JP2023067103A - resin composition - Google Patents

Abstract

To provide a resin composition capable of giving a cured product excellent in plating adhesion and suppressing unevenness after lamination.SOLUTION: The resin composition contains (A) a maleimide compound having a sulfur atom and a maleimide group, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler.SELECTED DRAWING: None

Description

The present invention relates to resin compositions.

2. Description of the Related Art As a technique for manufacturing a printed wiring board, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed from a cured product obtained by curing a resin composition (Patent Document 1).

JP 2020-23714 A

The cured product contained in the insulating layer is required to have a low dielectric loss tangent. One of the methods for obtaining a cured product with a low dielectric loss tangent is to mix an active ester compound and an inorganic filler at a high concentration in a resin composition. However, when a resin composition containing a high concentration of an active ester compound and an inorganic filler is used, the plating adhesion tends to be low, and the resin composition layer tends to be uneven.

Specifically, in some cases, an insulating layer is formed from a cured product of a resin composition, and a conductor layer is formed on the insulating layer by plating. However, when a resin composition containing a high concentration of an active ester compound and an inorganic filler is used, the adhesion between the insulating layer and the conductive layer formed by plating tends to be low.

Furthermore, in the process of manufacturing a printed wiring board, a resin composition layer containing a resin composition and an inner layer substrate are laminated, and the resin composition layer is cured to form an insulating layer on the inner layer substrate. However, when a resin composition containing a high concentration of an active ester compound and an inorganic filler is used, unevenness may occur in the resin composition layer after lamination. Specifically, the resin composition layer after lamination sometimes has a dent along the periphery of the inner layer substrate. Since such unevenness reduces the uniformity of the insulating layer, it is desired to suppress its occurrence.

The present invention has been invented in view of the above problems, a resin composition that can obtain a cured product having excellent plating adhesion and can suppress unevenness after lamination; a cured product of the resin composition; A sheet-like laminate material containing the resin composition; a resin sheet having a resin composition layer formed from the resin composition; a printed wiring board having an insulating layer containing a cured product of the resin composition; An object of the present invention is to provide a semiconductor device including a wiring board.

The inventors have made extensive studies to solve the above problems. As a result, the present inventors have found that a resin containing a combination of (A) a maleimide compound having a sulfur atom and a maleimide group, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler The present inventors have completed the present invention by finding that the composition can solve the above problems.
That is, the present invention includes the following.

（式（ａ１－１）において、Ｒ^１１～Ｒ^１４は、それぞれ独立に、水素原子、アルキル基及びハロゲン原子からなる群より選ばれる少なくとも１種を表し、Ｘは、芳香環を含む２価の有機基を表す。）
〔６〕 （ａ２）成分が、下記式（ａ２－１）又は式（ａ２－２）で表される、〔４〕又は〔５〕に記載の樹脂組成物。

（式（ａ２－１）において、Ｙは、環状構造を有する有機基を表し、Ｒ^２１は、それぞれ独立に、炭化水素基を含む２価の有機基を表し、Ｒ^２２は、それぞれ独立に、水素原子、アルキル基及びハロゲン原子からなる群より選択される少なくとも１種を表し、ｍ１は、２～１０の整数を表し、ｎ１は、０～８の整数を表す。
式（ａ２－２）において、Ｚは、炭素原子数１～６の有機基を表し、Ｒ^２３は、それぞれ独立に、炭化水素基を含む２価の有機基を表し、Ｒ^２４は、それぞれ独立に、水素原子、アルキル基及びハロゲン原子からなる群より選択される少なくとも１種を表し、ｍ２は、２～６の整数を表し、ｎ２は、０～４の整数を表し、ｍ２＋ｎ２は、２～６の整数である。）
〔７〕 単量体組成物が、更に（ａ３）１分子中に１以上の芳香環及び２以上のアリル基を含むアリル化合物を含む、〔４〕～〔６〕のいずれか一項に記載の樹脂組成物。
〔８〕 （ａ３）成分が、下記式（ａ３－１）～（ａ３－６）の少なくともいずれかで表される、〔７〕に記載の樹脂組成物。

（式（ａ３－６）において、ｎ３は、１～１０００の整数を表す。）
〔９〕 樹脂組成物中の不揮発成分を１００質量％とした場合、（Ａ）成分の含有量が０．１質量％以上１０質量％以下である、〔１〕～〔８〕のいずれか一項に記載の樹脂組成物。
〔１０〕 フェノール系硬化剤及びカルボジイミド系硬化剤からなる群より選ばれる１種類以上の（Ｅ）硬化剤を含む、〔１〕～〔９〕のいずれか一項に記載の樹脂組成物。
〔１１〕 （Ｆ）硬化促進剤を含む、〔１〕～〔１０〕のいずれか一項に記載の樹脂組成物。
〔１２〕 （Ｇ）熱可塑性樹脂を含む、〔１〕～〔１１〕のいずれか一項に記載の樹脂組成物。
〔１３〕 絶縁層形成用である、〔１〕～〔１２〕のいずれか一項に記載の樹脂組成物。
〔１４〕 〔１〕～〔１３〕の何れか１項に記載の樹脂組成物の硬化物。
〔１５〕 〔１〕～〔１３〕の何れか１項に記載の樹脂組成物を含有する、シート状積層材料。
〔１６〕 支持体と、当該支持体上に〔１〕～〔１３〕の何れか１項に記載の樹脂組成物で形成された樹脂組成物層と、を有する樹脂シート。
〔１７〕 〔１〕～〔１３〕の何れか１項に記載の樹脂組成物の硬化物を含む絶縁層を備える、プリント配線板。
〔１８〕 〔１７〕に記載のプリント配線板を備える、半導体装置。 [1] A resin composition comprising (A) a maleimide compound having a sulfur atom and a maleimide group, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler.
[2] When the non-volatile component in the resin composition is 100% by mass, the content of component (C) is 10% by mass or more and the content of component (D) is 60% by mass or more, [1 ] The resin composition as described in .
[3] The resin composition of [1] or [2], wherein component (A) contains an aromatic ring in the molecule.
[4] component (A) is
(a1) a maleimide compound having two or more maleimide groups in one molecule;
(a2) a thiol compound having two or more thiol groups in one molecule;
The resin composition according to any one of [1] to [3], which is a polymer of a monomer composition containing
[5] The resin composition according to [4], wherein the component (a1) is represented by the following formula (a1-1).

(In formula (a1-1), R ¹¹ to R ¹⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom, and X is a divalent aromatic ring-containing represents an organic group.)
[6] The resin composition according to [4] or [5], wherein the component (a2) is represented by the following formula (a2-1) or (a2-2).

(In formula (a2-1), Y represents an organic group having a cyclic structure, R ²¹ each independently represents a divalent organic group containing a hydrocarbon group, R ²² each independently represents at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom; m1 represents an integer of 2 to 10; n1 represents an integer of 0 to 8;
In formula (a2-2), Z represents an organic group having 1 to 6 carbon atoms, R ²³ each independently represents a divalent organic group containing a hydrocarbon group, and R ²⁴ each independently represents represents at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom, m2 represents an integer of 2 to 6, n2 represents an integer of 0 to 4, m2+n2 represents 2 to 6 integers. )
[7] Any one of [4] to [6], wherein the monomer composition further contains (a3) an allyl compound containing one or more aromatic rings and two or more allyl groups in one molecule. of the resin composition.
[8] The resin composition of [7], wherein component (a3) is represented by at least one of the following formulas (a3-1) to (a3-6).

(In formula (a3-6), n3 represents an integer of 1 to 1000.)
[9] Any one of [1] to [8], wherein the content of component (A) is 0.1% by mass or more and 10% by mass or less when the non-volatile component in the resin composition is 100% by mass. The resin composition according to Item.
[10] The resin composition according to any one of [1] to [9], containing one or more (E) curing agents selected from the group consisting of phenolic curing agents and carbodiimide curing agents.
[11] The resin composition according to any one of [1] to [10], which contains (F) a curing accelerator.
[12] The resin composition according to any one of [1] to [11], which contains (G) a thermoplastic resin.
[13] The resin composition according to any one of [1] to [12], which is used for forming an insulating layer.
[14] A cured product of the resin composition according to any one of [1] to [13].
[15] A sheet-like laminate material containing the resin composition according to any one of [1] to [13].
[16] A resin sheet comprising a support and a resin composition layer formed on the support from the resin composition according to any one of [1] to [13].
[17] A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of [1] to [13].
[18] A semiconductor device comprising the printed wiring board according to [17].

According to the present invention, a resin composition that can obtain a cured product having excellent plating adhesion and can suppress unevenness after lamination; a cured product of the resin composition; a sheet-like laminate containing the resin composition materials; a resin sheet having a resin composition layer formed from the resin composition; a printed wiring board having an insulating layer containing a cured product of the resin composition; and a semiconductor device having the printed wiring board; .

Hereinafter, the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified without departing from the scope of the claims and their equivalents.

In the following description, the term "(meth)acrylate" includes acrylates, methacrylates and combinations thereof unless otherwise specified.

[1. Overview of resin composition]
The resin composition according to one embodiment of the present invention comprises (A) a maleimide compound having a sulfur atom and a maleimide group, (B) an epoxy resin, (C) an active ester compound, (D) an inorganic filler, including in combination with In the following description, the (A) maleimide compound having a sulfur atom and a maleimide group as the (A) component may be referred to as "(A) a sulfur-containing maleimide compound". According to this resin composition, unevenness after lamination can be suppressed, and a cured product having excellent plating adhesion can be obtained. Moreover, the cured product of this resin composition can usually have a low dielectric loss tangent. Furthermore, the cured product of this resin composition can usually have a small surface roughness after roughening treatment.

