate, aliphatic glycidyl ester type bifunctional epoxy resins such as succinic acid diglycidyl ester, and tetrahydrophthalic acid diester. Examples thereof include alicyclic glycidyl ester type bifunctional epoxy resins such as glycidyl ester and hexahydrophthalic acid diglycidyl ester.

  Examples of the bifunctional alicyclic epoxy resin include bifunctional alicyclic epoxy resins such as alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate, vinylcyclohexene dioxide, and diglycidyl. Bifunctional heterocyclic epoxy resins such as hydantoin are listed. These bifunctional epoxy compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  From the standpoint of obtaining an insulating layer exhibiting high adhesion to the conductor layer and low dielectric loss tangent even when the roughness is low, the bifunctional epoxy compound is an aromatic diglycidyl ether type bifunctional epoxy resin or aromatic diglycidyl. An ester type epoxy resin is preferable, an aromatic diglycidyl ether type epoxy resin is more preferable, and a biphenyl type bifunctional epoxy resin is more preferable.

  Examples of commercially available bifunctional epoxy compounds include “YX4000”, “YX-4000H”, “YL6121H”, “YX7399” (biphenyl type bifunctional epoxy resin), “825” (bisphenol) manufactured by Mitsubishi Chemical Corporation. A type), “1750” (bisphenol F type), “YL7760” (bisphenol AF type) “HP4032D” manufactured by DIC Corporation, and the like. These may be used alone or in combination of two or more.

X can be preferably represented by the following formula (2).
_{^{- (R 10 -Z 1) n}} -X '- (Z 2 -R 11) m - (2)
(Wherein R ¹⁰ and R ¹¹ each independently represent an alkylene group having 1 to 3 carbon atoms, and Z ¹ and Z ² each independently represent —O—, —O—CO—, or -CO-O-, X 'represents the skeleton of a bifunctional epoxy compound, and n and m are each independently 0 or 1.)

In formula (2), examples of the alkylene group having 1 to 3 carbon atoms represented by R ¹⁰ and R ¹¹ include —CH ₂ —, — (CH ₂ ) ₂ —, and — (CH ₂ ) ₃ —. among these -CH ₂ - it is preferred. Z ¹ and Z ² are preferably —O—. n and m are preferably 1.

In formula (2), the skeleton of the bifunctional epoxy compound represented by X ′ is as described above, and may be determined according to the type of terminal group of the bifunctional epoxy compound. Regardless of the type of terminal group of the bifunctional epoxy compound, X ′ may be any of an aromatic skeleton, an aliphatic skeleton, and an alicyclic skeleton. When the terminal group of the bifunctional epoxy compound is an alicyclic epoxy group, X ′ may be a single bond, —O—, —S—, —SO—, or —SO ₂ —. X ′ preferably represents an aromatic skeleton, more preferably a biphenyl skeleton from the viewpoint of obtaining an insulating layer exhibiting a high adhesion to the conductor layer even when the roughness is low and exhibiting a low dielectric loss tangent. Note that the skeleton of the bifunctional epoxy compound represented by X ′ may have an alkyl group having 1 to 10 carbon atoms (including straight and branched) as a substituent.

  X ′ is particularly preferably as follows.

In the formula, R ⁵ and R ⁶ each represent a hydrocarbon group having 1 to 6 carbon atoms or halogen, and p1 and p2 each represent an integer of 0 to 4. Here, examples of the hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an alkynyl group having 1 to 6 carbon atoms. May be linear, branched or cyclic. R ⁵ and R ⁶ are preferably an alkyl group having 1 to 3 carbon atoms, and p1 and p2 are preferably 0 and 1.

In the formula, R ¹² and R ¹³ each represent a methyl group or a trifluoromethyl group, R ¹⁴ and R ¹⁵ each represent a hydrocarbon group having 1 to 6 carbon atoms or a halogen, and p3 and p4 each represent Represents an integer of 0 to 4; Here, examples of the hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an alkynyl group having 1 to 6 carbon atoms. May be linear, branched or cyclic. R ¹⁴ and R ¹⁵ are preferably an alkyl group having 1 to 3 carbon atoms, and p3 and p4 are preferably 0 and 1.

In formula (1), R ¹ and R ² are preferably hydrogen atoms, but R ¹ and R ² may be combined to form a ring. As a ring formed integrally by R ¹ and R ² , a cycloalkyl group having 3 to 10 carbon atoms is preferable, a cycloalkyl group having 4 to 8 carbon atoms is more preferable, and a cyclohexyl group is further preferable.

  In formula (1), Y represents a residue obtained by removing two phenolic hydroxyl groups from a bifunctional phenol compound. The bifunctional phenol compound is not particularly limited as long as it is a phenol compound having two phenolic hydroxyl groups per molecule. For example, bisphenol A, bisphenol acetophenone, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, Bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenols such as bisphenol trimethylcyclohexane and bisphenolcyclohexane, bisphenol fluorene, and alkyl groups having 1 to 10 carbon atoms such as biscresol fluorene are substituted. Bisphenolfluorenes, dihydroxybiphenyl compounds, dihydroxyphenyl compounds , Dihydroxynaphthalene compounds.

  Particularly preferable examples of Y include the following.

