JP2023167803A - resin composition - Google Patents

Abstract

To provide a resin composition that can yield a cured product with low dielectric loss tangent and superior crack resistance, and the like.SOLUTION: A resin composition contains (A) an epoxy resin, (B) an active ester compound, and (C) a hydrocarbon polymer having a terpene skeleton.SELECTED DRAWING: None

Description

The present invention relates to a resin composition. Furthermore, the present invention relates to a sheet-like laminate material, a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

As a manufacturing technique for printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductive layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing a resin composition.

Until now, maleimide compounds containing various non-aromatic ring skeletons have been known (Patent Document 1).

JP2019-203122A

In recent years, there has been a demand for insulating layers that have a low dielectric loss tangent and excellent crack resistance.

The object of the present invention is to provide a resin composition capable of obtaining a cured product with a low dielectric loss tangent and excellent crack resistance, a sheet-like laminate material, a resin sheet, a printed wiring board, and a semiconductor obtained using the resin composition. The goal is to provide equipment.

In order to achieve the objects of the present invention, the present inventors have made extensive studies and found that a resin composition is created by combining an epoxy resin, an active ester curing agent, and a hydrocarbon polymer containing a terpene skeleton as components of the resin composition. It was discovered that by incorporating it into a product, a cured product with a low dielectric loss tangent and excellent crack resistance could be obtained, and the present invention was completed.

That is, the present invention includes the following contents.
[1] (A) Epoxy resin,
A resin composition containing (B) an active ester compound and (C) a hydrocarbon polymer having a terpene skeleton.
[2] The resin composition according to [1], wherein component (C) contains either a polyterpene resin or an aromatic modified terpene resin.
[3] The resin composition according to [1] or [2], wherein component (C) does not have a polar group.
[4] The resin composition according to any one of [1] to [3], wherein the softening point of component (C) is 50° C. or higher.
[5] The resin composition according to any one of [1] to [4], wherein the content of component (C) is 1% by mass or more when the resin component is 100% by mass.
[6] The resin composition according to any one of [1] to [5], further containing (D) a radically polymerizable compound.
[7] The resin composition according to any one of [1] to [6], further comprising (E) an inorganic filler.
[8] The resin composition according to [7], wherein the content of component (E) is 40% by mass or more when the nonvolatile components in the resin composition are 100% by mass.
[9] The resin composition according to any one of [1] to [8], further containing (F) a curing agent.
[10] A sheet-like laminate material containing the resin composition according to any one of [1] to [9].
[11] A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of [1] to [9] provided on the support.
[12] A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of [1] to [9].
[13] A semiconductor device comprising the printed wiring board according to [12].

According to the resin composition of the present invention, a resin composition that can obtain a cured product with a low dielectric loss tangent and excellent crack resistance, a sheet-like laminate material, a resin sheet, and a printed wiring obtained using the resin composition. A board and a semiconductor device can be provided.

Hereinafter, the present invention will be explained in detail based on its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and may be implemented with arbitrary changes within the scope of the claims of the present invention and equivalents thereof. In the present invention, the content of each component in the resin composition is a value based on 100% by mass of nonvolatile components in the resin composition, unless otherwise specified. Moreover, in this specification, "permittivity" represents "relative permittivity" unless otherwise specified.

[Resin composition]
The resin composition of the present invention includes (A) an epoxy resin, (B) an active ester compound, and (C) a hydrocarbon polymer containing a terpene skeleton. By using such a resin composition, a cured product having a low dielectric loss tangent (Df) and excellent crack resistance can be obtained. Moreover, the resin composition can also provide a cured product having a high glass transition temperature (Tg) and a low dielectric constant (Dk).

It has been known that (C) hydrocarbon polymers containing a terpene skeleton are used as adhesives. However, the present inventor has discovered that by incorporating (C) a hydrocarbon polymer containing a terpene skeleton into a resin composition, it is possible to obtain a cured product with excellent dielectric loss tangent and crack resistance. It was found that the dielectric loss tangent is excellent even at high temperatures. (C) The technical idea of obtaining a cured product with excellent dielectric loss tangent and crack resistance by incorporating a hydrocarbon polymer containing a terpene skeleton into a resin composition used for insulation purposes is as follows: As far as I know, this has not been proposed in the past.

The resin composition of the present invention may further contain arbitrary components in combination with components (A) to (C). Examples of optional components include (D) a radically polymerizable compound, (E) an inorganic filler, (F) a curing agent, (G) a curing accelerator, (H) other additives, and (I) a solvent. Can be mentioned. Each component contained in the resin composition will be explained in detail below.

<(A) Epoxy resin>
The resin composition contains (A) an epoxy resin as the (A) component. Epoxy resin is a curable resin having an epoxy group.

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

It is preferable that the resin composition contains, as the epoxy resin (A), an epoxy resin having two or more epoxy groups in one molecule. (A) The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably is 70% by mass or more.

Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resins"). ). The resin composition may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, and ester skeleton. Alicyclic epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure are preferred, and naphthalene-type epoxy resins are more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. ", "Epicote 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical's "630", "630LSD", "604" (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycyol type epoxy resin); ADEKA's "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; "ZX1059" (bisphenol A type epoxy resin) manufactured by Nippon Steel Chemical & Material Chemical Co., Ltd. Mixture of bisphenol F type epoxy resin); “EX-721” manufactured by Nagase ChemteX (glycidyl ester type epoxy resin); “Celoxide 2021P” manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); Daicel "PB-3600" manufactured by Nippon Soda Co., Ltd., "JP-100", "JP-200" (epoxy resin with a butadiene structure) manufactured by Nippon Soda Co., Ltd.; "ZX1658", "ZX1658GS" manufactured by Nippon Steel Chemical & Material Chemical Co., Ltd. (liquid 1,4-glycidylcyclohexane type epoxy resin), etc. These may be used alone or in combination of two or more.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalyl Midine type epoxy resins and phenolphthalein type epoxy resins are preferred, and naphthalene type epoxy resins and biphenyl type epoxy resins are more preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC; “N-690” (cresol novolak type epoxy resin) manufactured by DIC; “N-695” (cresol novolac type epoxy resin) manufactured by DIC; “HP-7200”, “HP-7200HH”, “HP” manufactured by DIC -7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" manufactured by DIC ", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd. (trisphenol type epoxy resin); "NC7000L" manufactured by Nippon Kayaku Co., Ltd. (naphthol novolac type epoxy resin); “NC3000H”, “NC3000”, “NC3000L”, “NC3000FH”, “NC3100” manufactured by Nippon Kayaku Co., Ltd. (biphenyl type epoxy resin); “ESN475V” and “ESN4100V” manufactured by Nippon Steel Chemical & Materials Co., Ltd. (naphthalene type) epoxy resin); “ESN485” (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; “ESN375” (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical &Materials; “YX4000H” manufactured by Mitsubishi Chemical; "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin); Mitsubishi Chemical's "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical's "YX8800" (anthracene type epoxy resin); Mitsubishi “YX7700” manufactured by Chemical Co., Ltd. (phenol aralkyl type epoxy resin); “PG-100” and “CG-500” manufactured by Osaka Gas Chemical Company; “YL7760” manufactured by Mitsubishi Chemical Company (bisphenol AF type epoxy resin); Mitsubishi "YL7800" (fluorene type epoxy resin) manufactured by Chemical Company; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Company; Nippon Kayaku Examples include "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Co., Ltd. These may be used alone or in combination of two or more.

(A) When using a combination of a solid epoxy resin and a liquid epoxy resin as the epoxy resin, the mass ratio thereof (solid epoxy resin: liquid epoxy resin) is preferably 1:0.01 to 1:50, The ratio is more preferably 1:0.05 to 1:10, particularly preferably 1:0.1 to 1:3. By setting the ratio of the liquid epoxy resin to the solid epoxy resin within such a range, 1) appropriate tackiness is provided when used in the form of a resin sheet, and 2) when used in the form of a resin sheet. The following effects can be obtained: 3) sufficient flexibility can be obtained, handling properties are improved, and 3) a cured product having sufficient breaking strength can be obtained.

(A) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ～5,000g/eq. , more preferably 60g/eq. ~2,000g/eq. , more preferably 70g/eq. ～1,000g/eq. , even more preferably 80 g/eq. ～500g/eq. It is. Epoxy equivalent is the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

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

(A) From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin is preferably 1% by mass or more, and more preferably 1% by mass or more when the nonvolatile components in the resin composition are 100% by mass. Preferably it is 3% by mass or more, more preferably 5% by mass or more. The upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

(A) From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin is preferably 10% by mass or more, when the resin component in the resin composition is 100% by mass. Preferably it is 20% by mass or more, more preferably 30% by mass or more, and the upper limit thereof is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.

In the present invention, the "resin component" referred to in the resin composition refers to the non-volatile components constituting the resin composition excluding (E) the inorganic filler described below.

<(B) Active ester compound>
The resin composition contains (B) an active ester compound as the (B) component. (B) The active ester compound has the function of curing the (A) epoxy resin. The (B) active ester compound as the (B) component does not include those corresponding to the above-mentioned (A) component. (B) The active ester compound may be used alone or in combination of two or more.

(B) As the active ester compound, a compound having an active ester group as an active group that reacts with the (A) epoxy resin can be used. Specifically, it is preferable that component (B) contains either a compound having a structure represented by formula (B-1) or a compound containing an aromatic ester skeleton and an unsaturated bond.