The present inventor conjectures the mechanism by which the cured product of the resin composition according to the present embodiment can obtain such excellent advantages as follows. However, the technical scope of the present invention is not limited by the mechanism described below.

A cured product of a conventional resin composition containing an epoxy resin, an active ester compound, and an inorganic filler can generally have a low dielectric loss tangent. In particular, when the amount of active ester and inorganic filler is large, it is possible to effectively lower the dielectric loss tangent of the cured product.

However, when a resin composition layer containing a resin composition containing an epoxy resin, an active ester compound, and an inorganic filler is laminated with an inner layer substrate, unevenness may occur in the resin composition layer after lamination. In addition, when a conductor layer is formed on the cured product by plating, the cured product of the resin composition tends to have poor adhesion to the conductor layer.

In contrast, the resin composition according to the present embodiment further contains (A) a sulfur-containing maleimide compound in combination with (B) an epoxy resin, (C) an active ester compound and (D) an inorganic filler. Due to the action of the sulfur atom, (A) the sulfur-containing maleimide compound can have a high affinity for both (B) the epoxy resin and (C) the active ester compound. Therefore, the compatibility of the resin component contained in the resin composition is improved, so that the homogeneity of the resin composition is improved and unevenness can be suppressed.

In addition, (A) the sulfur-containing maleimide compound contained in the resin composition according to the present embodiment can be bonded to each other by reaction of the maleimide groups during curing of the resin composition. Furthermore, (A) when the sulfur-containing maleimide compound has a thiol group, and when the resin composition contains a suitable curing agent or curing accelerator capable of promoting the reaction between the maleimide group and the epoxy group, (A ) the sulfur-containing maleimide compound and (B) the epoxy resin can react and bond. According to the bonding, a crosslinked structure is formed in the cured product, so that the mechanical strength of the cured product can be improved. Therefore, since the resistance of the cured product to stress can be increased, delamination (delamination) accompanied by destruction of the cured product can be suppressed, and therefore the adhesion between the conductor layer and the cured product can be improved. .

Furthermore, the reaction between (A) the sulfur-containing maleimide compounds that occurs during curing of the resin composition can be mainly a radical polymerization reaction. A polar group such as a hydroxyl group is not normally generated by this radical polymerization reaction. Therefore, even if (A) the sulfur-containing maleimide compound is contained, the cured product can have a low polarity. Therefore, the cured product of the resin composition can usually have a low dielectric loss tangent.

Moreover, as described above, (A) the sulfur-containing maleimide compound can have excellent affinity with (B) the epoxy resin and (C) the active ester compound. Therefore, the phase separation of the resin components such as the (A) component, the (B) component and the (C) component is suppressed in the resin composition. If the resin component undergoes large phase separation, a large phase domain is formed in the cured product, and each phase domain is detached during the roughening treatment, which may increase the surface roughness. However, in the resin composition according to the present embodiment, since the phase separation of the resin components is suppressed, the formation of large phase domains is suppressed. Therefore, it can usually have a small surface roughness after roughening treatment.

[2. (A) Sulfur-containing maleimide compound]
The resin composition according to the present embodiment contains (A) a sulfur-containing maleimide compound as component (A). This (A) sulfur-containing maleimide compound has a sulfur atom and a maleimide group (ie, a 2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group).

(A) The number of sulfur atoms contained in the sulfur-containing maleimide compound is usually 1 or more, preferably 2 or more, and more preferably 3 or more per molecule. (A) The upper limit of the number of sulfur atoms per molecule contained in the sulfur-containing maleimide compound is not particularly limited, and may be, for example, 10 or less. A sulfur atom is preferably contained in (A) the sulfur-containing maleimide compound as part of a thiol group (--SH group) or a thioether group (C--S--C group).

(A) The number of maleimide groups contained in the sulfur-containing maleimide compound may be one, or two or more. The maleimide group is preferably an aromatic maleimide group in which the nitrogen atom of the maleimide group is bonded to an aromatic ring. Among them, the maleimide group is preferably contained in (A) the sulfur-containing maleimide compound in a state in which the nitrogen atom of the maleimide group is directly bonded to the carbon atom of the benzene ring.

(A) The sulfur-containing maleimide compound preferably contains an aromatic ring in its molecule. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon ring. The aromatic hydrocarbon ring may be an aromatic condensed ring such as a naphthalene ring, but is preferably a monocyclic aromatic hydrocarbon ring, and particularly preferably a benzene ring.

(A) The sulfur-containing maleimide compound may contain a hydroxyl group in its molecule. This hydroxyl group is preferably a phenolic hydroxyl group bonded to an aromatic ring.

(A) the sulfur-containing maleimide compound preferably contains (a1) a maleimide compound having two or more maleimide groups in one molecule and (a2) a thiol compound having two or more thiol groups in one molecule. It is a polymer of monomer composition. In the following description, (a1) a maleimide compound having two or more maleimide groups in one molecule may be referred to as "(a1) polyfunctional maleimide compound". In addition, (a2) a thiol compound having two or more thiol groups in one molecule may be referred to as "(a2) polyfunctional thiol compound". As long as the polymer has a structure obtained by polymerizing a monomer composition containing (a1) a polyfunctional maleimide compound and (a2) a polyfunctional thiol compound, the method for producing the polymer is not limited. , (a1) polyfunctional maleimide compound and (a2) polyfunctional thiol compound produced by polymerization reaction.

(a1) The polyfunctional maleimide compound is a compound having two or more maleimide groups in one molecule. This (a1) polyfunctional maleimide compound is preferably represented by the following formula (a1-1).

(In formula (a1-1), R ¹¹ to R ¹⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom, and X is a divalent aromatic ring-containing represents an organic group.)

In formula (a1-1), R ¹¹ to R ¹⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom. The number of carbon atoms in the alkyl group is preferably 1-6, more preferably 1-4, and particularly preferably 1-3. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl and hexyl groups. Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. Preferably, R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a fluorine atom (fluoro group), a chlorine atom (chloro group), a bromine atom (bromo group) and an iodine atom ( iodo group).

In formula (a1-1), X represents a divalent organic group containing an aromatic ring. The number of aromatic rings contained in X may be 1, or 2 or more. When X contains two or more aromatic rings, the multiple aromatic rings are ether groups (-O-), ester groups (-O-CO-), amide groups (-CO-N-), carbonyl groups (- CO—), an azamethylene group (eg —NH—), an alkylene group (eg —CH ₂ —) or the like, or may be directly linked. The aromatic ring contained in X may be an aromatic hydrocarbon ring such as a benzene ring, naphthalene ring, anthracene ring, or phenanthrene ring, or may be a heteroaromatic ring.

Specific examples of X include groups represented by the following formulas (a1-1-1) to (a1-1-6). In formulas (a1-1-1) to (a1-1-6), each R ¹⁵ is independently a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group; a methoxy group, an ethoxy alkoxy group such as propoxy group and butoxy group; represents at least one selected from the group consisting of; Moreover, * represents a bond.

(a1) Preferred examples of the polyfunctional maleimide compound include 4,4'-diphenylmethanebismaleimide. Moreover, (a1) polyfunctional maleimide compound may be used individually by 1 type, and may be used in combination of 2 or more types.

(a2) The polyfunctional thiol compound is a compound having two or more thiol groups in one molecule. This (a2) polyfunctional thiol compound is preferably represented by the following formula (a2-1) or (a2-2).

(In formula (a2-1),
Y represents an organic group having a cyclic structure,
R ²¹ each independently represents a divalent organic group containing a hydrocarbon group,
R ²² each independently represents at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom,
m1 represents an integer from 2 to 10,
n1 represents an integer from 0 to 8; )

In formula (a2-1), Y represents an organic group having a cyclic structure. The valence of the organic group represented by Y is usually m1+n1. The cyclic structure of the organic group Y may be an alicyclic structure or an aromatic ring structure. Moreover, the cyclic structure which the organic group Y has may be a hydrocarbon cyclic structure or a heterocyclic structure. Furthermore, the cyclic structure possessed by the organic group Y may be a monocyclic structure or a polycyclic structure.

Examples of the organic group Y having an aromatic ring structure include groups obtained by removing any number of hydrogen atoms from structures represented by the following formulas (a2-1-1) to (a2-1-4). .

Examples of the organic group Y having a heterocyclic structure include groups represented by the following formulas (a2-1-5) to (a2-1-6). When the organic group Y has a structure represented by formulas (a2-1-5) to (a2-1-6) above, (-R ²¹ -SH) are bonded to all nitrogen atoms contained in the ring. is preferred.

Examples of the organic group Y having a polycyclic structure include groups represented by the following formulas (a2-1-7) to (a2-1-10). Furthermore, examples of the organic group Y having a polycyclic structure also include groups having a structure in which 2 to 10 hydrogen atoms are optionally removed from a spiro compound.

In formula (a2-1), each R ²¹ independently represents a divalent organic group containing a hydrocarbon group. The hydrocarbon group contained in the organic group R ²¹ includes, for example, a chain aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a cyclic structure, and an aromatic hydrocarbon group. Moreover, the organic group R ²¹ may contain one of the above hydrocarbon groups alone, or may contain two or more of them in combination. A plurality of hydrocarbon groups contained in the organic group R ²¹ may be directly bonded, or may be bonded via a bond selected from the group consisting of an ester bond, an ether bond, an amide bond and a urethane bond.

The organic group R ²¹ is preferably a linear alkylene group which may contain one or more types of bond selected from the group consisting of an ester bond, an ether bond, an amide bond and a urethane bond. Moreover, the ester bond, ether bond, amide bond, and urethane bond are preferably not directly bonded to the nitrogen atom on the isocyanuric ring and the sulfur atom constituting the thiol group.

