CN113308168A

CN113308168A - Resin composition

Info

Publication number: CN113308168A
Application number: CN202110200826.2A
Authority: CN
Inventors: 川合贤司; 大石凌平; 野崎浩平
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2020-02-27
Filing date: 2021-02-23
Publication date: 2021-08-27
Anticipated expiration: 2041-02-23
Also published as: CN113308168B; KR20210109457A; JP2021134300A; TW202146574A; JP7259783B2; JP2023083345A

Abstract

The subject of the invention is to provide: a resin composition which can suppress unevenness generated when laminating the resin composition; a resin sheet comprising the resin composition; a printed wiring board and a semiconductor device are provided with an insulating layer formed by using the resin composition. The present invention provides a resin composition comprising (A) an epoxy resin, and (B) E(3) An active ester compound of at least any one of the groups shown. Wherein, represents a connecting bond. n represents an integer of 1 to 5.

Description

Resin composition

Technical Field

The present invention relates to a resin composition. Further, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device obtained using the resin composition.

Background

As a manufacturing technique of a printed wiring board, a manufacturing method based on a stack (build) method in which insulating layers and conductor layers are alternately stacked is known.

As an insulating material for a printed wiring board that can be used for such an insulating layer, for example, patent document 1 discloses a resin composition.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2018-199797.

Disclosure of Invention

Technical problem to be solved by the invention

The insulating layer is generally formed by laminating a resin composition layer on a substrate and thermally curing it. The present inventors have made extensive studies and, as a result, have found that: when an insulating layer is formed by laminating resin composition layers including a conventional resin composition, the uniformity of the surface of the insulating layer is reduced, and unevenness (unevenness after lamination) is likely to occur. When the surface of the insulating layer has such unevenness, the wiring formability of the insulating layer may be poor.

The invention provides a resin composition which can inhibit unevenness (ムラ) generated when laminating the resin composition; a resin sheet comprising the resin composition; a printed wiring board and a semiconductor device are provided with an insulating layer formed by using the resin composition.

Means for solving the technical problem

The present inventors have made extensive studies on the above problems, and as a result, have found that the above problems can be solved by containing an active ester compound having a specific group, thereby completing the present invention.

That is, the present invention includes the following items,

[1] a resin composition comprising

(A) An epoxy resin, and

(B) an active ester compound having at least one group selected from the group consisting of the groups represented by the following formulae (1) to (3),

[ chemical formula 1]

(wherein, represents a connecting bond, in the formula (3), n represents an integer of 1 to 5.)

[2] The resin composition according to [1], wherein the component (B) is an active ester compound represented by the following general formula (B-1),

[ chemical formula 2]

(in the general formula (b-1),

Ar¹¹each independently represents a group represented by the formula (1), a group represented by the formula (2), or a group represented by the formula (3),

Ar¹²each independently represents a divalent aromatic hydrocarbon group optionally having a substituent,

Ar¹³each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, a divalent aliphatic hydrocarbon group optionally having a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by combining these groups. a represents an integer of 1 to 6, and b represents an integer of 0 to 10. )

[3]According to [2]]The resin composition, wherein Ar in the general formula (b-1)¹³Each independently represents a divalent group in which a divalent aromatic hydrocarbon group optionally having a substituent and an oxygen atom are combined;

[4] the resin composition according to any one of [1] to [3], wherein the component (B) is an active ester compound represented by the following general formula (B-3),

[ chemical formula 3]

(in the general formula (b-3), Ar³¹Each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). a2 represents an integer of 1 to 6C2 represents an integer of 1 to 5, and d independently represents an integer of 0 to 6. )

[5] The resin composition according to any one of [1] to [4], further comprising (C) an inorganic filler;

[6] the resin composition according to any one of [1] to [5], which is used for forming an insulating layer;

[7] the resin composition according to any one of [1] to [6], which is used for forming an insulating layer for forming a conductor layer;

[8] a resin sheet, comprising:

a support, and

a resin composition layer comprising the resin composition according to any one of [1] to [7] provided on the support;

[9] a printed wiring board comprising an insulating layer formed by using a cured product of the resin composition according to any one of [1] to [7 ];

[10] a semiconductor device comprising the printed wiring board of [9 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: a resin composition which can suppress unevenness after lamination which occurs in the case of laminating a resin composition; a resin sheet comprising the resin composition; a printed wiring board and a semiconductor device are provided with an insulating layer formed by using a cured product of the resin composition.

Detailed Description

The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the embodiments and examples described below, and can be implemented by arbitrarily changing the embodiments without departing from the scope of the claims and the equivalent scope thereof.

[ resin composition ]

The resin composition of the present invention contains (A) an epoxy resin and (B) an active ester compound having at least one group selected from the group consisting of groups represented by the following formulas (1) to (3). By containing the component (B) in the resin composition, the occurrence of unevenness after lamination that can be generated in the case of laminating a resin composition layer containing the resin composition can be suppressed. In addition, in the present invention, a cured product having excellent plating peel strength, copper foil adhesion, and copper foil adhesion after HAST, low dielectric characteristics, and low arithmetic mean roughness (Ra) can be obtained,

[ chemical formula 4]

(wherein, represents a connecting bond; in the formula (3), n represents an integer of 1 to 5.).

