KR20230159296A - Resin composition - Google Patents

Abstract

[Problem] To provide a resin composition that can produce a cured product with a low dielectric loss tangent and excellent crack resistance.
[Solution] A resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) a hydrocarbon polymer having a terpene skeleton.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. It also relates to sheet-like laminated materials, resin sheets, printed wiring boards, and semiconductor devices obtained by using the resin composition.

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

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

[Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2019-203122

Recently, insulating layers with low dielectric loss tangent and excellent crack resistance are required.

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 obtained by using the resin composition, a resin sheet, a printed wiring board, and a semiconductor device. .

In order to achieve the object of the present invention, the present inventors have conducted extensive studies and found that, as components of the resin composition, an epoxy resin, an active ester-based curing agent, and a hydrocarbon polymer containing a terpene skeleton are combined and contained in the resin composition, thereby reducing the dielectric loss tangent. By discovering that a cured product with low crack resistance and excellent crack resistance could be obtained, the present invention was completed.

That is, the present invention includes the following contents.

[1] (A) epoxy resin,

(B) an active ester compound, and

(C) A resin composition containing a hydrocarbon polymer having a terpene skeleton.

[2] The resin composition according to [1], wherein the 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 comprising (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, assuming that the non-volatile component in the resin composition is 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 laminated material containing the resin composition according to any one of [1] to [9].

[11] A resin sheet having a support and a resin composition layer formed of the resin composition according to any one of [1] to [9] provided on the support.

[12] A printed wiring board provided with an insulating layer made of a cured product of the resin composition according to any one of [1] to [9].

[13] A semiconductor device including the printed wiring board according to [12].

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

Hereinafter, the present invention will be described 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 any modification without departing from the scope of the claims and equivalents thereof. Meanwhile, in the present invention, unless otherwise specified, the content of each component in the resin composition is a value assuming that the non-volatile component in the resin composition is 100% by mass, and the non-volatile component is the amount excluding the solvent in the resin composition. It refers to all non-volatile components. In addition, in this specification, “dielectric constant” refers to “relative dielectric constant” 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 with a low dielectric loss tangent (Df) and excellent crack resistance can be obtained. In addition, the resin composition can also produce a cured product with a high glass transition temperature (Tg) and a low relative dielectric constant (Dk).

Conventionally, it has been known that hydrocarbon polymers containing a (C) terpene skeleton are used as adhesives. However, the present inventors have discovered that by including (C) a hydrocarbon polymer containing a terpene skeleton in the resin composition, it is possible to obtain a cured product excellent in dielectric loss factor and crack resistance, and has excellent dielectric loss factor and crack resistance, especially under high temperatures. discovered that (C) As far as the present inventor knows, 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 has not been proposed at all in the past. You could say it wasn't.

The resin composition of the present invention may further contain arbitrary components in combination with components (A) to (C). Optional components include, for example, (D) a radically polymerizable compound, (E) an inorganic filler, (F) a curing agent, (G) a curing accelerator, (H) other additives, and (I) a solvent. Hereinafter, each component included in the resin composition will be described in detail.

<(A) Epoxy resin>

The resin composition contains (A) epoxy resin as (A) component. An epoxy resin is a curable resin having an epoxy group.

(A) As the epoxy resin, 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, tris. Phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin. , glycidyl ester type epoxy resin, cresol novolak 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, phenolphthalimine. Dean type epoxy resin, phenolphthalein type epoxy resin, etc. are mentioned. (A) Epoxy resins may be used individually or in combination of two or more types.

The resin composition preferably contains (A) an epoxy resin having two or more epoxy groups in one molecule. (A) With respect to 100% by mass of the non-volatile component of the epoxy resin, the ratio 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, especially 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”). There is. The resin composition may contain only a liquid epoxy resin as an epoxy resin, may contain only a solid epoxy resin, or may contain 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, and phenol novolak type epoxy resin. , alicyclic epoxy resins having an ester skeleton, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure are preferable, and naphthalene-type epoxy resins are more preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; “828US”, “828EL”, “jER828EL”, “825”, “Epicoat 828EL” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “jER807”, “1750” (bisphenol F type) manufactured by Mitsubishi Chemical Corporation epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “630”, “630LSD”, and “604” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “ED-523T” manufactured by ADEKA (glycirol type epoxy resin); “EP-3950L” and “EP-3980S” (glycidylamine type epoxy resin) manufactured by ADEKA Corporation; “EP-4088S” manufactured by ADEKA (dicyclopentadiene type epoxy resin); “ZX1059” manufactured by Nittetsu Chemical & Materials Chemicals Co., Ltd. (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin); “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Corporation; “Celoxide 2021P” manufactured by Daicel Corporation (alicyclic epoxy resin with an ester skeleton); “PB-3600” manufactured by Daicel Corporation, “JP-100” and “JP-200” manufactured by Nippon Soda Corporation (epoxy resin with a butadiene structure); “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nittetsu Chemical & Material Chemicals, Inc. are included. These may be used individually or in combination of two or more types.

As a solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups per molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups per molecule is more preferable.

As solid epoxy resins, xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol novolac-type epoxy resin, cresol novolak-type epoxy resin, dicyclopentadiene-type epoxy resin, and trisphenol-type epoxy resin. , naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol Phthalimidine type epoxy resin and phenolphthalein type epoxy resin are preferable, and naphthalene type epoxy resin and biphenyl type epoxy resin are more preferable.

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

(A) When using a combination of a solid epoxy resin and a liquid epoxy resin as an epoxy resin, their mass ratio (solid epoxy resin:liquid epoxy resin) is preferably 1:0.01 to 1:50, more preferably 1. :0.05 to 1:10, particularly preferably 1:0.1 to 1:3. By keeping the ratio of the liquid epoxy resin and the solid epoxy resin within this range, 1) appropriate adhesion can be obtained when used in the form of a resin sheet, 2) sufficient flexibility can be obtained when used in the form of a resin sheet, Handling is improved, and 3) a cured product with sufficient breaking strength can be obtained.

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

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

(A) The content of the epoxy resin is preferably 1% by mass or more, more preferably 100% by mass of the non-volatile component in the resin composition, from the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability. 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 mass% or less, more preferably 20 mass% or less, and even more preferably 15 mass% or less from the viewpoint of significantly obtaining the desired effect of the present invention.

(A) The content of the epoxy resin is preferably 10% by mass or more, more preferably 20% by mass, when the resin component in the resin composition is 100% by mass, from the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability. It is more than 30% by mass, more preferably 30% by mass or more, and the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

In the present invention, the "resin component" referring to a resin composition refers to a component excluding the inorganic filler (E) described later among the non-volatile components constituting the resin composition.

<(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 this (B) component does not include anything corresponding to the above-mentioned (A) component. (B) The active ester compound may be used individually or in combination of two or more types.

(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, the component (B) preferably contains either a compound having a structure represented by formula (B-1) or a compound containing an aromatic ester skeleton and an unsaturated bond.

(Compound having a structure represented by formula (B-1))

As one embodiment of the component (B), it is preferable that it is a compound having a structure represented by formula (B-1).

In the formula, R ¹ , R ² and R ³ are (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 represent hydrogen. represents an atom or a substituent, or (2) R ¹ and R ² combine as one to form an aromatic carbocycle which may have a substituent, and R ³ represents a hydrogen atom or a substituent, or (3) R ² and R ³ combine to form an aromatic carbocycle which may have a substituent, and R ¹ represents a hydrogen atom, 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 represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent; A represents -CH ₂ -, -CH(CH ₃ )-, -CO-, or -O-; * indicates a binding site.