式中、Ｒ^１、Ｒ^２及びＲ^３は、（１）Ｒ^１が、水素原子、ハロゲン原子、メチル基、又はＲ^１１－Ａ－を表し、且つＲ^２及びＲ^３が、それぞれ独立して、水素原子、又は置換基を表すか、（２）Ｒ^１及びＲ^２が一緒になって結合し、置換基を有していてもよい芳香族炭素環を形成し、且つＲ^３が、水素原子、又は置換基を表すか、或いは（３）Ｒ^２及びＲ^３が一緒になって結合し、置換基を有していてもよい芳香族炭素環を形成し、且つＲ^１が、水素原子、ハロゲン原子、メチル基、又はＲ^１１－Ａ－を表し；Ｒ^４及びＲ^５は、それぞれ独立して、水素原子、又は置換基を表し；Ｒ^１１は、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、又は置換基を有していてもよいアリール基を表し；Ａは、－ＣＨ_２－、－ＣＨ（ＣＨ_３）－、－ＣＯ－、又は－Ｏ－を表し；＊は、結合部位を表す。 (Compound having the structure represented by formula (B-1))
One embodiment of component (B) is preferably a compound having a structure represented by formula (B-1).

In the formula, R ¹ , R ² and R ³ represent (1) R ¹ represents a hydrogen atom, a halogen atom, a methyl group, or R ¹¹ -A-, and R ² and R ³ each independently , represents a hydrogen atom, or a substituent, or (2) R ¹ and R ² are bonded together to form an aromatic carbon ring which may have a substituent, and R ³ is hydrogen represents an atom or a substituent, or (3) R ² and R ³ are bonded together to form an aromatic carbon ring which may have a substituent, and R ¹ is a hydrogen atom , represents a halogen atom, a methyl group, or R ¹¹ -A-; R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent; R ¹¹ may have a substituent Represents an alkyl group, an alkenyl group which may have a substituent, or an aryl group which may have a substituent; A is -CH ₂ -, -CH(CH ₃ )-, -CO-, or represents -O-; * represents a binding site.

When R ¹ does not form an aromatic carbocycle, R 1 represents a hydrogen atom, a halogen atom, a methyl group, or R ¹¹ -A-. In one embodiment, when R ¹ does not form an aromatic carbocycle, it is preferably a hydrogen atom, a methyl group, or R ¹¹ -A-; more preferably a hydrogen atom or R ¹¹ -A- be.

A represents -CH ₂ -, -CH(CH ₃ )-, -CO-, or -O-. In one embodiment, A is preferably -CH ₂ - or -CH(CH ₃ )-; more preferably -CH(CH ₃ )-.

R ¹¹ represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent.

The alkyl group, alkenyl group, and aryl group represented by R ¹¹ may have a substituent. Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, aryl groups, aryl-alkyl groups (alkyl groups substituted with aryl groups), alkyl-aryl-alkyl groups (aryl groups substituted with alkyl groups), (substituted alkyl group), alkenyl-aryl-alkyl group (alkyl group substituted with an aryl group substituted with an alkenyl group), aryl-aryl-alkyl group (alkyl group substituted with an aryl group substituted with an aryl group) ), alkyl-aryl group, alkenyl-aryl group, aryl-aryl group, alkyl-oxy group, alkenyl-oxy group, aryl-oxy group, alkyl-carbonyl group, alkenyl-carbonyl group, aryl-carbonyl group, alkyl- Examples include oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group and the like.

In one embodiment, R ¹¹ is preferably an aryl group which may have a substituent; more preferably an aryl group; particularly preferably a phenyl group.

When R ² and R ³ do not form an aromatic carbocycle, each independently represents a hydrogen atom or a substituent.

The substituents represented by R ² and R ³ are the same as the substituents that the alkyl group, alkenyl group, and aryl group represented by R ¹¹ may have.

When R ² and R ³ do not form an aromatic carbocycle, each independently in one embodiment preferably represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, or an alkyl-aryl group. group; more preferably a hydrogen atom, an alkyl group, an aryl group, or an aryl-alkyl group.

When R ¹ , R ² and R ³ form an aromatic carbon ring, R ¹ and R ² or R ² and R ³ are bonded together and are an aromatic carbon which may have a substituent. form a ring.

The substituents on the aromatic carbon ring formed by R ¹ , R ² and R ³ are the same as the substituents that the alkyl group, alkenyl group and aryl group represented by R ¹¹ may have.

When R ¹ , R ² and R ³ form an aromatic carbocycle, in one embodiment, R ¹ and R ² or R ² and R ³ are bonded together and preferably have a substituent. more preferably a benzene ring which may be substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group. ; More preferably, an (unsubstituted) benzene ring is formed.

R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent.

The substituents represented by R ⁴ and R ⁵ are the same as the substituents that the alkyl group, alkenyl group, and aryl group represented by R ¹¹ may have.

R ⁴ and R ⁵ are each independently, in one embodiment, preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, or an alkyl-aryl group; more preferably hydrogen An atom, an alkyl group, an aryl group, or an aryl-alkyl group.

In the first embodiment, preferably R ¹ , R ² , R ⁴ and R 5 are hydrogen atoms, and R ³ is an alkyl group or an aryl group; more preferably R 1 , R ⁵ is a hydrogen atom, and R ³ is an alkyl group or an aryl group; ² , R ⁴ and R ⁵ are hydrogen atoms, and R ³ is a methyl group or a phenyl group.

In the second embodiment, preferably R ¹ is a hydrogen atom or R ¹¹ -A-, A is -CH ₂ - or -CH(CH ₃ )-, and R ¹¹ is aryl and R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms or aryl-alkyl groups (particularly preferably R ¹ is R ¹¹ -A- and/or R ² , R ³ , R ⁴ and R ⁵ is an aryl-alkyl group); More preferably, R ¹ is a hydrogen atom or R ¹¹ -A-, and A is -CH(CH ₃ ) -, R ¹¹ is a phenyl group, and R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms or α-methylbenzyl groups (particularly preferably, R ¹ is R ¹¹ -A - and/or at least one of R ² , R ³ , R ⁴ and R ⁵ is an α-methylbenzyl group).

In a third embodiment, preferably R ¹ and R ² are bonded together to form a benzene ring, and R ³ , R ⁴ and R ⁵ are hydrogen atoms, or R ² and R ³ are bonded together to form a benzene ring, and R ¹ , R ⁴ and R ⁵ are hydrogen atoms.

式中、環Ｘ^１は、それぞれ独立して、置換基を有していてもよい芳香族炭素環、又は置換基を有していてもよい非芳香族炭素環を表し；環Ｙ^１及び環Ｚ^１は、それぞれ独立して、置換基を有していてもよい芳香族炭素環を表し；Ｘ^ｂは、それぞれ独立して、単結合、－Ｃ（Ｒ^ｂ）_２－、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ－、－ＳＯ_２－、－ＣＯＮＨ－、又は－ＮＨＣＯ－を表し；Ｒ^ｂは、それぞれ独立して、水素原子、置換基を有していてもよいアルキル基、又は置換基を有していてもよいアリール基を表すか、或いは２個のＲ^ｂが一緒になって結合し、置換基を有していてもよい非芳香族炭素環を形成し；ｂ’は、０、又は１以上の整数を表し；ｃ’は、それぞれ独立して、０、１、２、又は３を表し；ｄ’は、それぞれ独立して、０又は１を表し；その他の記号は上記の通りである。ｂ’単位及びｃ’単位は、それぞれ、構造単位毎に同一であってもよいし、異なっていてもよい。 In a preferred embodiment, component (B) is a compound having a structure represented by formula (B-2).

In the formula, ring X ¹ each independently represents an aromatic carbocycle which may have a substituent or a non-aromatic carbocycle which may have a substituent; ring Y ¹ and ring Z ¹ each independently represents an aromatic carbon ring which may have a substituent; X ^b each independently represents a single bond, -C(R ^b ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO-; R ^b is each independently a hydrogen atom, an optionally substituted alkyl represents a group or an aryl group which may have a substituent, or two R ^b are bonded together to form a non-aromatic carbon ring which may have a substituent; b' represents 0 or an integer of 1 or more; c' each independently represents 0, 1, 2, or 3; d' each independently represents 0 or 1; other The symbols are as above. The b' units and c' units may be the same or different for each structural unit.

Each ring X ¹ independently represents an aromatic carbocycle which may have a substituent or a non-aromatic carbocycle which may have a substituent.

The substituents on the aromatic carbon ring represented by ring X ¹ are the same as the substituents that the alkyl group, alkenyl group, and aryl group represented by R ¹¹ may have.

In one embodiment, each ring X ¹ independently preferably has a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a substituent. a non-aromatic carbocyclic ring having 5 to 12 carbon atoms; more preferably substituted with a group selected from (1) an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group; (2) a naphthalene ring which may be substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group; or (3) an alkyl group, an alkenyl group. a non-aromatic carbocyclic ring having 5 to 12 carbon atoms (particularly preferably a tetrahydrodicyclopentadiene ring) which may be substituted with a group selected from a group, an aryl group, an aryl-alkyl group, an alkyl-aryl group, and an oxo group. It is.

Each ring Y ¹ independently represents an aromatic carbon ring which may have a substituent.

The substituents on the aromatic carbon ring represented by ring Y ¹ are the same as the substituents that the alkyl group, alkenyl group, and aryl group represented by R ¹¹ may have.