The resin composition may further contain any component in addition to the components (a) to (B). Examples of the optional components include (C) an inorganic filler, (D) a curing agent, (E) a curing accelerator, and (F) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

(A) epoxy resin

The resin composition contains (A) an epoxy resin as the component (A). Examples of the component (a) include a biscresol (bixylenol) type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolac (naphthol novolac) type epoxy resin, a phenol novolac (phenol novolac) type epoxy resin, a tert-butyl-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac (cresol novolac) type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, an epoxy resin having a spiro ring, a cyclohexane type epoxy resin, a bisphenol a epoxy resin, a dicyclopentadiene type epoxy resin, a bisphenol a epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, an anthracene type epoxy resin, a heterocyclic ring-containing epoxy resin, a cyclohexane type epoxy resin, a bisphenol a, Cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. The epoxy resin may be used alone in 1 kind, or in combination of 2 or more kinds.

The resin composition preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule as the component (a). From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the component (a).

The epoxy resin includes an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin which is solid at a temperature of 20 ℃ (hereinafter sometimes referred to as "solid epoxy resin"). The resin composition may contain only a liquid epoxy resin or only a solid epoxy resin as the component (a), or may contain a combination of a liquid epoxy resin and a solid epoxy resin.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.

The solid epoxy resin is preferably a biphenol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol AF-type epoxy resin, a tetraphenylethane-type epoxy resin, and more preferably a naphthol-type epoxy resin.

Specific examples of the solid epoxy resin include: HP4032H (naphthalene epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200", "HP-7200 HH" and "HP-7200H" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" and "HP 6000" (naphthylene ether type epoxy resins) manufactured by DIC corporation; EPPN-502H (trisphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H", "NC 3000L" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical company; "ESN 475V" (naphthol type epoxy resin) manufactured by NIPPON STEEL Chemical & Material co., Ltd.); ESN485 (naphthol novolac type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "YX 4000H", "YX 4000", "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical company; "YX 4000 HK" (bisphenol type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; PG-100 and CG-500 manufactured by Osaka gas chemical company; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 1010" (solid bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation, and the like. These can be used alone in 1 kind, also can be combined with more than 2 kinds.

The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.

The liquid epoxy resin is preferably bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin; glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure, more preferably naphthalene type epoxy resin.

Specific examples of the liquid epoxy resin include: "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene epoxy resins) manufactured by DIC; "828 US", "jER 828 EL", "825", "EPIKOTE 828 EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi chemical company; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630" and "630 LSD" (glycidyl amine type epoxy resins) manufactured by mitsubishi chemical corporation; "ZX 1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon iron chemical Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Dailuo corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Dailuo corporation; "ZX 1658" and "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) manufactured by Nippon iron chemical Co., Ltd. These can be used alone in 1 kind, also can be combined with more than 2 kinds.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (a), the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1: 1-1: 20, more preferably 1: 1.5-1: 15, particularly preferably 1: 2-1: 10. by making the amount ratio of the liquid epoxy resin to the solid epoxy resin within the range, the desired effects of the present invention can be remarkably obtained. Further, when the resin sheet is used in the form of a resin sheet, appropriate adhesiveness can be provided. In addition, when the resin sheet is used in the form of a resin sheet, sufficient flexibility is obtained, and handling properties are improved. Further, a cured product having a sufficient breaking strength can be usually obtained.

(A) The epoxy equivalent of the component (A) is preferably 50 to 5000g/eq, more preferably 50 to 3000g/eq, still more preferably 80 to 2000g/eq, still more preferably 110 to 1000g/eq. By setting the crosslinking density in this range, the cured product of the resin composition layer can have a sufficient crosslinking density, and an insulating layer having a small surface roughness can be formed. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of an epoxy group. The epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the component (A) is preferably 100 to 5000, more preferably 200 to 3000, further preferably 250 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the content of the component (a) is preferably 1 mass% or more, more preferably 5 mass% or more, and still more preferably 10 mass% or more, assuming that the nonvolatile component in the resin composition is 100 mass%. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, particularly preferably 15% by mass or less. In the present invention, unless otherwise explicitly stated, the content of each component in the resin composition is a value when the nonvolatile content in the resin composition is 100 mass%.

< (B) an active ester compound having at least one group represented by the following formulae (1) to (3)

The resin composition contains, as the component (B), an active ester compound having at least one of the groups represented by the following formulae (1) to (3). By containing the component (B) in the resin composition, the occurrence of unevenness after lamination can be suppressed. Further, by containing the component (B) in the resin composition, a cured product having excellent plating peel strength, copper foil adhesion, and copper foil adhesion after HAST, low dielectric characteristics, and low arithmetic mean roughness (Ra) can be obtained in general.

[ chemical formula 5]

(B) As component (A), a compound having at least one of the groups represented by the formulae (1) to (3) and having an active ester site reactive with component (A) can be used. The component (B) preferably has at least one group selected from the groups represented by the formulae (1) to (3) at the terminal. The component (B) may have different groups at both ends, or may have the same group at both ends.

The group represented by formula (1) may be a group derived from cresol shown below. The methyl group in the group represented by the formula (1) is preferably bonded at any of the ortho-position, meta-position and para-position with respect to the oxygen atom, more preferably bonded at the ortho-position,

[ chemical formula 6]

The group represented by formula (2) may be a group derived from phenylphenol shown below. The phenyl group in the group represented by the formula (2) is preferably bonded at any of the ortho-position, meta-position and para-position with respect to the oxygen atom at the phenol site, more preferably bonded at the ortho-position,

[ chemical formula 7]

The group represented by formula (3) may be a group derived from styrenated phenol shown below. The styrene moiety in the group represented by the formula (3) is preferably bonded at any of the ortho-position, meta-position and para-position with respect to the oxygen atom at the phenol moiety, more preferably bonded at the ortho-position.