When R ¹ does not form an aromatic carbocyclic ring, it 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 carbocyclic ring, it is preferably a hydrogen atom, a methyl group, or R ¹¹ -A-; More preferably, it is a hydrogen atom or R ¹¹ -A-.

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

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

The alkyl group, alkenyl group, and aryl group represented by R ¹¹ may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group (an alkyl group substituted with an aryl group), an alkyl-aryl-alkyl group (an alkyl group substituted with an aryl group substituted with an alkyl group), and alkenyl-aryl. -Alkyl group (alkyl group substituted with aryl group substituted with alkenyl group), aryl-aryl-alkyl group (alkyl group substituted with aryl group substituted with 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-oxy-carbonyl group, alkenyl-oxy-carbonyl group, aryl-oxy-carbonyl group, alkyl-carbonyl -oxy group, alkenyl-carbonyl-oxy group, aryl-carbonyl-oxy group, etc. can be mentioned.

In one embodiment, R ¹¹ is preferably an aryl group which may have a substituent; More preferably, it is an aryl group; Particularly preferably, it is a phenyl group.

When R ² and R ³ do not form an aromatic carbocycle, they each independently represent 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 carbocyclic ring, each independently, in one embodiment, is preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, or an alkyl-aryl group. ego; More preferably, it is 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 carbocycle, R ¹ and R ² or R ² and R ³ combine as one to form an aromatic carbocycle which may have a substituent.

The substituents on the aromatic carbocyclic 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 carbocyclic ring, in one embodiment, R ¹ and R ² or R ² and R ³ are combined as one, and preferably, even if they have a substituent. Forms a good benzene ring; More preferably, it forms a benzene ring which may be substituted with a group selected from alkyl group, alkenyl group, aryl group, aryl-alkyl group, and alkyl-aryl group; More preferably, it forms an (unsubstituted) benzene ring.

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 each independently, in one embodiment, are preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, or an alkyl-aryl group; More preferably, it is a hydrogen 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 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 an aryl group. and R ² , R ³ , R ⁴ and R ⁵ are a hydrogen atom or an aryl-alkyl group (particularly preferably, R ¹ is R ¹¹ -A- and/or R ² , R ³ , R ⁴ and at least one of R ⁵ is an aryl-alkyl group); More preferably, R ¹ is a hydrogen atom or R ¹¹ -A-, A is -CH(CH ₃ )-, R ¹¹ is a phenyl group, and R ² , R ³ , R ⁴ and R ⁵ is a hydrogen atom or an α-methylbenzyl group (particularly preferably, R ¹ is R ¹¹ -A- and/or at least one of R ² , R ³ , R ⁴ and R ⁵ is α-methylbenzyl kiida).

In the third embodiment, preferably, R ¹ and R ² combine as one to form a benzene ring, and R ³ , R ⁴ and R ⁵ are hydrogen atoms, or R ² and R ³ These combine as one to form a benzene ring, and R ¹ , R ⁴ and R ⁵ are hydrogen atoms.

In a preferred embodiment, component (B) is a compound having a structure represented by formula (B-2).

In the formula, ^each ring Ring Y ¹ and Ring Z ¹ each independently represent an aromatic carbocycle 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- represents; 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 are bonded as one and a non-aromatic carbocyclic ring which may have a substituent. forming; 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 symbols are as above. The b' unit and c' unit may be the same or different for each structural unit.

^Each of the rings

The substituent on the ^aromatic carbocyclic ring represented by ^ring

^Each ring ego; More preferably, (1) a benzene ring that may be substituted with a group selected from an alkyl group, alkenyl group, aryl group, aryl-alkyl group, and alkyl-aryl group, (2) an alkyl group, alkenyl group, aryl group, and aryl-alkyl group. , and a naphthalene ring that may be substituted with a group selected from an alkyl-aryl group, or (3) the number of carbon atoms that may be substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aryl-alkyl group, an alkyl-aryl group, and an oxo group. It is a 5 to 12 non-aromatic carbocyclic ring (particularly preferably a tetrahydrodicyclopentadiene ring).

Each ring Y ¹ independently represents an aromatic carbocyclic ring that may have a substituent.

The substituents on the aromatic carbocyclic 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.

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

Each ring Z ¹ independently represents an aromatic carbocyclic ring that may have a substituent.

The substituents on the aromatic carbocyclic 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.

Ring Z ¹ is each independently, in one embodiment, preferably a benzene ring which may have a substituent, or a naphthalene ring which may have a substituent; More preferably, it is a benzene ring that may be substituted with a group selected from (1) an alkyl group, alkenyl group, aryl group, aryl-alkyl group, and alkyl-aryl group, or (2) an alkyl group, alkenyl group, aryl group, aryl- It is a naphthalene ring that may be substituted with a group selected from an alkyl group and an alkyl-aryl group.

X ^b each independently represents a single bond, -C(R ^b ) ₂ -, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO- indicates. X ^b is each independently, and in one embodiment, preferably, a single bond, -C(R ^b ) ₂ -, or -O-; More preferably, it is 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 are bonded as one and a non-aromatic carbocyclic ring which may have a substituent. forms. 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 which may have a substituent; More preferably, it is a hydrogen atom or an alkyl group; Particularly preferably, it 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, it is 0 or an integer of 1 to 10; Particularly preferably, it is 0 or an integer of 1 to 5.

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

d' each independently represents 0 or 1.

Examples of the partial structure represented by formula (Y') in formula (B-2) include structures represented by formulas (Y-1) to (Y-12), etc.

In the formula, Y ¹ represents an aromatic carbocycle 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 the same as above.

Component (B) includes the resin represented by the formula (B-2), as well as the resin of the reaction intermediate generated during synthesis (e.g., one or both ends of which are hydroxyl groups and/or carboxyl groups, derived from raw material impurities). It may contain resin, etc.

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 similar thereto. Commercially available compounds having a structure represented by formula (B-1) include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-" 65T”, “HPC-8000L-65TM”, “HPC-8000H”, “HPC-8000H-65TM” (manufactured by DIC); As an active ester compound containing a naphthalene structure, “HP-B-8151-62T”, “EXB-8100L-65T”, “EXB-9416-70BK”, “EXB-8”, “HPC-8150-62T” (DIC (Manufactured by: As a phosphorus-containing active ester compound, “EXB9401” (manufactured by DIC), as an active ester compound that is an acetylate of phenol novolak, “DC808” (manufactured by Mitsubishi Chemical Corporation), and as an active ester compound that is a benzoylate of phenol novolac, “YLH1026.” ", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and "PC1300-02-65MA" (manufactured by Airwater Corporation) as an active ester compound containing a styryl group and a naphthalene structure.

(Compound containing aromatic ester skeleton and unsaturated bond)

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

A compound containing an aromatic ester skeleton and an unsaturated bond has an aromatic ester skeleton. The aromatic ester skeleton refers to a skeleton having an ester bond and an aromatic ring bonded to one or both ends of the ester bond. Among these, it is preferable to have aromatic rings at both ends of the ester bond. Examples of groups having such a skeleton include arylcarbonyloxy group, aryloxycarbonyl group, arylenecarbonyloxy group, aryleneoxycarbonyl group, arylcarbonyloxyarylene group, aryloxycarbonylarylene group, arylenecarboxyl group. A bornyloxyarylene group, an aryleneoxycarbonylarylene group, etc. are mentioned. In addition, the number of carbon atoms of 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 aryl groups and arylene groups may have substituents.