In one embodiment, each ring Y ¹ independently is preferably a benzene ring which may have a substituent or a naphthalene ring which may have a substituent; more preferably ( 1) a benzene ring optionally substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group, or (2) an alkyl group, an alkenyl group, an aryl group, an aryl- It is a naphthalene ring which may be substituted with a group selected from an alkyl group and an alkyl-aryl group.

Each ring Z ¹ independently represents an aromatic carbon ring which may have a substituent.

The substituents on the aromatic carbon ring represented by ring Z ¹ are the same as the substituents that the alkyl group, alkenyl group, and aryl group represented by R ¹¹ may have.

In one embodiment, each of the rings Z ¹ independently is preferably a benzene ring which may have a substituent or a naphthalene ring which may have a substituent; more preferably, ( 1) a benzene ring optionally substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, and an alkyl-aryl group, or (2) an alkyl group, an alkenyl group, an aryl group, an aryl- It is a naphthalene ring which may be substituted with a group selected from an alkyl group and an alkyl-aryl group.

X ^b is each independently a single bond, -C(R ^b ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO- represents. Each X ^b is independently, in one embodiment, preferably a single bond, -C(R ^b ) ₂ -, or -O-; more preferably a single bond or -O-.

R ^b each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, or two R ^b 's together represent and bond together to form a non-aromatic carbon ring which may have a substituent. The substituents in the alkyl group represented by R ^b are the same as the substituents that the alkyl group, alkenyl group, and aryl group represented by R ¹¹ may have.

R ^b is each independently, in one embodiment, preferably a hydrogen atom or an alkyl group that may have a substituent; more preferably a hydrogen atom or an alkyl group; particularly preferably is a hydrogen atom or a methyl group.

b' represents 0 or an integer of 1 or more. In one embodiment, b' is preferably 0 or an integer from 1 to 100; more preferably 0 or an integer from 1 to 10; particularly preferably 0 or an integer from 1 to 5. It is.

c' each independently represents 0, 1, 2, or 3; c' is each independently, in one embodiment, preferably 0, 1, or 2; more preferably 0 or 1.

d' each independently represents 0 or 1.

式中、Ｙ^１は置換基を有していてもよい芳香族炭素環を表す。

式中、Ｒ^ｙは、それぞれ独立して、アルキル基、アルケニル基、アリール基、アリール－アルキル基、又はアルキル－アリール基を示し；ｙは、それぞれ独立して、０、１、又は２を示し；その他の記号は上記の通り。 Examples of the partial structure represented by formula (Y') in formula (B-2) include structures represented by formulas (Y-1) to (Y-12).

In the formula, Y ¹ represents an aromatic carbon ring which may have a substituent.

In the formula, R ^y each independently represents an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, or an alkyl-aryl group; y each independently represents 0, 1, or 2 ;Other symbols are as above.

In addition to the resin represented by formula (B-2), component (B) includes resins that are reaction intermediates produced during synthesis (for example, one or both ends have a hydroxy group and/or carboxy group), and resins derived from raw material impurities. etc. may be included.

The compound having the structure represented by formula (B-1) may be a commercially available product, or may be synthesized using a known method or a method analogous thereto. Commercially available compounds having the structure represented by formula (B-1) include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000" as active ester compounds containing a dicyclopentadiene type diphenol structure. -65T", "HPC-8000L-65TM", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); "HP-B-8151-62T", " "EXB-8100L-65T", "EXB-9416-70BK", "EXB-8", "HPC-8150-62T" (manufactured by DIC); as a phosphorus-containing active ester compound, "EXB9401" (manufactured by DIC), "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound that is an acetylated product of phenol novolak, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound that is a benzoylated product of phenol novolak, Examples of active ester compounds containing a styryl group and a naphthalene structure include "PC1300-02-65MA" (manufactured by Air Water).

(Compound containing aromatic ester skeleton and unsaturated bond)
Another embodiment of component (B) is a compound containing an aromatic ester skeleton and an unsaturated bond.

The compound containing an aromatic ester skeleton and an unsaturated bond has an aromatic ester skeleton. The aromatic ester skeleton represents a skeleton having an ester bond and an aromatic ring bonded to one or both ends of the ester bond. Among these, those having aromatic rings at both ends of the ester bond are preferred. Examples of groups having such a skeleton include arylcarbonyloxy group, aryloxycarbonyl group, arylenecarbonyloxy group, aryleneoxycarbonyl group, arylcarbonyloxyarylene group, aryloxycarbonylarylene group, arylenecarbonyloxyarylene group, Examples include aryleneoxycarbonylarylene groups. Further, the number of carbon atoms in the group having such a skeleton is preferably 7 to 20, more preferably 7 to 15, and still more preferably 7 to 11. Aromatic hydrocarbon groups such as an aryl group and an arylene group may have a substituent.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. Examples of such aryl groups include phenyl group, furanyl group, pyrrolyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyridinyl group, pyrimidinyl group, pyridazinyl group, and pyrazinyl group. Monocyclic aromatic compounds such as triazinyl groups and monocyclic aromatic compounds with one hydrogen atom removed; naphthyl groups, anthracenyl groups, phenalenyl groups, phenanthrenyl groups, quinolinyl groups, isoquinolinyl groups, quinazolyl groups, phthalazinyl groups, pteridinyl groups, coumarinyl groups and fused ring aromatic compounds from which one hydrogen atom has been removed, such as a group, an indole group, a benzimidazolyl group, a benzofuranyl group, an acridinyl group, and the like.

The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group (-C ₆ H ₄ -C ₆ H ₄ -).

A compound containing an aromatic ester skeleton and an unsaturated bond contains an unsaturated bond. As a result, the cured product has an excellent dielectric constant. Moreover, the unsaturated bond contributes to the curing reaction of the resin composition. The contribution of the unsaturated bonds to the curing reaction prevents some ester sites of the aromatic ester skeleton from being used in the curing reaction, and as a result, the curing shrinkage rate is suppressed.

This unsaturated bond is preferably a carbon-carbon unsaturated bond such as an ethylenically unsaturated bond. The unsaturated bond is preferably contained in a substituent having at least one unsaturated bond. Examples of unsaturated bonds include unsaturated bonds contained in unsaturated hydrocarbon groups such as alkenyl groups having 2 to 30 carbon atoms and alkynyl groups having 2 to 30 carbon atoms. The unsaturated bond is preferably contained in the substituent of the aromatic hydrocarbon group at the terminal, and more preferably contained in the substituent of the aromatic hydrocarbon group at both ends.

Examples of the alkenyl group having 2 to 30 carbon atoms include vinyl group, allyl group, propenyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-hexenyl group. group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-octenyl group, 2-octenyl group, 1-undecenyl group, 1-pentadecenyl group, 3-pentadecenyl group, 7-pentadecenyl group group, 1-octadecenyl group, 2-octadecenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, 1,3-butadienyl group, 1,4-butadienyl group, hexa-1,3-dienyl group, hexa-2, Examples thereof include a 5-dienyl group, a pentadeca-4,7-dienyl group, a hexa-1,3,5-trienyl group, and a pentadeca-1,4,7-trienyl group.

Examples of the alkynyl group having 2 to 30 carbon atoms include ethynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1,3-butadiynyl group. Examples include groups.

Among these, an alkenyl group having 2 to 30 carbon atoms is preferred, an alkenyl group having 2 to 10 carbon atoms is more preferred, and an alkenyl group having 2 to 5 carbon atoms is even more preferred. , allyl group, isopropenyl group, and 1-propenyl group are even more preferable, and allyl group is particularly preferable.

The compound containing an aromatic ester skeleton and an unsaturated bond includes, in addition to the aromatic ester skeleton, an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, or a group consisting of a combination thereof. It may have. The term "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring, and the aromatic ring may be monocyclic, polycyclic, or heterocyclic.

The aromatic hydrocarbon group is preferably a divalent aromatic hydrocarbon group, more preferably an arylene group or an aralkylene group, and even more preferably an arylene group. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group. The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and even more preferably an aralkylene group having 7 to 15 carbon atoms. Among these, phenylene group is preferred.

The aliphatic hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent saturated aliphatic hydrocarbon group, and even more preferably an alkylene group or a cycloalkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, and a 1,2-dimethylethylene group. group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, etc.

The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and even more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and a cycloalkylene group represented by the following formulas (a) to (d). can be mentioned. In formulas (a) to (d), "*" represents a bond.

The aromatic ester skeleton, aromatic hydrocarbon group, aliphatic hydrocarbon group, and unsaturated hydrocarbon group may have a substituent. The substituent is the same as the substituent that the alkyl group, alkenyl group, and aryl group represented by R ¹¹ may have.

（一般式（Ｂ－３）中、Ａｒ^１１は、それぞれ独立に、置換基を有していてもよい１価の芳香族炭化水素基を表し、Ａｒ^１２は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基を表し、Ａｒ^１３は、それぞれ独立に、置換基を有していてもよい２価の芳香族炭化水素基、置換基を有していてもよい２価の脂肪族炭化水素基、酸素原子、硫黄原子、又はこれらの組み合わせからなる２価の基を表す。ｎは０～１０の整数を表す。）

（一般式（Ｂ－４）中、Ａｒ^２１は、置換基を有していてもよいｍ価の芳香族炭化水素基を表し、Ａｒ^２２は、それぞれ独立に置換基を有していてもよい１価の芳香族炭化水素基を表す。ｍは、２又は３の整数を表す。） The compound containing an aromatic ester skeleton and an unsaturated bond is preferably either a compound represented by the following general formula (B-3) or a compound represented by the following general formula (B-4). .