In the formula (3), n represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably an integer of 1 to 2,

[ chemical formula 8]

(wherein n1 is as defined above for n in formula (3))

(B) The component (B) is preferably a compound represented by the following general formula (b-1),

[ chemical formula 9]

(in the general formula (b-1), Ar¹¹Each independently represents a group represented by the formula (1), a group represented by the formula (2), or a group represented by the formula (3), Ar¹²Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, Ar¹³Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, a divalent aliphatic hydrocarbon group optionally having a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by combining these groups. a represents an integer of 1 to 6, and b represents an integer of 0 to 10. ).

In the general formula (b-1), Ar¹¹Each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). The groups represented by the formulae (1) to (3) are as described above. Among them, the group represented by the formula (1) and the group represented by the formula (2) are preferred.

In the general formula (b-1), Ar¹²Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent. The divalent aromatic hydrocarbon group includes an arylene group, an aralkylene group and the like, and an arylene group is preferred. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include phenylene, naphthylene, anthrylene, and biphenylene. The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and still more preferably an aralkylene group having 7 to 15 carbon atoms. Among them, a benzylidene group is preferred.

In the general formula (b-1), Ar¹³Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, a divalent aliphatic hydrocarbon group optionally having a substituent, an oxygen atom, a sulfur atom, or a divalent group composed of a combination of these groups, and preferably a divalent group composed of a combination of these groups. As a divalent aromatic hydrocarbon radical with Ar¹²The divalent aromatic hydrocarbon groups are the same.

The divalent aliphatic hydrocarbon group is more preferably a divalent saturated aliphatic hydrocarbon group, and is preferably an alkylene group or a cycloalkylene group, more preferably a cycloalkylene group.

The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a1, 1-dimethylmethylene group, a 1-methylethylene group, a1, 1-dimethylethylene group, a1, 2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, and a hexylene group.

The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and still more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and the like.

The divalent group composed of a combination of these groups is preferably a divalent group composed of a divalent aromatic hydrocarbon group optionally having substituents and oxygen atoms, more preferably a divalent group composed of 1 or more divalent aromatic hydrocarbon groups optionally having substituents and 1 or more oxygen atoms alternately combined, and still more preferably a divalent group composed of 1 or more naphthylene groups optionally having substituents and 1 or more oxygen atoms alternately combined. Therefore, further preferable is an optionally substituted naphthylene oxy group.

Ar¹²A divalent aromatic hydrocarbon group represented by, Ar¹³The divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group may have a substituent. The number of the substituents may be 1 or more. Examples of the substituent include an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and the like. The substituents may be contained alone or in combination of two or more.

Examples of the aryl group having 6 to 20 carbon atoms include benzyl, phenyl, naphthyl, anthryl, tolyl, xylyl, etc., with benzyl being preferred.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1, 2-dimethylpropyl, n-hexyl, isohexyl, n-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclononyl.

Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. The above-mentioned substituent may further have a substituent (hereinafter, sometimes referred to as "secondary substituent"). As the secondary substituent, the same substituents as those described above may be used unless otherwise specified.

In the general formula (b-1), a represents an integer of 1 to 6, preferably an integer of 1 to 5, more preferably an integer of 1 to 3. When the compound represented by the general formula (b-1) is an oligomer or a polymer, a represents the average value thereof.

In the general formula (b-1), b represents an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 3, further preferably 0. When the compound represented by the general formula (b-1) is an oligomer or a polymer, b represents the average value thereof.

(B) Component (b) is preferably a compound represented by the general formula (b-2),

[ chemical formula 10]

(in the general formula (b-2), Ar²¹Each independently represents a group represented by the formula (1), a group represented by the formula (2), or a group represented by the formula (3), Ar²²Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, Ar²³Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent. a1 represents an integer of 1 to 6, and c1 represents an integer of 1 to 5. ).

Ar²¹Each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). The groups represented by the formulae (1) to (3) are as described above. Among them, the group represented by the formula (1) and the group represented by the formula (2) are preferred.

Ar²²Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent. Ar (Ar)²²With Ar in the general formula (b-1)¹²The meaning is the same.

Ar²³Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent. Ar (Ar)²³With Ar in the general formula (b-1)¹³The divalent aromatic hydrocarbon group optionally having a substituent(s) has the same meaning.

In the general formula (b-2), a1 represents an integer of 1 to 6. a1 is the same as a in the general formula (b-1).

In the general formula (b-2), c1 represents an integer of 1 to 5. c1 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3.

(B) Component (b) is preferably a compound represented by the general formula (b-3),

[ chemical formula 11]

(in the general formula (b-3), Ar³¹Each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). a2 represents an integer of 1 to 6, c2 represents an integer of 1 to 5, and d independently represents an integer of 0 to 6. ).

Ar³¹Each independently represents a group represented by formula (1), a group represented by formula (2), or a group represented by formula (3). The groups represented by the formulae (1) to (3) are as described above. Among them, the group represented by the formula (1) and the group represented by the formula (2) are preferred.

In the general formula (b-3), a2 represents an integer of 1 to 6. a2 is the same as a in the general formula (b-1).

In the general formula (b-3), c2 represents an integer of 1 to 5. c2 has the same meaning as c1 in the general formula (b-2).

In the general formula (b-3), d independently represents an integer of 0 to 6. d is preferably an integer of 1 to 5, more preferably an integer of 1 to 4.

(B) The component (b) can be synthesized by a known method, and can be synthesized, for example, by the method described in the following examples. (B) The synthesis of the component (a) can be carried out, 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 component (B) is preferably 150 or more, more preferably 200 or more, further preferably 250 or more, preferably 4000 or less, more preferably 3000 or less, further preferably 2500 or less, from the viewpoint of remarkably obtaining the effects of the present invention. (B) The weight average molecular weight of the component (a) is a weight average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.