As an aryl group, an aryl group with 6 to 30 carbon atoms is preferable, an aryl group with 6 to 20 carbon atoms is more preferable, and an aryl group with 6 to 10 carbon atoms is still more preferable. 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, and pyridi. Monocyclic aromatic compounds such as nyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, triazinyl group, etc., in which one hydrogen atom has been removed; Naphthyl group, anthracenyl group, phenarenyl group, phenanthrenyl group, quinolinyl group, isoquinolinyl group, quinazolyl group, phthalazinyl group, pterizinyl group, coumarinyl group, indole group, benzoimidazolyl group, A compound in which one hydrogen atom has been removed from a condensed ring aromatic compound such as a benzofuranyl group or acridinyl group; etc. can be mentioned.

As an arylene group, an arylene group with 6 to 30 carbon atoms is preferable, an arylene group with 6 to 20 carbon atoms is more preferable, and an arylene group with 6 to 10 carbon atoms is still more preferable. Examples of such arylene groups include phenylene group, naphthylene group, anthracenylene group, and 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 excellent dielectric constant. Additionally, unsaturated bonds contribute to the curing reaction of the resin composition. As the unsaturated bond contributes to the curing reaction, use of part of the ester portion of the aromatic ester skeleton in the curing reaction is suppressed, 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 the unsaturated bond include unsaturated bonds contained in unsaturated hydrocarbon groups, such as an alkenyl group with 2 to 30 carbon atoms and an alkynyl group with 2 to 30 carbon atoms. The unsaturated bond is preferably contained in the substituent of the aromatic hydrocarbon group at the terminal, and is more preferably contained in the substituent of the aromatic hydrocarbon group at both terminals.

Examples of alkenyl groups 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, 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, 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-2,5-dienyl group, pentadeca-4,7-dienyl group, hexa-1,3,5-trienyl group, pentadeca -1,4,7-trienyl group, etc. are mentioned.

Examples of alkynyl groups 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 -Butadiinyl group, etc. can be mentioned.

Among these, an alkenyl group having 2 to 30 carbon atoms is preferable, an alkenyl group having 2 to 10 carbon atoms is more preferable, an alkenyl group having 2 to 5 carbon atoms is still more preferable, an allyl group, An isopropenyl group or a 1-propenyl group is more preferable, and an allyl group is particularly preferable.

The compound containing an aromatic ester skeleton and an unsaturated bond may have, in addition to the aromatic ester skeleton, any one of an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, and a combination thereof. The term “aromatic hydrocarbon group” refers to a hydrocarbon group containing an aromatic ring, and the aromatic ring may be any of monocyclic, polycyclic, and heterocyclic rings.

As the aromatic hydrocarbon group, a divalent aromatic hydrocarbon group is preferable, an arylene group and an aralkylene group are more preferable, and an arylene group is still more preferable. As an arylene group, an arylene group with 6 to 30 carbon atoms is preferable, an arylene group with 6 to 20 carbon atoms is more preferable, and an arylene group with 6 to 10 carbon atoms is still more preferable. Examples of such arylene groups include phenylene group, naphthylene group, anthracenylene group, and biphenylene group. As an aralkylene group, an aralkylene group with 7 to 30 carbon atoms is preferable, an aralkylene group with 7 to 20 carbon atoms is more preferable, and an aralkylene group with 7 to 15 carbon atoms is still more preferable. Among these, phenylene group is preferable.

As the aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group is preferable, a divalent saturated aliphatic hydrocarbon group is more preferable, and an alkylene group and a cycloalkylene group are still more preferable. As the alkylene group, an alkylene group with 1 to 10 carbon atoms is preferable, an alkylene group with 1 to 6 carbon atoms is more preferable, and an alkylene group with 1 to 3 carbon atoms is still more preferable. Examples of the alkylene group include methylene group, ethylene group, propylene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1-dimethylethylene group, and 1,2-dimethyl. Examples include ethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, and hexylene group.

As the cycloalkylene group, a cycloalkylene group with 3 to 20 carbon atoms is preferable, a cycloalkylene group with 3 to 15 carbon atoms is more preferable, and a cycloalkylene group with 5 to 10 carbon atoms is still more preferable. Examples of the cycloalkylene group include cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclopentylene group, cycloheptylene group, cycloalkylene group represented by the following formulas (a) to (d), etc. 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.

The compound containing an aromatic ester skeleton and an unsaturated bond is preferably one of a compound represented by the following general formula (B-3) and 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 divalent aromatic hydrocarbon group which may have a substituent, Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. n is 0 Represents an integer from 10 to 10.)

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

In general formula (B-3), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group that 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, Monocyclic aromatic compounds such as pyridinyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, and triazinyl group in which one hydrogen atom has been removed; Naphthyl group, anthracenyl group, phenalenyl group, phenanthrenyl group, quinolinyl group, isoquinolinyl group, quinazolyl group, phthalazinyl group, pteridinyl group, coumalinyl group, indole group, benzoimidazolyl group , one in which one hydrogen atom has been removed from a condensed ring aromatic compound such as a benzofuranyl group or an acridinyl group; etc. are mentioned, and among these, a phenyl group is preferable from the viewpoint of significantly obtaining the effect of the present invention. 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 for Ar ¹¹ contains an unsaturated bond.

Ar ¹² each independently represents a divalent aromatic hydrocarbon group that may have a substituent. Examples of the divalent aromatic hydrocarbon group include an arylene group and an aralkylene group, with an arylene group being preferable. As an arylene group, an arylene group with 6 to 30 carbon atoms is preferable, an arylene group with 6 to 20 carbon atoms is more preferable, and an arylene group with 6 to 10 carbon atoms is still more preferable. Examples of such arylene groups include phenylene group, naphthylene group, anthracenylene group, and biphenylene group. As an aralkylene group, an aralkylene group with 7 to 30 carbon atoms is preferable, an aralkylene group with 7 to 20 carbon atoms is more preferable, and an aralkylene group with 7 to 15 carbon atoms is still more preferable. Among these, phenylene group is preferable.

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 general formula (B-3), Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a combination thereof. It represents a divalent group consisting of, and a divalent group consisting of a combination of these is preferable. 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.

As the alkylene group, an alkylene group with 1 to 10 carbon atoms is preferable, an alkylene group with 1 to 6 carbon atoms is more preferable, and an alkylene group with 1 to 3 carbon atoms is still more preferable. Examples of the alkylene group include methylene group, ethylene group, propylene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1-dimethylethylene group, and 1,2-dimethyl. Examples include ethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, and hexylene group.

As the cycloalkylene group, a cycloalkylene group with 3 to 20 carbon atoms is preferable, a cycloalkylene group with 3 to 15 carbon atoms is more preferable, and a cycloalkylene group with 5 to 10 carbon atoms is still more preferable. Examples of the cycloalkylene group include cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclopentylene group, cycloheptylene group, cycloalkylene group represented by the above formulas (a) to (d), etc. , and a cycloalkylene group represented by formula (c) is preferable.

The divalent group consisting of a combination of these is preferably a divalent group that is a combination of a divalent aromatic hydrocarbon group that may have a substituent and a divalent aliphatic hydrocarbon group that may have a substituent, and a plurality of divalent groups that may have a substituent are preferred. More preferable is a divalent group in which an aromatic hydrocarbon group and a plurality of divalent aliphatic hydrocarbon groups which may have substituents are alternately combined. Specific examples of the above divalent groups include the following divalent groups (B1) to (B8). In the formula, b1 to b7 represent an integer of 0 to 10, and preferably an integer of 0 to 5. "*" represents a bonding hand, and the broken line represents a structure obtained by reacting an aromatic compound used when synthesizing component (B), an acid halide of an aromatic compound, or an ester of an aromatic compound.

The divalent aromatic hydrocarbon group and 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. On the other hand, when the compound represented by general formula (B-3) is an oligomer or polymer, n represents the average value.

