TW202337996A - Resin composition capable of obtaining a cured product that can further suppress a dielectric loss tangent even in a high-temperature environment and has excellent crack resistance after desmear treatment - Google Patents

Abstract

An object of the present invention is to provide a resin composition capable of obtaining a cured product that can further suppress a dielectric loss tangent even in a high-temperature environment and has an excellent crack resistance after a desmear treatment. The solution of the present invention is a resin composition containing (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound. The component (A) contains a structural unit represented by the following formula (a1) derived from the divinyl aromatic compound (a) and has a weight-average molecular weight of 40,000 or more. (In the formula, R<SP>1</SP> represents an aromatic hydrocarbon group having 6 to 30 carbon atoms).

Description

resin composition

The present invention relates to a resin composition containing an epoxy resin. Furthermore, it relates to cured products, sheet-like laminated materials, resin sheets, printed wiring boards and semiconductor devices obtained using the resin composition.

As a manufacturing technology of printed wiring boards, a manufacturing method based on a buildup method in which insulating layers and conductor layers are alternately laminated is known. In the manufacturing method based on the stacking method, the insulating layer is usually formed by hardening the resin composition. The insulating layer of a printed wiring board of a semiconductor device is required to exhibit good dielectric properties (low dielectric constant, low dielectric loss tangent) in order to suppress transmission loss when operating in a high-frequency environment.

As a resin composition that forms a cured product exhibiting good dielectric properties, for example, Patent Document 1 reports a resin composition containing an active ester compound as a curing agent for an epoxy resin, and Patent Document 2 reports a resin composition containing a specific Resin composition of copolymer of divinylbenzene and styrene.

Prior technical literature patent documents Patent Document 1: Japanese Patent Application Publication No. 2009-235165 Patent Document 2: International Publication No. 2018/181842.

The problem to be solved by the invention

A resin composition containing an active ester compound as a curing agent as described in Patent Document 1 can form a cured product with excellent dielectric properties compared with the case of using a normal phenol-based curing agent. However, on the other hand, On the other hand, there is a tendency for cracks to easily occur after the desmear treatment. In addition, it was discovered that there are cases where semiconductor devices are exposed to high-temperature environments such as when operating in high-frequency environments. Even materials that exhibit good dielectric properties in room temperature environments have poor dielectric properties (especially dielectric properties) in high-temperature environments. Loss tangent) may also deteriorate, and the desired dielectric characteristics may not be achieved in actual use environments.

An object of the present invention is to provide a resin composition capable of obtaining a cured product that can suppress the dielectric loss tangent to a low value even in a high-temperature environment and has excellent crack resistance after desmear treatment; and a resin composition using the resin composition. Cured products, sheet-like laminated materials, resin sheets, printed wiring boards and semiconductor devices obtained from the products. Means used to solve problems

In order to achieve the object of the present invention, the present inventors conducted in-depth research and unexpectedly discovered that by using an epoxy resin and an active ester compound as components of the resin composition, and further containing a divinyl aromatic compound and styrene, The present invention was completed by making it possible to obtain a copolymer that can suppress the dielectric loss tangent to a low value even in a high-temperature environment and that can suppress the occurrence of cracks after desmear treatment.

That is, the present invention includes the following contents; [1] A resin composition containing (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound Resin composition, component (A) contains a structural unit represented by the following formula (a1) derived from a divinyl aromatic compound (a), and has a weight average molecular weight of 40,000 or more, [Chemical Formula 1] (In the formula, R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms). [2] The resin composition as described in the above [1], wherein the component (C) has a carbon-carbon double bond; [3] The resin composition as described in the above [1] or [2], wherein The value obtained by adding all the values obtained by dividing the mass of the non-volatile component of the component (B) by the equivalent weight of the epoxy group is recorded as W _B , and dividing the mass of the non-volatile component of the component (C) by the active ester group When the value obtained by adding all the obtained values is recorded as W _C , W _C /W _B is 1.0 or more; [4] The resin composition as described in any one of the above [1] to [3], wherein , also containing (D) an inorganic filler material; [5] The resin composition as described in any one of the above [1] to [4], which further contains (E) a radically polymerizable compound; [6] Such as The resin composition described in any one of the above [1] to [5], which is used to form an interlayer insulating layer of a printed wiring board; [7] The resin composition described in any one of the above [1] to [6] A resin composition in which the component (A) contains, in addition to structural units derived from divinyl aromatic compounds (a) and styrene (b), a monovinyl aromatic compound derived from other than styrene. Structural unit of (c); [8] The resin composition as described in any one of the above [1] to [7], wherein the component (A) is derived from the divinyl aromatic compound (a) When the sum of structural units, structural units derived from styrene (b), and structural units derived from monovinyl aromatic compounds other than styrene (c) is 100 mol%, The structural unit of a) is 2 mol% or more and less than 95 mol%; [9] The resin composition as described in any one of the above [1] to [8], wherein the component (A) is in the copolymer The terminal contains at least any one terminal group represented by the following formula (t1), (t2) or (t3); [Chemical Formula 2] (In the formula, R ² represents an aromatic hydrocarbon group with 6 to 30 carbon atoms. Z ¹ represents a vinyl group, a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. * represents the bonding site with the main chain, and the meaning will be the same below. same). [Chemical formula 3] (In the formula, R ³ and R ⁴ each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms. ^{Z 3} and Z ⁴ each independently represent a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms). [Chemical formula 4] (In the formula, R ⁵ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. ^{Z 5} represents a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms). [10] The resin composition according to any one of the above [1] to [9], wherein the component (A) is composed of a structural unit derived from a divinyl aromatic compound (a), a structural unit derived from a styrene ( When the sum of the structural units of b) and the structural units derived from the monovinyl aromatic compound (c) other than styrene is 100 mol%, the structural unit represented by the formula (a1) and the formula (t1), The total sum of the terminal groups represented by (t2) and (t3) is in the range of 2 mol% or more and 80 mol% or less; [11] The resin according to any one of the above [1] to [10] A hardened product of the composition; [12] A sheet-like laminated material containing the resin composition as described in any one of [1] to [10] above; [13] A resin sheet having a support and a device A resin composition layer formed of the resin composition as described in any one of the above [1] to [10] on the support; [14] A printed wiring board having the resin composition as described in any of the above [1] to [10] 10] An insulating layer formed of a cured product of the resin composition according to any one of the above; [15] A semiconductor device including the printed wiring board according to the above [14]. Effect of the invention

According to the present invention, it is possible to provide a resin composition that can obtain a cured product that can suppress the dielectric loss tangent to a low level even in a high-temperature environment and has excellent crack resistance after desmear treatment; the resin composition can be provided A cured product; a sheet-like laminated material and a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device containing the cured product of the resin composition.

Hereinafter, the present invention will be described in detail using embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented within the scope of the patentable scope of the present invention and its equivalent range.

In the following description, unless otherwise specified, the amount of each component is the amount of non-volatile components. In the following description, the so-called "non-volatile components in the resin composition" may include (D) the inorganic filler unless otherwise specified, and the so-called "resin component" refers to the resin composition unless otherwise specified. Among the non-volatile components contained in , components other than (D) inorganic filler materials.

＜Resin composition＞ The resin composition of the present invention includes (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, it is possible to obtain a cured product that can suppress the dielectric loss tangent to a low value even in a high-temperature environment such as 90° C. and has excellent crack resistance after desmearing. In addition, in the present invention, it is generally possible to obtain a cured product that is also excellent in peeling strength between the insulating layer and the plated conductor layer (also simply referred to as “plating peeling strength” in this specification), and furthermore, it is possible to obtain a hardened product that can be used in a room such as 23° C. It is a hardened material with a low dielectric loss tangent in the warm or normal temperature range and a low relative dielectric constant in any environment including room temperature or normal temperature ranges such as 23°C and high temperature environments such as 90°C.

The resin composition of the present invention may further include (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound. Selected ingredients. Examples of optional components include (D) inorganic fillers, (E) radically polymerizable compounds, (F) other hardeners, (G) hardening accelerators, (H) other additives, and (K) organic Solvent. In this specification, each of the above-mentioned components (A) to (K) may be referred to as "component (A)", "component (B)", etc., respectively. Each component contained in the resin composition will be described in detail below.

<(A) Copolymer of divinyl aromatic compound and styrene> (A) Copolymer of divinyl aromatic compound and styrene contains the following formula (a1) derived from the divinyl aromatic compound (a) The structural unit shown, and the weight average molecular weight is more than 40,000, [Chemical Formula 5] (In the formula, R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms).

In this specification, the aromatic hydrocarbon group as ^R1 of the formula (a1) may be a condensed aromatic hydrocarbon group, for example, it may be a structure in which a plurality of aromatic hydrocarbon groups such as biphenyl are connected through a single bond. In the aromatic hydrocarbon group as ^R1 , the substitution position of the vinyl group represented by the formula (a1) with respect to the main chain of the repeating unit represented by the formula (a1), that is, _-CH2- CH- There is no particular limitation. It may be ortho-, meta-, para-isomers, or at least any one of these positional isomer mixtures, and is preferably meta-, para-, or these positional isomers. At least one of the mixtures. The number of carbon atoms of the aromatic hydrocarbon group as R ¹ is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6 to 10.

The so-called structural units in this specification include repeating units present in the main chain of the copolymer and units or terminal groups present in the terminals or side chains.

The component (A) preferably contains not only structural units derived from the divinyl aromatic compound (a) and styrene (b), but also a structure derived from the monovinyl aromatic compound (c) other than styrene. Polyfunctional vinyl aromatic copolymer of units.

As the structural unit derived from the monovinyl aromatic compound (c) other than styrene, for example, it is preferable to have R ¹ shown in the above formula (a1), that is, an aromatic hydrocarbon group having 6 to 30 carbon atoms. R ¹ , the above-mentioned matters regarding R ¹ in formula (a1) are applicable. The structural unit derived from (c) may be a structural unit having, for example, 1 to 2 substituents on the aromatic ring. Examples of the substituents include, for example, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. Preferably, A saturated aliphatic hydrocarbon group with 1 to 5 carbon atoms.

In the component (A), a structural unit derived from a divinyl aromatic compound (a), a structural unit derived from styrene (b), and a structural unit derived from a monovinyl aromatic compound (c) other than styrene are combined. When the total of is 100 mol%, the structural unit derived from the divinyl aromatic compound (a) is preferably 2 mol% or more and less than 95 mol%, and more preferably 10 mol% or more and 75 mol% Below, it is more preferably 15 mol% or more and 70 mol% or less.

In addition, in this specification, each compound (monomer) of the above-mentioned (a) to (c) may be abbreviated as "(a)", "(b)", and "(c)" respectively. The structural unit derived from the divinyl aromatic compound (a) can have various structures, such as a product in which only one of two vinyl groups reacts, or a product in which two of two vinyl groups react. Among them, when the sum of the structural units derived from (a), (b) and (c) is 100 mol%, it is preferable that the vinyl group represented by the above formula (a1) contains 2 to 80 mol%. The repeating unit (structural unit) obtained by reacting only one unit" is more preferably 5 to 70 mol%, further preferably 10 to 60 mol%, and particularly preferably 15 to 50 mol%.

In the component (A), a structural unit derived from a divinyl aromatic compound (a), a structural unit derived from styrene (b), and a structural unit derived from a monovinyl aromatic compound (c) other than styrene are combined. When the total of is 100 mol%, the total of the structural units derived from styrene (b) and the structural units derived from the monovinyl aromatic compound (c) other than styrene is preferably 5 mol% or more and less than 98 Mol%, more preferably 25 mol% or more and 90 mol% or less, still more preferably 30 mol% or more and 85 mol% or less.