From the viewpoint of remarkably obtaining the effect of the present invention, the active ester equivalent (unsaturated bond equivalent) of the component (B) is preferably 50g/eq or more, more preferably 100g/eq or more, further preferably 150g/eq or more, preferably 2000g/eq or less, further preferably 1000g/eq or less, further preferably 500g/eq or less. The active ester equivalent is the mass of the (B) component containing 1 equivalent of an unsaturated bond.

(A) The amount ratio of the component (a) to the component (B) is represented by [ (total number of epoxy groups of the component (a)): the ratio of [ (total number of active ester groups of component B) ] is preferably 1: 0.01-1: 20, preferably 1: 0.1-1: 10, more preferably 1: 0.5-1: 5. here, "the total number of epoxy groups of the component (a)" means a total value obtained by dividing the mass of nonvolatile components of the component (a) present in the resin composition by the epoxy equivalent weight. The expression "total number of active ester groups in the component (B)" means a total value of all the values obtained by dividing the mass of nonvolatile components of the component (B) present in the resin composition by the active ester group equivalent. By making the amount ratio of the component (a) to the component (B) within the above range, the effects of the present invention can be remarkably obtained.

From the viewpoint of suppressing the occurrence of unevenness after lamination, the content of the component (B) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, preferably 30% by mass or less, preferably 25% by mass or less, more preferably 20% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.

(C) inorganic filler

The resin composition may further contain an inorganic filler as the component (C) as an optional component in addition to the above components. By using (C) the inorganic filler, the dielectric characteristics and insulating properties of the cured product of the resin composition can be improved.

As a material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, zirconium phosphate, zirconium phosphotungstate, and the like. Among them, silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as the silica, spherical silica is preferable. (C) The inorganic filler may be used alone in 1 kind, or in combination of 2 or more kinds.

Examples of commercially available products of component (C) include "UFP-30" manufactured by DENKA corporation; "SP 60-05" and "SP 507-05" manufactured by Nissi iron-alloy materials Corp; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by Yadu Ma (Admatechs) of Kabushiki Kaisha; "SILFIL NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N" manufactured by Kyuyama, Inc.; "SC 2500 SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Yadu Ma, K.K.; and the like.

The specific surface area of the component (C) is preferably 1m²More than g, preferably 2m²More than g, particularly preferably 3m²More than g. The upper limit is not particularly limited, but is preferably 60m²Less than 50 m/g²Less than or equal to 40 m/g²The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area can be obtained by adsorbing nitrogen gas onto the surface of a sample by the BET method using a specific surface area measuring apparatus (Macsorb HM-1210 manufactured by Mountech corporation) and calculating the specific surface area by the BET multipoint method.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the average particle size of the component (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, more preferably 5 μm or less, further preferably 2 μm or less, further preferably 1 μm or less.

(C) The average particle diameter of the component can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, it can be determined by: the particle size distribution of the inorganic filler was prepared on a volume basis by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size was defined as an average particle size. The measurement sample may be a sample obtained by: 100mg of the inorganic filler and 10g of methyl ethyl ketone were weighed into a vial, and dispersed for 10 minutes by ultrasonic waves. For the measurement sample, the volume-based particle size distribution of component (C) was measured in a flow cell (flow cell) using a laser diffraction type particle size distribution measuring apparatus with the wavelength of the light source used being blue and red, and the average particle size was calculated from the obtained particle size distribution as the median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Ltd.

From the viewpoint of improving moisture resistance and dispersibility, component (C) is preferably treated with a surface-treating agent. Examples of the surface treatment agent include vinyl silane coupling agents, (meth) acrylic acid coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, alkoxysilanes, organosilicon nitrogen compounds, titanate coupling agents, and the like. Among these, vinyl silane-based coupling agents, (meth) acrylic acid-based coupling agents, and aminosilicone-based coupling agents are preferable from the viewpoint of remarkably obtaining the effects of the present invention. Further, 1 kind of the surface treatment agent may be used alone, or 2 or more kinds may be used in any combination.

Examples of commercially available surface treatment agents include: "KBM 1003" (vinyltriethoxysilane), "KBM 503" (3-methacryloxypropyltriethoxysilane), "KBM 403" (3-glycidoxypropyltrimethoxysilane), by Signal chemical industry, "KBM 803" (3-mercaptopropyltrimethoxysilane), by Signal chemical industry, "KBE 903" (3-aminopropyltriethoxysilane), by Signal chemical industry, "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane), by Signal chemical industry, "SZ-31" (hexamethyldisilazane), by Signal chemical industry, "KBM 103" (phenyltrimethoxysilane), by Signal chemical industry, "KBM-4803" (long-chain epoxy-type silane coupling agent), KBM-7103 (3,3, 3-trifluoropropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, Ltd.

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

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of the inorganic filler is preferably 0.02mg/m²Above, preferably 0.1mg/m²Above, more preferably 0.2mg/m²The above. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is preferably 1mg/m²The concentration is preferably 0.8mg/m or less²The concentration is preferably 0.5mg/m or less²The following.

The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after the surface treatment is washed with a solvent (for example, Methyl Ethyl Ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent may be added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic washing may be performed at 25 ℃ for 5 minutes. The supernatant liquid was removed, the solid components were dried, and then the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd., can be used.