In general formula (B-4), Ar ²¹ represents an m-valent aromatic hydrocarbon group that may have a substituent. The m-valent aromatic hydrocarbon group is preferably an m-valent aromatic hydrocarbon group with 6 to 30 carbon atoms, more preferably an m-valent aromatic hydrocarbon group with 6 to 20 carbon atoms, and an m-valent aromatic hydrocarbon group with 6 to 10 carbon atoms. It is more desirable. 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 general formula (B-4), Ar ²² each independently represents a monovalent aromatic hydrocarbon group that 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, and 2 is preferable.

Specific examples of compounds containing an aromatic ester skeleton and an unsaturated bond include the following compounds. In addition, specific examples of compounds containing an aromatic ester skeleton and an unsaturated bond include compounds described in paragraphs 0068 to 0071 of International Publication No. 2018/235424, and paragraphs 0113 to 0115 of International Publication No. 2018/235425. there is. However, 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.

A compound containing an aromatic ester skeleton and an unsaturated bond may be synthesized by a known method. The synthesis of a compound containing an aromatic ester skeleton and an unsaturated bond can be performed, 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, further preferably 250 or more, from the viewpoint of significantly obtaining the effects of the present invention. It is 3000 or less, more preferably 2000 or less, and even more preferably 1500 or less. The weight average molecular weight of a 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).

The unsaturated bond equivalent weight of the compound containing an aromatic ester skeleton and an unsaturated bond is preferably 50 g/eq or more, more preferably 100 g/eq, from the viewpoint of significantly obtaining the effects of the present invention. Above, more preferably 150 g/eq., and preferably 2000 g/eq. or less, more preferably 1000 g/eq. or less, more preferably 500 g/eq. It is as follows. The unsaturated bond equivalent is the mass of component (B) containing 1 equivalent of unsaturated bond.

The ratio of (A) the epoxy group equivalent of the epoxy resin and (B) the active ester group equivalent of the active ester compound (active ester group equivalent of the active ester compound/epoxy group equivalent of the epoxy resin) is preferably 0.4 or more, more preferably Preferably it is 0.5 or more, more preferably 0.6 or more, preferably 1.8 or less, more preferably 1.5 or less, and even more preferably 1.3 or less. Here, the “epoxy group equivalent of the epoxy resin” is a value obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, the “active ester group equivalent of the active ester compound” is a value obtained by dividing the mass of the non-volatile component of the active ester compound present in the resin composition by the active ester group equivalent. By keeping the amount ratio of the component (B) with the epoxy resin within this range, the effect of the present invention can be significantly achieved.

The content of component (B) is preferably 1 mass% or more, more preferably 3 mass% or more, when the non-volatile component in the resin composition is 100 mass%, from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 5 mass% or more, preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 20 mass% or less, or 15 mass% or less.

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, from the viewpoint of significantly obtaining the effect of the present invention. It is preferably 45 mass% or more, and the upper limit is preferably 70 mass% or less, more preferably 60 mass% or less, and even more preferably 55 mass% or less.

<(C) Hydrocarbon polymer containing terpene skeleton>

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

Terpene skeleton usually refers to a molecular skeleton having a structure formed by polymerizing terpene. Since terpenes generally have isoprene (C ₅ H ₈ ) as a structural unit, the hydrocarbon polymer containing the (C) terpene skeleton may be a hydrocarbon polymer containing isoprene as a structural unit, and preferably has a polar group. don't have As the terpene, cyclic terpene is preferable. Therefore, it is preferable that component (C) contains a cyclic terpene skeleton having a structure formed by polymerizing cyclic terpenes. A polar group refers to an atomic group with polarity, and examples include hydroxy group, amino group, carboxyl group, etc. (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); and aromatic modified terpene resins that are copolymers of the above-described cyclic terpenes and aromatic monomers. The component (C) preferably contains either a polyterpene resin or an aromatic modified terpene resin, and more preferably contains a polyterpene resin. The polyterpene resin is preferably a homopolymer of any one of α-pinene, β-pinene, and dipentene, and is more preferably a homopolymer of dipentene.

As the aromatic monomer, an aromatic monomer copolymerizable 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, further preferably 100°C or higher, or 120°C or higher, from the viewpoint of significantly obtaining the effect of the present invention. It 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.

(C) Component may be a commercially available product or may be synthesized using a known method or a method similar thereto. As a commercial item of polyterpene resin, "PX1250" manufactured by Yasuhara Chemical Company, etc. are mentioned, for example. Examples of commercially available aromatic modified terpene resins include "TO125" manufactured by Yasuhara Chemical Co., Ltd.

The weight average molecular weight of component (C) is preferably 500 or more, more preferably 600 or more, further preferably 700 or more, preferably 10,000 or less, from the viewpoint of significantly obtaining the effect of the present invention. is 6000 or less, more preferably 4000 or less.

The content of component (C) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 1 mass % or more, preferably 5 mass % or less, more preferably 3 mass % or less, and even more preferably 2 mass % or less.

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, from the viewpoint of significantly obtaining the effect of the present invention. It is preferably 3% by mass or more, and the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less.

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

<(D) Radical polymerizable compound>

The resin composition may contain (D) a radically polymerizable compound as an optional component. The radically polymerizable compound (D) as this component (D) does not include those corresponding to the components (A) to (C) described above. (D) Component may be used individually or in combination of two or more types.

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

(D) As other radically polymerizable compounds, known radically polymerizable compounds can be widely used and are not particularly limited, for example, maleimide-based radically polymerizable compounds having two or more maleimide groups, two or more Examples include vinylphenyl-based radically polymerizable compounds having a vinylphenyl group, and (meth)acrylic-based radically polymerizable compounds having two or more acryloyl groups and/or methacryloyl groups.

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. Commercially available products include, for example, Designer Molecule. "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compound containing dimerdiamine structure) manufactured by ZZ Corporation, and "BMI" manufactured by Designer Molecules. -6100" (aromatic maleimide compound), "MIR-5000-60T", "MIR-3000-70T", and "MIR-3000-70MT" (biphenyl aralkyl type maleimide compound) manufactured by Nippon Kayaku Co., Ltd., K.I. Examples include "BMI-70" and "BMI-80" manufactured by Kasei Corporation, "BMI-2300" and "BMI-TMH" manufactured by Yamato Kaseiko Corporation, and "SLK-2600" manufactured by Shinetsu Kagakuko Corporation. . Additionally, as a maleimide-based radically polymerizable compound, a maleimide resin (a maleimide compound containing an indan ring skeleton) disclosed in Public Invention Association Publication No. 2020-500211 may be used.

The vinylphenyl-based radically polymerizable compound is not particularly limited, but in one embodiment, it is preferably a thermoplastic resin having a vinylphenyl group, modified polyphenylene ether resin having a vinylphenyl group, and modified polystyrene having a vinylphenyl group. Resins selected from resins 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", and "ODV-XET-X05" (divinylbenzene/styrene copolymer) manufactured by Nittetsu Chemical & Materials Co., Ltd.; Examples include “A-DOG” manufactured by Shinnakamura Kagaku Kogyo Co., Ltd. and “DCP-A” manufactured by Kyoeisha Kagaku 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, and the (meth)acrylic radically polymerizable compound is preferably a thermoplastic resin having an acryloyl group and/or a methacryloyl group. Resins selected from modified polyphenylene ether resins having a digroup and modified polystyrene resins having an acryloyl group and/or methacryloyl group are more preferable, and commercially available products include, for example, those manufactured by SABIC Innovative Plastics. “SA9000”, “SA9000-111” (methacryl modified polyphenylene ether resin), etc. are mentioned.