When the organic group R ²¹ is a linear alkylene group that may contain one or more bonds selected from the group consisting of an ester bond, an ether bond, an amide bond and a urethane bond, the number of carbon atoms in the linear alkylene group is preferably 2-12. However, when the organic group ^R21 contains bonds such as ester bonds, ether bonds, amide bonds and urethane bonds, the carbon atoms forming the ester bonds, amide bonds and urethane bonds are included in the number of carbon atoms in the linear alkylene group. do not have. For example, when the organic group R ²¹ is a linear alkylene group having 12 carbon atoms containing one ester bond, the total number of carbon atoms of the organic group R ²¹ is 13.

Examples of linear alkylene groups having 2 to 12 carbon atoms include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group and the like. mentioned. In addition, the linear alkylene group which may contain one or more bonds selected from the group consisting of an ester bond, an ether bond, an amide bond and a urethane bond includes those described in JP-A-2016-74902. . Among them, the organic group R ²¹ is preferably a linear alkylene group having 2 to 12 carbon atoms and containing an ester bond.

Among linear alkylene groups having 2 to 12 carbon atoms containing an ester bond, a particularly preferred example of the organic group R ²¹ is a 2-oxa-3-oxopentylene group (--CH ₂ --O--CO--C ₂ H ₄ -), 3-oxa-4-oxopentylene group (-C ₂ H ₄ -O-CO-CH ₂ -), 2-oxa-3-oxohexylene group (-CH ₂ -O-CO- n—C ₃ H ₆ —), 3-oxa-4-oxohexylene group (—C ₂ H ₄ —O—CO—C ₂ H ₄ —), 2-oxa-3-oxoheptylene group (—CH ₂ — O—CO-n—C ₄ H ₈ —), 3-oxa-4-oxoheptylene group (—C ₂ H ₄ —O—CO-n-C ₃ H ₆ —), 2-oxa-3-oxooctylene group ( -CH ₂ -O-CO-n-C ₅ H ₁₀ -) and 3-oxa-4-oxooctylene groups (-C ₂ H ₄ -O-CO-n-C ₄ H ₈ -).

In formula (a2-1), each R ²² independently represents at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom. The number of carbon atoms in the alkyl group is preferably 1-6, more preferably 1-4, more preferably 1-3. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl and hexyl groups. Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. Preferably, each R ²² independently represents at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a propyl group, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In formula (a2-1), m1 represents an integer of 2-10, preferably an integer of 2-5. Also, n1 represents an integer of 0 to 8.

Examples of (a2) polyfunctional thiol compounds represented by formula (a2-1) include tris-[(3-mercaptopylopionyloxy)-ethyl]-isocyanurate, 1,3,5-tris(mercapto methyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,3,4,6-tetrakis(mercaptoethyl)glycoluril and the like.

(In formula (a2-2),
Z represents an organic group having 1 to 6 carbon atoms,
R ²³ each independently represents a divalent organic group containing a hydrocarbon group,
R ²⁴ each independently represents at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom,
m2 represents an integer from 2 to 6,
n2 represents an integer from 0 to 4,
m2+n2 is an integer of 2-6. )

In formula (a2-2), Z represents an organic group having 1 to 6 carbon atoms. The valence of the organic group represented by Z is usually m2+n2. The organic group Z may contain one or more types of bond selected from the group consisting of an ester bond, an ether bond, an amide bond and a urethane bond. The organic group Z is preferably a linear aliphatic hydrocarbon group which may contain one or more bonds selected from the group consisting of an ester bond, an ether bond, an amide bond and a urethane bond. Moreover, the number of carbon atoms in the linear aliphatic hydrocarbon group is preferably 1 to 4. As _the organic group Z, a linear aliphatic hydrocarbon group containing an ether bond is particularly preferable. -1) is preferred.

In formula (a2-2), each R ²³ independently represents a divalent organic group containing a hydrocarbon group. The scope of the organic group R ²³ can be the same as the organic group R ²¹ in formula (a2-1).

In formula (a2-2), each R ²⁴ independently represents at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom. The range of R ²⁴ may be the same as R ²² in formula (a2-1).

In formula (a2-2), m2 represents an integer of 2-6. The integer m2 is preferably 3 to 6, more preferably 4 to 6, and particularly preferably 6.
In formula (a2-2), n2 represents an integer of 0-4. However, m2+n2 is an integer of 2-6.

Examples of the polyfunctional thiol compound (a2) represented by the above formula (a2-2) include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and tetraethylene glycol. bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate) and the like.

(a2) Polyfunctional thiol compounds may be used singly or in combination of two or more.

The ratio of the amounts of (a1) polyfunctional maleimide compound and (a2) polyfunctional thiol compound contained in the monomer composition is not limited as long as the effects of the present invention are not significantly impaired. As a specific range, the mass ratio of (a1) polyfunctional maleimide compound to (a2) polyfunctional thiol compound ((a2) polyfunctional thiol compound/(a1) polyfunctional maleimide compound) is preferably 1/ 200 or more, more preferably 1/160 or more, still more preferably 1/100 or more, still more preferably 1/80 or more, particularly preferably 1/40 or more, preferably less than 1, more preferably 3/4 or less, More preferably 1/2 or less, particularly preferably 1/4 or less.

The monomer composition preferably contains (a1) a polyfunctional maleimide compound and (a2) a polyfunctional thiol compound in combination with (a3) one or more aromatic rings and two or more allyl groups in one molecule. Contains allyl compounds. In the following description, (a3) an allyl compound containing one or more aromatic rings and two or more allyl groups in one molecule may be referred to as "(a3) polyfunctional allyl compound".

(a3) The aromatic ring contained in the polyfunctional allyl compound is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The (a3) polyfunctional allyl compound containing one or more benzene rings and two or more allyl groups in one molecule includes, for example, diallylated bisphenol A, diallylated bisphenol AP, diallylated bisphenol AF, diallylated bisphenol B, diallyl bisphenol BP, diallylated bisphenol C, diallylated bisphenol E, diallylated bisphenol F, diallylated bisphenol G, diallylated bisphenol M, diallylated bisphenol S, diallylated bisphenol P, diallylated bisphenol PH, diallylated bisphenol TM, diallyl dialylated bisphenol compounds such as bisphenol Z; benzene poly(2-6) carboxylic acid poly(2-6) allyl esters; and allylated novolacs. (a3) Specific examples of the polyfunctional allyl compound include those described in JP-A-2016-74902.

Among them, as the (a3) polyfunctional allyl compound, those represented by the following formulas (a3-1) to (a3-6) are preferable. Therefore, the monomer composition preferably contains (a3) a polyfunctional allyl compound represented by at least one of formulas (a3-1) to (a3-6). In the following formula (a3-6), n3 represents an integer of 1-1000.

(a3) The polyfunctional allyl compound may be used singly or in combination of two or more.

The ratio of the amounts of (a1) polyfunctional maleimide compound and (a3) polyfunctional allyl compound contained in the monomer composition is not particularly limited as long as the effects of the present invention are not significantly impaired. Specifically, the mass ratio of (a1) polyfunctional maleimide compound to (a3) polyfunctional allyl compound ((a3) polyfunctional allyl compound/(a1) polyfunctional maleimide compound) is 0. may be greater than 0, preferably 1/10 or more, more preferably 1/8 or more, particularly preferably 1/4 or more, preferably 2 or less, more preferably 1 or less, particularly preferably 1 /2 or less.

The ratio of the amounts of (a2) polyfunctional thiol compound and (a3) polyfunctional allyl compound contained in the monomer composition is not limited as long as the effects of the present invention are not significantly impaired. To give a specific range, the mass ratio of (a2) polyfunctional thiol compound and (a3) polyfunctional allyl compound ((a3) polyfunctional allyl compound/(a2) polyfunctional thiol compound) is 0. It may be greater than 0, preferably 2/3 or more, more preferably 1 or more, particularly preferably 2 or more, preferably 20 or less, more preferably 10 or less.

In the polymerization of the monomer composition, monomers such as components (a1) to (a3) contained in the monomer composition can be polymerized. For example, the maleimide group of (a1) the polyfunctional maleimide compound and the thiol group of the (a2) polyfunctional thiol compound react to polymerize (a1) the polyfunctional maleimide compound and (a2) the polyfunctional thiol compound. Further, the maleimide group of the polyfunctional maleimide compound (a1) and the allyl group of the polyfunctional allyl compound (a3) can react to polymerize the polyfunctional maleimide compound (a1) and the polyfunctional allyl compound (a3). Further, the thiol group of the polyfunctional thiol compound (a2) and the allyl group of the polyfunctional allyl compound (a3) react to polymerize the polyfunctional thiol compound (a2) and the polyfunctional allyl compound (a3). Therefore, the polymer of the monomer composition may contain (a1) a maleimide group derived from a polyfunctional maleimide compound and (a2) a sulfur atom derived from a polyfunctional thiol compound, so that the polymer (A ) sulfur-containing maleimide compounds can be obtained. The polymerization can proceed, for example, by heating the monomer composition in a suitable environment.

(A) Examples of commercially available sulfur-containing maleimide compounds include "SA IMIDE 105HG" and "SA IMIDE 1705" manufactured by Sakai Chemical Industry Co., Ltd. The above "SA IMIDE 105HG" and "SA IMIDE 1705" are represented by the following formula (a-1) (a1) polyfunctional maleimide compound (4,4'-diphenylmethanebismaleimide), formula (a-2) (a2) polyfunctional thiol compound represented by (tris-[(3-mercaptopylopionyloxy)-ethyl]-isocyanurate), and (a3) polyfunctional allyl represented by formula (a-3) It is a compound obtained by polymerizing a monomer composition containing a compound (diallyl bisphenol A).

(A) The sulfur-containing maleimide compound may be used singly or in combination of two or more.