When the component (A) contains the structural unit (c1) derived from a monovinyl aromatic compound (c) other than styrene, as the structural unit (b1) derived from styrene (b) and derived from a monovinyl compound other than styrene, The ratio of the structural units (c1) of the aromatic compound (c) on a molar basis (b1): (c1) is preferably 99:1 to 20:80, and more preferably 98:2 to 30:70.

In this specification, “a structural unit derived from a divinyl aromatic compound (a), a structural unit derived from styrene (b), and a structural unit derived from a monovinyl aromatic compound (c) other than styrene” "Total", and the description based on this, component (A) does not contain a structural unit derived from "monovinyl aromatic compound (c) other than styrene" as an optional monomer (also known as In the case of "structural unit (c1)"), it refers to "the sum of the structural unit derived from the divinyl aromatic compound (a) and the structural unit derived from styrene (b)". When the structural unit (c1) is included In the case of , it means “a structural unit derived from a divinyl aromatic compound (a), a structural unit derived from styrene (b), and a structural unit derived from a monovinyl aromatic compound (c) other than styrene. the sum of". In addition, in this specification, regarding "divinyl aromatic compound (a), styrene (b) and optional monovinyl aromatic compound (c) other than styrene", and the description based on this Specifically, when the component (A) does not contain the optional structural unit (c1), it means "divinyl aromatic compound (a) and styrene (b)", and when the component (A) contains the structural unit In the case of (c1), it means "divinyl aromatic compound (a), styrene (b), and monovinyl aromatic compound (c) other than styrene."

In this specification, "the sum of structural units derived from styrene (b) and structural units derived from monovinyl aromatic compounds (c) other than styrene" and descriptions based on this are also in the same manner. When the component (A) does not contain the optional structural unit (c1), it means "the structural unit derived from styrene (b)". When the component (A) contains the structural unit (c1), it means " The sum of structural units derived from styrene (b) and structural units derived from monovinyl aromatic compounds (c) other than styrene”. In addition, in this specification, "styrene (b) and an optional monovinyl aromatic compound (c) other than styrene" and the description based on this are also the same unless (A) component does not contain In the case of the optional structural unit (c1), it means “styrene (b)”. When the component (A) contains the structural unit (c1), it means “styrene (b) and other components other than styrene. Monovinyl aromatic compound (c)”.

The component (A) may contain not only structural units derived from the divinyl aromatic compound (a) and styrene (b), but also structures derived from the optional monovinyl aromatic compound (c) other than styrene. The unit also contains a structural unit derived from the monomer (d) other than (a), (b) and (c). When the component (A) contains the structural unit (d1) derived from the monomer (d), the structural unit derived from the divinyl aromatic compound (a), the structural unit derived from the styrene (b), and the structural unit derived from other than styrene are combined. When the total of the structural unit of the monovinyl aromatic compound (c) and the structural unit (d1) is 100 mol%, the respective structural units derived from (a), (b) and optional (c) The total is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, even more preferably 80 mol% or more, particularly preferably 90 mol% or more.

The component (A) preferably contains at least one terminal group represented by the following formula (t1), (t2) or (t3) at the terminal of the copolymer. For the divinyl aromatic compound (a), styrene (b) and the optional monovinyl aromatic compound (c) other than styrene, not only the repeating unit (structure) including (a1) is formed by polymerization unit), and preferably form terminal groups represented by the following formulas (t1), (t2) and (t3) respectively as terminal groups, [Chemical Formula 6] (In the formula, R ² represents an aromatic hydrocarbon group with 6 to 30 carbon atoms. Z ¹ represents a vinyl group, a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. * represents the bonding site with the main chain, and the meaning will be the same below. same). [Chemical Formula 7] (In the formula, R ³ and R ⁴ each independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms. ^{Z 3} and Z ⁴ each independently represent a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms). [Chemical formula 8] (In the formula, R ⁵ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. ^{Z 5} represents a vinyl group, a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms).

In the component (A), a structural unit derived from a divinyl aromatic compound (a), a structural unit derived from styrene (b), and a structural unit derived from a monovinyl aromatic compound (c) other than styrene are combined. When the total of is 100 mol%, the total of the structural units represented by formula (a1) and the terminal groups represented by formulas (t1), (t2) and (t3) is, for example, in the range of 2 to 80 mol% , preferably 5 to 80 mol%, more preferably 10 to 70 mol%, particularly preferably 15 to 65 mol%. This represents the content of vinyl groups and terminal groups in the multifunctional vinyl aromatic copolymer.

In component (A), the introduction amount of the terminal group (tv) having a vinyl group is preferably 0.2 or more per molecule. Here, the terminal group (tv) having a vinyl group is all of (t1), a group in which Z ³ and/or Z ⁴ in (t2) is a vinyl group, and a group in which Z ⁵ in (t3) is a vinyl group. More preferably, it is 0.5 or more per molecule, and still more preferably, it is 0.6 or more.

In the component (A), when the sum of the terminal groups of the formulas (t1), (t2) and (t3) is 100 mol%, the terminal group of the formula (t3) is preferably 70 mol% or less. Here, the terminal group represented by formula (t3) is a terminal group having a vinylidene bond. More preferably, it is 60 mol% or less, and still more preferably, it is 50 mol% or less. In addition, in component (A), when the sum of the structural units represented by formula (a1) and the terminal groups of formulas (t1), (t2) and (t3) is 100 mol%, the terminal group of formula (t3) The base is preferably 30 mol% or less, more preferably 20 mol% or less.

The component (A), preferably the polyfunctional vinyl aromatic copolymer, has a weight average molecular weight (Mw) of 40,000 or more. By containing a multifunctional vinyl aromatic copolymer with an Mw of 40,000 or more, it is possible to obtain a product that can suppress the dielectric loss tangent to a low value even in a high-temperature environment such as 90°C and has excellent crack resistance after desmear treatment. hardened matter. The upper limit of Mw is preferably 20,000 or less, more preferably 15,000 or less, and still more preferably 10,000 or less. The weight average molecular weight of the component (A) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The number average molecular weight (Mn) of component (A), preferably the polyfunctional vinyl aromatic copolymer, is preferably 300 to 100,000, more preferably 400 to 50,000, and still more preferably 500 to 10,000. The number average molecular weight of the component (A) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). In addition, the value of the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to Mn is, for example, 100 or less, preferably 50 or less, more preferably 1.5 to 30, and most preferably 2.0 to 20.

The component (A), preferably the polyfunctional vinyl aromatic copolymer, is preferably a soluble polyfunctional vinyl aromatic copolymer soluble in at least one of toluene, xylene, tetrahydrofuran, dichloroethane or chloroform as a solvent. The copolymer is more preferably soluble in all the above solvents. Here, "soluble in a solvent" means that the soluble polyfunctional vinyl aromatic copolymer dissolves 5 g or more, more preferably 30 g or more, and particularly preferably 50 g or more per 100 g of the above-mentioned solvent.

Examples of the divinyl aromatic compound (a) are not particularly limited as long as they are aromatic compounds having two vinyl groups, and divinylbenzene (including each positional isomer or a mixture thereof) is preferably used. , divinylnaphthalene (including each positional isomer or a mixture thereof), divinylbiphenyl (including each positional isomer or a mixture thereof). In addition, these can be used individually or in combination of 2 or more types. More preferred is divinylbenzene (meta, para, or a mixture of these positional isomers).

Examples of the monovinyl aromatic compound (c) other than styrene are not particularly limited as long as it is an aromatic compound other than styrene having one vinyl group. Examples thereof include vinyl naphthalene and vinyl biphenyl. and other vinyl aromatic compounds; o-methylstyrene, m-methylstyrene, p-methylstyrene, o-, p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p- Core alkyl-substituted vinyl aromatic compounds such as ethylvinylbenzene; etc. Preferred are ethylvinylbenzene (including each positional isomer or a mixture thereof), ethylvinylbiphenyl (including each positional isomer or a mixture thereof), and ethylvinylnaphthalene (including each positional isomer or a mixture thereof). Positional isomers or mixtures thereof), more preferably ethylvinylbenzene (meta-isomers, para-isomers or mixtures of these isomers).

As the component (A), the polyfunctional vinyl aromatic copolymer described in Patent Document 2 can be used.

The content of component (A) is, for example, 0.1 mass% or more, preferably 0.3 mass% or more, more preferably 0.5 mass% or more, and still more preferably 1 or 1.0, based on 100 mass% of non-volatile components in the resin composition. Mass % or more, more preferably 1.05 mass % or more, for example 3 mass % or less, preferably 2 mass % or less, more preferably 1.5 mass % or less, still more preferably 1.3 mass % or less, still more preferably 1.1 mass% or less.

The content of component (A) is, for example, 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 1 mass% or more, still more preferably 2 mass% or more, based on 100 mass% of the resin component in the resin composition. , more preferably 3 mass% or more, particularly preferably 3.5 mass% or more, and for example, 15 mass% or less, preferably 10 mass% or less, more preferably 7 mass% or less, still more preferably 5 mass% or less, Still more preferably, it is 4.5 mass % or less.

＜(B) Epoxy resin＞ The resin composition of the present invention contains (B) epoxy resin. (B) Epoxy resin refers to a curable resin having an epoxy group.

Examples of the (B) epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol type epoxy resin. AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl -Catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac Varnish (cresol novolac) type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, Heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin , tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, phenolphthalein type epoxy resin, etc. (B) Epoxy resin may be used individually by 1 type, or in combination of 2 or more types.

The resin composition preferably contains an epoxy resin (B) having two or more epoxy groups per molecule as the epoxy resin (B). The proportion of the epoxy resin having two or more epoxy groups per molecule is preferably 50 mass% or more, more preferably 60 mass% or more, and particularly preferably 100 mass% of the non-volatile content of the epoxy resin (B). It is more than 70% by mass.

The epoxy resin includes an epoxy resin that is liquid at a temperature of 20° C. (hereinafter sometimes referred to as a “liquid epoxy resin”) and an epoxy resin that is solid at a temperature of 20° C. (hereinafter sometimes referred to as a “liquid epoxy resin”) for "solid epoxy resin"). The resin composition of the present invention may contain only liquid epoxy resin as the epoxy resin, or may contain only solid epoxy resin, or may contain liquid epoxy resin and solid epoxy resin in combination. epoxy resin. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin or a combination of a liquid epoxy resin and a solid epoxy resin, and is more preferably a solid epoxy resin.

As the liquid epoxy resin, one having two or more epoxy groups per molecule is preferred.

As the liquid epoxy resin, 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 ester type epoxy resin, and glycidyl epoxy resin are preferred. Amine type epoxy resin, phenol novolak type epoxy resin, cycloaliphatic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and those with butadiene structure Epoxy resin.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "828EL", and "Naphthalene type epoxy resin" manufactured by Mitsubishi Chemical Corporation. "jER828EL", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" manufactured by Mitsubishi Chemical Corporation "(phenol novolac type epoxy resin); "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (Glycirol type) manufactured by ADEKA Epoxy resin); "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA ; "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd. Oxygen resin); "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Corporation; "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP" manufactured by Nippon Soda Corporation -200" (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd., etc. 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 three or more epoxy groups per molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups per molecule.