The functional group equivalent of component (D) is preferably 100 g/eq. to 20000 g/eq., more preferably 200 g/eq. to 15000 g/eq., more preferably 300 g/eq. to 10000 g/eq. The functional group equivalent of component (D) is the mass of (D) other radically polymerizable compounds per equivalent of 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 compounds is preferably 500 to 50,000, more preferably 700 to 20,000. The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured using gel permeation chromatography (GPC).

The content of component (D) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 0.3 mass% or more, preferably 3 mass% or less, more preferably 2 mass% or less, and even more preferably 1.5 mass% or less.

The content of component (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, when the resin component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. It is preferably 1% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

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 0.2 or more from the viewpoint of significantly obtaining the effect of the present invention. , more preferably 0.3 or more, preferably 3 or less, more preferably 1 or less, particularly preferably 0.8 or less.

<(E) Weapon 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) As the material for the inorganic filler, an inorganic compound is used. (E) Inorganic filler materials include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and hydroxide. Aluminum, 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, Examples include 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. Additionally, spherical silica is preferred as the silica. (E) Inorganic fillers may be used individually, or two or more types may be used in combination at any ratio.

(E) The average particle diameter of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, even more preferably 1 μm or less, especially Preferably it is 0.7㎛ or less. (E) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, particularly preferably 0.2 μm or more. . (E) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured as the average particle size. As a measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone can be weighed and placed in a vial bottle, and then dispersed by ultrasonic waves for 10 minutes. For the measurement sample, using a laser diffraction type particle size distribution measuring device, the light source wavelength used is blue and red, the particle size distribution based on the volume of the inorganic filler is measured using a flow cell method, and the median diameter is determined from the obtained particle size distribution. The average particle diameter was calculated as . Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba Sesakusho Co., Ltd.

(E) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m2/g or more, more preferably 0.5 m2/g or more, further preferably 1 m2/g or more, especially preferably 3. It is more than ㎡/g. (E) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m2/g or less, more preferably 70 m2/g or less, further preferably 50 m2/g or less, especially preferably is less than 40㎡/g. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas to the surface of the sample 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 multi-point method. there is.

(E) The inorganic filler may be a non-hollow inorganic filler (preferably non-hollow silica) with a porosity of 0% by volume, or a hollow inorganic filler (preferably hollow silica) with a porosity exceeding 0% by volume, and includes both. It’s okay to do it. The porosity of the hollow inorganic filler is preferably 70 volume% or less, more preferably 50 volume% or less, and especially preferably 30 volume% or less. (E) The lower limit of the porosity of the inorganic filler can be, for example, greater than 0 volume%, 1 volume% or more, 5 volume% or more, or 10 volume% or more. The porosity P (volume %) of an inorganic filler is the volume-based ratio of the total volume of one or two or more pores inside the particle to the entire volume of the particle based on the outer surface of the particle (total volume of pores/ volume of particles), for example, the measured value of the actual density of the inorganic filler, D _M (g/cm 3 ), and the theoretical value of the material density of the material forming the inorganic filler, D _T (g/cm 3 ). It is calculated using the following formula (1).

(E) The actual density of the inorganic filler can be measured using, for example, a true density measuring device. As a true density measuring device, ULTRAPYCNOMETER1000 manufactured by QUANTACHROME, etc. are mentioned, for example. As a measurement gas, for example, nitrogen is used.

(E) Commercially available inorganic fillers can be used. (E) Commercially available inorganic fillers include, for example, “UFP-30” manufactured by Denka Chemical Co., Ltd.; “SP60-05” and “SP507-05” manufactured by Shin-Ni-Tetsu Sumikin Materials, Inc.; “YC100C”, “YA050C”, “YA050C-MJE”, and “YA010C” manufactured by Adomatex Corporation; “UFP-30” manufactured by Denka Corporation; “Silpen NSS-3N”, “Silpen NSS-4N”, and “Silpen NSS-5N” manufactured by Tokuyama Corporation; “SC2500SQ”, “SO-C4”, “SO-C2”, and “SO-C1” manufactured by Adomatex Corporation; “DAW-03” and “FB-105FD” manufactured by Denka Corporation; and "BA-S" manufactured by Nikki Shokubai Kasei.

(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 coupling agents. Ringer, etc. can be mentioned. In addition, one type of surface treatment agent may be used individually, and two or more types may be used in arbitrary combination.

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

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 0.2% by mass to 5% by mass of a surface treatment agent, more preferably 0.3% by mass by 0.3% by mass. It is more preferable that the surface is treated in an amount of 2 to 2% by mass.

The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility 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 still more preferably 0.2 mg/m 2 or more. 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, 1.0 mg/m2 or less is preferable, 0.8 mg/m2 or less is more preferable, and 0.5 mg/m2 or less is still more preferable. .

(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 surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Sesakusho, etc. can be used.

(E) The content of the inorganic filler is preferably 40% by mass or more, more preferably 50% by mass or more, assuming that the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. More preferably, it is 60 mass% or more, or 70 mass% or more, preferably 90 mass% or less, more preferably 85 mass% or less, and even more preferably 80 mass% or less.

The mass ratio of component (C) to the 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, and even more preferably 60 or less.

<(F) Hardener>

The resin composition may contain (F) a curing agent (excluding those corresponding to component (B)) as an optional component. The (F) hardening agent as this (F) component does not include those corresponding to the above-mentioned (A) to (E) components. (F) Components may be used individually or in combination of two or more types.

Examples of the component (F) include phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. Among them, from the viewpoint of significantly obtaining the effects of the present invention, the component (F) is preferably at least one of a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent, and is preferably a phenol-based curing agent. It is more preferable that it is either a curing agent or a naphthol-based curing agent, and it is even more preferable that it contains a phenol-based curing agent.

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

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

Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Kobunshi Co., Ltd., and “P-d” and “F-a” manufactured by Shikoku Kaseikogyo Co., Ltd.

Examples of cyanate ester-based curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylenecyanate), and 4,4'-methylenebis(2,6- dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolac, etc., some of these cyanate resins are triazineized. Prepolymers, etc. can be mentioned. Specific examples of cyanate ester-based 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 Co., Ltd. ", "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazylated to form a trimer), etc.

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

When a curing agent is contained as component (F), the amount ratio of component (A), component (B), and component (F) is [total number of epoxy groups of component (A)]: [component (B) and (F) ) The ratio of the total number of active groups of the components is preferably in the range of 1:0.01 to 1:5, more preferably in the range of 1:0.05 to 1:3, and even more preferably in the range of 1:0.1 to 1:2. Here, the “epoxy group number of component (A)” is a value obtained by dividing the mass of the non-volatile component of component (A) present in the resin composition by the epoxy equivalent. In addition, “the number of active groups of component (B) and component (F)” is the sum of the mass of the non-volatile components of component (B) and (F) present in the resin composition divided by the equivalent of the active group. . By keeping the amount ratio of component (B) and component (F) with component (A) within this range, the effect of the present invention can be significantly achieved.

When containing a curing agent as component (F), the amount ratio of component (A) and all (F) components is [total number of epoxy groups in component (A)]:[total number of active groups in component (F)]. The ratio is preferably in the range of 1:0.01 to 1:1, more preferably 1:0.03 to 1:0.5, and even more preferably 1:0.05 to 1:0.3. Here, the “active group number of component (F)” is a value obtained by dividing the mass of the non-volatile component of component (F) present in the resin composition by the active group equivalent. By keeping the amount ratio of component (A) and component (F) within this range, the effects of the present invention can be significantly achieved.

The content of component (F) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention, More preferably, it is 0.5 mass% or more, preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1.5 mass% or less.

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, from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 3.5 mass% or more, preferably 8 mass% or less, more preferably 6 mass% or less, and even more preferably 5 mass% or less.