In the formula, R ¹⁶ , R ¹⁷ and R ¹⁹ each represent a hydrocarbon group having 1 to 6 carbon atoms or halogen, r1, r2 and r3 each represents an integer of 0 to 4, and R ¹⁸ represents a hydrogen atom or Represents a hydrocarbon group having 1 to 6 carbon atoms or halogen. Here, examples of the hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an alkynyl group having 1 to 6 carbon atoms. May be linear, branched or cyclic. R ¹⁶ , R ¹⁷ and R ¹⁹ are preferably alkyl groups having 1 to 3 carbon atoms, r1, r2 and r3 are preferably 0 and 1, and R ¹⁸ is a hydrogen atom and 1 to 3 carbon atoms. Are preferred.

In the formula, R ²⁰ , R ²¹ , R ²² and R ²³ each represent a hydrocarbon group having 1 to 6 carbon atoms or halogen, and r4, r5, r6 and r7 each represents an integer of 0 to 4. Here, examples of the hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an alkynyl group having 1 to 6 carbon atoms. May be linear, branched or cyclic. R ²⁰ , R ²¹ , R ²² and R ²³ are preferably alkyl groups having 1 to 3 carbon atoms, and r4, r5, r6 and r7 are preferably 0 and 1.

In the formula, R ²⁴ and R ²⁵ represent a methyl group or a trifluoromethyl group, R ²⁶ and R ²⁷ each represent a hydrocarbon group having 1 to 6 carbon atoms or a halogen, and r8 and r9 are each 0. Represents an integer of ~ 4. Here, examples of the hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an alkynyl group having 1 to 6 carbon atoms. May be linear, branched or cyclic. R ²⁶ and R ²⁷ are preferably alkyl groups having 1 to 3 carbon atoms, and r8 and r9 are preferably 0 and 1.

  Bifunctional phenol compounds such as bisphenol A, bisphenol acetophenone, bisphenol AF, bisphenol fluorene, and biscresol are used from the viewpoint of obtaining an insulating layer that exhibits high adhesion to the conductor layer even when the roughness is low, and exhibits a low dielectric loss tangent. Fluorene is preferred.

In Formula (1), R ³ is a monovalent aliphatic hydrocarbon group, a monovalent hydrocarbon group having an aliphatic ring, or a monovalent hydrocarbon group having an aromatic ring.
Examples of the monovalent aliphatic hydrocarbon group for R ³ include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, and the like. It may be linear or branched. As the monovalent aliphatic hydrocarbon group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.

Examples of the monovalent hydrocarbon group having an aliphatic ring of R ³ include a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, and a cycloalkylalkyl group having 3 to 20 carbon atoms. These may have an alkyl group having 1 to 10 carbon atoms as a substituent. As the monovalent hydrocarbon group having an aliphatic ring, a cycloalkyl group having 6 to 10 carbon atoms and a cycloalkylalkyl group having 6 to 10 carbon atoms are preferable.

Examples of the monovalent hydrocarbon group having an aromatic ring of R ³ include an aromatic hydrocarbon group having 5 to 20 carbon atoms and a hydrocarbon group having 1 to 10 carbon atoms as substituents having 5 to 5 carbon atoms. There are 20 aromatic hydrocarbon groups. Here, examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, and an alkynyl group having 1 to 10 carbon atoms. The monovalent hydrocarbon group having an aromatic ring which may be linear, branched or cyclic is preferably an aromatic hydrocarbon group having 5 to 20 carbon atoms.

R ³ is preferably an alkyl group having 1 to 10 carbon atoms and a monovalent hydrocarbon group having an aromatic ring, and an alkyl group having 1 to 6 carbon atoms and an aromatic group having 5 to 20 carbon atoms. It is more preferably a hydrocarbon group, and further preferably an aromatic hydrocarbon group having 5 to 10 carbon atoms. Specifically, as R ³ , methyl group, ethyl group, propyl group, butyl group, tertbutylmethyl group, pentyl group, hexyl group, phenyl group, naphthyl group, methylphenyl group, ethylphenyl group, methylnaphthyl group, And an ethylnaphthyl group are preferable, and a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, an ethylnaphthyl group, and the like are more preferable.

The compound (A) is, for example, an active ester compound of a bifunctional phenol compound (R ³ COO-Y-OCOR ³ ; wherein R ³ and Y are as described above, and the two R ³ are the same or different from each other. And a bifunctional epoxy compound (W—X—W; in the formula, X is as described above, and W represents an epoxy group). In addition, when a bifunctional epoxy compound is a bifunctional alicyclic epoxy group, the "epoxy group" said about W represents an alicyclic epoxy group.

From the viewpoint of lowering the dielectric loss tangent of the insulating layer that is a cured product of the resin composition, the terminal of the compound (A) is preferably an ester group (R ³ COO group). In order to obtain the (A) compound having an ester group at the end, the bifunctional epoxy compound may be reacted so that the amount of the active ester compound of the bifunctional phenol compound becomes excessive.

  (A) The active ester compound of the bifunctional phenol compound used for the preparation of the compound is a compound produced by acylating two phenolic hydroxyl groups of the bifunctional phenol compound. As the active ester group, one or more ester groups selected from the group consisting of an aromatic ester group, an aliphatic ester group, and an alicyclic ester group are preferable, and an aromatic ester group is particularly preferable. That is, the carboxylic acid compound of the bifunctional phenol compound is preferably an aromatic active ester compound of the bifunctional phenol compound.