(In general formula (B-3), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, and Ar ¹² each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent; Represents a divalent group consisting of a good divalent aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, or a combination thereof. n represents an integer from 0 to 10.)

(In general formula (B-4), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent, and Ar ²² each independently may have a substituent. Represents a monovalent aromatic hydrocarbon group. m represents an integer of 2 or 3.)

In general formula (B-3), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. Examples of monovalent aromatic hydrocarbon groups include phenyl group, furanyl group, pyrrolyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyridinyl group, pyrimidinyl group, and pyridazinyl group. monocyclic aromatic compounds with one hydrogen atom removed such as pyrazinyl, triazinyl, naphthyl, anthracenyl, phenalenyl, phenanthrenyl, quinolinyl, isoquinolinyl, quinazolyl, phthalazinyl, pteridinyl A fused-ring aromatic compound with one hydrogen atom removed, such as a coumarinyl group, an indole group, a benzimidazolyl group, a benzofuranyl group, or an acridinyl group; Therefore, a phenyl group is preferred. The monovalent aromatic hydrocarbon group represented by Ar ¹¹ may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have. Among these, it is preferable that the substituent of Ar ¹¹ contains an unsaturated bond.
Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent. Examples of the divalent aromatic hydrocarbon group include an arylene group and an aralkylene group, with an arylene group being preferred. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group. The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and even more preferably an aralkylene group having 7 to 15 carbon atoms. Among these, phenylene group is preferred.

The divalent aromatic hydrocarbon group represented by Ar ¹² may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.

In the general formula (B-3), 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, and It represents a divalent group consisting of a hydrogen group, an oxygen atom, a sulfur atom, or a combination thereof, and a divalent group consisting of a combination thereof is preferred. The divalent aromatic hydrocarbon group is the same as the divalent aromatic hydrocarbon group represented by Ar ¹² .

As the divalent aliphatic hydrocarbon group, a divalent saturated aliphatic hydrocarbon group is more preferable, an alkylene group and a cycloalkylene group are preferable, and a cycloalkylene group is more preferable.

The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, and a 1,2-dimethylethylene group. group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, etc.

The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and even more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and a cycloalkylene group represented by the above formulas (a) to (d). are mentioned, and a cycloalkylene group represented by formula (c) is preferred.

A divalent group consisting of a combination of these includes a divalent aromatic hydrocarbon group which may have a substituent, and a divalent aliphatic hydrocarbon group which may have a substituent. A plurality of divalent aromatic hydrocarbon groups which may have a substituent, and a plurality of divalent aliphatic hydrocarbon groups which may have a substituent are preferred. A divalent group in which these are alternately combined is more preferred. Specific examples of the divalent groups mentioned above include the following divalent groups (B1) to (B8). In the formula, b1 to b7 represent an integer of 0 to 10, preferably an integer of 0 to 5. "*" represents a bond, and the wavy line represents a structure obtained by reacting an aromatic compound, an acid halide of an aromatic compound, or an esterified product of an aromatic compound used to synthesize component (B). represent.

The divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group represented by Ar ¹³ may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.

In general formula (B-3), n represents an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3. Note that when the compound represented by general formula (B-3) is an oligomer or polymer, n represents its average value.

In the general formula (B-4), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent. The m-valent aromatic hydrocarbon group is preferably an m-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an m-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, More preferred is an m-valent aromatic hydrocarbon group having 6 to 10 carbon atoms. The m-valent aromatic hydrocarbon group represented by Ar ²¹ may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.

In the general formula (B-4), Ar ²² each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. Ar ²² is the same as the aromatic hydrocarbon group represented by Ar ¹¹ in general formula (B-3). The monovalent aromatic hydrocarbon group represented by Ar ²² may have a substituent. The substituent is the same as the substituent that the aromatic ester skeleton may have.

In general formula (B-4), m represents an integer of 2 or 3, preferably 2.

Specific examples of compounds containing an aromatic ester skeleton and unsaturated bonds include the following compounds. Further, as specific examples of compounds containing an aromatic ester skeleton and an unsaturated bond, paragraphs 0068 to 0071 described in International Publication No. 2018/235424, and paragraphs 0113 to 0115 described in International Publication No. 2018/235425, Examples include compounds described in . However, the compounds containing an aromatic ester skeleton and an unsaturated bond are not limited to these specific examples. In the formula, s represents an integer of 0 or 1 or more, and r represents an integer of 1 to 10.

The compound containing an aromatic ester skeleton and an unsaturated bond may be synthesized by a known method. A compound containing an aromatic ester skeleton and an unsaturated bond can be synthesized, for example, by the method described in International Publication No. 2018/235424 or International Publication No. 2018/235425.

The weight average molecular weight of the compound containing an aromatic ester skeleton and an unsaturated bond is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, from the viewpoint of significantly obtaining the effects of the present invention. is 3000 or less, more preferably 2000 or less, even more preferably 1500 or less. The weight average molecular weight of the compound containing an aromatic ester skeleton and an unsaturated bond is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

The unsaturated bond equivalent of the compound containing an aromatic ester skeleton and an unsaturated bond is preferably 50 g/eq or more, more preferably 100 g/eq. Above, more preferably 150g/eq. and preferably 2000g/eq. Below, more preferably 1000g/eq. Below, more preferably 500g/eq. It is as follows. The unsaturated bond equivalent is the mass of component (B) containing 1 equivalent of unsaturated bond.

The ratio of the epoxy group equivalent of (A) epoxy resin to the active ester group equivalent of (B) active ester compound (active ester group equivalent of active ester compound/epoxy group equivalent of epoxy resin) is preferably 0. 0.4 or more, more preferably 0.5 or more, still more preferably 0.6 or more, preferably 1.8 or less, more preferably 1.5 or less, still more preferably 1.3 or less. Here, the "epoxy group equivalent of the epoxy resin" is the sum of all the values obtained by dividing the mass of nonvolatile components of the epoxy resin present in the resin composition by the epoxy equivalent. Moreover, the "active ester group equivalent of the active ester compound" is the sum of all the values obtained by dividing the mass of the nonvolatile components of the active ester compound present in the resin composition by the active ester group equivalent. By setting the amount ratio of component (B) to the epoxy resin within this range, the effects of the present invention can be significantly obtained.

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (B) is preferably 1% by mass or more, more preferably 3% by mass or more when the nonvolatile component in the resin composition is 100% by mass. , more preferably 5% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, or 15% by mass or less.

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (B) is preferably 30% by mass or more, more preferably 35% by mass or more, when the resin component in the resin composition is 100% by mass, More preferably, it is 45% by mass or more, and its upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less.

<(C) Hydrocarbon polymer containing a terpene skeleton>
The resin composition contains (C) a hydrocarbon polymer containing a terpene skeleton as the (C) component. The (C) hydrocarbon polymer containing a terpene skeleton as the component (C) does not include those corresponding to the components (A) to (B) described above. By including component (C) in the resin composition, it becomes possible to obtain a cured product with excellent dielectric loss tangent and crack resistance. Component (C) may be used alone or in combination of two or more.

The terpene skeleton usually refers to a molecular skeleton having a structure formed by polymerizing terpenes. Since terpenes generally have isoprene (C ₅ H ₈ ) as a structural unit, (C) the hydrocarbon polymer containing a terpene skeleton can be a hydrocarbon polymer containing isoprene as a structural unit, and preferably has a polar group. does not have The terpene is preferably a cyclic terpene, and therefore, component (C) preferably contains a cyclic terpene skeleton having a structure formed by polymerizing a cyclic terpene. A polar group refers to a polar atomic group, and includes, for example, a hydroxy group, an amino group, a carboxyl group, and the like. (C) Specific examples of hydrocarbon polymers containing a terpene skeleton include polyterpene resins that are homopolymers or copolymers of cyclic terpenes such as α-pinene, β-pinene, and dipentene (limonene); Examples include aromatic modified terpene resins that are copolymers of terpenes and aromatic monomers. The component (C) preferably contains either a polyterpene resin or an aromatic modified terpene resin, and more preferably a polyterpene resin. The polyterpene resin is preferably a homopolymer of a cyclic terpene such as α-pinene, β-pinene, or dipentene, and more preferably a homopolymer of dipentene.

As the aromatic monomer, an aromatic monomer that can be copolymerized with a cyclic terpene can be used. Examples of such aromatic monomers include styrene and the like. The aromatic monomer may have a substituent. The substituent is the same as the substituent that the alkyl group, alkenyl group, and aryl group represented by R ¹¹ in component (B) may have. The aromatic monomer preferably does not have a polar group from the viewpoint of significantly obtaining the effects of the present invention.

The softening point of component (C) is preferably 50°C or higher, more preferably 75°C or higher, still more preferably 100°C or higher, or 120°C or higher, from the viewpoint of significantly obtaining the effects of the present invention. The temperature is 200°C or lower, more preferably 180°C or lower, even more preferably 150°C or lower, or 130°C or lower. The softening point is a value measured based on JIS K7234.

Component (C) may be a commercially available product, or may be synthesized using a known method or a method analogous thereto. Examples of commercially available polyterpene resins include "PX1250" manufactured by Yasuhara Chemical Co., Ltd. Commercially available aromatic modified terpene resins include "TO125" manufactured by Yasuhara Chemical Co., Ltd., and the like.

The weight average molecular weight of component (C) is preferably 500 or more, more preferably 600 or more, even more preferably 700 or more, and preferably 10,000 or less, more preferably 6,000 or more, from the viewpoint of significantly obtaining the effects of the present invention. It is preferably 4000 or less.