<(G) Curing accelerator>

The resin composition may contain (G) a curing accelerator as an optional component. The (G) hardening accelerator as this (G) component does not include those corresponding to the above-mentioned (A) to (F) components. (G) The curing accelerator has a function as a curing catalyst that promotes curing of the (A) epoxy resin. (G) A hardening accelerator may be used individually, or may be used in combination of two or more types arbitrarily.

(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, and amine-based curing accelerators. Among these, a curing accelerator selected from amine-based curing accelerators and metal-based curing accelerators is preferable, and an amine-based curing accelerator is particularly preferable.

Examples of phosphorus-based curing accelerators include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, and bis(tetrabutylphosphonium)pyrro. Mellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium Aliphatic phosphonium salts such as tetraphenyl borate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra- p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetrap-tolyl borate, triphenylethylphosphonium tetraphenyl borate, tris (3-methylphenyl) ethylphosphonium tetraphenyl borate, tris (2-methyl aromatic phosphonium salts such as toxyphenyl)ethylphosphonium tetraphenyl borate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; Aromatic phosphine/quinone addition reactants such as triphenylphosphine/p-benzoquinone addition reactants; Tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, Aliphatic phosphines such as tricyclohexylphosphine; Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolyl Phosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, Tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2, 6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine , tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl- 2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2- and aromatic phosphines such as bis(diphenylphosphino)acetylene and 2,2'-bis(diphenylphosphino)diphenyl ether.

Examples of urea-based curing accelerators include 1,1-dimethylurea; Aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3- Chloro-4-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)bis(N',N'-dimethylurea ), aromatic dimethyl ureas such as N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea], and the like.

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, Examples include 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, and 1-(o-tolyl) biguanide.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimida Zolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-unde Cylimidazolyl-(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-phenylimidazoleisocyanuric acid Adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 2-a] Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and imidazole compounds and epoxy resins Adduct forms of .

As the imidazole-based curing accelerator, commercial products may be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW", and "C11Z-A" manufactured by Shikoku Kasei Kogyo Co., Ltd., and "C11Z-A" manufactured by Mitsubishi Chemical Corporation. “P200-H50” etc. can be mentioned.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of 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, 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 organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

As an amine-type hardening accelerator, a commercial item may be used, for example, "MY-25" manufactured by Ajinomoto Fine Techno Co., Ltd., etc.

The content of component (G) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 0.1 mass% or more, preferably 1.5 mass% or less, more preferably 1 mass% or less, and even more preferably 0.5 mass% or less.

The content of component (G) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, when the resin component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 0.5 mass% or more, preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1.5 mass% or less.

<(H) Other additives>

The resin composition of the present invention may further contain arbitrary additives as non-volatile components. Such additives include, for example, thermoplastic resins; Radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; Thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polysulfone resin, polyether sulfone resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, and polyester resin; Organic fillers such as rubber particles; Organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; Polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; Leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; Thickeners such as bentone and montmorillonite; Antifoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; UV absorbers such as benzotriazole-based UV absorbers; Adhesion improvers such as urea silane; Adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; Antioxidants such as hindered phenol antioxidants; Fluorescent whitening agents such as stilbene derivatives; Surfactants such as fluorine-based surfactants and silicone-based surfactants; Flame retardants such as phosphorus-based flame retardants (e.g., phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, nitrogen-based flame retardants (e.g., melamine sulfate, halogen-based flame retardants, inorganic flame retardants (e.g., antimony trioxide); phosphoric acid esters) Dispersants such as polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, and isocyanate-based stabilizers. , carboxylic acid-based stabilizers, carboxylic acid anhydride-based stabilizers, etc. (H) Other additives may be used individually, or two or more types may be used in combination in any ratio. (H ) The content of other additives can be appropriately set by those skilled in the art.

<(I) Solvent>

The resin composition may further contain an arbitrary solvent as a volatile component in addition to the non-volatile component described above. (I) As a solvent, a known solvent can be used as appropriate, and the type is not particularly limited, and an organic solvent is preferable. (I) Examples of the solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, Ether ester solvents such as methyl toxypropionate; Ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butylcarbitol); amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; Sulfoxide-based solvents such as dimethyl sulfoxide; Nitrile-based solvents such as acetonitrile and propionitrile; Aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (I) Solvents may be used individually, or two or more types may be used in combination at any ratio.

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

<Method for producing resin composition>

In the resin composition of the present invention, for example, components (A) to (C) and, if necessary, (D) to (I) are added to an optional preparation container in any order and/or in part or all at the same time. It can be manufactured by mixing. Additionally, in the process of adding and mixing each component, the temperature may be appropriately set, and may be heated and/or cooled temporarily or over time. Additionally, during or after the addition and mixing process, the resin composition may be uniformly dispersed by stirring or shaking using, for example, a stirring device or shaking device such as a mixer. Additionally, degassing may be performed simultaneously with stirring or shaking under low pressure conditions such as under vacuum.

<Characteristics of resin composition>

By using a resin composition containing components (A) to (C) in combination, a cured product with a low dielectric loss tangent (Df) and excellent crack resistance can be obtained. Additionally, the resin composition can also produce a cured product with a high glass transition temperature (Tg) and a low relative dielectric constant (Dk).

The cured product obtained by curing the resin composition at 190°C for 90 minutes exhibits the characteristic of low dielectric loss tangent (Df) at room temperature. Therefore, an insulating layer with excellent dielectric loss tangent is formed. 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, and more preferably 0.003 or less. There is no particular limit to the lower limit, but it can be 0.00001 or more. The dielectric loss tangent at 23°C can be measured by the method described in the Examples described later.

The cured product obtained by curing the resin composition at 190°C for 90 minutes usually exhibits the characteristic of low dielectric loss tangent (Df) at high temperatures. Therefore, an insulating layer with excellent dielectric loss tangent is formed. 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. There is no particular limit to the lower limit, but it can be 0.00001 or more. The dielectric loss tangent at 90°C can be measured by the method described in the Examples described later.

The 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 formed. 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 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 the Examples described later.

The cured product obtained by curing the resin composition at 190°C for 90 minutes usually exhibits the characteristic of low dielectric constant (Dk) at room temperature. Therefore, an insulating layer with excellent dielectric constant is formed. 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. There is no particular limit to the lower limit, but it can be 0.1 or more. The dielectric constant at 23°C can be measured by the method described in the Examples described later.

The cured product obtained by curing the resin composition at 190°C for 90 minutes usually exhibits the characteristic of low dielectric constant (Dk) at high temperatures. Therefore, an insulating layer with excellent dielectric constant is formed. 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 can be set to 0.1 or more. The dielectric constant at 90°C can be measured by the method described in the Examples described later.

The cured product obtained by curing the resin composition at 190°C for 90 minutes usually exhibits the characteristic of 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 even more preferably 120°C or higher. There is no particular upper limit, but it can be set to 500°C or lower. The glass transition temperature can be measured by DSC (differential scanning calorimetry) at a temperature increase rate of 10°C/min.

<Use 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 insulating layer. Specifically, it can be suitably used as a resin composition for forming the insulating layer (resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. there is. In addition, in the printed wiring board 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 applications requiring a resin composition, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor sealants, hole filling resins, and component filling resins. It can be used widely.

In addition, for example, when a semiconductor chip package is manufactured through the following processes (1) to (6), the resin composition of the present invention is a resin composition for a redistribution forming layer as an insulating layer for forming a redistribution layer ( It can also be suitably used as a resin composition for forming a redistribution layer) and a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor chip). When a semiconductor chip package is manufactured, a redistribution layer may be additionally formed on the sealing layer.