  Aromatic ester groups include aryl ester groups. The number of carbon atoms of the aryl ester group is preferably 7-15, more preferably 7-11. As the aliphatic ester group, an alkyl ester group is preferable, and the number of carbon atoms thereof is preferably 2 to 7, more preferably 2 to 5, and further preferably 2 or 3. As the alicyclic ester group, a cycloalkyl ester group is preferable, and the number of carbon atoms thereof is preferably 4 to 7.

Active ester compound of the difunctional phenol compound, for example, bifunctional phenol compounds exemplified in the description of Y in the formula (1) and (HO-Y-OH), carboxylic acid compound ^(R 3 COOH; wherein, ^{R 3} Can be prepared by a condensation reaction (acylation reaction) with the above.

  As the carboxylic acid compound used in the acylation reaction of the bifunctional phenol compound, one or more carboxylic acids selected from the group consisting of aromatic carboxylic acids, aliphatic carboxylic acids, and alicyclic carboxylic acids are preferable. Carboxylic acid is preferred. Aromatic carboxylic acids include aryl carboxylic acids. The number of carbon atoms of the arylcarboxylic acid is preferably 7-15, more preferably 7-11. As the aliphatic carboxylic acid, an alkyl carboxylic acid is preferable, and the number of carbon atoms thereof is preferably 2 to 7, more preferably 2 to 5, and further preferably 2 or 3. As the alicyclic carboxylic acid, a cycloalkyl carboxylic acid is preferable, and the number of carbon atoms thereof is preferably 4 to 7. Preferable examples of the carboxylic acid compound include benzoic acid, naphthalene carboxylic acid, anthracene carboxylic acid, acetic acid, propionic acid and the like. Of these, benzoic acid is particularly preferred.

  From the viewpoint of obtaining an insulating layer exhibiting high adhesion to the conductor layer and low dielectric loss tangent even if the roughness is low, the compound (A) is a polymer compound, and its weight average molecular weight is 8000 to 100,000. It is preferred that it is 10,000 to 80,000, more preferably 12,000 to 50,000. Here, the weight average molecular weight of the compound (A) is a polystyrene equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

  From the viewpoint of obtaining an insulating layer exhibiting a high adhesion to the conductor layer even when the roughness is low and exhibiting a low dielectric loss tangent, the epoxy equivalent of the compound (A) is preferably 1000 to 50000, more preferably. It is 3000-40000, More preferably, it is 5000-38000. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  From the viewpoint of further reducing the dielectric loss tangent of the insulating layer, which is a cured product of the resin composition, the epoxy equivalent of the compound (A) is preferably larger than the weight average molecular weight of the compound (A).

The content of the component (A) in the resin composition is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. More preferably, it is 1.0 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 15 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 7 mass% or less.
Therefore, the content of the component (A) in the resin composition is preferably 0.5 to 15% by mass, more preferably 0.7 to 10% by mass, and still more preferably 1.0 to 7% by mass.

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

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

  As the epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol type epoxy resin such as bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, composite Cyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the epoxy resin include a bisphenol type epoxy resin, a fluorine-containing epoxy resin (for example, bisphenol AF type epoxy resin), a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a mixture of these epoxy resins. It is preferable to use one or two or more selected epoxy resins.

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

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

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

Epoxy resin, if it contains solid epoxy resin and a liquid epoxy resin, the ratio of the mass M _S of a solid epoxy resin to the weight M _L of the liquid epoxy resin (M S _{/ M L)} is 1 to 10 is preferably in the range of . The M S _/ M _L, With such a range, i) moderate tackiness is brought when used in the form of adhesive film, ii) sufficient flexibility when used in the form of an adhesive film Is obtained, the handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained.

The content of the component (B) in the resin composition is preferably 0.1% by mass or more, more preferably 5% by mass or more, and still more preferably from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. Is 10% by 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 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 22 mass% or less.
Therefore, the content of the component (B) in the resin composition is preferably 0.1 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 10 to 22% by mass.

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

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

<(C) Curing agent>
The resin composition of the present invention contains (C) a curing agent (hereinafter referred to as “(C) component”).
(C) The curing agent is not particularly limited as long as it has a function of curing an epoxy resin. For example, a phenol curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate ester curing. Agents and carbodiimide curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the conductor layer (circuit wiring), a nitrogen-containing phenol-based curing agent is preferable, and a triazine structure-containing phenol resin and a triazine structure-containing alkyl phenol resin are more preferable. Especially, it is preferable to use a triazine structure containing phenol type hardening | curing agent from a viewpoint which satisfies heat resistance, water resistance, and adhesiveness (peeling strength) with a conductor layer highly.

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

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadienyl diphenol, phenol novolac and the like.

  Specifically, an active ester compound containing a dicyclopentadienyl diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolak, and an active ester compound containing a benzoylated product of a phenol novolak are preferred. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadienyl diphenol structure are more preferred.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (DIC Corporation) as active ester compounds containing a dicyclopentadienyl diphenol structure. Manufactured product), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, Examples of the active ester compound containing a benzoylated compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).