As the solid epoxy resin, preferred are dixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol novolac-type epoxy resin, cresol novolac-type epoxy resin, and bicyclic epoxy resin. Pentylene epoxy resin, trisphenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy Resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol benzopyrrolone type epoxy resin, phenolphthalein type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation Resin); “N-690” (cresol novolak type epoxy resin) manufactured by DIC; “N-695” (cresol novolak type epoxy resin) manufactured by DIC; “HP- 7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", " EXA-7311-G4", "EXA-7311-G4S", "HP6000" (alkylene ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Japan "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Chemical Company; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Chemical Company Resin); "ESN475V" (naphthol-type epoxy resin) manufactured by NIPPON STEEL Chemical & Material Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. ); "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation Resin); "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl type) manufactured by Mitsubishi Chemical Corporation Epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene type epoxy resin); "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Nippon Chemical Corporation "WHR991S" (phenol benzopyrrolone type epoxy resin) made by These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used together as (B) epoxy resin, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin/solid epoxy resin ) is not particularly limited, but is preferably 10 or less, more preferably 5 or less, and even more preferably 1 or less.

(B) The epoxy group equivalent of the epoxy resin is preferably 50g/eq.~5,000g/eq., more preferably 60g/eq.~2,000g/eq., further preferably 70g/eq.~1,000g/eq. ., further preferably 80g/eq.~500g/eq. The epoxy equivalent weight is the mass of the resin corresponding to 1 equivalent of epoxy group. The epoxy group equivalent can be measured in accordance with 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, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene-converted value using gel permeation chromatography (GPC).

The content of component (B) is, for example, 1 mass% or more, preferably 3 mass% or more, more preferably 5 mass% or more, and even more preferably 8 mass%, based on 100 mass% of non-volatile components in the resin composition. Mass % or more, more preferably 10 mass % or more, for example 30 mass % or less, preferably 20 mass % or less, more preferably 15 mass % or less, still more preferably 13 mass % or less, still more preferably 11 mass% or less.

The content of component (B) is, for example, 10 mass% or more, preferably 15 mass% or more, more preferably 20 mass% or more, still more preferably 25 mass%, based on 100 mass% of the resin component in the resin composition. % or more, more preferably 30 mass% or more, particularly preferably 35 mass% or more, and for example, 60 mass% or less, preferably 55 mass% or less, more preferably 50 mass% or less, still more preferably 45 mass% below, and more preferably 43% by mass or less.

＜(C) Active ester compound＞ The resin composition of the present invention contains (C) an active ester compound. (C) The active ester compound may be used individually by 1 type, or may be used in combination of 2 or more types at arbitrary ratios, and the same applies to the (C1) component and (C2) component mentioned later. (C) The active ester compound may react with (B) epoxy resin to cross-link the (B) epoxy resin. (C) The active ester compound may be a compound having a carbon-carbon unsaturated bond. The unsaturated bond is preferably a carbon-carbon double bond. For example, it may be a compound having a carbon-carbon unsaturated bond with the component (C1) described below. The same bond as a saturated bond.

As the (C) active ester compound, usually, those having two or more highly reactive compounds per molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, can be preferably used. Ester-based compounds. The active ester compound is preferably obtained by a condensation reaction of 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 (phenol compound) and/or a naphthol compound is more preferred. ester compounds. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of phenolic compounds (phenol compounds) or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthaloline, methylated bisphenol A, and toluene. Sylated 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, phloroglucinol, phloroglucinol, dicyclopentadiene Type diphenol compounds, novolac resin (Phenolic Novolac), etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene and two molecules of phenol.

Specifically, (C) the active ester compound is preferably a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetate of a novolac resin, or an active ester compound containing a novolak resin. Among the active ester compounds of benzyl chloride, at least one selected from the group consisting of dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferred, and dicyclopentadiene-type active ester compounds are further preferred. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred. The "dicyclopentadiene-type diphenol structure" refers to a bivalent structural unit composed of a phenylene group-dicyclopentyl-phenylene group.

Regarding commercially available products of (C) active ester compounds, examples of active ester compounds containing a dicyclopentadiene-type diphenol structure include “EXB9451”, “EXB9460”, “EXB9460S”, “EXB-8000L”, and “EXB -8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" ( DIC Corporation); Examples of the active ester compound containing a naphthalene structure include "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", " HPC-8150-60T" and "HPC-8150-62T" (manufactured by DIC Corporation); examples of active ester compounds containing phosphorus include "EXB9401" (manufactured by DIC Corporation), which is an acetate compound of novolac resin Examples of the active ester compound include "DC808" (manufactured by Mitsubishi Chemical Corporation), and examples of the active ester compound which is a benzyl compound of novolak resin include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation). (manufactured by Air Water Co., Ltd.), and examples of the active ester compound containing a styrene group and a naphthalene structure include "PC1300-02-65MA" (manufactured by Air Water Co., Ltd.).

(C) The active ester group equivalent of the active ester compound is preferably 50 g/eq. to 500 g/eq., more preferably 50 g/eq. to 400 g/eq., further preferably 100 g/eq. to 300 g/eq. The active ester group equivalent is the mass of the active ester compound corresponding to 1 equivalent of active ester group.

＜(C1) Compounds containing aromatic ester skeleton and unsaturated bonds＞ As (C) the active ester compound, (C1) a compound containing an aromatic ester skeleton and an unsaturated bond (also referred to as "(C1) component" in this specification) can be used.

The component (C1) is preferably a compound represented by the following general formula (AE1-1); [Chemical Formula 9] (In the general formula (AE1-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ¹³ each independently represents represents a divalent aromatic hydrocarbon group that may have a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by a combination of these (groups). n represents 0 ~10 integer).

Examples of the monovalent aromatic hydrocarbon group represented by Ar ¹¹ include phenyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, Pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl and other groups obtained by removing one hydrogen atom from a monocyclic aromatic compound; naphthyl, anthracenyl, phenalenyl, phenanthreneyl Base, quinolyl, isoquinolinyl, quinazolinyl, phthalazinyl, pteridinyl, coumarinyl, indolyl, benzimidazolyl, benzofuranyl, acridinyl, etc. A group obtained by removing one hydrogen atom from a condensed ring aromatic compound; etc., among which, a phenyl group is preferred.

Examples of the divalent aromatic hydrocarbon group represented by Ar ¹² include an aryl group, an aralkylene group, and the like, and an aryl group is preferred. As the aryl group, an aryl group having 6 to 30 carbon atoms is preferred, an aryl group having 6 to 20 carbon atoms is more preferred, and an aryl group having 6 to 10 carbon atoms is still more preferred. Examples of such aryl groups include phenylene group, naphthylene group, anthracenyl group, biphenylene group, and the like. Among them, phenylene group is preferred.

Ar ¹³ is preferably a divalent group formed by a combination of these (groups). The divalent aromatic hydrocarbon group represented by Ar ¹³ has the same meaning as the divalent aromatic hydrocarbon group represented by Ar ¹² . As the divalent aliphatic hydrocarbon group represented by Ar ¹³ , a divalent saturated aliphatic hydrocarbon group is more preferred, an alkylene group and a cycloalkylene group are preferred, and a cycloalkylene group is more preferred.

As the cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms is preferred, a cycloalkylene group having 3 to 15 carbon atoms is more preferred, and a cycloalkylene group having 5 to 10 carbon atoms is even more preferred. Examples of the cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, and cycloheptylene, and those represented by the following formulas (a) to (d). cycloalkyl group represented by formula (c), etc., preferably cycloalkyl group represented by formula (c); [Chemical Formula 10] (In formulas (a)~(d), "*" represents chemical bond).

Examples of substituents that the monovalent aromatic hydrocarbon group represented by Ar ¹¹ , the divalent aromatic hydrocarbon group represented by Ar ¹² , the divalent aromatic hydrocarbon group represented by Ar ¹³ and the divalent aliphatic hydrocarbon group may have include unsaturated hydrocarbon groups. , alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, halogen atoms, etc. The substituent may be contained individually or in combination of 2 or more types. Among them, the substituent of Ar ¹¹ preferably contains an unsaturated bond.

When the compound represented by the general formula (AE1-1) is an oligomer or a polymer, n represents the average value.

Specific examples of the component (C1) include the following compounds. Specific examples of the component (C1) include compounds described in paragraphs 0068 to 0071 of International Publication No. 2018/235424 and paragraphs 0113 to 0115 of International Publication No. 2018/235425. . In the formula, s represents an integer above 0 or 1, and r represents an integer from 1 to 10; [Chemical Formula 11] .

The weight average molecular weight of the component (C1) is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, preferably 3000 or less, more preferably 2000 or less, from the viewpoint of significantly obtaining the effects of the present invention. Preferably it is 1500 or less. The weight average molecular weight of the component (C1) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The active ester equivalent (unsaturated bond equivalent) of component (C1) is preferably 50 g/eq. or more, more preferably 100 g/eq. or more, and even more preferably 150 g/eq. from the viewpoint of significantly obtaining the effects of the present invention. eq. or more, preferably 2000 g/eq. or less, more preferably 1000 g/eq. or less, still more preferably 500 g/eq. or less. The active ester equivalent (unsaturated bond equivalent) is the mass of component (C1) containing 1 equivalent of unsaturated bond.

<(C2) Active ester compound having at least one of the groups represented by the following formulas (1) to (3)> As (C) active ester compound, (C2) having the following formula (1) can be used An active ester compound (also referred to as "(C2) component" in this specification) of at least one of the groups represented by ) to (3); [Chemical Formula 12] (In the formula, * represents a chemical bond. In formula (3), n represents an integer from 1 to 5).

As the component (C2), a compound having at least one of the groups represented by the formulas (1) to (3) and an active ester moiety that can react with the component (A) can be used. The component (C2) preferably has at least one of the groups represented by formulas (1) to (3) at the terminal. As the component (C2), both ends may be different groups, or both ends may be the same group.

The methyl group in the group represented by formula (1), the phenyl group in the group represented by formula (2), and the styrene moiety in the group represented by formula (3) are each preferably relative to the chemical bond represented by * , bonded to any one of the ortho, meta and para positions, more preferably bonded to the ortho position.

The component (C2) is preferably a compound represented by the following general formula (AE2-1); [Chemical Formula 13] (In general formula (AE2-1), Ar ¹¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3), and Ar ¹² each independently represents A divalent aromatic hydrocarbon group that may have a substituent. Ar ¹³ each independently represents a divalent aromatic hydrocarbon group that may have a substituent, a divalent aliphatic hydrocarbon group that may have a substituent, an oxygen atom, a sulfur atom, or a divalent aromatic hydrocarbon group that may have a substituent. A divalent group formed by the combination of these (groups). a represents an integer from 1 to 6, and b represents an integer from 0 to 10).

Ar ¹¹ is preferably a group represented by formula (1) and a group represented by formula (2).

Ar ¹² and Ar ¹³ have the same meanings as Ar ¹² and Ar ¹³ in the general formula (AE1-1), respectively, as a divalent aromatic hydrocarbon group represented by Ar ¹² , a divalent aromatic hydrocarbon group represented by Ar ¹³ , and a divalent aliphatic Examples of substituents that the hydrocarbon group may have include an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a halogen atom. The substituent may be contained individually or in combination of 2 or more types.

The divalent group represented by Ar ¹³ formed from a combination of these (groups) is preferably a divalent aromatic hydrocarbon group that may have a substituent and an oxygen atom, and more preferably one or more A divalent group consisting of an optionally substituted divalent aromatic hydrocarbon group and one or more oxygen atoms alternately combined, and more preferably one or more optionally substituted naphthylene groups and one or more oxygen atoms. Bivalent bases formed by alternating combinations. Therefore, a naphthyloxy group which may have a substituent is further preferred.

When the compound represented by the general formula (AE2-1) is an oligomer or a polymer, a represents the average value. b has the same meaning as n in the general formula (AE1-1), and is preferably 0.