The content of the inorganic filler is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, preferably 90% by mass or less, further preferably 80% by mass or less, further preferably 75% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of remarkably obtaining the effect of the present invention.

(D) curing agent

The resin composition may further contain a curing agent as the component (D) as an optional component in addition to the above components. Wherein the component (B) is not included.

As the curing agent (D), a compound which can react with the component (a) to cure the resin composition can be used, and examples thereof include an active ester-based curing agent, a phenol-based curing agent, a benzoxazine-based curing agent, a carbodiimide-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, a cyanate ester-based curing agent, a maleimide-based curing agent, a polyphenylene ether-based curing agent (styrene-based curing agent), and the like which are not the component (B). Among them, from the viewpoint of remarkably obtaining the effect of the present invention, any of a phenol-based curing agent, a carbodiimide-based curing agent, a maleimide-based curing agent and a polyphenylene ether-based curing agent is preferable.

Examples of the active ester-based curing agent include those having 1 or more active ester groups in 1 molecule. Among them, as the active ester-based curing agent, compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, are preferable. The active ester-based curing agent is preferably a curing agent obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac resin (phenol novolac), and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 1 molecule of dicyclopentadiene with 2 molecules of phenol.

Preferred specific examples of the active ester-based curing agent include: an active ester compound having a dicyclopentadiene structure-containing diphenol structure, an active ester compound having a naphthalene structure, an active ester compound comprising an acetyl compound of a phenol novolac resin, and an active ester compound comprising a benzoyl compound of a phenol novolac resin, and among these, an active ester compound having a naphthalene structure and an active ester compound having a dicyclopentadiene structure-containing diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" means a divalent structure formed from phenylene-dicyclopentylene-phenylene.

As the commercially available products of the active ester-based curing agents, examples of the active ester compound having a dicyclopentadiene type diphenol structure include "EXB 9451", "EXB 9460S", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65 TM", "EXB-8000L-65 TM" (manufactured by DIC Co., Ltd.); examples of the active ester compound having a naphthalene structure include "HPC-8150-62T", "EXB-8100L-65T", "EXB-8150L-65T", "EXB 9416-70 BK" and "HPC-8900-70 BK" (manufactured by DIC); examples of the active ester compound containing an acetylated phenol novolac resin include "DC 808" (manufactured by Mitsubishi chemical corporation); examples of the active ester compound of the benzoyl compound containing a phenol novolac resin include "YLH 1026" (manufactured by mitsubishi chemical corporation); examples of the active ester-based curing agent for the acetylated phenol novolac resin include "DC 808" (manufactured by mitsubishi chemical corporation); examples of the active ester curing agent for the benzoylate of the phenol novolac resin include "YLH 1026" (manufactured by mitsubishi chemical corporation), "YLH 1030" (manufactured by mitsubishi chemical corporation), and "YLH 1048" (manufactured by mitsubishi chemical corporation).

Examples of the phenol-based curing agent include those having 1 or more, preferably 2 or more hydroxyl groups bonded to aromatic rings (benzene rings, naphthalene rings, etc.) in 1 molecule. Among them, compounds having a hydroxyl group bonded to a benzene ring are preferred. In addition, a phenol-based curing agent having a novolac resin (novolac) structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferable, and a phenol-based curing agent having a triazine skeleton is more preferable. Particularly preferred is a phenol novolac resin curing agent containing a triazine skeleton from the viewpoint of highly satisfying heat resistance, water resistance and adhesion.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include: MEH-7700, MEH-7810, MEH-7851, MEH-8000H, manufactured by Ming and Cheng chemical company; "NHN", "CBN" and "GPH" manufactured by Nippon chemical Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495V", "SN-375", "SN-395", manufactured by Nissan chemical materials Ltd; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165", manufactured by DIC; GDP-6115L, GDP-6115H, ELPC75, etc., manufactured by Rongche chemical Co.

Specific examples of the benzoxazine-based curing agent include "HFB 2006M" manufactured by Showa Polymer Co., Ltd, "P-d", "F-a", "ALP-d" manufactured by four national chemical industries, and "ODA-BOZ" manufactured by JFE chemical industries.

Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", "V-07" manufactured by Nisshinbo chemical Co., Ltd; stabaxol (registered trademark) P manufactured by Rhein Chemie, Inc.

Examples of the acid anhydride-based curing agent include a curing agent having 1 or more acid anhydride groups in one molecule. Specific examples of the acid anhydride-based curing agent include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic anhydride, 3,3'-4,4' -diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2), 5-dioxo-3-furyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerizing styrene with maleic acid, and other polymer-type acid anhydrides. As the acid anhydride-based curing agent, commercially available products such as "MH-700" manufactured by Nissian chemical Co., Ltd.

Examples of the amine-based curing agent include those having 1 or more amino groups in 1 molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like, and among them, aromatic amines are preferable from the viewpoint of exhibiting the desired effect of the present invention. The amine-based curing agent is preferably a primary or secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4 '-methylenebis (2, 6-dimethylaniline), diphenyldiaminosulfone, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4 '-diaminodiphenyl ether, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethanediamine, and, 2, 2-bis (4-aminophenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone and the like. As the amine-based curing agent, commercially available ones can be used, and examples thereof include "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARDA-B", "KAYAHARDA-S" manufactured by Nippon chemical company, and "EPICURE W" manufactured by Mitsubishi chemical company.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1, 5-phenylene cyanate), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, difunctional cyanate ester resins such as 2, 2-bis (4-cyanate ester) phenylpropane, 1-bis (4-cyanate ester phenylmethane), bis (4-cyanate ester-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate ester-phenyl-1- (methylethylidene)) benzene, bis (4-cyanate ester-phenyl) sulfide, and bis (4-cyanate ester-phenyl) ether; polyfunctional cyanate ester resins derived from phenol novolac resins, cresol novolac resins, and the like; prepolymers obtained by triazinating a part of these cyanate ester resins, and the like. Specific examples of cyanate ester-based curing agents include: "PT 30" and "PT 60" (both phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Japan corporation; "ULL-950S" (polyfunctional cyanate ester resin); "BA 230" and "BA 230S 75" (prepolymers in which a part or all of bisphenol A dicyanate is triazinated to form a trimer).