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

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylene bis (2,6-dimethylphenyl cyanate), 4, 4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Phenol novolac and Polyfunctional cyanate resin derived from resol novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolak polyfunctional cyanate ester resins) and “BA230” (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. Are pre-polymerized as a trimer), “BA-3000”, “ULL-950S”, “HTL-300” and the like.

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

  In the present invention, (C) the curing agent preferably contains at least one selected from a phenolic curing agent, a cyanate ester curing agent and an active ester curing agent, and includes a triazine structure-containing phenolic resin and a triazine structure. More preferably, it contains at least one selected from a containing alkylphenol-based resin, a cyanate ester-based curing agent, and an active ester-based curing agent.

The content of the component (C) in the resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, from the viewpoint of obtaining an insulating layer having high peel strength and a low dielectric loss tangent. More preferably, it is 5 mass% or more. The upper limit of the content of the component (C) is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. .
Therefore, the content of the component (C) in the resin composition is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably 5 to 20% by mass.

  The amount ratio of (B) epoxy resin to (C) curing agent is a ratio of [(B) total number of epoxy groups of epoxy resin]: [(C) total number of reactive groups of curing agent]. The range of 0.2 to 1: 2 is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1 is 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. The total number of epoxy groups in the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for the (B) epoxy resin, 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 reactive group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

<(D) Inorganic filler>
The resin composition of the present invention may contain (D) an inorganic filler (hereinafter also referred to as “component (D)”).
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. 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. Examples of commercially available inorganic fillers include “SO-C2” and “SO-C1” manufactured by Admatechs Corporation.

  The average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less, from the viewpoint of obtaining an insulating layer having a small surface roughness and improving the fine wiring formability. Even more preferable is 2 μm or less, 1 μm or less, 0.7 μm or less, 0.5 μm or less, or 0.4 μm or less. On the other hand, from the viewpoint of obtaining a resin varnish having an appropriate viscosity and good handleability when forming a resin varnish using the resin composition, the average particle size of the inorganic filler is preferably 0.01 μm or more, 0.03 μm or more is more preferable, 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more is more preferable. Therefore, the average particle size of the inorganic filler is preferably 0.01 μm to 5 μm, more preferably 0.03 μm to 4 μm.

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

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferable that it is processed with 1 or more types of surface treating agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane) manufactured by KK, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type) Silane coupling agent).

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 preventing an increase in the melt viscosity of the resin varnish or the sheet form. preferable.

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

  Although content of (D) component in a resin composition is not specifically limited, From a viewpoint of obtaining an insulating layer with a low coefficient of thermal expansion, Preferably it is 30 mass% or more, More preferably, it is 50 mass% or more, More preferably, it is 60 mass. % Or more or 65 mass% or more. The upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less. Therefore, the content of the inorganic filler (D) when the nonvolatile component in the resin composition is 100% by mass is preferably 30 to 95% by mass, more preferably 30 to 90% by mass, More preferably, it is 50-90 mass%.

  The resin composition of the present invention may contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles in addition to the components (A) to (D).

-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 thereof include thermoplastic resins such as ether ketone resins and polyester resins, and among these, 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 equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YL6954BH30”, “YX7553”, “YL7769BH30” manufactured by Mitsubishi Chemical Co., Ltd., “YL6794”, “YL7213”, “YL7290”, “YL7482” and the like.

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

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

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

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

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

Among these, phenoxy resin and polyvinyl acetal resin are preferable as the thermoplastic resin from the viewpoint of obtaining an insulating layer having a lower surface roughness and superior adhesion to the conductor layer in combination with other components. 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.
When the phenoxy resin is used, the epoxy equivalent of the phenoxy resin is preferably 6000 to 30000, more preferably 7000 to 20000, and further preferably 9000 to 15000. The weight average molecular weight in terms of polystyrene of the phenoxy resin is preferably in the range of 8,000 to 200,000, more preferably in the range of 10,000 to 100,000, and still more preferably in the range of 20,000 to 60,000.

  The content of the thermoplastic resin in the resin composition is not particularly limited, but is preferably 0% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and even more preferably 1% by mass to 5% by mass. %.

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

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

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

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Examples include imidazole compounds such as 3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2-phenyl. Imidazole is preferred.

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

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

  Although content of the hardening accelerator in a resin composition is not specifically limited, It is preferable to use in 0.05 mass%-3 mass%.

-Flame retardant-
The resin composition of the present invention may contain 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, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd.

  The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and even more preferably 1.5% by mass to 10% by mass. % Is more preferable.

-Organic filler-
The resin composition may further contain an organic filler. As the organic filler, any organic filler that can be used for forming an insulating layer of a printed wiring board may be used. Examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable.

  A commercially available product may be used as the rubber particles, and examples thereof include “AC3816N” manufactured by Aika Industry Co., Ltd.

  The content of the organic filler in the resin composition is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 10% by mass.

  The resin composition may further contain other additives other than the flame retardant and the organic filler, if necessary. Examples of such other additives include an organic copper compound, an organic zinc compound, and Examples thereof include organic metal compounds such as organic cobalt compounds, and resin additives such as organic fillers, thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and coloring agents.