(A) The weight average molecular weight of the sulfur-containing maleimide compound is preferably 500 or more, more preferably 800 or more, particularly preferably 1000 or more, and preferably 5000 or less, from the viewpoint of significantly obtaining the desired effects of the present invention. It is more preferably 4000 or less, particularly preferably 3000 or less. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The mass ratio W _A /W _{B of the mass W A of (A) the sulfur-containing maleimide compound and the mass W B of the} (B) epoxy resin in the resin composition is preferably 0.01 or more, more preferably 0.05. above, more preferably 0.10 or more, particularly preferably 0.15 or more, preferably 1.0 or less, more preferably 0.6 or less, still more preferably 0.4 or less, particularly preferably 0.3 or less is. When the mass ratio W _A /W _B is in the above range, it is possible to suppress unevenness after lamination, improve the plating adhesion of the cured product, decrease the dielectric loss tangent of the cured product, and improve the surface roughness after roughening treatment. An effect such as reduction can be obtained remarkably.

The mass ratio W _A /W _{C of the mass W A of (A) the sulfur-containing maleimide compound and the mass W C of the} (C) active ester compound in the resin composition is preferably 0.01 or more, more preferably 0.01. 02 or more, more preferably 0.04 or more, particularly preferably 0.06 or more, preferably 1.0 or less, more preferably 0.5 or less, still more preferably 0.2 or less, particularly preferably 0.1 It is below. When the mass ratio W _A /W _C is within the above range, it is possible to suppress unevenness after lamination, improve the plating adhesion of the cured product, reduce the dielectric loss tangent of the cured product, and improve the surface roughness after roughening treatment. An effect such as reduction can be obtained remarkably.

The mass ratio of the mass W A of (A) the sulfur-containing maleimide compound to the mass W _A of the (B) epoxy resin and the total mass W _B +W _C of the (C) active ester compound in the resin composition W _A /(W _B + W _C ) is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 0.03 or more, particularly preferably 0.04 or more, preferably 1.0 or less, more preferably 0.5 or less. , more preferably 0.2 or less, particularly preferably 0.1 or less. When the mass ratio W _A /(W _B +W _C ) is in the above range, the unevenness after lamination is suppressed, the plating adhesion of the cured product is improved, the dielectric loss tangent of the cured product is reduced, and after roughening treatment An effect such as a reduction in surface roughness can be obtained remarkably.

The mass ratio W _A /W _D of the mass W A of (A) the sulfur-containing maleimide compound and the mass W _D of the (D) inorganic filler in the resin _composition is preferably 0.01 or more, more preferably 0.01. 02 or more, preferably 0.1 or less, more preferably 0.05 or less, and particularly preferably 0.03 or less. When the mass ratio W _A /W _D is within the above range, it is possible to suppress unevenness after lamination, improve the plating adhesion of the cured product, reduce the dielectric loss tangent of the cured product, and improve the surface roughness after roughening treatment. An effect such as reduction can be obtained remarkably.

The content of (A) the sulfur-containing maleimide compound in the resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, when the non-volatile component in the resin composition is 100% by mass. , particularly preferably 1.0% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 2% by mass or less. (A) When the content of the sulfur-containing maleimide compound is within the above range, suppression of unevenness after lamination, improvement in plating adhesion of the cured product, reduction in dielectric loss tangent of the cured product, and surface roughness after roughening treatment Effect such as reduction in intensity can be obtained remarkably.

The content of (A) the sulfur-containing maleimide compound in the resin composition is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, when the resin component in the resin composition is 100% by mass. , particularly preferably 2.0% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 8% by mass or less. The resin component of the resin composition represents the non-volatile components of the resin composition excluding (D) the inorganic filler. (A) When the content of the sulfur-containing maleimide compound is within the above range, suppression of unevenness after lamination, improvement in plating adhesion of the cured product, reduction in dielectric loss tangent of the cured product, and surface roughness after roughening treatment Effect such as reduction in intensity can be obtained remarkably.

[3. (B) Epoxy resin]
The resin composition according to the present embodiment contains (B) an epoxy resin as the (B) component. (B) The epoxy resin may be a curable resin having an epoxy group.

(B) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxy resins. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, isocyanurate-type epoxy resin, phenolphthalimidine-type epoxy resin, and the like. . (B) Epoxy resins may be used singly or in combination of two or more.

(B) The epoxy resin preferably contains an epoxy resin containing an aromatic structure from the viewpoint of obtaining a cured product having excellent heat resistance. Aromatic structures are chemical structures generally defined as aromatic and also include polycyclic aromatic and heteroaromatic rings. Examples of epoxy resins containing an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bixylenol type epoxy resin, glycidylamine type epoxy having an aromatic structure Resin, glycidyl ester type epoxy resin having aromatic structure, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having aromatic structure, epoxy resin having butadiene structure having aromatic structure, aromatic Structured alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin having aromatic structure, cyclohexane dimethanol type epoxy resin having aromatic structure, naphthylene ether type epoxy resin, having aromatic structure A trimethylol type epoxy resin, a tetraphenylethane type epoxy resin having an aromatic structure, and the like are included.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (B) the epoxy resin. (B) The ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the non-volatile components of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably is 70% by mass or more.

Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ). As the epoxy resin, the resin composition may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. good.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, ester skeleton. An alicyclic epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, and an epoxy resin having a butadiene structure are preferable.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation; ", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycirrol type epoxy resin) manufactured by ADEKA; "EP-3950L" manufactured by ADEKA; "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; Bisphenol F type epoxy resin mixture); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); Daicel "PB-3600" manufactured by Nippon Soda Co., Ltd., "JP-100" and "JP-200" (epoxy resins having a butadiene structure); 1,4-glycidylcyclohexane type epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, cresol novolak 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, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthalate A mijin-type epoxy resin is preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP -7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" ", "HP6000" (naphthylene ether type epoxy resin); Nippon Kayaku "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku; epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "YX4000H" manufactured by Mitsubishi Chemical, "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin); "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi "YX7700" (phenol aralkyl epoxy resin) manufactured by Chemical Company; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" manufactured by Mitsubishi Chemical (bisphenol AF type epoxy resin); Mitsubishi Chemical Company "YL7800" (fluorene type epoxy resin); Mitsubishi Chemical Corporation "jER1010" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation "jER1031S" (tetraphenylethane type epoxy resin); Nippon Kayaku "WHR991S" (phenol phthalimidine type epoxy resin) manufactured by Co., Ltd., and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:20, more preferably is 10:1 to 1:10, particularly preferably 7:1 to 1:7.

(B) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ~5,000 g/eq. , more preferably 60 g/eq. ~3,000 g/eq. , more preferably 80 g/eq. ~2,000 g/eq. , particularly preferably 110 g/eq. ~1,000 g/eq. is. Epoxy equivalent weight represents the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

(B) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The content of the (B) epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 4% by mass, when the non-volatile component in the resin composition is 100% by mass. % or more, preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less. (B) When the amount of epoxy resin is within the above range, suppression of unevenness after lamination, improvement of plating adhesion of cured product, reduction of dielectric loss tangent of cured product, and reduction of surface roughness after roughening treatment. Such an effect can be obtained remarkably.

The content of the (B) epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass, when the resin component in the resin composition is 100% by mass. % or more, preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less. (B) When the amount of epoxy resin is within the above range, suppression of unevenness after lamination, improvement of plating adhesion of cured product, reduction of dielectric loss tangent of cured product, and reduction of surface roughness after roughening treatment. Such an effect can be obtained remarkably.

[4. (C) Active ester compound]
The resin composition according to the present embodiment contains (C) an active ester compound as the (C) component. (C) The active ester compound can function as an epoxy resin curing agent that reacts with the (B) epoxy resin to cure the resin composition. (C) Active ester compounds may be used singly or in combination of two or more.

(C) The active ester compound generally contains two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. is preferably used. The active ester compound 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 compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, the (C) active ester compound includes a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolak. Active ester compounds are preferred, and among them, at least one selected from dicyclopentadiene type active ester compounds and naphthalene type active ester compounds is more preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.

(C) Commercially available active ester compounds include, for example, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L" and "EXB-8000L" as active ester compounds containing a dicyclopentadiene type diphenol structure. -65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (DIC Corporation ); as active ester compounds containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416- 70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester compound; acetyl of phenol novolac "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound that is a compound; "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds that are benzoyl compounds of phenol novolak; styryl group and naphthalene Examples of active ester compounds containing structures include "PC1300-02-65MA" (manufactured by Air Water).

(C) The active ester group equivalent of the active ester compound is preferably 50 g/eq. ~500 g/eq. , more preferably 50 g/eq. ~400 g/eq. , more preferably 100 g/eq. ~300 g/eq. is. The active ester group equivalent represents the mass of the active ester compound per equivalent of active ester group.

When the number of epoxy groups in the epoxy resin (B) is 1, the number of active ester groups in the active ester compound (C) is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more. , preferably 5.0 or less, more preferably 4.0 or less, and particularly preferably 3.0 or less. The "number of epoxy groups in (B) epoxy resin" means the sum of all the values obtained by dividing the mass of the non-volatile component of (B) epoxy resin present in the resin composition by the epoxy equivalent. In addition, "(C) the number of active ester groups of the active ester compound" is the sum of all the values obtained by dividing the mass of the non-volatile components of the (C) active ester compound present in the resin composition by the active ester group equivalent. show.

The content of (C) the active ester compound in the resin composition is preferably 10% by mass or more, more preferably 12% by mass or more, and still more preferably 14% by mass when the non-volatile component in the resin composition is 100% by mass. % by mass or more, particularly preferably 16% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less. (C) When the amount of the active ester compound is within the above range, it suppresses unevenness after lamination, improves the plating adhesion of the cured product, decreases the dielectric loss tangent of the cured product, and improves the surface roughness after roughening treatment. An effect such as reduction can be obtained remarkably.