(1) A process of laminating a temporarily fixed film on a substrate,

(2) A process of temporarily fixing a semiconductor chip on a temporarily fixing film,

(3) Process of forming a sealing layer on the semiconductor chip,

(4) A process of peeling the base material and temporarily fixed film from the semiconductor chip,

(5) A process of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and temporarily fixed film are peeled, and

(6) Process of forming a redistribution layer as a conductor layer on the redistribution formation layer

In addition, since the resin composition of the present invention forms an insulating layer with good component embedding properties, 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 a varnish state, it is generally suitable industrially to use it in the form of a sheet-like laminated material containing the resin composition.

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

In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support, 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 40 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film. . 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 films made of plastic materials, metal foils, and release papers, and films and metal foils made of plastic materials 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”). .), polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic, polymethyl methacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), and polyether sulfide (PES). ), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using a metal foil as a support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferable. As the copper foil, a foil made of the simple metal of copper may be used, or a foil made of an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good night.

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

Additionally, as the support, you may use a support with a mold release layer that has a mold release layer on the surface bonded to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include at least one type of release agent selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. The support with the release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-" manufactured by Lintec, which are PET films with a release layer containing an alkyd resin-based release agent as a main component. 7”, “Lumira T60” manufactured by Torres, “Purex” manufactured by Teijin, and “Unifill” manufactured by Unichika.

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

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

For example, the resin sheet is prepared by preparing a resin varnish using the liquid resin composition as is or dissolving the resin composition in an organic solvent, applying this to a support using a die coater, etc., and further drying to form a resin composition layer. It can be manufactured by:

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

Drying may be performed by known methods such as heating or hot air spraying. Drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. It also varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, but for example, when using a resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent, the temperature is 50°C to 150°C for 3 minutes to 10 minutes. By drying, a resin composition layer can be formed.

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it becomes usable 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 substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fiber base is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited. Usually, it is 10㎛ or more.

Prepreg can be manufactured by known methods such as hot melt method and solvent method.

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

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

[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, by a method including the following steps (I) and (II) using the above-mentioned resin sheet.

(I) A process of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate.

(II) Process of forming an insulating layer by curing (e.g., heat curing) the resin composition layer.

The “inner layer substrate” used in step (I) is a member that becomes the substrate of the printed wiring board, for example, glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, and thermosetting polyphenylene. Ether substrates, etc. can be mentioned. Additionally, the substrate may have a conductor layer on one or both sides, and this conductor layer may be pattern-processed. An inner layer substrate on which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes referred to as an “inner layer circuit board.” Additionally, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and/or a conductor layer must be additionally formed is also included in the "inner layer substrate" referred to in the present invention. If the printed wiring board is a circuit board with embedded components, an inner layer board with embedded components may be used.

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of the member that heat-presses the resin sheet to the inner layer substrate (hereinafter also referred to as “heat-press member”) include a heated metal plate (SUS head plate, etc.) or a metal roll (SUS roll). On the other hand, it is preferable not to press the heat-compression member directly on the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heat-compression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination can be preferably carried out under reduced pressure conditions 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 pressurization laminator manufactured by Meiki Sesakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurized laminator.

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

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

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

The heat curing conditions of 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. ℃ to 210℃. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and 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 heat curing the resin composition layer, the resin composition layer is cured at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more. Preheating may be performed preferably for 5 minutes to 150 minutes, more preferably for 15 minutes to 120 minutes, and even more preferably for 15 minutes to 100 minutes.

When manufacturing a printed wiring board, (III) a step of perforating the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) may be performed according to various methods known to those skilled in the art that are used in the production of printed wiring boards. On the other hand, when the support is removed after step (II), the support is removed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and ( V) It may be carried out in between. Additionally, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board.

In another embodiment, the printed wiring board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when using a resin sheet.

Process (III) is a process of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed 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 appropriately according to the design of the printed wiring board.

Process (IV) is a process of roughening the insulating layer. Usually, in this step (IV), removal of smear is also performed. The procedures and conditions of the roughening process are not particularly limited, and known procedures and conditions normally used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order.

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

The oxidizing agent used in the roughening treatment is not particularly limited, but examples include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate 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 to 30 minutes. Additionally, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securiganth P” manufactured by Atotech Japan.

In addition, as the neutralizing liquid used in the roughening treatment, an acidic aqueous solution is preferable, and examples of commercial products include "Reduction Solution Securigant P" manufactured by Atotech Japan.

Treatment with a neutralizing liquid can be performed by immersing the treated surface that has been roughened with an oxidizing agent in a neutralizing liquid at 30°C to 80°C for 5 to 30 minutes. In terms of workability, etc., a method of immersing an object that has been roughened with an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes is preferable.

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 even more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, 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 in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. 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 (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium A layer formed of an alloy) may be mentioned. Among them, from the viewpoint of versatility of forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy or copper-nickel alloy , an alloy layer of a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper is more preferable. This is more preferable.

The conductor layer may have a single-layer structure or a multi-layer 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 multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 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 on the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full additive method, and from the viewpoint of ease of manufacturing, the semi-additive method can be used. It is preferable to form it by the additive method. Hereinafter, an example of forming a conductor layer by a semi-additive method will be shown.

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

In another embodiment, the conductor layer may be formed using metal foil. When forming a conductor layer using metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The conditions for lamination may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventionally known techniques such as the subtractive method and the modified semiadditive method.

Metal foil can be manufactured by known methods such as electrolysis and rolling, for example. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nikko Nisseki Kinzoku Corporation, 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Kozan Corporation.

[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.

Semiconductor devices include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trams, ships, aircraft, etc.). there is.

[Example]

Hereinafter, the present invention will be specifically explained by examples. The present invention is not limited to these examples. Meanwhile, in the following, “part” and “%” indicating quantity mean “part by mass” and “% by mass”, respectively, unless otherwise specified. In particular, when temperature and pressure are not specified, 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)>

In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a dividing tube, and a stirrer, add 320 g (2.0 mol) of 2,7-dihydroxynaphthalene, 184 g (1.7 mol) of benzyl alcohol, and 5.0 g of p-toluenesulfonic acid monohydrate. It was injected and stirred while blowing nitrogen at room temperature. After that, the temperature was raised to 150°C, and the resulting water was distilled off to the outside of the system and stirred for 4 hours. After completion of the reaction, 900 g of methyl isobutyl ketone and 5.4 g of 20% sodium hydroxide aqueous solution were added to neutralize, the water layer was removed by liquid separation, washed three times with 280 g of water, and methyl isobutyl ketone was removed under reduced pressure. 460 g of benzyl-modified naphthalene compound (A-1) was obtained. The obtained benzyl-modified naphthalene compound (A-1) was a black solid, and the hydroxyl equivalent weight was 180 grams/equivalent.

203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0 mol) and 1400 g of toluene were injected into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a flow distribution tube, and a stirrer, and the system was dissolved by purging the system with reduced pressure nitrogen. Next, 113.9 g (0.67 mol) of orthophenylphenol and 240 g (number of moles of phenolic hydroxyl group: 1.33 mol) of benzyl-modified naphthalene compound (A-1) were added, and the system was dissolved by purging with reduced pressure nitrogen. After that, 0.70 g of tetrabutylammonium bromide was dissolved, the inside of the system was controlled to 60°C or lower while purging nitrogen gas, and 400 g of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hours under these conditions. After completion of the reaction, the liquid was separated and the aqueous layer was removed. Additionally, water was added to the toluene layer in which the reactant was dissolved, stirred and mixed for 15 minutes, and the water layer was removed by standing liquid separation. This operation was repeated until the pH of the water layer reached 7. Afterwards, water was removed by decanter dehydration to obtain the active ester compound (B-1) in a toluene solution with a non-volatile content of 61.5% by mass. The active ester equivalent weight of the obtained active ester compound (B-1) was 238 g/eq.