The component (C2) is preferably a compound represented by the general formula (AE2-2); [Chemical Formula 14] (In general formula (AE2-2), Ar ²¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3), and Ar ²² each independently represents any A divalent aromatic hydrocarbon group having a substituent is selected, and Ar ²³ each independently represents a divalent aromatic hydrocarbon group optionally having a substituent. a1 represents an integer of 1 to 6, and c1 represents an integer of 1 to 5).

Ar ²¹ and Ar ²² have the same meanings as Ar ¹¹ and Ar ¹² in the general formula (AE2-1), respectively.

Ar ²³ has the same meaning as the optionally substituted divalent aromatic hydrocarbon group of Ar ¹³ in the general formula (AE2-1). a1 has the same meaning as a in the general formula (AE2-1).

The component (C2) is preferably a compound represented by the general formula (AE2-3); [Chemical Formula 15] (In general formula (AE2-3), Ar ³¹ each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). a2 represents an integer of 1 to 6 , c2 represents an integer from 1 to 5, and d independently represents an integer from 0 to 6).

Ar ³¹ has the same meaning as Ar ¹¹ in the general formula (AE2-1). a2 and c2 have the same meanings as a and c1 in the general formula (AE2-1) respectively. d preferably represents an integer of 1 to 5, and more preferably represents an integer of 1 to 4.

The component (C2) can be synthesized by a known method. For example, it can be synthesized by the method described in the following Examples. The component (C2) can be synthesized by the method described in International Publication No. 2018/235424 or International Publication No. 2018/235425, for example.

The weight average molecular weight of component (C2) is preferably 150 or more, more preferably 200 or more, further preferably 250 or more, preferably 4000 or less, more preferably 3000 or less, from the viewpoint of significantly obtaining the effects of the present invention. Preferably it is 2500 or less. The weight average molecular weight of the component (C2) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The active ester equivalent (unsaturated bond equivalent) of component (C2) is the same as that of component (C1).

Regarding the quantitative ratio of component (B) to component (C), the value obtained by adding all the values obtained by dividing the mass of the non-volatile component of component (B) by the epoxy group equivalent is expressed as W _B , and When the value obtained by adding all the values obtained by dividing the mass of the nonvolatile component of component (C) by the active ester group equivalent is expressed as _WC , _WC /W _B is preferably 1.0 or more, and more preferably 1.01 or more. It is more preferably 1.03 or more, still more preferably 1.05 or more, particularly preferably 1.06 or more. In addition, it is preferably 2.0 or less, more preferably 1.75 or less, still more preferably 1.5 or less, still more preferably 1.4 or less, and particularly preferably 1.3 or less. . By making the quantity ratio of (B) component and (C) component into the said range, the effect of this invention can be obtained easily.

The content of component (C) is, for example, 3 mass% or more, preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 13 mass%, based on 100 mass% of non-volatile components in the resin composition. In addition, for example, the content is 30 mass% or less, preferably 25 mass% or less, more preferably 20 mass% or less, and still more preferably 15 mass% or less.

The content of component (C) is, for example, 30 mass% or more, preferably 40 mass% or more, more preferably 45 mass% or more, and still more preferably 48 mass%, based on 100 mass% of the resin component in the resin composition. In addition, for example, the content is 70 mass% or less, preferably 60 mass% or less, more preferably 55 mass% or less, and even more preferably 53 mass% or less.

＜(D) Inorganic filler＞ The resin composition of the present invention may contain (D) an inorganic filler as an optional component. (D) The inorganic filler is contained in the resin composition in a particle state. (D) Inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

As the material of (D) the inorganic filler, an inorganic compound is used. (D) Examples of the inorganic filler material include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and boron. Stone, aluminum hydroxide, 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, etc. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, as the silica, spherical silica is preferred. (D) Inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types at arbitrary ratios.

Examples of commercially available inorganic fillers (D) include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "SC2500SQ" manufactured by Admatechs Co., Ltd.; "SO-C4", "SO-C2", "SO-C1", "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30", "DAW" made by DENKA Co., Ltd. -03", "FB-105FD"; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; manufactured by Taiheiyo-Cement Co., Ltd. "CellSpheres" ("MGH-005"); "S-Feerique" ("BA-S") manufactured by Nikko Catalyst Corporation, etc.

(D) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.7 μm or less. (D) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, particularly preferably 0.2 μm or more. (D) The average particle size of the inorganic filler material can be measured using the laser diffraction-scattering method based on the Mie scattering theory. Specifically, it can be measured by using a laser diffraction and scattering particle size distribution measuring device to prepare the particle size distribution of the inorganic filler on a volume basis, and taking the median particle size as the average particle size. As a measurement sample, a product obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture using ultrasonic waves for 10 minutes can be used. For the measurement sample, a laser diffraction particle size distribution measuring device was used, and the wavelength of the light source was set to blue and red, and the volume-based particle size distribution of the inorganic filler was measured by a flow cell method. From the obtained particles The average particle diameter was calculated as the median particle diameter from the diameter distribution. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

(D) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, further preferably 1 m ² /g or more, particularly preferably 3 m ² /g or more. (D) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m ² /g or less, more preferably 70 m ² /g or less, further preferably 50 m ² /g or less, particularly preferably 40 m ² /g or less. The specific surface area of the inorganic filler material can be obtained by adsorbing nitrogen gas on the surface of the sample 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 multi-point method.

(D) The inorganic filler material is preferably surface-treated with an appropriate surface treatment agent. By performing surface treatment, the moisture resistance and dispersibility of (D) the inorganic filler material can be improved. Examples of surface treatment agents include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane , 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 - Epoxy silane coupling agents such as glycidoxypropyltriethoxysilane; styryl silane coupling agents such as p-styryltrimethoxysilane; 3-methacryloxypropyl Methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl Methacrylic silane coupling agents such as triethoxysilane; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-amine Propylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxy Amino-based silanes such as N-phenyl-8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, etc. Coupling agent; isocyanurate-based silane coupling agent such as tris(trimethoxysilylpropyl)isocyanurate; 3-ureidopropyltrialkoxysilane and other ureido-based silane coupling agents coupling agent; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling such as 3-isocyanatopropyltriethoxysilane agent; anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; silane coupling agents such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane Silane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, Non-silane such as hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, etc. Coupling-alkoxysilane compounds, etc. In addition, one type of surface treatment agent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Commercially available surface treatment agents include, for example, "KBM-1003" and "KBE-1003" (vinyl-based silane coupling agents) manufactured by Shin-Etsu Chemical Industry Co., Ltd.; "KBM-303" and "KBM-402" ”, “KBM-403”, “KBE-402”, “KBE-403” (epoxy silane coupling agent); “KBM-1403” (styrene silane coupling agent); “KBM-502” , "KBM-503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", " KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (amine-based silane coupling agent); "KBM-9659" ( Isocyanurate silane coupling agent); "KBE-585" (ureido silane coupling agent); "KBM-802", "KBM-803" (mercapto silane coupling agent); "KBE- 9007N" (isocyanate-based silane coupling agent); "X-12-967C" (anhydride-based silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13" , "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", " KBM-3066", "KBM-7103" (non-silane coupling-alkoxysilane compound), etc.

From the viewpoint of improving the dispersibility of the inorganic filler, it is preferable to control the degree of surface treatment with a surface treatment agent within a predetermined range. Specifically, 100% by mass of the inorganic filler material is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, more preferably 0.2% to 3% by mass of a surface treatment agent, and further Preferably, the surface is treated with a surface treatment agent of 0.3% by mass to 2% by mass.

The degree of surface treatment based on the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler material. 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 even more preferably 0.2 mg from the viewpoint of improving the dispersibility of the inorganic filler. /m ² or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 1.0 mg/m 2 or less. 0.5mg/ ^m2 or less.

(D) The carbon amount per unit surface area of the inorganic filler material can be measured after washing the surface-treated inorganic filler material with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent can be added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning can be performed at 25° C. for 5 minutes. The supernatant liquid was removed and the solid content was dried, and then the amount of carbon per unit surface area of the inorganic filler material was measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

The content of the (D) inorganic filler in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it may be preferably 95% by mass or less, more preferably 90% by mass or less, and further Preferably it is 88 mass % or less. The lower limit of the content of (D) inorganic filler in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it may be, for example, 0% by mass or more, 1% by mass or more, or 10% by mass. % or more, 20 mass% or more, 30 mass% or more, etc., it can be preferably 40 mass% or more, more preferably 50 mass% or more, still more preferably 60 mass% or more, still more preferably 65 mass% or more, and particularly preferably More than 70% by mass.

＜(E) Radically polymerizable compound＞ The resin composition of the present invention may contain (E) a radically polymerizable compound as an optional component. (E) A radically polymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily.

The radically polymerizable compound is not particularly limited as long as it has one or more (preferably two or more) radically polymerizable unsaturated groups in one molecule. Examples of radically polymerizable compounds include those having a maleimide group, a vinyl group, an allyl group, a styryl group, a vinylphenyl group, an acrylyl group, a methacryloyl group, and a fumaryl group. and one or more compounds having a maleyl group as a radically polymerizable unsaturated group. Among these, it is preferable to include (E1) a maleimide compound and/or (E2) other radically polymerizable compounds from the viewpoint of easily obtaining a cured product excellent in dielectric properties. (E2) The other radically polymerizable compound is a compound that does not have a maleimide group but has a radically polymerizable unsaturated group other than a maleimide group. Among them, it is preferable to include a compound selected from the group consisting of (methyl ) One or more types of acrylic resin and styrene resin.

(E1) The maleimide compound is any compound having one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H) in one molecule. -pyrrol-1-yl), and its type is not particularly limited. Examples of maleimide compounds include "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", and "BMI-689" (all Maleimine resin containing an aliphatic skeleton with 36 carbon atoms derived from dimer diamine, such as Designer Molecules Co., Ltd.; described in the Japan Invention Association Technical Publication No. 2020-500211 Maleimide resin containing an indane skeleton; "MIR-3000-70MT", "MIR-5000-60T" (all manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Yamato Chemical Co., Ltd.), Maleimide resins including "BMI-80" (manufactured by KI Chemicals Co., Ltd.) and other maleimide resins include an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group.

The (meth)acrylic resin is not particularly limited as long as it has one or more (preferably two or more) (meth)acrylyl groups in one molecule. Here, the term "(meth)acrylyl group" is a general term for acrylyl group and methacrylyl group. Examples of the methacrylic resin include "A-DOG" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), "DCP-A" (manufactured by Kyeisha Chemical Co., Ltd.), "NPDGA", "FM-400", " (Meth)acrylic resins such as R-687", "THE-330", "PET-30", and "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.).

The styrene resin is not particularly limited as long as it has one or more (preferably two or more) styrene groups or vinylphenyl groups in one molecule. Examples of styrene resins include styrene resins such as "OPE-2St", "OPE-2St 1200", and "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Co., Ltd.).

The content of (E) radically polymerizable compound in the resin composition may be 0% by mass, or may be greater than 0% by mass, and is preferably 0.01% by mass, assuming that the non-volatile component in the resin composition is 100% by mass. The above is more preferably 0.1 mass% or more, particularly preferably 0.5 mass% or more. In addition, for example, it is 10 mass% or less, preferably 5 mass% or less, more preferably 3 mass% or less, and particularly preferably 1.5 mass% or less.

The content of (E) radically polymerizable compound in the resin composition may be 0 mass% or more than 0 mass% when the resin component in the resin composition is 100 mass%, and is preferably 0.1 mass% or more. , more preferably 1 mass% or more, particularly preferably 2 mass% or more, and, for example, 20 mass% or less, preferably 10 mass% or less, more preferably 7 mass% or less, particularly preferably 5 mass% or less.