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (C) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more when the nonvolatile components in the resin composition are 100% by mass. The content is 5% by mass or more, more preferably 1% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less.

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (C) is preferably 1% by mass or more, more preferably 2% by mass or more, when the resin component in the resin composition is 100% by mass. More preferably, it is 3% by mass or more, and its upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less.

The mass ratio of component (C) to epoxy resin (A) in the resin composition (component (A)/component (C)) is preferably 1 or more, more preferably 1 or more, from the viewpoint of significantly obtaining the effects of the present invention. It is 3 or more, more preferably 5 or more, preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less.

The mass ratio of component (C) to active ester compound (B) in the resin composition (component (B)/component (C)) is preferably 1 or more, more preferably 1 or more, from the viewpoint of significantly obtaining the effects of the present invention. is 3 or more, particularly preferably 5 or more, preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less.

<(D) Radical polymerizable compound>
The resin composition may contain (D) a radically polymerizable compound as an optional component. The (D) radically polymerizable compound as the (D) component does not include those corresponding to the above-mentioned components (A) to (C). Component (D) may be used alone or in combination of two or more.

(D) The radically polymerizable compound may be, for example, a compound having a radically polymerizable unsaturated group. The radically polymerizable unsaturated group is not particularly limited as long as it is radically polymerizable, but an ethylenically unsaturated group having a terminal or internal carbon-carbon double bond is preferable, and specifically, an allyl group , 3-cyclohexenyl group; unsaturated aliphatic group-containing aromatic groups such as p-vinylphenyl group, m-vinylphenyl group, styryl group; acryloyl group, methacryloyl group, maleoyl group (imide (maleimide group), α,β-unsaturated carbonyl group such as fumaroyl group, etc. (D) The radically polymerizable compound preferably has one or more radically polymerizable unsaturated groups, more preferably two or more.

(D) As the other radically polymerizable compound, a wide range of known radically polymerizable compounds can be used, and is not particularly limited. For example, a maleimide-based radically polymerizable compound having two or more maleimide groups compounds, vinyl phenyl radically polymerizable compounds having two or more vinylphenyl groups, (meth)acrylic radically polymerizable compounds having two or more acryloyl groups and/or methacryloyl groups, and the like.

The maleimide-based radically polymerizable compound is not particularly limited, and may be an aliphatic maleimide compound containing an aliphatic amine skeleton or an aromatic maleimide compound containing an aromatic amine skeleton. For example, "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compound containing dimer diamine structure) manufactured by Designer Molecules, Designer "BMI-6100" (aromatic maleimide compound) manufactured by Molecules, "MIR-5000-60T" and "MIR-3000-70MT" (biphenylaralkyl maleimide compound) manufactured by Nippon Kayaku Co., Ltd., K.I. Examples include "BMI-70" and "BMI-80" manufactured by Kasei Co., Ltd., "BMI-2300" and "BMI-TMH" manufactured by Daiwa Kasei Co., Ltd., and "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd. Furthermore, as the maleimide-based radically polymerizable compound, a maleimide resin (maleimide compound containing an indane ring skeleton) disclosed in Japan Institute of Invention and Innovation Publication No. 2020-500211 may be used.

The vinyl phenyl radically polymerizable compound is not particularly limited, but in one embodiment, it is preferably a thermoplastic resin having a vinyl phenyl group, a modified polyphenylene ether resin having a vinyl phenyl group, and a vinyl phenyl group. Resins selected from modified polystyrene resins having groups are more preferable, and commercially available products include, for example, "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.; "ODV-XET-X03", "ODV-XET-X04", "ODV-XET-X05" (divinylbenzene/styrene copolymer) manufactured by Iron Chemical & Materials Co., Ltd.; "A" manufactured by Shin-Nakamura Chemical Co., Ltd. -DOG” and “DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.

The (meth)acrylic radically polymerizable compound is not particularly limited, but in one embodiment, it is preferably a thermoplastic resin having an acryloyl group and/or a methacryloyl group; Resins selected from modified polyphenylene ether resins having the following and modified polystyrene resins having an acryloyl group and/or methacryloyl group are more preferable, and commercially available products include, for example, "SA9000" and "SA9000-111" manufactured by SABIC Innovative Plastics. (methacrylic modified polyphenylene ether resin).

The functional group equivalent of component (D) is preferably 100 g/eq. ～20000g/eq. , more preferably 200g/eq. ～15000g/eq. , more preferably 300g/eq. ～10000g/eq. It is. The functional group equivalent of component (D) is the mass of the other radically polymerizable compound (D) per equivalent of a radically polymerizable unsaturated group (i.e., maleimide group, vinylphenyl group, acryloyl group, methacryloyl group, etc.).

The weight average molecular weight (Mw) of component (D) is preferably 500 to 50,000, more preferably 700 to 20,000. (D) The number average molecular weight (Mn) of the other radically polymerizable compound is preferably 500 to 50,000, more preferably 700 to 20,000. The weight average molecular weight is a polystyrene equivalent weight average molecular weight measured using gel permeation chromatography (GPC).

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (D) is preferably 0.1% by mass or more, more preferably 0.2% by mass when the nonvolatile components in the resin composition are 100% by mass. It is at least 0.3% by mass, more preferably at least 0.3% by mass, preferably at most 3% by mass, more preferably at most 2% by mass, even more preferably at most 1.5% by mass.

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass when the resin component in the resin composition is 100% by mass. It is at least 1% by mass, more preferably at least 1% by mass, preferably at most 10% by mass, more preferably at most 8% by mass, even more preferably at most 5% by mass.

The mass ratio of component (C) to component (D) in the resin composition (component (D)/component (C)) is preferably 0.1 or more, more preferably 0.1 or more, from the viewpoint of significantly obtaining the effects of the present invention. is 0.2 or more, more preferably 0.3 or more, preferably 3 or less, more preferably 1 or less, particularly preferably 0.8 or less.

<(E) Inorganic filler>
The resin composition of the present invention may contain (E) an inorganic filler as an optional component. (E) The inorganic filler is contained in the resin composition in the form of particles.

(E) An inorganic compound is used as the material for the inorganic filler. (E) Materials for the inorganic filler include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. (E) One type of inorganic filler may be used alone, or two or more types may be used in combination in any ratio.

(E) 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, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.5 μm or less. It is 7 μm or less. (E) 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, even more preferably 0.1 μm or more, particularly preferably 0. .2 μm or more. (E) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, it can be measured by creating the particle size distribution of the inorganic filler on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and using the median diameter as the average particle size. The measurement sample can be obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them using ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction particle size distribution measuring device using a light source wavelength of blue and red, and the volume-based particle size distribution of the inorganic filler was measured using a flow cell method. The average particle size was calculated as the median diameter. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

(E) 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, even more preferably 1 m ² /g or more, Particularly preferably, it is 3 m ² /g or more. (E) 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, even more preferably 50 m ² /g or less, particularly preferably is 40 m ² /g or less. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multipoint method. You can get it by doing that.

(E) The inorganic filler may be a non-hollow inorganic filler with a porosity of 0% by volume (preferably non-hollow silica) or a hollow inorganic filler with a porosity of more than 0% by volume (preferably hollow silica). or may include both. The porosity of the hollow inorganic filler is preferably 70% by volume or less, more preferably 50% by volume or less, particularly preferably 30% by volume or less. (E) The lower limit of the porosity of the inorganic filler can be, for example, more than 0 volume %, 1 volume % or more, 5 volume % or more, 10 volume % or more. The porosity P (volume %) of an inorganic filler is the volume-based ratio of the total volume of one or more pores existing inside the particle to the volume of the entire particle based on the outer surface of the particle (the volume percentage of the pores existing inside the particle). For example, the measured actual density of the inorganic filler D _M (g/cm 3 ) and the theoretical material density D _T (g/cm ³ ) of the material forming the inorganic filler. /cm ³ ) using the following formula (1).

(E) The actual density of the inorganic filler can be measured using, for example, a true density measuring device. Examples of the true density measuring device include ULTRAPYCNOMETER 1000 manufactured by QUANTACHROME. For example, nitrogen is used as the measurement gas.

(E) Commercially available products can be used as the inorganic filler. (E) Commercially available inorganic fillers include, for example, "UFP-30" manufactured by Denka Kagaku Kogyo Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; and “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C”; “UFP-30” manufactured by Denka; “Silfill NSS-3N”, “Silfill NSS-4N”, “Silfill NSS-” manufactured by Tokuyama 5N”; “SC2500SQ”, “SO-C4”, “SO-C2”, “SO-C1” manufactured by Admatex; “DAW-03”, “FB-105FD” manufactured by Denka; JGC Catalysts & Chemicals Examples include "BA-S" manufactured by Kogyo.

(E) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate-based coupling agents. Coupling agents and the like can be mentioned. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Kagaku Kogyo, "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "SZ-31" manufactured by Shin-Etsu Chemical ( hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical, "KBM-4803" (long chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical, "KBM-" manufactured by Shin-Etsu Chemical 7103'' (3,3,3-trifluoropropyltrimethoxysilane).

The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% by mass to 5% by mass, and preferably 0.2% by mass to 3% by mass. It is more preferable that the surface is treated in an amount of 0.3% by mass to 2% by mass.

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

(E) The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler whose surface has been treated with a surface treatment agent, and the mixture is subjected to ultrasonic cleaning at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.