  The resin composition of the present invention can be suitably used as a resin composition (resin composition for an insulating layer of a printed wiring board) for forming an insulating layer in the production of a printed wiring board. Moreover, the resin composition of this invention can be used conveniently also as a resin composition (resin composition for buildup layers of a printed wiring board) for forming a buildup layer.

[Sheet laminated material]
The sheet-like laminated material of the present invention contains the resin composition of the present invention. Examples of the sheet-like laminated material include an adhesive film and a prepreg.
(Adhesive film)
The adhesive film contains the resin composition of the present invention. An adhesive film has a support body and the resin composition layer provided on this support body containing the resin composition of this invention, for example.

  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 thinning the insulating layer. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more, etc.

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

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

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

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

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

  A protective film according to the support can be further laminated on the surface of the adhesive film that is not joined to the support of the resin composition layer (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. For example, a polypropylene film (“Alphan MA-430” manufactured by Oji F-Tex Co., Ltd., thickness 20 μm) can be laminated as the protective film so as to be bonded to the resin composition layer.

[Prepreg]
The prepreg includes the resin composition of the present invention. The prepreg is characterized in that the resin composition of the present invention is impregnated in a sheet-like fiber base material.

  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 thinning the insulating layer, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and even more preferably 20 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it is 10 micrometers or more.

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

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

  The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (printing) (For an interlayer insulating layer of a wiring board).

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer obtained by thermosetting the resin composition of the present invention or the sheet-like laminated material of the present invention.

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

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

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

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

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

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

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

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

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

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

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

  The insulating layer formed using the resin composition of the present invention exhibits a 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, and 0.008 or less, 0.007 or less, or 0.006 or less. Further preferred. The lower limit of the dielectric loss tangent is preferably as low as possible, but can usually be 0.001 or more. The dielectric loss tangent is described later in 4. It can be measured by the method described in the measurement of dielectric loss tangent. Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23 ° C. by the cavity resonator perturbation method.

  The insulating layer formed using the resin composition of the present invention can maintain a low dielectric loss tangent even when stored under high humidity conditions. For example, when the initial dielectric loss tangent is tan δ1 and the dielectric loss tangent after storage for 3 days at 35 ° C. and a relative humidity of 85% is tan δ2, the insulating layer formed using the resin composition of the present invention. The dielectric loss tangent increase rate calculated by the following formula is preferably 120% or less, more preferably 118% or less, still more preferably 116% or less, 114% or less, 112% or less, or 110% or less.

  Dielectric loss tangent increase rate (%) = (tan δ2) / (tan δ1) × 100

  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).

  The printed wiring board of this invention can be manufactured using the above-mentioned prepreg, for example. The manufacturing method is basically the same as when an adhesive film is used.

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

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

  The arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 280 nm or less, further preferably 260 nm or less, 240 nm or less, 220 nm or less, or 200 nm or less. The lower limit of Ra is not particularly limited, but can usually be 1 nm or more, 3 nm or more, 5 nm or more, and the like. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments is cited.

  The root mean square roughness Rq of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 380 nm or less, still more preferably 360 nm or less, 340 nm or less, 320 nm or less, or 300 nm or less. The lower limit of Rq is not particularly limited, but can usually be 1 nm or more, 3 nm or more, 5 nm or more, and the like. The root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact type surface roughness meter, similarly to Ra.

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

  The conductor material used for the conductor layer is not particularly limited. Preferably, the conductor layer includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. . 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.

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

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

  The insulating layer formed using the resin composition of the present invention exhibits high peel strength with respect to the conductor layer. The peel strength is preferably 0.40 kgf / cm or more, more preferably 0.45 kgf / cm or more, and further preferably 0.50 kgf / cm or more. The upper limit value of the peel strength is not particularly limited, but is 1.2 kgf / cm or less, 0.90 kgf / cm or less, and the like. In the present invention, although the arithmetic average roughness Ra and the root mean square roughness Rq (roughness) of the surface of the insulating layer after the roughening treatment are small, an insulating layer exhibiting such a high peel strength is formed. Therefore, it contributes significantly to miniaturization of circuit wiring. In the present invention, the peel strength between the insulating layer and the conductor layer refers to a peel strength (90-degree peel strength) when the conductor layer is peeled off in a direction perpendicular to the insulating layer (90-degree direction). The peel strength when the layer is peeled in the direction perpendicular to the insulating layer (90-degree direction) can be determined by measuring with a tensile tester. Examples of the tensile tester include “AC-50C-SL” manufactured by TSE Corporation.

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

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

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

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

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

<Synthesis Example 1>
A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 281.1 g of benzoyl chloride (number of moles of acid chloride group: 2.0 mol) and 1200 g of methyl isobutyl ketone (MIBK). The inside was purged with nitrogen under reduced pressure and mixed. Next, 290 g of bisphenol acetophenone (number of moles of phenolic hydroxyl group: 2.0 mol) was charged, and the inside of the system was purged with nitrogen under reduced pressure and dissolved. Thereafter, 1.1 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while performing nitrogen gas purge, and 400 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stir for hours.
After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Next, water was added to the MIBK phase in which the reaction product was dissolved, and the mixture was stirred and mixed for 15 minutes. After this operation was repeated until the pH of the aqueous layer reached 7, the water was removed by decanter dehydration to form a MIBK solution, and MIBK was distilled off under reduced pressure to give a benzoylated acetophenone benzoylated active ester compound ( a-1) [Active ester equivalent: 249] was obtained.