The maleimide curing agent is a compound containing a maleimide group represented by the following formula (D-1) in the molecule. The maleimide curing agent may be used singly or in combination of two or more,

[ chemical formula 12]

From the viewpoint of remarkably obtaining the desired effect of the present invention, the number of maleimide groups per 1 molecule of the maleimide-based curing agent is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, preferably 10 or less, more preferably 6 or less, particularly preferably 3 or less.

From the viewpoint of remarkably obtaining the effect desired by the present invention, the maleimide-based curing agent preferably has any one of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and more preferably has an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

The aliphatic hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent saturated aliphatic hydrocarbon group, and further preferably an alkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an alkylene group having 1 to 3 carbon atoms, particularly preferably a methylene group.

The aromatic hydrocarbon group is preferably a monovalent or divalent aromatic hydrocarbon group, more preferably an aryl group or an arylene group. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include phenylene, naphthylene, anthrylene, aralkyl, biphenylene, and biphenylaralkyl groups, and among them, phenylene, aralkyl, biphenylene, and biphenylaralkyl groups are preferable, and phenylene, aralkyl, and biphenylene are more preferable. The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, still more preferably an aryl group having 6 to 10 carbon atoms, and particularly preferably a phenyl group.

In the maleimide-based curing agent, it is preferable that the nitrogen atom of the maleimide group is directly bonded to a monovalent or divalent aromatic hydrocarbon group, from the viewpoint of remarkably obtaining the effect desired in the present invention. Here, "directly" means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

The maleimide-based curing agent is preferably, for example, a structure represented by the following formula (D-2),

[ chemical formula 13]

In the formula (D-2), R³¹And R³⁶Represents a maleimido group, R³²、R³³、R³⁴And R³⁵Each independently represents a hydrogen atom, an alkyl group or an aryl group, and each D independently represents a divalent aromatic group. m1 and m2 each independently represent an integer of 1 to 10, and a represents an integer of 1 to 100.

R in the formula (D-2)³²、R³³、R³⁴And R³⁵Each independently represents a hydrogen atom, an alkyl group, or an aryl group, preferably a hydrogen atom.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and an isopropyl group.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may be a single ring or a condensed ring. Examples of such aryl groups include phenyl, naphthyl, and anthracenyl.

The alkyl group and the aryl group may have a substituent. Examples of the substituent include a halogen atom, -OH, -O-C_1-6Alkyl, -N (C)_1-10Alkyl radical)₂、C_1-10Alkyl radical, C_6-10Aryl, -NH₂、-CN、-C(O)O-C_1-10Alkyl, -COOH, -C (O) H, -NO₂And the like. Herein, the term "C_p-q"(p and q are positive integers, and p < q) means that the organic group described immediately after the term has p to q carbon atoms. For example, "C_1-10The expression "alkyl" denotes an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a condensed ring.

D in the formula (D-2) represents a divalent aromatic group. Examples of the divalent aromatic group include phenylene, naphthylene, anthrylene, aralkyl, biphenylene, and biphenylaralkyl groups, and among them, biphenylene and biphenylaralkyl groups are preferable, and biphenylene is more preferable. The divalent aromatic group may have a substituent. As a substituent, with R in the general formula (D-2)³²The substituents which the alkyl groups may have are the same.

m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, further preferably 1 to 2, further preferably 1.

a represents an integer of 1 to 100, preferably 1 to 50, more preferably 1 to 20, further preferably 1 to 5.

As the maleimide-based curing agent, a resin represented by the formula (D-3) is preferred,

[ chemical formula 14]

In the formula (D-3), R³⁷And R³⁸Represents a maleimide group. a1 represents an integer of 1 to 100.

a1 has the same meaning as a in the formula (D-2), and the same preferable ranges are also applicable.

Commercially available maleimide curing agents can be used. Examples of commercially available products include "MIR-3000-70 MT" manufactured by Nippon chemical Co., Ltd.

In addition, another embodiment of the maleimide curing agent is a compound having at least one maleimide group in the molecule.

In the maleimide-based curing agent, it is preferred that the aliphatic group having 5 or more carbon atoms is directly bonded to the nitrogen atom of the maleimide group. Examples of the aliphatic group having 5 or more carbon atoms include an alkyl group, an alkylene group, and an alkenylene group.

The number of maleimide groups per 1 molecule of the maleimide-based curing agent may be 1, preferably 2 or more, preferably 10 or less, more preferably 6 or less, particularly preferably 3 or less. The effect of the present invention can be remarkably obtained by using a maleimide-based curing agent having 2 or more maleimide groups per 1 molecule.

The maleimide-based curing agent is preferably represented by the following general formula (D-4),

[ chemical formula 15]

In the general formula (D-4), M represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and L represents a single bond or a divalent linking group.