＜(F)Other hardeners＞ The resin composition of the present invention may contain (F) other hardeners as optional components. This (F) other hardener does not include substances belonging to the above-mentioned components (A) to (C) and (E). (F) The other hardener may function as an epoxy resin hardener that reacts with (B) the epoxy resin to harden the resin composition, similarly to the above-mentioned (C) active ester compound. (F) Other hardeners may be used individually by 1 type or in combination of 2 or more types.

(F) Other hardeners include, for example, phenol-based hardeners, carbodiimide-based hardeners, acid anhydride-based hardeners, amine-based hardeners, benzoxazine-based hardeners, and cyanate ester-based hardeners. and thiol hardeners. Among them, it is preferable to use one or more types of curing agents selected from the group consisting of phenol-based curing agents and carbodiimide-based curing agents.

As the phenolic curing agent, one having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. From the viewpoint of heat resistance and water resistance, a phenol-based hardener having a phenolic structure (Novolac structure) is preferred. In addition, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferred, and a phenol-based curing agent containing a triazine skeleton is more preferred. Among them, a novolac resin (Phenolic Novolac Resin) containing a triazine skeleton is preferred from the viewpoint of highly satisfying heat resistance, water resistance and adhesion. Specific examples of the phenolic hardener include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN- 375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", " TD-2090-60M” etc.

As the carbodiimide-based curing agent, one having one or more, preferably two or more carbodiimide structures in one molecule can be used. Specific examples of carbodiimide-based hardeners include tetramethylene-bis(tert-butylcarbodiimide), cyclohexanebis(methylene-tert-butylcarbodiimide), etc. Aliphatic biscarbodiimides; aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide) and other biscarbodiimides; polyhexamethylenecarbodiimide, polytrimethylmethane Aliphatic polycarbons such as hexamethylene carbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide) Diimines; poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide) amine), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide) methylcarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), poly [Methylenebis(methylphenylene)carbodiimide] and other aromatic polycarbodiimides and other polycarbodiimides. Commercially available carbodiimide hardeners include, for example, "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and "CARBODILITE V-07" manufactured by Nisshinbo Chemical Co., Ltd. "CARBODILITE V-09"; "Stabaxol P", "Stabaxol P400", "Hycasyl 510" manufactured by Rhein Chemie, etc.

As the acid anhydride-based curing agent, one having one or more acid anhydride groups per molecule can be used, and one having two or more acid anhydride groups per molecule is preferred. Specific examples of acid anhydride-based hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Phthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3 -Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, diphenyl tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid Dianhydride, oxybisphthalic dianhydride, 3,3'-4,4'-diphenyltetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetracarboxylic acid Hydrogen-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate), styrene and Polymer-type acid anhydrides such as styrene-maleic acid resin copolymerized with maleic acid. Examples of commercially available acid anhydride hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Rika Co., Ltd.; and Mitsubishi Chemical Corporation's "YH-306" and "YH-307"; "HN-2200" and "HN-5500" made by Hitachi Chemical; "EF-30" and "EF-40" made by Cray Valley "EF-60", "EF-80", etc.

As the amine-based curing agent, one having one or more, preferably two or more amine groups in one molecule can be used. Examples of amine-based curing agents include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like. Among them, aromatic amines are preferred. The amine-based hardener is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine-based hardener include: 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4' -Diaminodiphenyl terine, 3,3'-diaminodiphenyl terine, m-phenylenediamine, m-phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl Ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybiphenyl Aniline, 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)sine, bis(4-(3-aminophenoxy)phenyl)sine, etc. Examples of commercially available amine-based hardeners include "SEIKACURE-S" manufactured by SEIKA; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", and "KAYAHARD" manufactured by Nippon Kayaku Co., Ltd. A-B", "KAYAHARD A-S"; "EPICUREW" made by Mitsubishi Chemical Corporation; "DTDA" made by Sumitomo Seika Co., Ltd., etc.

Specific examples of the benzoxazine-based hardener include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; " P-d”, “F-a”, etc.

Examples of the cyanate-based hardener include bisphenol A dicyanate, polyphenol cyanate, oligomer (3-methylene-1,5-phenylene cyanate), 4, 4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2, 2-bis(4-cyanato)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylphenyl) )methane, 1,3-bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatophenyl)sulfide, and bis(4-cyano) Difunctional cyanate ester resins such as acid ester phenyl ethers; multifunctional cyanate ester resins derived from phenol novolak resin and cresol novolac resin; part of these cyanate ester resins are triazinized Obtained prepolymer, etc. Specific examples of the cyanate ester-based hardener include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate ester resins) manufactured by Lonza Japan, "BA230", and "BA230S75" (dual Prepolymers obtained by triazinating part or all of phenol A dicyanate to form a trimer), etc.

Examples of thiol-based hardeners include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate. wait.

(F) The active group equivalent of other hardeners is preferably 50g/eq.~3000g/eq., more preferably 100g/eq.~1000g/eq., further preferably 100g/eq.~500g/eq., and particularly preferably It is 100g/eq.~300g/eq.. Active group equivalent represents the mass of hardener corresponding to 1 equivalent of active group.

The mass ratio of the epoxy resin to the hardener, that is, the mass ratio of "component (B)" to "component (C) and component (F)" is calculated by dividing the mass of the nonvolatile component of component (B) by The value obtained by adding all the epoxy group equivalents is expressed as W _B , and the value obtained by dividing the mass of the non-volatile component of component (C) by the active ester group equivalent is expressed as When W _C is W C and the value obtained by dividing the mass of the non-volatile component of the component (F) by the active group equivalent is added together and the value is expressed as W _F , ( _WC + W _F )/W _B is preferred It is 1.0 or more, more preferably 1.01 or more, still more preferably 1.1 or 1.10 or more, still more preferably 1.15 or more, particularly preferably 1.2 or more, and preferably 2.0 or less, more preferably 1.75 or less, still more preferably 1.5 or less, It is more preferably 1.4 or 1.40 or less, and particularly preferably 1.35 or less. By setting the amount ratio of the epoxy resin to the hardener within the above range, the effects of the present invention can be easily obtained.

Regarding the content of (F) other hardeners in the resin composition, when the non-volatile component in the resin composition is 100 mass %, it may be 0 mass %, may be greater than 0 mass %, and is preferably 0.01 mass %. Above, it is 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, and particularly preferably 5% by mass or less.

Regarding the content of (F) other hardeners in the resin composition, when the resin component in the resin composition is 100 mass %, it may be 0 mass % or more than 0 mass %, preferably 0.1 mass % or more. , more preferably 1.0 mass% or more, particularly preferably 5.0 mass% or more, preferably 50 mass% or less, more preferably 20 mass% or less, particularly preferably 10 mass% or less.

＜(G) Hardening accelerator＞ The resin composition of the present invention may contain (G) a hardening accelerator as an optional component.

Examples of the hardening accelerator include phosphorus-based hardening accelerators, urea-based hardening accelerators, guanidine-based hardening accelerators, imidazole-based hardening accelerators, metal-based hardening accelerators, and amine-based hardening accelerators. (G) The hardening accelerator may be used individually by 1 type, or in combination of 2 or more types.

Examples of the phosphorus-based hardening accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (Tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrohexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl Aliphatic phosphonium salts such as ]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium Bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate Salt, tetraphenylphosphonium tetraphenylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxy) Phenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc. Aromatic phosphonium salts; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; Tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexyl Aliphatic phosphine such as phosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, Triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropyl) phenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-di Methylphenyl)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-ethyl) Oxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphine)ethane, 1,3-bis( Diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,2-bis(diphenylphosphine)acetylene, 2,2'-bis(diphenylphosphine)diphenyl ether Aromatic phosphines, etc.

Examples of urea-based hardening accelerators include: 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, and 3-cyclohexyl -aliphatic dimethylureas such as 1,1-dimethylurea and 3-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-methylbenzene) base)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethyl Urea, 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 base)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl base)phenyl]-1,1-dimethylurea, N,N-(1,4-phenyl)bis(N',N'-dimethylurea), N,N-(4-methyl Aromatic dimethylureas such as methyl-1,3-phenyl)bis(N',N'-dimethylurea) [toluene bisdimethylurea], etc.

Examples of the guanidine-based hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dicyandiamide. Methylguanidine, 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, etc.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4- Methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 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-diamine Base-6-[2'-Undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuride Acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-Dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, Imidazole compounds such as 2-phenylimidazoline and adducts of imidazole compounds and epoxy resins.

As the imidazole-based hardening accelerator, commercially available products can be used, and examples thereof include “1B2PZ”, “2MZA-PW”, and “2PHZ-PW” manufactured by Shikoku Chemical Industry Co., Ltd., and “P200-H50” manufactured by Mitsubishi Chemical Corporation. wait.

Examples of metal-based hardening accelerators include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt acetyl acetonate (II) and cobalt acetyl acetonate (III), organic copper complexes such as copper acetyl acetonate (II), Organic zinc complexes such as zinc acetyl acetonate (II), organic iron complexes such as iron acetyl acetonate (III), organic nickel complexes such as nickel acetyl acetonate, manganese acetyl acetonate (II), etc. Organic manganese complexes, etc. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris( Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc.

As the amine-based hardening accelerator, commercially available products can be used, and examples thereof include “MY-25” manufactured by Ajinomoto Fine-Techno Co., Inc. and the like.

The content of the (G) hardening accelerator in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably It is 5 mass % or less, and it is especially preferable that it is 3 mass % or less. The lower limit of the content of (E) the hardening accelerator in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it may be, for example, 0% by mass or more, 0.001% by mass or more, or 0.01% by mass. % or more, 0.1 mass% or more, 0.5 mass% or more, etc.

＜(H)Other additives＞ The resin composition of the present invention may further contain optional additives as non-volatile components. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; phenol-based hardeners (phenol-based hardeners), naphthols, etc. Hardeners, acid anhydride-based hardeners, thiol-based hardeners, benzoxazine-based hardeners, cyanate ester-based hardeners, carbodiimide-based hardeners, imidazole-based hardeners, etc., other than active ester compounds Epoxy hardener; phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyester resin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin and other thermoplastics Resins; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorings such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, etc. Agents; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as organosilicon leveling agents and acrylic polymer leveling agents; Benton, montmorillonite, etc. and other thickeners; defoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, vinyl resin-based defoaming agents, etc.; UV absorbers such as benzotriazole-based UV absorbers; urea Adhesion improving agents such as silane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; hindered phenol-based antioxidants, hindered amine-based adhesion-imparting agents Antioxidants such as antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and organosilicon-based surfactants; phosphorus-based flame retardants (such as phosphate ester compounds, phosphazene compounds, phosphine Acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic-based flame retardants (such as antimony trioxide) and other flame retardants; phosphate ester dispersants, polyoxyalkanes Dispersants such as base dispersants, acetylenic dispersants, organosilicon dispersants, anionic dispersants, cationic dispersants; borate ester stabilizers, titanate ester stabilizers, aluminate ester stabilizers, Stabilizers such as zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers, etc. (F) Other additives may be used individually by 1 type or in combination of 2 or more types at arbitrary ratios. (H) The content of other additives can be appropriately set by those skilled in the art of the present invention.