The content of (C) the active ester compound in the resin composition is preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass, when the resin component in the resin composition is 100% by mass. % by mass or more, particularly preferably 50% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, particularly preferably 70% by mass or less. (C) When the amount of the active ester compound is within the above range, it suppresses unevenness after lamination, improves the plating adhesion of the cured product, decreases the dielectric loss tangent of the cured product, and improves the surface roughness after roughening treatment. An effect such as reduction can be obtained remarkably.

[5. (D) Inorganic filler]
The resin composition according to the present embodiment contains (D) an inorganic filler. (D) The inorganic filler is usually contained in the resin composition in the form of particles.

(D) An inorganic compound is used as the material of the inorganic filler. (D) Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and 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. Among these, silica and alumina are preferred, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. (D) The inorganic filler may be used singly or in combination of two or more.

(D) Commercially available inorganic fillers include, for example, “UFP-30” manufactured by Denka Kagaku Kogyo; “SP60-05” and “SP507-05” manufactured by Nippon Steel & Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; 5N”; “SC2500SQ”, “SO-C4”, “SO-C2” and “SO-C1” manufactured by Admatechs; “DAW-03” and “FB-105FD” manufactured by Denka.

(D) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably from the viewpoint of significantly obtaining the desired effects of the present invention. is 0.2 μm or more, preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, and particularly preferably 1 μm or less.

(D) The average particle size 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 is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle size can be calculated as the median size. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

(D) The specific surface area of the inorganic filler is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, and still more preferably 1 m ² from the viewpoint of significantly obtaining the desired effects of the present invention. /g or more, particularly preferably 3 m ² /g or more, preferably 100 m ² /g or less, more preferably 70 m ² /g or less, even more preferably 50 m ² /g or less, particularly preferably 40 m ² /g or less. be. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. can be measured by

(D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate compounds. A coupling agent etc. are mentioned. One type of surface treatment agent may be used alone, or two or more types may be used in combination.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( Hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM- 7103” (3,3,3-trifluoropropyltrimethoxysilane).

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, and a surface treatment agent of 0.2% to 3% by mass. It is more preferably surface-treated, and more preferably surface-treated with 0.3% by mass to 2% by mass of a surface treating agent.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition from increasing, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and even more preferably 0.5 mg/m ² or less.

(D) 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 (eg, 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 ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

The content of the inorganic filler (D) in the resin composition is preferably 60% by mass or more, more preferably 65% by mass or more, particularly preferably 69% by mass, when the non-volatile component in the resin composition is 100% by mass. % or more, preferably 86% by mass or less, more preferably 82% by mass or less, and particularly preferably 78% by mass or less. (D) When the amount of the inorganic filler is in the above range, suppression of unevenness after lamination, improvement of plating adhesion of the cured product, reduction of dielectric loss tangent of the cured product, and improvement of surface roughness after roughening treatment An effect such as reduction can be obtained remarkably.

[6. (E) optional curing agent]
The resin composition according to the present embodiment may further contain (E) an optional curing agent as an optional component in combination with the above-described components (A) to (D). The (E) optional curing agent as the (E) component does not include those corresponding to the above-described components (A) to (D). The (E) optional curing agent can function as an epoxy resin curing agent that reacts with the (B) epoxy resin to cure the resin composition, like the (C) active ester compound described above. (E) Any curing agent may be used singly or in combination of two or more.

(E) Examples of optional curing agents include phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and thiol-based curing agents. agents. Among them, it is preferable to use one or more curing agents selected from the group consisting of phenolic curing agents and carbodiimide curing agents.

As the phenol-based curing agent, a curing agent having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring per molecule can be used. From the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure is preferred. From the viewpoint of adhesion, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of the phenol-based curing agent include, for example, Meiwa Chemical Co., Ltd. "MEH-7700", "MEH-7810", "MEH-7851", Nippon Kayaku Co., Ltd. "NHN", "CBN", " GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN- 375", "SN-395", DIC's "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", " TD-2090-60M" and the like.

As the carbodiimide-based curing agent, a curing agent having one or more, preferably two or more carbodiimide structures in one molecule can be used. Specific examples of carbodiimide-based curing agents include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); biscarbodiimides such as biscarbodiimide; aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), Poly(naphthylenecarbodiimide), Poly(tolylenecarbodiimide), Poly(methyldiisopropylphenylenecarbodiimide), Poly(triethylphenylenecarbodiimide), Poly(diethylphenylenecarbodiimide), Poly(triisopropylphenylenecarbodiimide), Poly(diisopropylphenylenecarbodiimide) , poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), poly[methylenebis(methylphenylene)carbodiimide] and other aromatic polycarbodiimides. Examples of commercially available carbodiimide curing agents include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07" and "Carbodilite V-09" manufactured by Nisshinbo Chemical Co., Ltd. "Stabaxol P", "Stabaxol P400", and "Hykasil 510" manufactured by Rhein Chemie.

As the acid anhydride-based curing agent, a curing agent having one or more acid anhydride groups in one molecule can be used, and a curing agent having two or more acid anhydride groups in one molecule is used. preferable. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1 , 3-dione, ethylene glycol bis(anhydrotrimellitate), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid. Examples of commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA" and "OSA" manufactured by Shin Nippon Rika; "YH-306", "YH-307" of Hitachi Chemical Co., Ltd. "HN-2200", "HN-5500"; Clay Valley Co., Ltd. "EF-30", "EF-40" "EF-60", "EF-80" and the like.

As the amine-based curing agent, a curing agent having one or more, preferably two or more amino groups in one molecule can be used. Examples of amine-based curing agents include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. , m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′ -diaminobiphenyl, 3,3′-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2, 2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4- (3-aminophenoxy)phenyl)sulfone, and the like. Examples of commercially available amine-based curing agents include "SEIKACURE-S" manufactured by Seika; AB", "Kayahard AS"; "Epicure W" manufactured by Mitsubishi Chemical; "DTDA" manufactured by Sumitomo Seika.

Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; Examples include "Fa".

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4, 4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, Polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer that is entirely triazined to form a trimer), and the like.

Examples of thiol curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl)isocyanurate and the like.

(E) The active group equivalent of any curing agent is preferably 50 g/eq. ~3000g/eq. , more preferably 100 g/eq. ~1000 g/eq. , more preferably 100 g/eq. ~500 g/eq. , particularly preferably 100 g/eq. ~300 g/eq. is. Active group equivalents represent the mass of curing agent per equivalent of active groups.

The content of the optional curing agent (E) in the resin composition may be 0% by mass or greater than 0% by mass when the non-volatile component in the resin composition is 100% by mass. It is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1.0% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass. % by mass or less.

The content of the optional curing agent (E) in the resin composition may be 0% by mass or greater than 0% by mass when the resin component in the resin composition is 100% by mass, It is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, particularly preferably 5.0% by mass or more, preferably 50% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass. % by mass or less.

[7. (F) Curing accelerator]
The resin composition according to the present embodiment may further contain (F) a curing accelerator as an optional component in combination with the components (A) to (E) described above. The (F) curing accelerator as the (F) component does not include those corresponding to the above-described components (A) to (E). (F) The curing accelerator functions as a curing catalyst that accelerates the curing of (A) the epoxy resin.

Examples of (F) curing accelerators include phosphorus curing accelerators, urea curing accelerators, guanidine curing accelerators, imidazole curing accelerators, metal curing accelerators, and amine curing accelerators. . Among them, imidazole-based curing accelerators are preferred. (F) The curing accelerator may be used alone or in combination of two or more.

Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 -methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, aromatic phosphonium salts such as butyltriphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; 2-butenyl)phosphine, aliphatic phosphines such as tricyclohexylphosphine; -tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butyl) phenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris( 3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4- methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis( diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, 2,2′-bis(diphenylphosphino)diphenyl ether, and other aromatic phosphines. be done.

Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] etc.

Guanidine curing accelerators include, for example, 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] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like.

Examples of imidazole curing accelerators 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'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins. Examples of commercially available imidazole curing accelerators include, for example, Shikoku Kasei Co., Ltd. "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK- PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A"; and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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. As the amine-based curing accelerator, a commercially available product may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.

The content of the (F) curing accelerator in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably when the non-volatile component in the resin composition is 100% by mass. is 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.05% by mass or more, preferably 1.0% by mass or less, more preferably 0.5% by mass or less, especially Preferably, it is 0.1% by mass or less.

The content of the (F) curing accelerator in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably when the resin component in the resin composition is 100% by mass. is 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.10% by mass or more, preferably 2.0% by mass or less, more preferably 1.0% by mass or less, especially Preferably, it is 0.5% by mass or less.

[8. (G) Thermoplastic resin]
The resin composition according to the present embodiment may further contain (G) a thermoplastic resin as an optional component in combination with the components (A) to (F) described above. The (G) thermoplastic resin as the (G) component does not include those corresponding to the above-described components (A) to (F).

(G) Thermoplastic resins include, for example, phenoxy resins, polyimide resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, and polycarbonate resins. , polyether ether ketone resin, polyester resin, and the like. (G) The thermoplastic resin may be used alone or in combination of two or more.

Examples of phenoxy resins 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, and terpene. Examples include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of the phenoxy resin include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30";

Specific examples of the polyimide resin include “SLK-6100” manufactured by Shin-Etsu Chemical Co., Ltd., “Likacoat SN20” and “Ricacoat PN20” manufactured by Shin Nippon Rika Co., Ltd., and the like.

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP manufactured by Sekisui Chemical Co., Ltd. S-LEC BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series;

Examples of polyolefin resins include ethylene-based copolymers such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. Resin: polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, and isocyanate group-containing resins. Examples include polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether-polybutadiene resin, and the like.

Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimides) manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

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

Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "Ultem" manufactured by GE.

Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxy group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, "C-1090" and "C-2090" manufactured by Kuraray Co., Ltd. , “C-3090” (polycarbonate diol) and the like. Specific examples of the polyetheretherketone resin include "Sumiproy K" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, and the like.