M represents a divalent aliphatic group having 5 or more carbon atoms and optionally having a substituent. The divalent aliphatic group having 5 or more carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, still more preferably 50 or less, still more preferably 45 or less, and still more preferably 40 or less carbon atoms. Examples of the divalent aliphatic group include an alkylene group and an alkenylene group. As a substituent of M, with R in the general formula (D-2)³²The alkyl group represented by the above formula may have the same substituent, and the substituent is preferably an alkyl group having 5 or more carbon atoms.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include alkylene, alkenylene, alkynylene, arylene, -C (═ O) -O-, -NR⁰-(R⁰Hydrogen atom, alkyl group having 1 to 3 carbon atoms), oxygen atom, sulfur atom, C (═ O) NR⁰Divalent radical derived from phthalimide, di-radical derived from pyromellitic diimideA divalent group, a combination of 2 or more divalent groups among them, and the like. The alkylene group, the alkenylene group, the alkynylene group, the arylene group, the divalent group derived from phthalimide, the divalent group derived from pyromellitic diimide, and a group in which 2 or more kinds of divalent groups are combined may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide means a divalent group derived from phthalimide, specifically a group represented by the general formula (D-5). The divalent group derived from pyromellitic diimide means a divalent group derived from pyromellitic diimide, specifically a group represented by the general formula (D-6). Wherein "" represents a connecting bond,

[ chemical formula 16]

The alkylene group as the divalent linking group in L is preferably an alkylene group having 1 to 50 carbon atoms, more preferably an alkylene group having 1 to 45 carbon atoms, particularly preferably an alkylene group having 1 to 40 carbon atoms. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylethylene group, a cyclohexylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a heptadecylene group, a hexadecylene group, a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

The alkenylene group as the divalent linking group in L is preferably an alkenylene group having 2 to 20 carbon atoms, more preferably an alkenylene group having 2 to 15 carbon atoms, particularly preferably an alkenylene group having 2 to 10 carbon atoms. The alkenylene group may be linear, branched or cyclic. Examples of such alkenylene groups include methylvinylene, cyclohexenylene, pentenylene, hexenylene, heptenylene, octenylene, and the like.

The alkynylene group as the divalent linking group in L is preferably an alkynylene group having 2 to 20 carbon atoms, more preferably an alkynylene group having 2 to 15 carbon atoms, particularly preferably an alkynylene group having 2 to 10 carbon atoms. The alkynylene group may be linear, branched or cyclic. Examples of such an alkynylene group include methylacetylene, cyclohexylene, pentylene, hexylene, heptylene, octylene, and the like.

The arylene group as the divalent linking group in L is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, still more preferably an arylene group having 6 to 14 carbon atoms, and yet more preferably an arylene group having 6 to 10 carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

The alkylene group, alkenylene group, alkynylene group, and arylene group as the divalent linking group in L may have a substituent. As a substituent, with R in the general formula (D-2)³²As the substituent which the alkyl group may have, an alkyl group having 5 or more carbon atoms is preferred.

Examples of the group consisting of a combination of 2 or more kinds of divalent groups in L include, for example, a divalent group consisting of a combination of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; a divalent group composed of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a divalent group composed of a combination of an alkylene group and a divalent group derived from pyromellitic diimide; and so on. Groups composed of a combination of 2 or more divalent groups can form a ring such as a condensed ring by the combination of the groups. In addition, the group formed by combining more than 2 divalent groups can be a repeating unit with the number of repeating units being 1-10.

Among them, L in the general formula (D-4) is preferably an oxygen atom, an arylene group having 6 to 24 carbon atoms which may be substituted, an alkylene group having 1 to 50 carbon atoms which may be substituted, an alkyl group having 5 or more carbon atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic diimide, or a divalent group formed by combining 2 or more of these groups. Among them, as L, it is more preferable that: an alkylene group; a divalent group having a structure of alkylene-a divalent group derived from phthalimide-an oxygen atom-a divalent group derived from phthalimide; a divalent group having a structure of alkylene-a divalent group derived from phthalimide-oxygen atom-arylene-alkylene-arylene-oxygen atom-a divalent group derived from phthalimide; divalent groups having the structure of alkylene-divalent groups derived from pyromellitic diimide.

The maleimide-based curing agent represented by the general formula (D-4) is preferably represented by the general formula (D-7),

[ chemical formula 17]

In the general formula (D-7), M¹Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent, and each Z independently represents an alkylene group having 5 or more carbon atoms which may have a substituent, or a divalent group having an aromatic ring which may have a substituent. t represents an integer of 1 to 10.

M¹Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M¹As in the general formula (D-4), M represents an alkylene group or an alkenylene group.

Each Z independently represents an optionally substituted alkylene group having 5 or more carbon atoms or an optionally substituted divalent group having an aromatic ring. The alkylene group in Z may be any of a linear, branched or cyclic alkylene group, and among them, a cyclic alkylene group having 5 or more carbon atoms, which may have a substituent, is preferable. The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, further preferably 50 or less, further preferably 45 or less, further preferably 40 or less. Examples of such an alkylene group include a group having an octylene-cyclohexylene structure, a group having an octylene-cyclohexylene-octylene structure, and a group having a propylene-cyclohexylene-octylene structure.

Examples of the aromatic ring in the divalent group having an aromatic ring represented by Z include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic diimide ring, an aromatic heterocycle, etc., and a benzene ring, a phthalimide ring, and a pyromellitic diimide ring are preferable. That is, as the divalent group having an aromatic ring, a divalent group having a benzene ring which may be substituted, a divalent group having a phthalimide ring which may be substituted, and a divalent group having a pyromellitic diimide ring which may be substituted are preferable. Examples of the divalent group having an aromatic ring include a group composed of a divalent group derived from phthalimide and an oxygen atom in combination; a group composed of a divalent group derived from phthalimide, an oxygen atom, an arylene group, and an alkylene group; a group composed of an alkylene group and a divalent group derived from pyromellitic diimide; a divalent group derived from pyromellitic diimide; a group composed of a divalent group derived from phthalimide and an alkylene group; and so on. The arylene group and the alkylene group are the same as those in the divalent linking group represented by L in the general formula (F-4).