＜(K) Organic solvent＞ The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the non-volatile components described above. As (K) the organic solvent, a known organic solvent can be used appropriately, and the type thereof is not particularly limited. Examples of (K) organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate. , isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone and other ester solvents; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, Ether solvents such as dibutyl ether and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, Ether ester solvents such as diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (ethyl diglycol acetate), γ-butyrolactone, methyl methoxypropionate, etc.; methyl lactate , ethyl lactate, methyl 2-hydroxyisobutyrate and other ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol Ether alcohol solvents such as alcohol monobutyl ether (butylcarbitol); N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other solvents Amine solvents; dimethyl styrene and other teresine solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane and other aliphatic hydrocarbon solvents; benzene, toluene , xylene, ethylbenzene, trimethylbenzene and other aromatic hydrocarbon solvents. (K) One type of organic solvent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

In one embodiment, the content of the organic solvent (K) is not particularly limited. When all the components in the resin composition are 100% by mass, it may be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass. Mass% or less, 15 mass% or less, 10 mass% or less, etc.

＜Manufacturing method of resin composition＞ The resin composition of the present invention can be produced, for example, by adding (A) a copolymer of a divinyl aromatic compound and styrene to any preparation container in any order and/or partially or entirely simultaneously; (B) Epoxy resin, and (C) active ester compound, as needed (D) inorganic filler material, as needed (E) radically polymerizable compound, as needed (F) other hardeners, as needed (G) Hardening accelerator, (H) other additives if necessary, and (K) organic solvent if necessary are mixed. In addition, in the process of adding each component and mixing, the temperature can be set appropriately, and heating and/or cooling can be performed temporarily or continuously. In addition, during or after the addition and mixing, the resin composition may be stirred or shaken using a stirring device such as a mixer or an oscillating device to uniformly disperse the resin composition. In addition, degassing can be performed under low-pressure conditions such as vacuum while stirring or shaking.

＜Characteristics of resin composition＞ The resin composition of the present invention includes (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, it is possible to obtain a cured product that can suppress the dielectric loss tangent to a low value even in a high-temperature environment such as 90° C. and has excellent crack resistance after desmear treatment. It is preferable to obtain a further plated product. It is a hardened material that is also excellent in peel strength (copper adhesion), has a low dielectric loss tangent at room temperature or normal temperature ranges such as 23°C, and has a low relative dielectric constant in any environment including room temperature or normal temperature ranges and high-temperature environments. .

The cured product of the resin composition of the present invention may have the characteristic of being able to suppress the occurrence of cracks after the desmear treatment (roughening treatment). Therefore, in one embodiment, after the circuit board is produced and desmeared as in Test Example 3 below, and then 100 copper pad portions of the circuit board are observed, the number of cracks may preferably be 10 or less (10% or less).

The cured product of the resin composition of the present invention can have a characteristic that the dielectric loss tangent (Df) is low even in a high temperature environment such as 90°C. Therefore, in one embodiment, as in Test Example 2 below, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 90°C can be preferably 0.020 or less and 0.010 or less, more preferably It is 0.009 or less and 0.008 or less, more preferably 0.007 or less and 0.006 or less, particularly preferably 0.005 or less and 0.004 or less.

The cured product of the resin composition of the present invention can have a characteristic that the dielectric loss tangent (Df) is low even at room temperature such as 23° C. or normal temperature. Therefore, in one embodiment, as in Test Example 2 below, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23°C can be preferably 0.020 or less and 0.010 or less, more preferably It is 0.009 or less and 0.008 or less, more preferably 0.007 or less and 0.006 or less, still more preferably 0.005 or less and 0.004 or less, particularly preferably 0.003 or less.

The cured product of the resin composition of the present invention can have a characteristic that the relative dielectric constant (Dk) is low even in a high temperature environment such as 90°C. Therefore, in one embodiment, as in Test Example 2 below, the relative dielectric constant (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 90° C. is preferably 5.0 or less, and more preferably 4.0 or less. , is further preferably 3.5 or less. When hollow silica is contained as the (D) inorganic filler, it can be further reduced. It is preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.5 or less, and particularly preferably 3.0. the following.

The cured product of the resin composition of the present invention may have a characteristic that the relative dielectric constant (Dk) is low even at room temperature such as 23° C. or normal temperature. Therefore, in one embodiment, as in Test Example 2 below, the relative dielectric constant (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. is preferably 5.0 or less, and more preferably 4.0 or less. , is further preferably 3.5 or less. When hollow silica is contained as the (D) inorganic filler, it can be further reduced. It is preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.5 or less, and particularly preferably 3.0. the following.

The cured product of the resin composition of the present invention can have characteristics of excellent copper adhesion. Therefore, in one embodiment, as in Test Example 1 below, a copper-plated conductor layer is formed on the hardened material in accordance with JIS C6481, and the copper-plated peeling strength calculated from the load when peeling off the copper-plated conductor layer in the vertical direction can preferably be 0.2. kgf/cm or more, more preferably 0.3 kgf/cm or more, further preferably 0.35 kgf/cm or more, particularly preferably 0.4 kgf/cm or more. The upper limit is not particularly limited, but may be, for example, 10 kgf/cm or less, 5 kgf/cm or less, 3 kgf/cm or less, 1 or 1.0 kgf/cm or less, etc.

＜Applications of resin composition＞ The resin composition of the present invention can be suitably used as a resin composition for insulating purposes, particularly a resin composition for forming an insulating layer. Specifically, it is suitable as a resin composition for forming an insulating layer (including a rewiring layer) formed on an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer). use. In addition, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board) in a printed wiring board to be described later. The resin composition of the present invention can also be used in sheet-like laminated materials such as resin sheets and prepregs, solder resists, underfill materials, wafer bonding materials, semiconductor sealing materials, filling resins, part embedding resins, etc. where the resin composition is required widely used in applications.

In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be used as "a rewiring forming layer serving as an insulating layer for forming a rewiring layer" "Resin composition (resin composition for rewiring formation layer formation)" and "resin composition for sealing semiconductor wafer (resin composition for semiconductor wafer sealing)" are appropriately used. When manufacturing semiconductor chip packages, a rewiring layer can be further formed on the sealing layer; (1) The step of laminating a temporary fixing film on the base material, (2) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) The step of forming a sealing layer on the semiconductor wafer, (4) The step of peeling the base material and the temporary fixing film from the semiconductor wafer, (5) The step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor wafer from which the base material and the temporary fixing film are peeled off, and (6) The step of forming a rewiring layer as a conductor layer on the rewiring forming layer.

In addition, since the resin composition of the present invention forms an insulating layer with good parts-embedding properties, it can be suitably used when a printed wiring board is a circuit board with built-in components.

＜Sheet laminated materials＞ The resin composition of the present invention may be applied and used in a varnish state, but industrially, it is usually preferably used in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminated material, resin sheets and prepregs shown below are preferred.

In one embodiment, the resin sheet includes a support body and a resin composition layer provided on the support body, and the resin composition layer is formed of the resin composition of the present invention.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoint of thinning the printed wiring board and providing a cured product of the resin composition with excellent insulation properties even if it is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but may generally be 5 μm or more, 10 μm or more, or the like.

Examples of the support include a film, a metal foil, and a release paper made of a plastic material. Preferably, a film or a metal foil made of a plastic material is used.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PET"), Polyesters such as (sometimes referred to as "PEN"), polycarbonate (hereinafter sometimes referred to as "PC"), acrylic polymers such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetyl fibers (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When a metal foil is used as a support, examples of the metal foil include copper foil, aluminum foil, and the like, and copper foil is preferred. As the copper foil, a foil formed of copper as a single metal may be used, or a foil formed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

The surface of the support that is bonded to the resin composition layer may be subjected to matting treatment, corona treatment, or antistatic treatment.

Moreover, as a support body, the support body with a release layer which has a release layer on the surface joined to a resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include at least one selected from the group consisting of alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Release agent. A commercially available product can be used as a support with a release layer. For example, "SK-1" manufactured by Lintec Corporation, which is a PET film having a release layer containing an alkyd resin release agent as a main component, can be used. ", "AL-5", "AL-7", "Lumirror T60" made by Toray, "Purex" made by Teijin, "Unipeel" made by UNITIKA wait.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Moreover, when using the support body with a release layer, it is preferable that the thickness of the entire support body with a release layer is in the said range.

In one embodiment, the resin sheet may further include any layer as necessary. Examples of the optional layer include, for example, a protective film selected according to the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, dust and the like can be prevented from adhering to the surface of the resin composition layer or causing damage to the surface of the resin composition layer.

The resin sheet can be produced, for example, by directly applying a liquid resin composition on a support using a die coater or the like, or by dissolving the resin composition in an organic solvent. The resin varnish is applied on the support and dried to form a resin composition layer.

Examples of the organic solvent include the same organic solvents as those described as components of the resin composition. One type of organic solvent may be used alone, or two or more types may be used in combination.

Drying can be performed by known methods such as heating and blowing hot air. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. Although it differs depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when using a resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent, the boiling point can be maintained at 50°C to 150°C. Dry at ℃ for 3 to 10 minutes to form a resin composition layer.

The resin sheet can be wound into a roll shape 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 of the present invention.

The sheet fiber base material used for the prepreg is not particularly limited, and sheet fibers commonly used as base materials for prepregs such as glass cloth, aromatic polyamide nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. base material. 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, further 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. Usually above 10μm.

Prepregs can be produced by known methods such as hot melt method and solvent method.

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

The sheet-like laminated material of the present invention can be preferably used to form an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be more preferably used to form an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board). ).

＜Printed wiring board＞ The printed wiring board of the present invention includes an insulating layer formed of a cured product obtained by curing the resin composition of the present invention.

The printed wiring board can be manufactured, for example, using the above-mentioned resin sheet by a method including the following steps (I) and (II); (I) The step of laminating the resin sheet on the inner substrate in such a manner that the resin composition layer of the resin sheet is bonded to the inner substrate, (II) A step of hardening (for example, thermal hardening) the resin composition layer to form an insulating layer.

The "inner layer substrate" used in step (I) refers to a member that becomes the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, and BT resin substrates. Thermosetting polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner-layer substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes called an "inner-layer circuit substrate." In addition, an intermediate product on which an insulating layer and/or a conductor layer is further formed when manufacturing a printed wiring board is also included in the so-called "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in components, an inner substrate with built-in components can be used.

The inner layer substrate and the resin sheet can be laminated, for example, by thermally and press-bonding the resin sheet to the inner layer substrate from the support side. Examples of a member for heat and pressure bonding the resin sheet to the inner substrate (hereinafter also referred to as "heat and pressure bonding member") include a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) wait. Furthermore, it is preferable to press the heat-pressing bonding member not directly onto the resin sheet but through an elastic material such as heat-resistant rubber so that the resin sheet can fully follow the surface irregularities of the inner substrate.

The inner substrate and the resin sheet can be laminated by a vacuum lamination method. In the vacuum lamination method, the heating and crimping temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and crimping pressure is preferably in the range of 0.098MPa to 1.77MPa, and more preferably 0.29MPa to 1.47MPa. range, the heating and crimping time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. Lamination can preferably be performed under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko-Materials Co., Ltd., and an intermittent vacuum pressurizer. Laminator etc.

After lamination, the laminated resin sheets can be smoothed by pressing the heated and pressure-bonded member from the support side under normal pressure (atmospheric pressure), for example. The stamping conditions for the smoothing treatment can be set to the same conditions as those for the above-mentioned lamination heat and pressure bonding conditions. Smoothing can be performed with a commercially available laminator. Moreover, lamination and smoothing processing can be performed continuously using the above-mentioned commercially available vacuum laminator.

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

In step (II), the resin composition layer is hardened (for example, thermally hardened) to form an insulating layer formed of a hardened product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally used when forming an insulating layer of a printed wiring board can be used.

For example, the thermal hardening conditions of the resin composition layer vary depending on the type of the resin composition. In one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 170°C. 210℃. The hardening time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, further preferably 15 minutes to 100 minutes.