(G) The weight average molecular weight (Mw) of the thermoplastic resin is preferably greater than 5,000, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and preferably is 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, and particularly preferably 50,000 or less.

The content of the (G) thermoplastic resin in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably when the non-volatile component in the resin composition is 100% by mass. is 0.01% by mass or more, more preferably 0.10% by mass or more, particularly preferably 0.20% by mass or more, preferably 5.0% by mass or less, more preferably 2.0% by mass or less, especially Preferably, it is 1.0% by mass or less.

The content of the (G) thermoplastic resin in the resin composition may be 0% by mass, or may be greater than 0% by mass, preferably when the resin component in the resin composition is 100% by mass. is 0.01% by mass or more, more preferably 0.10% by mass or more, particularly preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 5.0% by mass or less, particularly preferably It is 3.0% by mass or less.

[9. (H) radically polymerizable compound]
The resin composition according to the present embodiment may further contain (H) any radically polymerizable compound as an optional component in combination with the components (A) to (G) described above. The (H) radically polymerizable compound as the (H) component does not include those corresponding to the above-described components (A) to (G). (H) Radically polymerizable compounds may be used singly or in combination of two or more.

(H) The radically polymerizable compound may have an ethylenically unsaturated bond. (H) Radically polymerizable compound is, for example, an allyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, p-vinylphenyl group, m-vinylphenyl group, o-vinylphenyl group and other unsaturated hydrocarbon groups ; an acryloyl group, a methacryloyl group, a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group), an α,β-unsaturated carbonyl group; may have. (H) The radically polymerizable compound preferably has two or more radically polymerizable groups.

(H) Radically polymerizable compounds include, for example, (meth)acrylic radically polymerizable compounds, styrene radically polymerizable compounds, allyl radically polymerizable compounds, and maleimide radically polymerizable compounds.

The (meth)acrylic radically polymerizable compound is, for example, a compound having one or more, preferably two or more acryloyl groups and/or methacryloyl groups. Examples of (meth)acrylic radically polymerizable compounds include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, neo Pentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol Di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylic acid ester compounds such as; 9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene , ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate and other low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylic acid ester compounds; Low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylic acid ester compounds such as (meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate; High molecular weight (molecular weight 1000 or more) acrylic acid ester compounds such as (meth)acrylic-modified polyphenylene ether resins and the like can be mentioned. Examples of commercially available (meth)acrylic radically polymerizable compounds include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclode) manufactured by Kyoeisha Chemical Co., Ltd. candimethanol diacrylate), "DCP" (tricyclodecanedimethanol dimethacrylate), Nippon Kayaku Co., Ltd.'s "KAYARAD R-684" (tricyclodecanedimethanol diacrylate), "KAYARAD R-604" (dioxane glycol diacrylate), and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

The styrene-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more vinyl groups directly bonded to an aromatic carbon atom. Examples of styrene-based radically polymerizable compounds include divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4′-divinylbiphenyl, 1,2-bis(4 -vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether and other low molecular weight (molecular weight less than 1000) styrene compounds; vinylbenzyl-modified polyphenylene ether resin, styrene- High-molecular weight (molecular weight 1000 or more) styrene compounds such as divinylbenzene copolymers can be used. Examples of commercially available styrene-based radical polymerizable compounds include "ODV-XET (X03)", "ODV-XET (X04)", and "ODV-XET (X05)" (styrene -divinylbenzene copolymer), Mitsubishi Gas Chemical Company's "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin).

The allyl-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more allyl groups. Examples of allyl-based radically polymerizable compounds include diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenecarboxylate. aromatic carboxylic acid allyl ester compounds; 1,3,5-triallyl isocyanurate, isocyanurate allyl ester compounds such as 1,3-diallyl-5-glycidyl isocyanurate; 2,2-bis[3-allyl-4 -epoxy-containing aromatic allyl compounds such as (glycidyloxy)phenyl]propane; bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane benzoxazine-containing aromatic allyl compounds; ether-containing aromatic allyl compounds such as 1,3,5-triallyletherbenzene; and allylsilane compounds such as diallyldiphenylsilane. Examples of commercially available allyl-based radical polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Co., Ltd., and "DAD" (diallyl diphenate) manufactured by Nissho Techno Fine Chemical Co., Ltd. , "TRIAM-705" manufactured by Wako Pure Chemical Industries, Ltd. (triallyl trimellitate), trade name "DAND" manufactured by Nippon Distillery Co., Ltd. (diallyl 2,3-naphthalenecarboxylate), manufactured by Shikoku Chemical Industry Co., Ltd. "ALP- d” (Bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane), “RE-810NM” manufactured by Nippon Kayaku Co., Ltd. (2, 2-bis[3-allyl-4-(glycidyloxy)phenyl]propane), "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Co., Ltd., and the like.

The maleimide-based radically polymerizable compound is, for example, a compound having one or more, preferably two or more maleimide groups. The maleimide-based radical polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. Examples of commercially available maleimide-based radically polymerizable compounds include "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", and "BMI-3000J" manufactured by Designer Molecules. , "BMI-689", "BMI-2500" (maleimide compound containing dimer diamine structure), "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecules, "MIR-5000" manufactured by Nippon Kayaku Co., Ltd. -60T", "MIR-3000-70MT" (biphenylaralkyl-type maleimide compound), "BMI-70" and "BMI-80" manufactured by K-I Kasei Co., Ltd., "BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd., " BMI-TMH" and the like. Further, as the maleimide-based radically polymerizable compound, a maleimide resin (a maleimide compound containing an indane ring skeleton) disclosed in Technical Report No. 2020-500211 of the Japan Institute of Invention and Innovation may be used.

(H) The ethylenically unsaturated bond equivalent of the radically polymerizable compound is preferably 20 g/eq. ~3000g/eq. , more preferably 50 g/eq. ~2500 g/eq. , more preferably 70 g/eq. ~2000g/eq. , particularly preferably 90 g/eq. ~1500 g/eq. is. The ethylenically unsaturated bond equivalent represents the mass of the radically polymerizable compound per equivalent of ethylenically unsaturated bond.

(H) The weight average molecular weight (Mw) of the radically polymerizable compound is preferably 40,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, but can be, for example, 150 or more.

The content of the (H) radically polymerizable compound in the resin composition may be 0% by mass or greater than 0% by mass when the non-volatile component in the resin composition is 100% by mass. Preferably 0.01% by mass or more, more preferably 0.10% by mass or more, particularly preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, particularly preferably 6 % by mass or less.

The content of (H) the radically polymerizable compound in the resin composition may be 0% by mass or greater than 0% by mass when the resin component in the resin composition is 100% by mass. It is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, particularly preferably 1.0% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, particularly preferably 10% by mass. % by mass or less.

[10. (I) optional additive]
The resin composition according to the present embodiment may further contain (I) an optional additive as an optional non-volatile component in combination with the components (A) to (H) described above. (I) Optional additives include, for example, radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine Thermosetting resins other than epoxy resins such as resins, unsaturated polyester resins, phenolic resins, melamine resins and silicone resins; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine; silicone leveling agents, acrylic polymer leveling agents leveling agents such as; thickeners such as bentone and montmorillonite; defoaming agents such as silicone-based defoaming agents, acrylic defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; benzotriazole-based UV absorbers UV absorbers such as UV absorbers; adhesion improvers such as urea silane; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, and triazine-based adhesion promoters; antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus), nitrogen flame retardants (e.g. melamine sulfate), halogen flame retardants, inorganic flame retardants (e.g. antimony trioxide); phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants agent, silicone dispersant, anionic dispersant, cationic dispersant; borate stabilizer, titanate stabilizer, aluminate stabilizer, zirconate stabilizer, isocyanate stabilizer, carboxylic acid stabilizer Stabilizers, stabilizers such as carboxylic acid anhydride-based stabilizers. (I) Optional additives may be used singly or in combination of two or more.

[11. (J) Solvent]
The resin composition according to the present embodiment may contain (J) a solvent as an optional volatile component in combination with the non-volatile components such as components (A) to (I) described above. (J) As the solvent, an organic solvent is usually used. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol; acetic acid Ether ester solvents such as 2-ethoxyethyl, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate, etc. ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) and other ether alcohol solvents; N,N-dimethylformamide, N, Amide solvents such as N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethylsulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatics such as hexane, cyclopentane, cyclohexane, and methylcyclohexane Hydrocarbon-based solvents: aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, and the like can be mentioned. (J) The solvent may be used alone or in combination of two or more.

(J) The content of the solvent is not particularly limited, but when all components in the resin composition are 100% by mass, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, It may be 20% by mass or less, 15% by mass or less, 10% by mass or less, or the like, and may be 0% by mass.

[12. Method for producing a resin composition]
The resin composition according to this embodiment can be produced, for example, by mixing the components described above. Some or all of the components described above may be mixed at the same time, or may be mixed in order. During the course of mixing each component, the temperature may be set accordingly, and thus may be temporarily or permanently heated and/or cooled. Moreover, you may perform stirring or shaking in the process of mixing each component.

[13. Physical properties of the resin composition]
The resin composition according to the present embodiment can suppress unevenness in the resin composition layer after lamination when a resin composition layer containing the resin composition is laminated with an inner layer substrate. For example, when the resin composition layer and the inner layer substrate are laminated under the conditions described in the section [Test Example 2: Evaluation of unevenness after lamination] in Examples described later, the resin along the periphery of the inner layer substrate It is possible to suppress the occurrence of unevenness as a recess.