(E) From the viewpoint of significantly obtaining the effects of the present invention, the content of the inorganic filler is preferably 40% by mass or more, more preferably 50% by mass when the nonvolatile component in the resin composition is 100% by mass. The content is more preferably 60% by mass or more, or 70% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

The mass ratio of component (C) to inorganic filler (E) in the resin composition (component (E)/component (C)) is preferably 10 or more, more preferably 20 or more, even more preferably 30 or more, 40 or more, or 50 or more, preferably 80 or less, more preferably 70 or less, still more preferably 60 or less.

<(F) Curing agent>
The resin composition may contain (F) a curing agent (excluding those corresponding to component (B)) as an optional component. The (F) curing agent as the (F) component does not include those corresponding to the above-mentioned components (A) to (E). Component (F) may be used alone or in combination of two or more.

Examples of the component (F) include phenolic curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, and carbodiimide curing agents. Among them, from the viewpoint of significantly obtaining the effects of the present invention, component (F) is preferably any one or more of a phenol curing agent, a naphthol curing agent, a cyanate ester curing agent, and a carbodiimide curing agent. Preferably, the curing agent is either a phenol curing agent or a naphthol curing agent, and more preferably a phenol curing agent is included.

As the phenol curing agent and the naphthol curing agent, from the viewpoint of heat resistance and water resistance, a phenol curing agent having a novolak structure or a naphthol curing agent having a novolak structure is preferable. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable.

Specific examples of phenolic curing agents and naphthol curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA3018-50P", and "EXB-9500" manufactured by DIC Corporation.

Specific examples of benzoxazine curing agents include "HFB2006M" manufactured by Showa Kobunshi Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Kasei Kogyo Co., Ltd.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4 '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol Examples include polyfunctional cyanate resins derived from novolacs and cresol novolaks, and prepolymers in which these cyanate resins are partially triazinized. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolak type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazinized to form a trimer), and the like.

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

When containing a curing agent as component (F), the quantitative ratio of component (A) to component (B) and component (F) is [total number of epoxy groups in component (A)]:[component (B)] and the total number of active groups of component (F)] is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.05 to 1:3, and 1:0.1 to 1. :2 is more preferable. Here, "the number of epoxy groups in component (A)" is the sum of all the values obtained by dividing the mass of nonvolatile components of component (A) present in the resin composition by the epoxy equivalent. In addition, "the number of active groups of components (B) and (F)" refers to all the values obtained by dividing the mass of the nonvolatile components of components (B) and (F) present in the resin composition by the active group equivalent. This is the total value. By controlling the ratio of component (B) and component (F) to component (A) within this range, the effects of the present invention can be significantly obtained.

When containing a curing agent as component (F), the quantitative ratio of component (A) to all (F) components is [total number of epoxy groups in component (A)]:[active groups in component (F)] The ratio of the total number of preferable. Here, "the number of active groups of component (F)" is the sum of all the values obtained by dividing the mass of nonvolatile components of component (F) present in the resin composition by the active group equivalent. By controlling the ratio of component (A) to component (F) within this range, the effects of the present invention can be significantly obtained.

From the viewpoint of significantly obtaining the desired effects of the present invention, the content of component (F) is preferably 0.1% by mass or more, more preferably The content is 0.3% by mass or more, more preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1.5% by mass or less.

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (F) is preferably 2% by mass or more, more preferably 3% by mass or more, when the resin component in the resin composition is 100% by mass. More preferably, it is 3.5% by mass or more, preferably 8% by mass or less, more preferably 6% by mass or less, and even more preferably 5% by mass or less.

<(G) Curing accelerator>
The resin composition may contain (G) a curing accelerator as an optional component. The curing accelerator (G) as component (G) does not include any of the components (A) to (F) described above. (G) The curing accelerator has a function as a curing catalyst that promotes curing of the (A) epoxy resin. (G) The curing accelerator may be used alone or in any combination of two or more types.

(G) Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. . Among these, curing accelerators selected from amine-based curing accelerators and metal-based curing accelerators are preferred, and amine-based curing accelerators are particularly preferred.

Examples of the phosphorus curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, and tetrabutylphosphonium hydro Aliphatic phosphonium salts such as denhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl Phosphonium tetraphenylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 - Aromatic phosphonium salts such as methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl- Aliphatic phosphine such as 2-butenyl)phosphine, tricyclohexylphosphine; 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-isopropylphenyl)phosphine, tris(4-butyl) phenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris( 3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4- methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis( Examples include aromatic phosphines such as diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether. It will be done.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl) )-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4- methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4- methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3- [4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea] etc.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide and the like.

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

As the imidazole curing accelerator, commercially available products may be used, such as "1B2PZ", "2MZA-PW", "2PHZ-PW", "C11Z-A" manufactured by Shikoku Chemical Co., Ltd., and "C11Z-A" manufactured by Mitsubishi Chemical Corporation. Examples include "P200-H50".

Examples of the metal hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include organic zinc complexes such as , organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

As the amine curing accelerator, commercially available products may be used, such as "MY-25" manufactured by Ajinomoto Fine Techno.

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (G) is preferably 0.01% by mass or more, more preferably 0.05% by mass when the nonvolatile components in the resin composition are 100% by mass. It is at least 0.1% by mass, more preferably at least 0.1% by mass, preferably at most 1.5% by mass, more preferably at most 1% by mass, even more preferably at most 0.5% by mass.

From the viewpoint of significantly obtaining the effects of the present invention, the content of component (G) is preferably 0.1% by mass or more, more preferably 0.3% by mass when the resin component in the resin composition is 100% by mass. It is at least 0.5% by mass, more preferably at least 0.5% by mass, preferably at most 5% by mass, more preferably at most 3% by mass, even more preferably at most 1.5% by mass.

<(H) Other additives>
The resin composition of the present invention may further contain arbitrary additives as nonvolatile components. Examples of such additives include thermoplastic resins; radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, and Thermoplastic resins such as ether sulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; Coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; silicone leveling agents, acrylic polymer leveling agents, etc. Leveling agents; Thickeners such as bentone and montmorillonite; Antifoaming agents such as silicone antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, and vinyl resin antifoaming agents; Benzotriazole ultraviolet absorbers, etc. UV absorbers; adhesion improvers such as urea silane; adhesion agents such as triazole adhesion agents, tetrazole adhesion agents, and triazine adhesion agents; hindered phenol antioxidants, etc. Antioxidants; Fluorescent brighteners such as stilbene derivatives; Surfactants such as fluorosurfactants and silicone surfactants; Phosphorus flame retardants (e.g. phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus) ), nitrogen-based flame retardants (e.g. melamine sulfate), halogen-based flame retardants, inorganic flame retardants (e.g. antimony trioxide); phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants , silicone dispersants, anionic dispersants, cationic dispersants, etc.; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers stabilizers such as carboxylic acid anhydride stabilizers and the like. (H) Other additives may be used alone or in combination of two or more in any ratio. (H) The content of other additives can be determined as appropriate by those skilled in the art.

<(I) Solvent>
In addition to the above-mentioned nonvolatile components, the resin composition may further contain an arbitrary solvent as a volatile component. As the solvent (I), any known solvent can be used as appropriate, and the type thereof is not particularly limited, and organic solvents are preferred. (I) Solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone. Ester solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole; Alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc. ; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, 2-hydroxyisobutyric acid Ester alcohol solvents such as methyl; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide, Amide solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone; Sulfoxide solvents such as dimethyl sulfoxide; Nitrile solvents such as acetonitrile and propionitrile; Hexane, cyclopentane, cyclohexane, methylcyclohexane, etc. Aliphatic hydrocarbon solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The solvent (I) may be used alone or in combination of two or more in any ratio.

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

<Method for manufacturing resin composition>
The resin composition of the present invention can be prepared by, for example, adding components (A) to (C) and optionally components (D) to (I) in any preparation container in any order and/or in part or all at the same time. It can be manufactured by adding and mixing. Further, in the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or throughout. In addition, during or after the addition and mixing process, the resin composition may be stirred or shaken using a stirring device or shaking device such as a mixer to uniformly disperse the resin composition. Moreover, simultaneously with stirring or shaking, defoaming may be performed under low pressure conditions such as under vacuum.

<Characteristics of resin composition>
By using a resin composition containing a combination of components (A) to (C), a cured product with a low dielectric loss tangent (Df) and excellent crack resistance can be obtained. Moreover, the resin composition can also provide a cured product having a high glass transition temperature (Tg) and a low dielectric constant (Dk).

A cured product obtained by curing the resin composition at 190° C. for 90 minutes exhibits a property of having a low dielectric loss tangent (Df) at room temperature. Therefore, an insulating layer with excellent dielectric loss tangent is obtained. The dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. is preferably 0.005 or less, 0.004 or less, more preferably 0.003 or less. The lower limit is not particularly limited, but may be 0.00001 or more. The dielectric loss tangent at 23° C. can be measured by the method described in Examples below.

A cured product obtained by curing a resin composition at 190° C. for 90 minutes usually exhibits a low dielectric loss tangent (Df) at high temperatures. Therefore, an insulating layer with excellent dielectric loss tangent is obtained. The dielectric loss tangent (Df) of the cured product when measured at 5.8 GHz and 90° C. is preferably 0.0032 or less, 0.003 or less, and more preferably 0.0029 or less. The lower limit is not particularly limited, but may be 0.00001 or more. The dielectric loss tangent at 90° C. can be measured by the method described in Examples below.