<Synthesis Example 2>
Except that the amount of MIBK charged was 1400 g, and 380 g of biscresol fluorene (number of moles of phenolic hydroxyl group: 2.0 mol) was used instead of 290 g of bisphenolacetophenone, The benzoylated active ester compound (a-2) [active ester equivalent: 294] of biscresol fluorene was obtained.

<Synthesis Example 3>
In place of 281.1 g of benzoyl chloride and 1200 g of MIBK, 157.0 g of acetyl chloride (number of moles of acid chloride group: 2.0 mol) and 900 g of MIBK were charged, and the inside of the system when dropping a 20% aqueous sodium hydroxide solution was added. Except having controlled to 50 degrees C or less, it carried out similarly to the synthesis example 1, and obtained the acetylation active ester compound (a-3) [active ester equivalent: 187 of bisphenol acetophenone].

(Compound Synthesis Example 1)
Into a reaction vessel, 191 g of bixylenol type epoxy resin (Mitsubishi Chemical Corporation YX4000, epoxy equivalent 185), benzoylated active ester compound of bisphenolacetophenone (a-1) [active ester equivalent: 249] 249 g, cyclohexanone 200 g And dissolved by stirring. Next, 37.8 g of a 5% by weight cyclohexanone solution of dimethylaminopyridine was added dropwise and reacted at 180 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was filtered using a filter cloth and diluted with a solvent to obtain compound (A-1) (a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass).
With respect to compound (A-1), the weight average molecular weight (Mw) was measured by gel permeation chromatography, and the epoxy equivalent was measured by potentiometric titration. The Mw (polystyrene equivalent value) was 18000 and the epoxy equivalent was 7000. It was.

(Synthesis Example 2 of Compound)
The amount of bixylenol-type epoxy resin (Mitsubishi Chemical Co., Ltd. YX4000, epoxy equivalent 185) was 189 g, benzoylation of biscresol fluorene instead of 249 g of benzoyl acetophenone benzoylation active ester compound (a-1) Compound (A-2) was obtained in the same manner as Compound Synthesis Example 1 except that 294 g of active ester compound (a-2) [active ester equivalent: 294] was used (MEK having a solid content of 30% by mass). And a 1: 1 solution of cyclohexanone).
When the weight average molecular weight (Mw) and the epoxy equivalent were measured similarly to the compound (A-1), the Mw (polystyrene conversion value) of the compound (A-2) was 18000, and the epoxy equivalent was 7000.

(Compound Synthesis Example 3)
Example of compound synthesis, except that 187 g of bisphenol acetophenone benzoylated active ester compound (a-1) acetylated active ester compound (a-3) [active ester equivalent: 187] of bisphenol acetophenone was used In the same manner as in Example 1, compound (A-3) was obtained (a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass).
When the weight average molecular weight (Mw) and the epoxy equivalent were measured similarly to the compound (A-1), Mw (polystyrene conversion value) of the compound (A-3) was 15000, and the epoxy equivalent was 5500.

(Compound Synthesis Example 4)
Compound (A-4) was obtained in the same manner as in Compound Synthesis Example 1 except that the amount of the bixylenol type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185) was 181 g (solid content) 30% by weight MEK and cyclohexanone 1: 1 solution).
When the weight average molecular weight (Mw) and the epoxy equivalent were measured in the same manner as in the compound (A-1), the Mw (polystyrene equivalent value) of the compound (A-4) was 21000, and the epoxy equivalent was 35000.

<Example 1>
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), fluorinated epoxy resin (manufactured by Mitsubishi Chemical Corporation) YL7760 ”, 10 parts of an epoxy equivalent of 238) and 20 parts of dicyclopentadiene type epoxy resin (“ HP-7200H ”manufactured by DIC Corporation, epoxy equivalent of 275) are dissolved in 35 parts of solvent naphtha while stirring. It was. What was dissolved by heating was cooled to room temperature, and 24 parts of the compound (A-1), active ester compound (“HPC8000-65T” manufactured by DIC Corporation, weight average molecular weight of about 2700, active group equivalent of about 223) 20 parts of a toluene solution having a non-volatile content of 65% by mass), a triazine skeleton-containing phenol-based curing agent (DIC Corporation "LA-3018-50P", hydroxyl equivalent of about 151, solid content of 50% 2-methoxypropanol solution hydroxyl equivalent 151 parts of MEK solution with a solid content of 151%, 3 parts of curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 2% by mass), flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd.) 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm 2 parts and spherical silica (average particle size 0.5 μm, manufactured by Admatechs Co., Ltd., “SOC2”), unit treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 180 parts of carbon per area (0.39 mg / m ² ) were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.
Next, a resin varnish is uniformly applied on the release surface of the polyethylene terephthalate film with a release treatment so that the thickness of the resin composition layer after drying is 30 μm, and the resin varnish is 4 at 80 to 120 ° C. (average 100 ° C.). It was made to dry for minutes and the adhesive film 1 was produced.
Here, as a polyethylene terephthalate film for producing an adhesive film, “PET501010” (thickness 50 μm) manufactured by Lintec Co., Ltd. is used for producing a cured product for measuring fracture elongation and linear thermal expansion coefficient (CTE). Used for the production of a cured product for measuring other than elongation at break and CTE, “AL5” (thickness: 38 μm) manufactured by Lintec Corporation was used.