A cured product having excellent plating adhesion can be obtained from the resin composition according to the present embodiment. That is, when a conductor layer is formed on the cured product of the resin composition by plating, high adhesion can be obtained between the conductor layer and the cured product. For example, the peel strength can be increased when the peel strength is measured under the conditions described in the section [Test Example 4: Measurement of Peel Strength] in Examples described later. The peel strength represents the magnitude of the force required to peel off the conductor layer formed on the cured product of the resin composition by plating, and the greater the peel strength, the better the plating adhesion. The peel strength is preferably 0.30 kgf/cm or more, more preferably 0.32 kgf/cm or more, and particularly preferably 0.35 kgf/cm or more.

The resin composition according to the present embodiment can usually obtain a cured product with a low dielectric loss tangent. For example, a low dielectric loss tangent can be obtained when the dielectric loss tangent of the cured product is measured under the conditions described in the section [Test Example 1: Measurement of Dielectric Loss Tangent] in Examples described later. The dielectric loss tangent of the cured product is preferably 0.0040 or less, more preferably 0.0030 or less, and particularly preferably 0.0028 or less.

A cured product of the resin composition according to the present embodiment can usually have a small surface roughness when subjected to a roughening treatment. For example, when the arithmetic average roughness Ra of the roughened cured product after roughening treatment was measured under the conditions described in the section [Test Example 3: Measurement of arithmetic mean roughness (Ra)] in the examples described later, A small arithmetic mean roughness Ra can be obtained. The arithmetic mean roughness Ra is preferably 150 nm or less, more preferably 130 nm or less, and particularly preferably 100 nm or less. The lower limit is not particularly limited, and may be 30 nm or more, 40 nm or more, and the like.

[14. Applications of the resin composition]
The resin composition according to the present embodiment can be used as a resin composition for insulation, and in particular can be suitably used as a resin composition for forming an insulation layer (resin composition for forming an insulation layer). . For example, the resin composition according to the present embodiment can be used as a resin composition for forming an insulating layer of a printed wiring board, and a resin composition for forming an interlayer insulating layer (resin composition for interlayer insulation). can be suitably used as

Further, the resin composition according to the present embodiment may be used as a resin composition for forming a rewiring layer (resin composition for forming a rewiring layer). A rewiring formation layer represents an insulating layer for forming a rewiring layer. Further, the rewiring layer represents a conductor layer formed on a rewiring forming layer as an insulating layer. For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to the present embodiment may be used as a resin composition for forming a rewiring layer. . Further, when the semiconductor chip package is manufactured by the following steps (1) to (6), a rewiring layer may be further formed on the sealing layer.
(1) a step of laminating a temporary fixing film on a substrate;
(2) temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the base material and the temporary fixing film from the semiconductor chip;
(5) forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed; and (6) forming a rewiring layer as a conductor layer on the rewiring layer. forming process

Furthermore, the resin composition according to the present embodiment includes, for example, a resin sheet, a sheet-like laminated material such as prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a hole-filling resin, a part-embedding resin, etc. It can be used in a wide range of applications in which the composition is used.

[15. Sheet laminated material]
Although the resin composition according to the present embodiment may be applied in the form of a varnish, it is industrially preferable to use it in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminate material, resin sheets and prepregs shown below are preferable.

In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support. The resin composition layer is formed of the resin composition according to this embodiment. Therefore, the resin composition layer usually contains the resin composition, and preferably contains only the resin composition.

The thickness of the resin composition layer is preferably 50 μm or less, more It is preferably 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be 5 μm or more, 10 μm or more, or the like.

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 sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. 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 other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

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

As the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, 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 Co., Ltd., "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In one embodiment, the resin sheet may further contain any layer as necessary. Examples of such an optional layer include a protective film conforming to the support provided on the surface of the resin composition layer not bonded to the support (that is, the surface opposite to the support). be done. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust and scratches on the surface of the resin composition layer.

For the resin sheet, for example, a liquid (varnish) resin composition is used as it is, or a liquid (varnish) resin composition is prepared by dissolving the resin composition in a solvent, and this is coated using a die coater or the like. It can be produced by coating on a support and further drying to form a resin composition layer.

Examples of the solvent include the same solvents as those described as components of the resin composition. A solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

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

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

As the sheet-like fiber base material used for the prepreg, for example, those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited, and is usually 10 µm or more.

A prepreg can be produced by a hot melt method, a solvent method, or the like.

The thickness of the prepreg may be in the same range as the resin composition layer in the resin sheet described above.

The sheet-like laminated material can be suitably used for forming the insulating layer of the printed wiring board (for the insulating layer of the printed wiring board), and for forming the interlayer insulating layer of the printed wiring board (for the printed wiring board). for interlayer insulating layers).

[16. Printed wiring board]
A printed wiring board according to one embodiment of the present invention includes an insulating layer containing a cured product obtained by curing the resin composition according to the present embodiment. This printed wiring board can be manufactured, for example, using the resin sheet described above by a method including the following steps (I) and (II).
(I) A step of laminating a resin sheet on the inner layer substrate such that the resin composition layer of the resin sheet is bonded to the inner layer substrate.
(II) A step of curing the resin composition layer to form an insulating layer.

The "inner layer substrate" used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are further formed when manufacturing a printed wiring board is also included in the above-mentioned "inner layer board". When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions with a pressure of 26.7 hPa or less.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.

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

In step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. Curing of the resin composition layer is usually performed by heat curing. As the specific curing conditions for the resin composition layer, the conditions that are usually employed when forming the insulating layer of a printed wiring board may be used.

For example, the thermosetting conditions for the resin composition layer vary depending on the type of resin composition and the like. It is preferably 170°C to 210°C. Curing time may preferably be from 5 minutes to 120 minutes, more preferably from 10 minutes to 100 minutes, even more preferably from 15 minutes to 100 minutes.

Before thermosetting the resin composition layer, 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 cured at a temperature of 50° C. to 150° C., preferably 60° C. to 140° C., more preferably 70° C. to 130° C. for 5 minutes or more, It may be preheated for preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 15 minutes to 100 minutes.

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step ( It may be carried out between IV) and step (V). If necessary, the steps (I) to (V) of forming the insulating layer and the conductor layer may be repeated to form a multilayer wiring board.

In other embodiments, printed wiring boards can be manufactured using the prepregs described above. The manufacturing method can be basically the same as in the case of using a resin sheet.

Step (III) is a step of making holes 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 to form 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. Smear is usually also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards 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 neutralizing treatment with a neutralizing liquid in this order.

The swelling liquid used for the roughening treatment includes, for example, an alkaline solution, a surfactant solution, etc., preferably an alkaline solution. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment with a swelling liquid can be performed, for example, by immersing the insulating layer in a swelling liquid at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

Examples of the oxidizing agent used for the roughening treatment include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes. The permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.

As the neutralizing solution used for the roughening treatment, an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, and can be, for example, 1 nm or more, 2 nm or more. The root mean square roughness (Rq) of the surface of the insulating layer after roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, and can be, for example, 1 nm or more, 2 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

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

The conductor layer may have a single layer structure, or may have a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds 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.

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. A semi-additive method is preferable from the viewpoint of manufacturing simplicity. An example of forming a conductor layer by a semi-additive method is shown below.

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

In other embodiments, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Then, step (II) is performed to form an insulating layer. After that, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.

A metal foil can be manufactured by a known method such as an electrolysis method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.

[17. semiconductor device]
A semiconductor device according to an embodiment of the present invention includes the printed wiring board described above. A semiconductor device can be manufactured using a printed wiring board.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "mass parts" and "mass%", respectively, unless otherwise specified. Further, the temperature and pressure conditions were room temperature (25° C.) and atmospheric pressure (1 atm) unless otherwise specified.

[Example 1]
Biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g / eq.) 8 parts, and naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyl 2 parts of oxy)naphthalene (epoxy equivalent: about 145 g/eq.) were heated and dissolved in 15 parts of solvent naphtha with stirring. This was cooled to room temperature to prepare an epoxy resin dissolved composition.

2 parts of a sulfur-containing maleimide compound (“SA-IMIDE 105HG” manufactured by Sakai Chemical Industry Co., Ltd., weight average molecular weight 1200), an active ester compound (“HPC-8150-62T” manufactured by DIC, active 40 parts of a toluene solution with an ester group equivalent of about 220 g / eq. "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m ² /g) 100 parts, triazine skeleton-containing phenolic curing agent (DIC "LA-3018-50P", active group equivalent about 151 g / eq., 2-methoxypropanol solution with a non-volatile content of 50%) 2 parts, carbodiimide curing agent (manufactured by Nisshinbo Chemical Co., Ltd. "V-03", active group equivalent weight of about 216 g / eq., non-volatile content of 50% toluene solution ) 5 parts, imidazole-based curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole) 0.1 part, phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX7553BH30", nonvolatile content of 30% by mass 2 parts of a 1:1 solution of MEK and cyclohexanone) were mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin composition.