A cured product obtained by curing the resin composition at 130° C. for 30 minutes and then at 170° C. for 30 minutes exhibits excellent crack resistance. Therefore, an insulating layer with excellent crack resistance is provided. Specifically, a layer made of a cured resin composition is formed on a core material having 100 copper pad portions. The layer made of the cured product is subjected to a roughening treatment, and 100 copper pad portions after the roughening treatment are observed to confirm the presence or absence of cracks. In this case, the number of cracks is preferably 10 or less. Evaluation of crack resistance can be measured by the method described in Examples described later.

A cured product obtained by curing a resin composition at 190° C. for 90 minutes usually exhibits a characteristic of having a low dielectric constant (Dk) at room temperature. Therefore, an insulating layer with excellent dielectric constant is obtained. The 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, more preferably 4.0 or less, and still more preferably 3.5 or less. The lower limit is not particularly limited, but may be 0.1 or more. The dielectric constant at 23° C. can be measured by the method described in Examples below.

A cured product obtained by curing a resin composition at 190° C. for 90 minutes usually exhibits a property of having a low dielectric constant (Dk) at high temperatures. Therefore, an insulating layer with excellent dielectric constant is obtained. The 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, more preferably 4.0 or less, and still more preferably 3.5 or less. The lower limit is not particularly limited, but may be 0.1 or more. The dielectric constant at 90° C. can be measured by the method described in Examples below.

A cured product obtained by curing a resin composition at 190° C. for 90 minutes usually exhibits a high glass transition temperature (Tg). The glass transition temperature (Tg) of the cured product is preferably 100°C or higher, more preferably 110°C or higher, and still more preferably 120°C or higher. The upper limit is not particularly limited, but may be 500°C or less. The glass transition temperature can be measured by DSC (differential scanning calorimetry) at a heating rate of 10° C./min.

<Applications of resin composition>
The resin composition of the present invention can be suitably used as a resin composition for insulation purposes, particularly as a resin composition for forming an insulation layer. Specifically, a resin composition for forming an insulating layer (including a rewiring layer) formed on an insulating layer (a resin for forming an insulating layer for forming a conductor layer) is used. composition). Further, in a printed wiring board to be described later, it can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for forming an insulating layer of a printed wiring board). 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, die bonding materials, semiconductor encapsulating materials, hole-filling resins, component embedding resins, etc. that require resin compositions. Can be used in a wide range of applications.

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be used as a rewiring formation layer as an insulating layer for forming a rewiring layer. It can also be suitably used as a resin composition (resin composition for forming a rewiring formation layer) and a resin composition for sealing a semiconductor chip (resin composition for semiconductor chip sealing). When the semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer.
(1) The step of laminating a temporary fixing film on the base material,
(2) Temporarily fixing the semiconductor chip on the temporary fixing film,
(3) forming a sealing layer on the semiconductor chip;
(4) Peeling the base material and temporary fixing film from the semiconductor chip,
(5) Forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled; and (6) Forming a rewiring layer as a conductive layer on the rewiring layer. Forming process

Moreover, since the resin composition of the present invention provides an insulating layer with good component embeddability, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

[Sheet-like laminated material]
Although the resin composition of the present invention can be used by applying it in the form of a varnish, it is generally preferable for industrial use to use it in the form of a sheet-like laminate material containing the resin composition.

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

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

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

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

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polyesters such as polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . The support with a release layer may be a commercially available product, such as "SK-1" manufactured by Lintec Corporation, which is a PET film having a release layer containing an alkyd resin mold release agent as a main component. Examples include "AL-5", "AL-7", "Lumirror T60" manufactured by Toray Industries, "Purex" manufactured by Teijin, and "Unipeel" manufactured by Unitika.

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

In one embodiment, the resin sheet may further include an arbitrary layer as necessary. Examples of such an arbitrary layer include a protective film similar to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). It will be done. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

The resin sheet can be made, for example, by using a liquid resin composition as it is, or by preparing a resin varnish by dissolving the resin composition in an organic solvent, applying it onto a support using a die coater, and then drying it. It can be manufactured by forming a resin composition layer.

Examples of the organic solvent include those similar to the organic solvents 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 may be performed by a known method such as heating or blowing hot air. Although drying conditions are not particularly limited, drying is performed so that the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies 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 organic solvent, the temperature is 50°C to 150°C for 3 minutes to 10 minutes. By drying for minutes, a resin composition layer can be formed.

The resin sheet can be stored by winding it up into a roll. 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-like fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of making the printed wiring board thinner, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10 μm or more.

Prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

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

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

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer made of a cured product obtained by curing the resin composition of the present invention.

A 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) Step of laminating the resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) Forming an insulating layer by curing (e.g., thermosetting) the resin composition layer. process of doing

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

The inner layer substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member for hot-pressing the resin sheet to the inner layer substrate (hereinafter also referred to as "heat-pressing member") include a heated metal plate (SUS mirror plate, etc.), a metal roll (SUS roll), and the like. Note that, instead of pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

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

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressure laminator.

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

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

In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions commonly employed for forming an insulating layer of a printed wiring board may be used.

The thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., but 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. ℃～210℃. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, even more preferably 15 minutes to 100 minutes.

Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured for 5 minutes or more at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C. Preheating may be performed preferably for 5 minutes to 150 minutes, more preferably for 15 minutes to 120 minutes, even more preferably for 15 minutes to 100 minutes.

When manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be performed according to various methods known to those skilled in the art that are used in the manufacture of printed wiring boards. Note that 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 during step (IV). IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductive 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 manufactured using the prepreg described above. The manufacturing method is basically the same as when using a resin sheet.

Step (III) is a step of drilling a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole may be determined as appropriate depending on the design of the printed wiring board.

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

The swelling liquid used in the roughening treatment is not particularly limited, but includes alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, and more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. Swelling treatment with a swelling liquid is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling liquid at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, but includes, for example, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline 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 minutes to 30 minutes. Further, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigance P" manufactured by Atotech Japan.

Further, as the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferable, and a commercially available product includes, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.

The treatment with the neutralizing liquid can be carried out by immersing the treated surface, which has been roughened with an oxidizing agent, in the neutralizing liquid at 30° C. to 80° C. for 5 minutes to 30 minutes. From the viewpoint of workability, it is preferable to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 minutes to 20 minutes.

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

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

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of an insulating layer using a conventionally known technique such as a semi-additive method or a fully additive method. It is preferable to form by a method. An example of forming a conductor layer by a semi-additive method will be shown below.

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

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

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

[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 (eg, computers, mobile phones, digital cameras, televisions, etc.), vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.), and the like.

Hereinafter, the present invention will be specifically explained with reference to Examples. The present invention is not limited to these examples. In addition, in the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In the case where there is no particular specification of temperature and pressure, the temperature and pressure conditions are room temperature (23° C.) and atmospheric pressure (1 atm).

<Synthesis Example 1: Synthesis of active ester compound (B-1)>
Into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 320 g (2.0 mol) of 2,7-dihydroxynaphthalene, 184 g (1.7 mol) of benzyl alcohol, and para-toluenesulfonic acid. 5.0 g of monohydrate was charged and stirred at room temperature while blowing nitrogen. Thereafter, the temperature was raised to 150° C., and the mixture was stirred for 4 hours while distilling the generated water out of the system. After the reaction was completed, 900 g of methyl isobutyl ketone and 5.4 g of a 20% aqueous sodium hydroxide solution were added to neutralize, and then the aqueous layer was removed by liquid separation, washed three times with 280 g of water, and methyl isobutyl ketone was removed under reduced pressure. The residue was removed to obtain 460 g of benzyl-modified naphthalene compound (A-1). The obtained benzyl-modified naphthalene compound (A-1) was a black solid, and the hydroxyl group equivalent was 180 g/equivalent.

203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0 mol) and 1400 g of toluene were charged into a flask equipped with a thermometer, dropping funnel, condenser tube, fractionator tube, and stirrer, and the pressure inside the system was reduced. The mixture was replaced with nitrogen and dissolved. Next, 113.9 g (0.67 mol) of ortho-phenylphenol and 240 g (mol number of phenolic hydroxyl group: 1.33 mol) of benzyl-modified naphthalene compound (A-1) were charged, and the system was replaced with nitrogen under reduced pressure to dissolve them. Ta. Thereafter, 0.70 g of tetrabutylammonium bromide was dissolved, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the system to 60° C. or lower while purging with nitrogen gas. Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand still for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for 15 minutes, and the mixture was allowed to stand still for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by dehydration using a decanter to obtain an active ester compound (B-1) in the form of a toluene solution with a nonvolatile content of 61.5% by mass. The active ester equivalent of the obtained active ester compound (B-1) was 238 g/eq. Met.

<Synthesis Example 2: Synthesis of active ester compound (B-2)>
In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 165 g of polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/eq., softening point 85°C) and orthoallylphenol were placed. 134 g (1.0 mol) and 1200 g of toluene were charged, and the inside of the system was purged with nitrogen under reduced pressure. Next, 203 g (1.0 mol) of isophthalic acid chloride was charged, and the inside of the system was purged with nitrogen under reduced pressure. 0.6 g of tetrabutylammonium bromide was added, and 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the inside of the system to 60° C. or lower while performing nitrogen gas purge treatment. After the dropwise addition was completed, the mixture was stirred for 1.0 hour. After the reaction was completed, the aqueous layer was removed by static separation. Water was further added to the obtained toluene layer, stirred for 15 minutes, and the aqueous layer was removed by static separation. This operation was repeated until the pH of the aqueous layer became 7. Then, by heating and drying to adjust the nonvolatile content to 70% by mass, an active ester compound (B-2) represented by the following formula was obtained. In the formula, s is each independently an integer of 0 or 1 or more, and the average value of r calculated from the preparation ratio is 1. Moreover, the broken line in the formula is a structure obtained by reacting isophthalic acid chloride, a polyaddition reaction resin of phenol, and/or orthoallylphenol. When the ester group equivalent of the obtained active ester resin was calculated from the charging ratio, it was 214 g/eq. Met.