Before thermally hardening the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before thermally hardening the resin composition layer, the resin composition layer is heated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, and more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes. ~150 minutes, more preferably 15 minutes to 120 minutes, further preferably 15 minutes to 100 minutes for preheating.

When manufacturing the printed wiring board, the steps of (III) opening holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer may be further performed. These steps (III) to (V) can be implemented according to various methods known to those skilled in the field of the present invention that can be used in the production of printed wiring boards. Furthermore, 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 between step (IV) and step (IV). Implemented between steps (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

In other embodiments, the printed wiring board of the present invention can be produced using the above prepreg. The manufacturing method is basically the same as when using a resin sheet.

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

Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), the slag is also removed. The steps and conditions of the roughening treatment are not particularly limited, and known steps and conditions generally used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by sequentially performing swelling treatment using a swelling liquid, roughening treatment using an oxidizing agent, and neutralization treatment using a neutralizing liquid.

The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include alkaline solutions, surfactant solutions, and the like. Alkaline solutions are preferred, and sodium hydroxide solutions and potassium hydroxide solutions are more preferred as the alkaline solutions. Examples of commercially available swelling solutions include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN Co., Ltd. The swelling treatment based on the swelling liquid is not particularly limited. For example, the insulation layer can be immersed in a swelling liquid of 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to a moderate level, it is preferable to immerse the insulating layer in a swelling liquid of 40°C to 80°C for 5 minutes to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd.

In addition, the neutralizing liquid used in the roughening treatment is preferably an acidic aqueous solution, and an example of a commercially available product is "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd.

The treatment by the neutralizing liquid can be performed by immersing the treated surface that has completed the roughening treatment by the oxidizing agent in a neutralizing liquid of 30°C to 80°C for 5 to 30 minutes. From the aspects of operability and other aspects, it is preferable to immerse the object that has been roughened by an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes.

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. There are no particular restrictions on the conductor material used in the conductor layer.

In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. . The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above group (for example, nickel-chromium alloys, copper-nickel alloys, and copper alloys). - titanium alloy) layer. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy is preferred from the viewpoint of versatility, cost, ease of patterning, etc. of conductor layer formation. , an alloy layer of copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, further preferably copper single metal layer.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, conventionally known techniques such as a semi-additive method and a fully-additive method can be used to plate the surface of the insulating layer to form a conductor layer having a desired wiring pattern. This is preferred from the viewpoint of ease of production. Formed using the semi-additive method. Hereinafter, an example of forming a conductor layer using a semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern is formed to expose a part of the plating seed layer in accordance with a desired wiring pattern. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

In other embodiments, the conductor layer may be formed using metal foil. When forming the conductor layer using 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 surface of the exposed resin composition layer. The layer of the resin composition and the metal foil can be laminated by a vacuum lamination method. The conditions for lamination may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventionally known techniques such as the subtractive method and the improved semi-additive method.

The metal foil can be produced by known methods such as electrolysis and rolling. Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Metals Co., Ltd., and the like.

＜Semiconductor Device＞ The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

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

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited by these embodiments. In the following, unless otherwise specified, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass" respectively. The temperature condition is room temperature (25°C) unless the temperature is specified.

<Synthesis Example 1: Synthesis of divinylbenzene-styrene copolymer> According to Example 1 of Patent Document 2, 3.0 moles of divinylbenzene (390.6g), 1.8 moles of ethylvinylbenzene (229.4g), 10.2 moles of styrene (1066.3g), and 15.0 moles of n-propyl acetate were mixed. Moles (1532.0 g) were put into a 5.0 L reactor, 600 millimoles of boron trifluoride diethyl ether complex was added at 70° C., and the reaction was carried out for 4 hours. After the polymerization solution was quenched with sodium bicarbonate aqueous solution, the oil layer was washed three times with pure water, and devolatilized under reduced pressure at 60° C. to recover the copolymer. The obtained copolymer was weighed and it was confirmed that 896.7 g of copolymer A was obtained. The weight average molecular weight (Mw) of copolymer A is 41300; Based on NMR measurement, GC analysis, and number average molecular weight converted to standard polystyrene, the structural units of copolymer A were calculated as follows according to the description of Patent Document 2; Structural units from divinylbenzene (a): 30.4 mol% Structural units from styrene (b): 57.4 mol% Structural units from ethylvinylbenzene (c): 12.2 mol% Structural units with residual vinyl groups from divinylbenzene (a): 23.9 mol % The amount of introduction of vinyl-containing terminal groups (tv): 0.66 (pieces/molecule) Terminal group of formula (t1): 1.49 mol% Terminal group of formula (t2): 1.31 mol% Terminal group of formula (t3): 2.21 mol%.

<Synthesis Example 2: Synthesis of Active Ester Compound A> Into a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 203.0 g of isophthalic acid chloride (the number of moles of the chloride group: 2.0 moles) and 1400 g of toluene were added. Perform nitrogen replacement under reduced pressure to dissolve. Next, 113.9 g (0.67 mol) of o-phenylphenol and 240 g (mol number of phenolic hydroxyl groups: 1.33 mol) of benzyl-modified naphthalene compound were charged, and the system was replaced with nitrogen under reduced pressure to dissolve them. . Then, 0.70 g of tetrabutylammonium bromide was dissolved, the inside of the system was controlled to 60° C. or lower while purging with nitrogen, and 400 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Next, stirring was continued under these conditions for 1.0 hours. After the reaction is completed, let it stand for liquid separation and remove the water layer. Furthermore, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for 15 minutes. The mixture was allowed to stand for liquid separation, and the water layer was removed. This operation was repeated until the pH of the water layer became 7. Then, water was removed by decanter dehydration to obtain active ester compound A in a toluene solution state with a non-volatile content of 62% by mass. The active ester equivalent of the obtained active ester compound A was 238 g/eq.

<Synthesis Example 3: Synthesis of Active Ester Compound B> Addition polymerization reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165g/equivalent (eq, softening point 85°C), 134g o-allylphenol (1.0 mol), and 1200g toluene, and replaced the system with nitrogen under reduced pressure. Next, 203 g (1.0 mol) of isophthalic acid chloride was charged, and the system was replaced with nitrogen under reduced pressure. 0.6 g of tetrabutylammonium bromide was added, and the system was controlled to be below 60°C while purging with nitrogen. 412 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the dropwise addition was completed, stirring was performed for 1.0 hours. After the reaction was completed, the aqueous layer was removed by standing and liquid separation. Water was further added to the obtained toluene layer, the mixture was stirred for 15 minutes, and the water layer was removed by liquid separation by standing still. This operation was repeated until the pH of the water layer became 7. Then, the non-volatile content was adjusted to 70% by mass by heating and drying, thereby obtaining an active ester resin represented by the following chemical formula; [Chemical Formula 16] .

In the above chemical formula, S is each independently an integer of 0 or 1 or more, and the average value of r calculated from the charging ratio is 1. In addition, the dotted line in the chemical formula is a structure obtained by reacting isophthalic acid chloride, an addition polymerization reaction resin of phenol, and/or o-allylphenol. The ester group equivalent of the active ester resin calculated from the charging ratio is 214g/equivalent (eq.).

[Example 1] Mix 10 parts of naphthalene-type epoxy resin ("HP-4032-SS" manufactured by DIC Corporation, epoxy group equivalent: 144 g/eq.) and naphthalene aralkyl-type epoxy resin (Nippon Steel Chemical Materials Co., Ltd. 5 parts of "ESN-475V", epoxy equivalent weight: 330g/eq.), biphenyl aralkyl type epoxy resin ("NC-3100", manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: 258g/eq.) ) 5 parts, active ester hardener ("HPC-8150-62T", toluene solution with active group equivalent weight 229g/eq., non-volatile content 61.5% by mass), 43 parts other hardeners (phenol hardener, DIC "LA-3018-50P" manufactured by the company, with a hydroxyl equivalent of 151 g/eq., 5 parts of a 1-methoxy 2-propanol solution (50% by mass non-volatile content), obtained in Synthesis Example 1 as component (A) 4 parts of the compound (50% by mass toluene solution), spherical silica (Matto Co., Ltd.) surface-treated with an inorganic filler (amine alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) Made of Marble, "SO-C2", average particle size 0.5 μm, specific surface area 5.8 m ² /g) 135 parts, hardening accelerator (manufactured by Shikoku Chemical Industry Co., Ltd., "1B2PZ") 0.5 parts, MEK 10 parts, 10 parts of cyclohexanone are evenly dispersed using a high-speed rotating mixer to obtain a resin varnish.

[Example 2] In Example 1, 43 parts of the active ester hardener ("HPC-8150-62T", a toluene solution with an active group equivalent of 223 g/eq. and a non-volatile content of 61.5% by mass) was changed to an active ester hardener (DIC The company's "HPC-8000-65T" has an active radical equivalent of 223g/eq., 40 parts of a toluene solution with a non-volatile content of 65% by mass). Except for the above matters, it carried out similarly to Example 1, and obtained the resin varnish.

[Example 3] In Example 1, 43 parts of the active ester hardener ("HPC-8150-62T", active group equivalent: 223 g/eq., toluene solution of 61.5 mass% non-volatile content) was changed to the active agent obtained in Synthesis Example 2 43 parts of ester A (toluene solution with an active group equivalent of 238 g/eq. and a non-volatile content of 61.5% by mass). Except for the above matters, it carried out similarly to Example 1, and obtained the resin varnish.

[Example 4] In Example 1, 43 parts of the active ester hardener ("HPC-8150-62T", active group equivalent: 223 g/eq., toluene solution of 61.5 mass% non-volatile content) was changed to the active agent obtained in Synthesis Example 3 37 parts of ester B (toluene solution with an active group equivalent of 214 g/eq. and a non-volatile content of 70% by mass). Except for the above matters, it carried out similarly to Example 1, and obtained the resin varnish.

[Example 5] In Example 1, 43 parts of the active ester hardener ("HPC-8150-62T", a toluene solution with an active group equivalent of 223 g/eq. and a non-volatile content of 61.5% by mass) was changed to an active ester hardener (Air "PC1300-02-65MA" manufactured by Water Co., Ltd., methylamyl ketone solution with an active radical equivalent of 199g/eq. and a non-volatile content of 65% by mass), 37 parts. Except for the above matters, it carried out similarly to Example 1, and obtained the resin varnish.

[Example 6] In Example 1, maleimide represented by the following formula (M) synthesized by the method described in Synthesis Example 1 of Japan Invention Association Publication Technical Report No. 2020-500211 was further used. 2 parts of MEK solution (non-volatile content 62% by mass) of compound A (Mw/Mn=1.81, t”=1.47 (mainly 1, 2 or 3)). Except for the above matters, operate in the same manner as in Example 1 , obtain resin varnish; [Chemical Formula 17] .

[Example 7] In Example 1, 2 parts of another thermosetting resin (maleimide resin ("MIR-5000-60T" manufactured by Nippon Kayaku Co., Ltd., a toluene solution with a non-volatile content of 60 mass %) was further used. In addition to the above matters, The same operation as in Example 1 was performed to obtain a resin varnish.

[Example 8] In Example 1, 2 parts of another thermosetting resin (maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., a toluene/MEK mixed solution with a non-volatile content of 70% by mass)) was further used. In addition to the above Except for the matters, it was carried out similarly to Example 1, and the resin varnish was obtained.

[Example 9] In Example 1, 2 parts of another thermosetting resin (maleimide resin ("BMI-689" manufactured by Design Corporation) was further used. Except for the above matters, the same operation as in Example 1 was performed to obtain a resin varnish.