<Synthesis Example 2: Synthesis of active ester compound (B-2)>

In a flask equipped with a thermometer, a dropping funnel, a cooling pipe, a flow pipe, and a stirrer, 165 g of polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent weight: 165 g/eq., softening point 85°C) and 134 g (1.0 g) of orthoallylphenol. mol) and 1200 g of toluene were injected, and the system was purged with reduced pressure nitrogen. Next, 203 g (1.0 mol) of isophthalic acid chloride was injected, and the system was purged with reduced pressure nitrogen. 0.6 g of tetrabutylammonium bromide was added, nitrogen gas purge treatment was performed, the inside of the system was controlled to 60°C or lower, and 412 g of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After the dropwise addition was completed, the mixture was stirred for 1.0 hours. After completion of the reaction, the aqueous layer was removed by static liquid separation. Water was additionally added to the obtained toluene layer, stirred for 15 minutes, and the water layer was removed by static liquid separation. This operation was repeated until the pH of the water layer reached 7. Then, the non-volatile content was adjusted to 70% by mass by heat drying to obtain an active ester compound (B-2) represented by the following formula. In the formula, s is each independently an integer of 0 or 1 or more, and the average value of r calculated from the injection ratio is 1. In addition, the broken line in the formula is a structure obtained by reacting isophthalic acid chloride, polyaddition reaction resin of phenol, and/or orthoallyl phenol. The ester group equivalent weight of the obtained activated ester resin was calculated from the injection ratio and was 214 g/eq.

<Manufacture of resin varnish>

Each component was weighed by the mass parts shown in the table below, and 10 parts of MEK and 10 parts of cyclohexanone were further mixed and uniformly dispersed using a high-speed rotating mixer to obtain a resin varnish. Meanwhile, the details of each component listed in the table are as follows.

(A) Ingredients:

·HP-4032-SS: Functional group equivalent weight 144g/eq., manufactured by DIC.

·ESN-475V: Functional group equivalent weight 330g/eq., manufactured by Nittetsu Chemical & Materials.

· NC-3100: Functional group equivalent weight 258 g/eq., manufactured by Nippon Kayaku.

(B) Ingredients:

HPC-8150-62T: Toluene solution with a functional group equivalent weight of 223 g/eq. and a non-volatile content of 62% by mass, manufactured by DIC.

HPC-8000-65T: Toluene solution with a functional group equivalent of 229 g/eq. and a 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: Methyl amyl ketone solution with a functional group equivalent of 199 g/eq. and a non-volatile content of 65% by mass, manufactured by Air Water Performance Chemicals.

(C) Ingredients:

・PX1250: Terpene resin with a softening point of 125°C, manufactured by Yasuhara Chemical Co., Ltd.

TO125: Aromatic modified terpene resin with a softening point of 125°C, manufactured by Yasuhara Chemical Co., Ltd.

(D) Ingredients:

Maleimide A: A compound represented by the following formula (1) synthesized by the method described in Synthesis Example 1 of Invention Association 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 60% by mass of non-volatile matter, manufactured by Nippon Kayaku Co., Ltd.

・MIR-3000-70T: manufactured by Nippon Kayakusa

·BMI-689: Manufactured by Designer Molecules.

・A-DOG: Manufactured by Nippon Kayakusa

OPE-2St-1200: Toluene solution with 65% by mass of non-volatile content, manufactured by Mitsubishi Gas Chemical Co., Ltd.

・SLK-2600: Anisole solution with 50% by mass of non-volatile content, manufactured by Shinetsu Chemical Co., Ltd.

(E) Ingredients:

SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 0.5㎛, specific surface area 5.8㎡/g, manufactured by Adomatex.

BA-S: spherical silica with a hollow portion surface-treated with an amine-based alkoxysilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle diameter 2 to 3 μm, manufactured by Nikki Shokubai Kasei Co., Ltd.

(F) Ingredients:

LA-3018-50P: 1-methoxy-2-propanol solution with functional group equivalent weight of 151 g/eq. and non-volatile content of 50% by mass, manufactured by DIC.

(G) Ingredients:

・1B2PZ: Manufactured by Shikoku Kaseiko Teachers

*In the table, the content of component (C) represents the content (% by mass) assuming that the resin component is 100% by mass, and the content of component (E) represents the content (% by mass) assuming that the nonvolatile component in the resin composition is 100% by mass. Indicates the content (% by mass).

<Measurement of dielectric constant and dielectric loss tangent>

(1) Production of resin sheet A with a resin composition layer thickness of 40 μm

As a support, a polyethylene terephthalate film (“AL5” manufactured by Lintec, thickness 38 μm) with a release layer was prepared. On the release layer of this support, the resin varnish obtained in the examples and comparative examples was uniformly applied so that the thickness of the dried resin composition layer 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 containing a support and a resin composition layer.

(2) Production of hardened 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 to 80 mm in length and 2 mm in width, and measured using the cavity resonance perturbation method using “HP8362B” manufactured by Agilent Technologies, with a frequency of 5.8 GHz and a measurement temperature of 23°C and 90°C. In , the values of dielectric constant and dielectric loss tangent (Dk value and Df value) were measured. Measurements were performed on two test pieces, and the average was calculated.

(4) Measurement of glass transition temperature (Tg)

For each cured product for evaluation, it was cut to a length of 20 mm and a width of 6 mm to serve as an evaluation sample. The glass transition temperature (Tg) of this evaluation sample was measured at a temperature increase rate of 5°C/min from 25°C to 250°C using a TMA device manufactured by Rigaku Corporation. Measurements were made twice on the same test piece, 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, thickness 38 μm) with a release layer was prepared. On the release layer of this support, the resin varnish obtained in Examples and Comparative Examples was uniformly applied so that the thickness of the dried resin composition layer was 25 μm, and dried at 70°C to 80°C (average 75°C) for 2.5 minutes. Resin sheet B containing a support and a resin composition layer was obtained.

<Evaluation of crack resistance after desmear treatment>

A core material (manufactured by Hitachi Kaseiko Co., Ltd.) is formed by forming circular copper pads (copper thickness 35 ㎛) with a diameter of 350 ㎛ in a lattice shape at 400 ㎛ intervals on the resin sheet B with a thickness of 25 ㎛ produced above to achieve a drift rate of 60%. Using a batch type vacuum pressurization laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials) on both sides of the "E705GR" (thickness 400㎛), the resin composition layer is bonded to the inner layer substrate on both sides of the inner layer substrate. It was laminated to. This laminate was performed by decompressing for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then pressing for 30 seconds at a temperature of 100°C and a pressure of 0.74 MPa. This was placed in an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 170°C and heated for 30 minutes. Additionally, the support layer was peeled off, and the obtained circuit board was immersed in Swelling Deep Securigant P manufactured by Atotech Japan, a swelling liquid, 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, which is a roughening solution, at 80°C for 30 minutes. Finally, it was immersed in the neutralizing solution, Securigant P, a reduction solution manufactured by Atotech Japan, at 40°C for 5 minutes. 100 copper pad portions of the circuit board after the roughening treatment were observed, the presence or absence of cracks in the resin composition layer was confirmed, and evaluated based on the following criteria.

○: 10 or less cracks

×: More than 10 cracks

Claims (13)

(A) epoxy resin,
(B) an active ester compound, and
(C) A resin composition containing 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 component (C) has a softening point of 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 component (E) is 40% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to claim 1, further comprising (F) a curing agent. A sheet-like laminated material containing the resin composition according to any one of claims 1 to 9. A resin sheet having 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.