・ＭＩＲ－５０００－６０Ｔ：不揮発分６０質量％のトルエン溶液、日本化薬社製
・ＭＩＲ－３０００－７０Ｔ：
・ＢＭＩ－６８９：デジグナーモレキュールズ社製
・Ａ－ＤＯＧ：日本化薬社製
・ＯＰＥ－２Ｓｔ－１２００：不揮発分６５質量％のトルエン溶液、三菱瓦斯化学社製
・ＳＬＫ－２６００：不揮発分５０質量％のアニソール溶液、信越化学工業社製
（Ｅ）成分：
・ＳＯ－Ｃ２：アミン系アルコキシシラン化合物（信越化学工業社製「ＫＢＭ５７３」）で表面処理された球形シリカ、平均粒径０．５μｍ、比表面積５．８ｍ^２／ｇ、アドマテックス社製
・ＢＡ－Ｓ：アミン系アルコキシシラン化合物（信越化学工業社製「ＫＢＭ５７３」）で表面処理された中空部分を有する球形シリカ、平均粒径２～３μｍ、日揮触媒化成社製
（Ｆ）成分：
・ＬＡ－３０１８－５０Ｐ：官能基当量１５１ｇ／ｅｑ．、不揮発分５０質量％の１－メトキシ－２－プロパノール溶液、ＤＩＣ社製
（Ｇ）成分：
・１Ｂ２ＰＺ：四国化成工業社製 <Manufacture of resin varnish>
Each component was weighed in parts by mass as shown in the table below, further mixed with 10 parts of MEK and 10 parts of cyclohexanone, and uniformly dispersed using a high-speed rotating mixer to obtain a resin varnish. The details of each component listed in the table are as follows.
(A) Component:
・HP-4032-SS: Functional group equivalent 144g/eq. , manufactured by DIC Corporation, ESN-475V: functional group equivalent 330 g/eq. , manufactured by Nippon Steel Chemical & Material Co., Ltd., NC-3100: Functional group equivalent 258 g/eq. , manufactured by Nippon Kayaku Co., Ltd. Component (B):
・HPC-8150-62T: Functional group equivalent weight 223g/eq. , toluene solution with non-volatile content of 62% by mass, manufactured by DIC, HPC-8000-65T: functional group equivalent 229 g/eq. , toluene solution with non-volatile content of 65% by mass, manufactured by DIC・Active ester compound (B-1): Synthesized in Synthesis Example 1・Active ester compound (B-2): Synthesized in Synthesis Example 2・PC1300- 02: Functional group equivalent 199g/eq. , methyl amyl ketone solution with nonvolatile content of 65% by mass, manufactured by Air Water Performance Chemical Co., Ltd. Component (C):
・PX1250: Terpene resin with a softening point of 125°C, manufactured by Yasuhara Chemical Company ・TO125: Aromatically modified terpene resin with a softening point of 125°C, manufactured by Yasuhara Chemical Company (D) Component:
・Maleimide A: Compound represented by the following formula (1) synthesized by the method described in Synthesis Example 1 of Japan Institute of Invention and Innovation Publication No. 2020-500211 (Mw/Mn=1.81, t'' = 1.47 (mainly 1, 2 or 3)), MEK solution with 62% by mass of non-volatile components

・MIR-5000-60T: Toluene solution with nonvolatile content of 60% by mass, manufactured by Nippon Kayaku Co., Ltd. ・MIR-3000-70T:
・BMI-689: Manufactured by Designer Molecules ・A-DOG: Manufactured by Nippon Kayaku Co., Ltd. ・OPE-2St-1200: Toluene solution with non-volatile content of 65% by mass, manufactured by Mitsubishi Gas Chemical Co., Ltd. ・SLK-2600: Non-volatile content 50% by mass anisole solution, manufactured by Shin-Etsu Chemical Co., Ltd. (E) component:
・SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 μm, specific surface area 5.8 m ² /g, manufactured by Admatex, BA -S: Spherical silica with a hollow portion surface-treated with an amine alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 2 to 3 μm, manufactured by JGC Catalysts & Chemicals Co., Ltd. (F) component:
・LA-3018-50P: Functional group equivalent weight 151 g/eq. , 1-methoxy-2-propanol solution with non-volatile content of 50% by mass, component (G) manufactured by DIC:
・1B2PZ: Manufactured by Shikoku Kasei Kogyo Co., Ltd.

＊表中、（Ｃ）成分の含有量は、樹脂成分を１００質量％とした場合の含有量（質量％）を表し、（Ｅ）成分の含有量は、樹脂組成物中の不揮発成分を１００質量％とした場合の含有量（質量％）を表す。

*In the table, the content of component (C) represents the content (mass%) when the resin component is 100% by mass, and the content of component (E) represents the content (mass%) when the nonvolatile component in the resin composition is 100%. Represents the content (mass%) when expressed as mass%.

<Measurement of permittivity and dielectric loss tangent>
(1) Production of resin sheet A with a resin composition layer having a thickness of 40 μm A polyethylene terephthalate film (“AL5” manufactured by Lintec Corporation, thickness 38 μm) provided with a release layer was prepared as a support. The resin varnishes obtained in Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80° C. to 100° C. (average 90° C.) for 4 minutes to obtain a resin sheet A including a support and a resin composition layer.

(2) Preparation of cured product Resin sheet A obtained in Examples and Comparative Examples was cured in an oven at 190°C for 90 minutes. By peeling off the support from the resin sheet A taken out of the oven, a cured product of the resin composition layer was obtained.

(3) Measurement of dielectric constant and dielectric loss tangent Each cured product for evaluation was cut into pieces 80 mm long and 2 mm wide, and measured at a frequency of 5.8 GHz using the cavity resonance perturbation method using HP8362B manufactured by Agilent Technologies. The dielectric constant and dielectric loss tangent values (Dk value and Df value) were measured at measurement temperatures of 23°C and 90°C. Measurements were performed using two test pieces, and the average thereof was calculated.

(4) Measurement of Glass Transition Temperature (Tg) Each cured product for evaluation was cut out to a length of 20 mm and a width of 6 mm to prepare evaluation samples. The glass transition temperature (Tg) of this evaluation sample was measured using a Rigaku TMA device from 25°C to 250°C at a heating rate of 5°C/min. Measurements were taken twice on the same specimen and the second value was recorded.

<Production 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) provided with a release layer was prepared. On the release layer of this support, the resin varnishes obtained in Examples and Comparative Examples were uniformly applied so that the thickness of the resin composition layer after drying was 25 μm, and the coating was applied at 70°C to 80°C (average 75° C.) for 2.5 minutes to obtain a resin sheet B including a support and a resin composition layer.

<Evaluation of crack resistance after desmear treatment>
A core material (manufactured by Hitachi Chemical Co., Ltd.) in which circular copper pads (copper thickness 35 μm) with a diameter of 350 μm are formed in a lattice shape at 400 μm intervals on the resin sheet B with a thickness of 25 μm produced above so that the residual copper ratio is 60%. A batch vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials) was used on both sides of "E705GR" (thickness 400 μm) so that the resin composition layer was bonded to the inner layer substrate. Then, it was laminated on both sides of the inner layer substrate. This lamination was carried out by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then press-bonding at a temperature of 100° C. and a pressure of 0.74 MPa for 30 seconds. This was placed in an oven at 130°C and heated for 30 minutes, then transferred to an oven at 170°C and heated for 30 minutes. Further, the support layer was peeled off, and the obtained circuit board was immersed in a swelling liquid, Swelling Dip Securigant P manufactured by Atotech Japan, at 60° C. for 10 minutes. Next, it was immersed in Concentrate Compact P (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L) manufactured by Atotech Japan Co., Ltd., which is a roughening liquid, at 80° C. for 30 minutes. Finally, it was immersed in a neutralizing solution, Reduction Solution Securigant P manufactured by Atotech Japan, at 40° C. for 5 minutes. 100 copper pads of the circuit board after the roughening treatment were observed to check for cracks in the resin composition layer, and evaluated based on the following criteria.
〇: 10 or less cracks ×: More than 10 cracks

Claims (13)

(A) epoxy resin,
A resin composition containing (B) an active ester compound and (C) a hydrocarbon polymer having a terpene skeleton. The resin composition according to claim 1, wherein component (C) contains either a polyterpene resin or an aromatic modified terpene resin. The resin composition according to claim 1, wherein component (C) does not have a polar group. The resin composition according to claim 1, wherein the softening point of component (C) is 50°C or higher. The resin composition according to claim 1, wherein the content of component (C) is 1% by mass or more when the resin component is 100% by mass. The resin composition according to claim 1, further comprising (D) a radically polymerizable compound. The resin composition according to claim 1, further comprising (E) an inorganic filler. The resin composition according to claim 7, wherein the content of the component (E) is 40% by mass or more when the nonvolatile components in the resin composition are 100% by mass. The resin composition according to claim 1, further comprising (F) a curing agent. A sheet-like laminate material containing the resin composition according to any one of claims 1 to 9. A resin sheet comprising a support and a resin composition layer formed from the resin composition according to any one of claims 1 to 9 provided on the support. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 9. A semiconductor device comprising the printed wiring board according to claim 12.