[Example 2]
Instead of 2 parts of a sulfur-containing maleimide compound ("SA-IMIDE 105HG" manufactured by Sakai Chemical Industry Co., Ltd.), 2 parts of sulfur-containing maleimide ("SA-IMIDE 1705" manufactured by Sakai Chemical Industry Co., Ltd., weight average molecular weight 2200) was used. Furthermore, instead of 40 parts of an active ester compound ("HPC-8150-62T" manufactured by DIC, active ester group equivalent of about 220 g / eq., a toluene solution with a nonvolatile content of 62% by mass), an active ester compound (manufactured by DIC 40 parts of "HPC-8000-65T", a toluene solution with an active ester group equivalent weight of about 223 g/eq. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 3]
The amount of the sulfur-containing maleimide compound (“SA-IMIDE 105HG” manufactured by Sakai Chemical Industry Co., Ltd.) was changed from 2 parts to 4 parts. In addition, biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g / eq.) 8 parts and naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyl 10 parts of a biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) was used instead of the combination of 2 parts of oxy)naphthalene, epoxy equivalent of about 145 g/eq. In addition, spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m ² / The amount of g) was changed from 100 parts to 120 parts. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 4]
The amount of the sulfur-containing maleimide compound (“SA-IMIDE 105HG” manufactured by Sakai Chemical Industry Co., Ltd.) was changed from 2 parts to 1 part. Also, 1 part of a sulfur-containing maleimide compound (“SA-IMIDE 1705” manufactured by Sakai Chemical Industry Co., Ltd.) was added to the resin composition. Furthermore, biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g / eq.) 8 parts and naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyl oxy)naphthalene, epoxy equivalent of about 145 g/eq.) instead of a combination with 2 parts of naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent 10 parts of about 145 g/eq.) were used. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 5]
2 parts of a biphenyl aralkyl novolac type maleimide compound (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., MEK/toluene mixed solution with a non-volatile content of 70%) was added to the resin composition. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 6]
Two parts of methacrylic-modified polyphenylene ether (“SA9000-111” manufactured by SABIC Innovative Plastics) were added to the resin composition. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Example 7]
2 parts of vinylbenzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content of 65%) was added to the resin composition. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Comparative Example 1]
A sulfur-containing maleimide compound (“SA-IMIDE 105HG” manufactured by Sakai Chemical Industry Co., Ltd.) was not used. In addition, biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g / eq.) 8 parts and naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyl oxy)naphthalene, epoxy equivalent of about 145 g/eq.) instead of a combination with 2 parts of naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyloxy)naphthalene, epoxy equivalent 10 parts of about 145 g/eq.) were used. Furthermore, instead of 40 parts of an active ester compound ("HPC-8150-62T" manufactured by DIC, active ester group equivalent of about 220 g / eq., a toluene solution with a nonvolatile content of 62% by mass), an active ester compound (manufactured by DIC 40 parts of "HPC-8000-65T", a toluene solution with an active ester group equivalent weight of about 223 g/eq. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Comparative Example 2]
A sulfur-containing maleimide compound (“SA-IMIDE 105HG” manufactured by Sakai Chemical Industry Co., Ltd.) was not used. In addition, biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g / eq.) 8 parts and naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC, 1,6-bis(glycidyl 10 parts of a biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g/eq.) was used instead of the combination of 2 parts of oxy)naphthalene, epoxy equivalent of about 145 g/eq. In addition, spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, specific surface area 5.8 m ² / The amount of g) was changed from 100 parts to 120 parts. A resin composition was prepared in the same manner as in Example 1 except for the above matters.

[Test Example 1: Measurement of dielectric loss tangent]
(1) Preparation of resin sheet A having a resin composition layer thickness of 40 μm:
As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared. On the release layer of this support, the resin compositions obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet A including a support and a resin composition layer.

(2) Preparation of cured product B for evaluation:
The resin sheet A was heated in an oven at 190° C. for 90 minutes to cure the resin composition layer. The resin sheet A was taken out from the oven and the support was peeled off to obtain a cured product of the resin composition layer. The cured product was cut into a piece having a length of 80 mm and a width of 2 mm to obtain a cured product B for evaluation.

(3) Measurement of dielectric constant and dielectric loss tangent:
For the cured product B for evaluation, the dielectric loss tangent value (Df value) was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by the cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies. . Two test pieces were measured, and the average was calculated.

[Test Example 2: Evaluation of unevenness after lamination]
(1) Preparation of inner layer substrate:
As an inner layer substrate having a copper layer on the surface and an inner layer circuit formed, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, manufactured by Panasonic Corporation " R1515A”) was prepared. Both surfaces of the inner layer substrate were etched by 1 μm with a micro-etching agent (“CZ8101” manufactured by MEC) to roughen the copper surface.

(2) Lamination of resin sheet A:
Using a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), the resin sheet A obtained in the step (1) of Test Example 1 was coated with the resin composition layer as the inner layer. Both sides of the inner layer substrate were laminated so as to be in contact with the substrate. Lamination was carried out by pressure bonding for 30 seconds at 120° C. and pressure of 0.74 MPa after reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Evaluation of unevenness after lamination:
After lamination, the resin composition layer was observed to evaluate unevenness. When resin dents were observed along the periphery of the inner layer substrate, the unevenness was evaluated as "presence", and when no dents were observed, the unevenness was evaluated as "absent".

[Test Example 3: Measurement of arithmetic mean roughness (Ra)]
(1) Thermosetting of resin composition layer:
The inner layer substrate laminated with the resin sheet A in the step (2) of Test Example 2 was placed in an oven at 130°C and heated for 30 minutes, then transferred to an oven at 170°C and heated for 30 minutes to obtain a resin composition. The layer was heat cured to form an insulating layer. After that, the support was peeled off to obtain a cured substrate A having an insulating layer, an inner layer substrate and an insulating layer in this order.

(2) Roughening treatment:
The cured substrate A was subjected to a desmearing treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.
(Wet desmear treatment)
The cured substrate A is immersed in a swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, and then an oxidizing agent solution (Atotech Japan "Concentrate Compact CP" manufactured by Co., Ltd., an aqueous solution with a potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80° C. for 20 minutes. Then, it was immersed in a neutralizing solution ("Reduction Solution Securigant P" manufactured by Atotech Japan, sulfuric acid aqueous solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(3) Measurement of arithmetic mean roughness (Ra) of insulating layer surface after roughening treatment:
The arithmetic mean roughness (Ra) of the insulating layer surface after the roughening treatment is measured using a non-contact surface roughness meter (Bruker WYKO NT3300) in VSI mode with a 50x lens with a measurement range of 121 μm × 92 μm. It was calculated from the numerical values obtained. Measurement was performed at 10 points, and the average value was obtained.

[Test Example 4: Measurement of peel strength]
(1) Formation of conductor layer:
According to the semi-additive method, a conductor layer was formed on the roughened surface of the insulating layer of the cured substrate A roughened in the step (2) of Test Example 3. That is, the cured substrate A after the roughening treatment was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Then, after annealing by heating at 150° C. for 30 minutes, an etching resist was formed and a pattern was formed by etching. Thereafter, copper sulfate electroplating was performed to form a conductor layer having a thickness of 25 μm, and annealing treatment was performed at 190° C. for 60 minutes. The obtained substrate is called "evaluation substrate B".

(2) Measurement of peel strength of plated conductor layer:
The peel strength of the insulating layer and conductor layer was measured according to Japanese Industrial Standards (JIS C6481). Specifically, the conductor layer of the evaluation substrate B was cut to surround a portion having a width of 10 mm and a length of 100 mm. One end of this section was peeled off and grasped with a grapple. At room temperature (25° C.), the film was pulled vertically at a speed of 50 mm/min, and the load (kgf/cm) when 35 mm was peeled off was measured as the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[result]
The results of the examples and comparative examples described above are shown in the table below.

In the examples, it was confirmed that the same results as in the above examples were obtained even when the components (E) to (H) were not contained, although there was a difference in degree.

Claims (18)

A resin composition comprising (A) a maleimide compound having a sulfur atom and a maleimide group, (B) an epoxy resin, (C) an active ester compound, and (D) an inorganic filler. The content of component (C) is 10% by mass or more and the content of component (D) is 60% by mass or more, when the non-volatile component in the resin composition is 100% by mass. of the resin composition. 3. The resin composition according to claim 1, wherein component (A) contains an aromatic ring in the molecule. (A) component is
(a1) a maleimide compound having two or more maleimide groups in one molecule;
(a2) a thiol compound having two or more thiol groups in one molecule;
The resin composition according to any one of claims 1 to 3, which is a polymer of a monomer composition containing. 5. The resin composition according to claim 4, wherein the component (a1) is represented by the following formula (a1-1).

(In formula (a1-1), R ¹¹ to R ¹⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom, and X is a divalent aromatic ring-containing represents an organic group.) 6. The resin composition according to claim 4, wherein the component (a2) is represented by the following formula (a2-1) or (a2-2).

(In formula (a2-1), Y represents an organic group having a cyclic structure, R ²¹ each independently represents a divalent organic group containing a hydrocarbon group, R ²² each independently represents at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom; m1 represents an integer of 2 to 10; n1 represents an integer of 0 to 8;
In formula (a2-2), Z represents an organic group having 1 to 6 carbon atoms, R ²³ each independently represents a divalent organic group containing a hydrocarbon group, and R ²⁴ each independently represents represents at least one selected from the group consisting of a hydrogen atom, an alkyl group and a halogen atom, m2 represents an integer of 2 to 6, n2 represents an integer of 0 to 4, m2+n2 represents 2 to 6 integers. ) 7. The resin composition according to any one of claims 4 to 6, wherein the monomer composition further contains (a3) an allyl compound containing one or more aromatic rings and two or more allyl groups in one molecule. 8. The resin composition according to claim 7, wherein the component (a3) is represented by at least one of the following formulas (a3-1) to (a3-6).

(In formula (a3-6), n3 represents an integer of 1 to 1000.) The resin according to any one of claims 1 to 8, wherein the content of component (A) is 0.1% by mass or more and 10% by mass or less when the nonvolatile component in the resin composition is 100% by mass. Composition. The resin composition according to any one of claims 1 to 9, comprising one or more (E) curing agents selected from the group consisting of phenolic curing agents and carbodiimide curing agents. (F) The resin composition according to any one of claims 1 to 10, comprising a curing accelerator. (G) The resin composition according to any one of claims 1 to 11, comprising a thermoplastic resin. The resin composition according to any one of claims 1 to 12, which is used for forming an insulating layer. A cured product of the resin composition according to any one of claims 1 to 13. A sheet-like laminate material containing the resin composition according to any one of claims 1 to 13. A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 13 on the support. A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 13. A semiconductor device comprising the printed wiring board according to claim 17 .