<Example 2>
5 parts of liquid naphthalene type epoxy resin (epoxy equivalent 144, “HP4032SS” manufactured by DIC Corporation), 6 parts of fluorine-based epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238), biphenyl type epoxy resin ( 12 parts “NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269) was dissolved in 25 parts of solvent naphtha with stirring. After heating and dissolving to room temperature, 5 parts of compound (A-2), active ester compound (“HPC8000-65T” manufactured by DIC Corporation, weight average molecular weight of about 2700, active group equivalent) 6 parts of a non-volatile content 65% by weight toluene solution of about 223), 16 parts of a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 232, MEK solution having a non-volatile content of 75% by weight), phenol Novolac type polyfunctional cyanate ester resin ("PT30S" manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 133, MEK solution having a nonvolatile content of 85% by mass), 5 parts of curing accelerator (4-dimethylaminopyridine, solid content of 2% by mass) 1 part of MEK solution), curing accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetylacetonate Co (III) Ac, MEK solution having a solid content of 1% by mass] 3 parts, rubber particles (manufactured by Ganz Kasei Co., Ltd., Staphyloid AC3816N), flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10 2 parts of-(2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) and a phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.) 80 parts of spherical silica (average particle size: 0.24 μm, “SOC1” manufactured by Admatechs Co., Ltd., carbon amount: 0.36 mg / m ² ) surface-treated with “KBM573” (manufactured by Co., Ltd.) The mixture was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish, and then an adhesive film 2 was prepared in the same manner as in Example 1.

<Example 3>
An adhesive film 3 was produced in the same manner as in Example 1 except that 24 parts of the compound (A-1) in Example 1 was replaced with 24 parts of the compound (A-3).

<Example 4>
An adhesive film 4 was produced in the same manner as in Example 1 except that 24 parts of the compound (A-1) in Example 1 was replaced with 24 parts of the compound (A-4).

<Comparative Example 1>
24 parts of compound (A-1) of Example 1 is 18 parts of bisphenol A type phenoxy resin ("E1256B40" manufactured by Mitsubishi Chemical Corporation, MEK solution having a solid content of 40% by mass, epoxy equivalent 8000, weight average molecular weight 50000). An adhesive film 5 was produced in the same manner as in Example 1 except that the above was replaced.

<Comparative Example 2>
5 parts of the compound (A-2) of Example 2 was added to a phenoxy resin composed of a bixylenol structure and a bisphenolacetophenone structure (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation, MEK: cyclohexanone = 1: 1 solution with a solid content of 30% by mass). , Epoxy equivalent 13000, weight average molecular weight 35000) Adhesive film 6 was produced in the same manner as in Example 2 except that it was changed to 5 parts.

<Evaluation test>
Using the adhesive films prepared in Examples and Comparative Examples, an evaluation substrate was prepared by the following method and evaluated.

1. Peel strength and roughness [arithmetic mean roughness (Ra value), root mean square roughness (Rq value)] Preparation of samples for measurement (1) Substrate treatment of laminated board Glass cloth base epoxy resin double-sided copper-clad laminate ( The copper surface was roughened by etching 1 μm on both sides of a copper foil thickness of 18 μm, a substrate thickness of 0.3 mm, and R5715ES manufactured by Matsushita Electric Works Co., Ltd. (CZ8100). It was.

(2) Lamination of adhesive film The adhesive film produced in the examples and comparative examples was obtained by using a batch type vacuum pressure laminator (Nichigo-Morton Co., Ltd. 2-stage buildup laminator “CVP700”). Was laminated on both sides of the substrate so as to be bonded to the substrate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Subsequently, the laminated adhesive film was smoothed by hot pressing at 100 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure.

(3) Curing of resin composition layer After laminating the adhesive film, the resin composition layer was heat-cured (100 ° C for 30 minutes and then at 175 ° C for 30 minutes) to form cured bodies on both sides of the substrate. At that time, for Examples 1, 3, 4 and Comparative Example 1, the resin composition layer was thermally cured with a PET film as a support attached. Regarding Example 2 and Comparative Example 2, the resin composition layer was thermally cured after peeling off the PET film as the support.

(4) Roughening treatment The laminated plate on which the insulating layer is formed is a swelling liquid, a swelling ring dip securigant P (glycol ethers, aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. And dipped at 60 ° C. for 10 minutes. Then the roughening solution, concentrate compact P of Atotech Japan Co., Ltd. in _{(KMnO 4:: 60g / L} , NaOH aqueous solution of 40 g / L), was immersed at 80 ° C. 20 min. Finally, as a neutralizing solution, it was immersed for 5 minutes at 40 ° C. in Reduction Sholysin Securigant P (an aqueous solution of sulfuric acid) of Atotech Japan Co., Ltd. After drying at 80 ° C. for 30 minutes, this substrate was designated as evaluation substrate A.