[Example 10] In Example 1, 2 parts of another thermosetting resin (acrylate resin ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.)) was further used. Except for the above matters, the same operation as in Example 1 was performed to obtain a resin varnish.

[Example 11] In Example 1, 2 parts of another thermosetting resin (styrene resin ("OPE-2St-1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content of 65% by mass)) was further used. In addition to the above matters, the The same procedure as in Example 1 was performed to obtain a resin varnish.

[Example 12] In Example 1, an inorganic filler (spherical silica (manufactured by Yaduma Co., Ltd.) surface-treated with an amine alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was used , "SO-C2", with an average particle diameter of 0.5 μm and a specific surface area of 5.8 m ² /g), 135 parts was changed to 100 parts, and an inorganic filler having a hollow part (an amine-based alkoxysilane compound (Shin-Etsu) was added The procedure was carried out in the same manner as in Example 1, except that 35 parts of spherical silica having a hollow portion ("BA-S" manufactured by Japan Chemical Industry Co., Ltd.) and surface-treated "KBM573" manufactured by Chemical Industry Co., Ltd. , to obtain resin varnish.

[Comparative example 1] In Example 1, a resin varnish was obtained in the same manner as in Example 1, except that 4 parts of the compound obtained in Synthesis Example 1 (50 mass % toluene solution) was not used as the component (A).

[Comparative example 2] In Example 10, a resin varnish was obtained in the same manner as in Example 10, except that 4 parts of the compound (50 mass % toluene solution) obtained in Synthesis Example 1 was not used as the component (A).

[Comparative example 3] In Example 11, a resin varnish was obtained in the same manner as in Example 11, except that 4 parts of the compound (50 mass % toluene solution) obtained in Synthesis Example 1 was not used as the component (A).

<Production Example 1: Preparation of evaluation substrate A including an insulating layer and a conductor layer formed of resin sheet A> (1) Preparation of resin sheet A with a resin composition layer thickness of 40 μm As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness: 38 μm) having a release layer was prepared. The resin varnish obtained in the Example and the Comparative Example was uniformly applied on the release layer of the support so that the thickness of the dried resin composition layer became 40 μm. Then, the resin composition is 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 inner substrate Using micro-etching agent ("CZ8101" manufactured by MEC Corporation), the glass cloth base material epoxy resin double-sided copper-clad laminate with the inner layer circuit formed (the thickness of the copper foil is 18 μm, the thickness of the substrate is 0.4 mm, manufactured by Panasonic Corporation) "R1515A") is etched with 1μm on both sides to roughen the copper surface.

(3) Lamination of resin sheet A Using an intermittent vacuum pressure laminator (2-stage stacking laminator "CVP700" manufactured by Nikko-Materials Co., Ltd.), the resin composition layer is laminated on both sides of the inner substrate so that the resin composition layer is in contact with the inner substrate. Resin sheet A. Lamination was performed in the following manner: pressure reduction was performed for 30 seconds, the air pressure was adjusted to 13 hPa or less, and then pressure bonding was performed for 30 seconds at 120°C and a pressure of 0.74 MPa. Next, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

(4) Thermal hardening of the resin composition layer Then, the inner-layer substrate on which the resin sheet A was laminated was put into an oven at 130° C. and heated for 30 minutes. Then, it was transferred to an oven at 170° C. and heated for 30 minutes to heat the resin composition layer. Hardens to form an insulating layer. Then, the support body is peeled off, and the cured substrate A which has an insulating layer, an inner layer substrate, and an insulating layer in this order is obtained.

(5) Roughening treatment The hardened substrate A is subjected to a desmearing process as a roughening process. As desmearing treatment, the following wet desmearing treatment is carried out.

The hardened substrate A was immersed in a swelling solution ("Swelling Dip Securiganth 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 immersed in an oxidizing agent. The solution ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., an aqueous solution with a potassium permanganate concentration of approximately 6% and a sodium hydroxide concentration of approximately 4%) was immersed at 80°C for 20 minutes. Next, it was immersed in a neutralizing solution ("Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd., sulfuric acid aqueous solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(6) The conductor layer is formed according to the semi-additive method, and the conductor layer is formed on the roughened surface of the insulating layer. That is, the roughened substrate was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Next, heating was performed at 150° C. for 30 minutes and annealing treatment was performed. Then, a resist layer was formed, and patterning was performed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 25 μm, and annealing treatment was performed at 190° C. for 60 minutes. The obtained substrate is called "evaluation substrate A".

<Test example 1: Measurement of peel strength of plated conductor layer> The peeling strength of the insulating layer and the conductor layer was measured in accordance with Japanese Industrial Standards (JIS C6481). Specifically, a cut with a width of 10 mm and a length of 100 mm was made on the conductor layer of the evaluation substrate A, one end was peeled off, and the cut was clamped with a clamp, and measured along a vertical direction at a speed of 50 mm/min at room temperature. The load (kgf/cm) when peeling off 35mm in the direction was used to calculate the peeling strength. A tensile testing machine ("AC-50C-SL" manufactured by TSE Corporation) was used for the measurement.

<Test Example 2: Measurement of relative dielectric constant and dielectric loss tangent> The resin sheet A obtained in Production Example 1 (1) using the resin varnish obtained in Examples and Comparative Examples was hardened in an oven at 190° C. for 90 minutes. The support is peeled off from the resin sheet A taken out from the oven, thereby obtaining a cured product of the resin composition layer. The hardened material was cut into a length of 80 mm and a width of 2 mm to prepare a hardened material for evaluation.

For each hardened product for evaluation, the relative dielectric constant (Dk value) was measured using the resonant cavity perturbation method using "HP8362B" manufactured by Agilent Technologies at a frequency of 5.8 GHz and temperatures of 23°C and 90°C. And the value of dielectric loss tangent (Df value). Measurement was performed on two test pieces, and the average value was calculated.

<Preparation Example 2: Preparation of resin sheet B with a resin composition layer thickness of 25 μm> As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness: 38 μm) having a release layer was prepared. The resin varnish obtained in the Examples and Comparative Examples was uniformly coated on the release layer of the support so that the thickness of the dried resin composition layer became 25 μm, and the process was carried out at 70°C to 80°C (average 75°C) for 2.5 minutes. After drying, a resin sheet B including a support and a resin composition layer is obtained.

<Test Example 3: Evaluation of crack resistance after desmearing> A circular copper pad (copper thickness: 35 μm) with a diameter of 350 μm was formed into a grid shape at intervals of 400 μm so that the residual copper rate became 60%. An intermittent vacuum pressure laminating machine (2-stage stacking laminator "CVP700" manufactured by Nikko-Materials Co., Ltd.) was used on both sides of the core material ("E705GR" manufactured by Hitachi Chemical Industries, Ltd., thickness 400 μm). The resin sheet B with a thickness of 25 μm produced in Production Example 2 was laminated on both sides of the inner layer substrate so that the resin composition layer was bonded to the inner layer substrate. This lamination was performed by depressurizing for 30 seconds until the air pressure became 13 hPa or less, and then performing pressure bonding for 30 seconds under the conditions of a temperature of 100° C. and a pressure of 0.74 MPa. This was put into an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 170°C and heated for 30 minutes. Furthermore, the support was peeled off, and the obtained circuit board was immersed in Swelling Dip Securiganth P of Atotech Japan Co., Ltd. as a swelling liquid at 60° C. for 10 minutes. Next, it was immersed in Atotech Japan Co., Ltd.'s Concentrate Compact P (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L) as a roughening liquid at 80° C. for 30 minutes. Finally, it was immersed in Reduction Solution Securiganth P of Atotech Japan Co., Ltd. as a neutralizing solution at 40° C. for 5 minutes. 100 copper pad portions of the circuit board after the roughening treatment were observed to confirm whether there were cracks in the resin composition layer. If the number of cracks is 10 or less, it is evaluated as "○", and if there are more than 10 cracks, it is evaluated as "×".

Table 1 below shows the usage amounts (parts by mass) of components (A) to (G) including volatile components in the resin compositions of Examples and Comparative Examples, and the measurement results of the test examples. In Table 1, the nonvolatile content (mass %) of each component is described in the "N.V." column.

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From the above, it can be seen that by using a resin composition containing (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (B) an active ester compound, it is possible to obtain a product even at 90° C., etc. It is a hardened product with low dielectric loss tangent (Df) even in high-temperature environments and excellent crack resistance after desmear treatment. It is also found that this hardened product has excellent plating peel strength (copper adhesion) and has a low dielectric loss tangent (Df) in room temperature or normal temperature ranges such as 23°C, and can be used in both room and normal temperature ranges and high-temperature environments. The relative dielectric constant (Dk) is low in the environment.

Claims (15)

A resin composition comprising (A) a copolymer of a divinyl aromatic compound and styrene, (B) an epoxy resin, and (C) an active ester compound, wherein the component (A) contains A structural unit represented by the following formula (a1) of a divinyl aromatic compound (a), and a weight average molecular weight of 40,000 or more, In the formula, R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. The resin composition of claim 1, wherein the component (C) has a carbon-carbon double bond. The resin composition of Claim 1, wherein the value obtained by adding all the values obtained by dividing the mass of the non-volatile component of the component (B) by the epoxy group equivalent is recorded as W _B , and (C) When the value obtained by adding all the values obtained by dividing the mass of the nonvolatile component of the component by the active ester group equivalent is expressed as _WC , _WC /W _B is 1.0 or more. The resin composition of claim 1, further comprising (D) an inorganic filler. The resin composition of claim 1, further comprising (E) a radically polymerizable compound. The resin composition of claim 1 is used to form an interlayer insulating layer of a printed circuit board. The resin composition of claim 1, wherein the component (A) contains, in addition to structural units derived from the divinyl aromatic compound (a) and styrene (b), a component derived from a monomer other than styrene. Structural unit of vinyl aromatic compound (c). The resin composition of Claim 1, wherein the component (A) is composed of a structural unit derived from a divinyl aromatic compound (a), a structural unit derived from styrene (b), and a structural unit derived from a monomer other than styrene. When the sum of the structural units of the vinyl aromatic compound (c) is 100 mol%, The structural unit derived from the divinyl aromatic compound (a) is 2 mol% or more and less than 95 mol%. The resin composition of claim 1, wherein the component (A) contains at least one terminal group represented by the following formula (t1), (t2) or (t3) at the terminal of the copolymer, In the formula, R ² represents an aromatic hydrocarbon group with 6 to 30 carbon atoms, Z ¹ represents a vinyl group, a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms, * represents the bonding site with the main chain, and has the same meaning below. ; In the formula, R ³ and R ⁴ each independently represent an aromatic hydrocarbon group with 6 to 30 carbon atoms, and Z ³ and Z ⁴ each independently represent a vinyl group, a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms; In the formula, R ⁵ represents an aromatic hydrocarbon group with 6 to 30 carbon atoms, and Z ⁵ represents a vinyl group, a hydrogen atom or a hydrocarbon group with 1 to 18 carbon atoms. The resin composition of Claim 1, wherein the component (A) is composed of a structural unit derived from a divinyl aromatic compound (a), a structural unit derived from styrene (b), and a structural unit derived from a monomer other than styrene. When the sum of the structural units of the vinyl aromatic compound (c) is 100 mol%, The total of the structural units represented by formula (a1) and the terminal groups represented by formulas (t1), (t2) and (t3) is in the range of 2 mol% or more and 80 mol% or less. A cured product, which is a cured product of the resin composition according to any one of claims 1 to 10. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 10. A resin sheet having: support, and A resin composition layer formed of the resin composition according to any one of claims 1 to 10 is provided on the support. A printed wiring board provided with an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 10. A semiconductor device including the printed wiring board of claim 14.