(5) Plating by semi-additive method Evaluation board A produced in (4) is immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then in an electroless copper plating solution at 25 ° C. for 20 minutes. Soaked. After annealing for 30 minutes at 150 ° C., an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm. Next, the substrate obtained by performing the annealing treatment at 200 ° C. for 60 minutes was used as an evaluation substrate B.

2. Roughness [Arithmetic Average Roughness (Ra Value), Root Mean Square Roughness (Rq Value) Measurement Using a non-contact type surface roughness meter (WYKO NT3300, manufactured by Beec Instruments), VSI contact mode The Ra value and the Rq value were obtained from numerical values obtained with a measurement range of 121 μm × 92 μm using a 50 × lens. The average value of 10 points was calculated and shown in Table 1.

3. Measurement of Peeling Strength (Peel Strength) of Plating Conductor Layer Cut the 10 mm width and 100 mm length into the conductor layer of the evaluation board B, peel off one end, and grasp the tool (TS Co., Ltd.) E, load by auto-comb type tester AC-50C-SL) and peeling 35mm vertically at a speed of 50mm / min at room temperature (25 ° C) (kgf / cm (N / cm) ) Was measured.

4). Measurement of dielectric loss tangent Adhesive films prepared in Examples and Comparative Examples were heated at 200 ° C. for 90 minutes to thermally cure the resin composition layer, and then the PET film was peeled off to obtain a cured product C for evaluation. It was. The evaluation cured product C was cut into a test piece having a width of 2 mm and a length of 80 mm, and the test piece was measured by a cavity resonance perturbation method using a “HP 8362B” manufactured by Agilent Technologies, with a measurement frequency of 5.8 GHz and a measurement temperature of 23. The dielectric loss tangent was measured at ° C. Two test pieces were measured and the average value was calculated and shown in Table 1 (tan δ1).

5). Environmental stability test of dielectric loss tangent After leaving the test piece of the cured product C for evaluation having a width of 2 mm and a length of 80 mm in a thermo-hygrostat (35 ° C., 85% RH) for 3 days, Using “HP8362B” manufactured by Agilent Technologies, the dielectric loss tangent was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by the cavity resonance perturbation method. Two test pieces were measured, and the average value was calculated and shown in Table 1 (tan δ2).
Further, the rate of increase in dielectric loss tangent before and after being left in a constant temperature and humidity chamber was calculated by the following formula and shown in Table 1.
Dielectric loss tangent increase rate (%) = (tan δ2 / tan δ1) × 100

  In Table 1, together with the evaluation results, the materials used in Examples 1 to 4 and Comparative Examples 1 and 2 and their blending amounts (parts by mass of nonvolatile content) are also shown.

Claims (17)

(A) A resin composition containing a compound having a structural unit represented by the following formula (1), (B) an epoxy resin, and (C) a curing agent.

(Wherein X represents a residue obtained by removing two epoxy groups from a bifunctional epoxy compound, Y represents a residue obtained by removing two phenolic hydroxyl groups from a bifunctional phenol compound, and R ¹ and R ² Represents a hydrogen atom, or R ¹ and R ² may be combined to form a ring, and R ³ is a monovalent aliphatic hydrocarbon group or a monovalent carbon having an aliphatic ring. Represents a hydrogen group or a monovalent hydrocarbon group having an aromatic ring.)   (A) The resin composition of Claim 1 whose compound is a high molecular compound and whose weight average molecular weight is 8000-100,000.   (A) The resin composition of Claim 1 or 2 whose terminal of a compound is an ester group. The resin composition according to any one of claims 1 to 3, wherein R ³ represents a monovalent hydrocarbon group having an aromatic ring.   The resin composition according to any one of claims 1 to 4, wherein the content of the compound (A) when the nonvolatile component in the resin composition is 100% is 0.5 mass% to 15 mass%. .   (B) The epoxy resin is one or more selected from the group consisting of bisphenol type epoxy resins, fluorine-containing epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, and mixtures thereof. The resin composition according to any one of claims 1 to 5, wherein   (C) The resin composition of any one of Claims 1-6 in which a hardening | curing agent contains 1 or more types selected from a phenol type hardening | curing agent, a cyanate ester type hardening | curing agent, and an active ester type hardening | curing agent.   (C) The curing agent includes one or more selected from a triazine structure-containing phenolic resin, a triazine structure-containing alkylphenol resin, a cyanate ester curing agent, and an active ester curing agent. 2. The resin composition according to item 1.   Furthermore, (D) The resin composition of any one of Claims 1-8 containing an inorganic filler.   (D) The resin composition of Claim 9 whose average particle diameter of an inorganic filler is 0.01 micrometer-5 micrometers.   The resin composition according to claim 9 or 10, wherein the content of the inorganic filler (D) is 30 to 90% by mass when the nonvolatile component in the resin composition is 100% by mass.   (D) The resin composition according to any one of claims 9 to 11, wherein the inorganic filler is silica.   The resin composition according to claim 1, which is for an insulating layer of a printed wiring board.   It is for buildup layers of a printed wiring board, The resin composition of any one of Claims 1-12.   The sheet-like laminated material containing the resin composition of any one of Claims 1-14.   The printed wiring board which has an insulating layer containing the thermosetting body of the resin composition of any one of Claims 1-14, or the sheet-like laminated material of Claim 15.   A semiconductor device comprising the printed wiring board according to claim 16.