The alkylene group represented by Z and the divalent group having an aromatic ring may have a substituent. As a substituent, with R in the general formula (D-2)³²The same applies to the substituents which the alkyl group may have.

Specific examples of the group represented by Z include the following groups. Wherein "" represents a connecting bond,

[ chemical formula 18]

[ chemical formula 19]

The maleimide-based curing agent represented by the general formula (D-4) is preferably any one of the maleimide-based curing agents represented by the general formula (D-8) and the maleimide-based curing agents represented by the general formula (D-9),

[ chemical formula 20]

In the general formula (D-8), M²And M³Each independently represents a divalent aliphatic group having 5 or more carbon atoms and optionally having a substituent, R⁴⁰Each independently represents an oxygen atom, an arylene group, an alkylene group, or a divalent group formed by combining 2 or more of these groups. t1 represents an integer of 1 to 10;

in the general formula (D-9), M⁴、M⁶And M⁷Each independently represents a divalent aliphatic group having 5 or more carbon atoms optionally having a substituent, M⁵Each independently represents a divalent group having an aromatic ring optionally having a substituent, R⁴¹And R⁴²Each independently represents an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0 to 10, and u1 and u2 each independently represent an integer of 0 to 4.

M²And M³Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M²And M³As with the divalent aliphatic group having 5 or more carbon atoms represented by M in the general formula (D-4), it represents an alkylene group or an alkenylene group, preferably a trioxadecylene group.

R⁴⁰Each independently represents an oxygen atom, an arylene group, an alkylene group, or a combination of 2 or more divalent groups thereof. The arylene group and the alkylene group are the same as those in the divalent linking group represented by L in the general formula (F-4). As R⁴⁰Preferably, the group is a combination of 2 or more divalent groups or an oxygen atom.

As R⁴⁰The group composed of a combination of 2 or more kinds of divalent groups in (1) includes a combination of an oxygen atom, an arylene group, and an alkylene group. Specific examples of the group consisting of a combination of 2 or more kinds of divalent groups include the following groups.

Wherein "" represents a connecting bond,

[ chemical formula 21]

M⁴、M⁶And M⁷Each independently represents a divalent aliphatic group having 5 or more carbon atoms which may have a substituent. M⁴、M⁶And M⁷As with the optionally substituted divalent aliphatic group having 5 or more carbon atoms represented by M in the general formula (D-4), it represents an alkylene group or an alkenylene group, preferably a hexylene group, heptylene group, octylene group, nonylene group or decylene group, more preferably an octylene group.

M⁵Each independently represents a divalent group having an aromatic ring which may have a substituent. M⁵As the divalent group having an aromatic ring optionally having a substituent represented by Z in the general formula (D-7), a combination of an alkylene group and a divalent group derived from pyromellitic diimide is preferable; the group comprising a combination of a divalent group derived from phthalimide and an alkylene group, more preferably a combination of an alkylene group and a divalent group derived from pyromellitic diimide. The arylene group and the alkylene group are the same as those in the divalent linking group represented by L in the general formula (D-4).

As M⁵Specific examples of the group include the following groups. Wherein "" represents a connecting bond,

[ chemical formula 22]

R⁴¹And R⁴²Each independently represents an alkyl group having 5 or more carbon atoms. R⁴¹And R⁴²As with the above-mentioned alkyl group having 5 or more carbon atoms, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group are preferred, and a hexyl group and an octyl group are more preferred.

u1 and u2 each independently represent an integer of 1 to 15, preferably an integer of 1 to 10.

Specific examples of the maleimide curing agent include the following compounds (D1) to (D3). However, the maleimide-based curing agent is not limited to these specific examples. Wherein v represents an integer of 1 to 10,

[ chemical formula 23]

[ chemical formula 24]

Specific examples of the maleimide curing agent include "BMI 1500" (a compound of formula (D1) ")," BMI1700 "(a compound of formula (D2)"), and "BMI 689" (a compound of formula (D3)), which are manufactured by DMI.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the maleimide-based curing agent preferably has a maleimide group equivalent of 50g/eq to 2000g/eq, more preferably 100g/eq to 1000g/eq, and still more preferably 150g/eq to 500g/eq. The maleimide group equivalent is the mass of the maleimide-based curing agent containing 1 equivalent of maleimide group.

The polyphenylene ether-based curing agent is a curing agent having a vinyl phenyl group. Vinylphenyl refers to a group having the structure shown below,

[ chemical formula 25]

(. sup. represents a connecting bond.).

From the viewpoint of obtaining a cured product having a low dielectric loss tangent, the polyphenylene ether-based curing agent preferably has 2 or more vinylphenyl groups per 1 molecule.

The polyphenylene ether-based curing agent preferably has a cyclic structure from the viewpoint of obtaining a cured product having a low dielectric loss tangent. As the cyclic structure, a divalent cyclic group is preferred. The divalent cyclic group may be any of a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic ring structure. In addition, there may be a plurality of divalent cyclic groups.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, further preferably a 5-membered ring or more, preferably a 20-membered ring or less, further preferably a 15-membered ring or less, further preferably a 10-membered ring or less. The divalent cyclic group may have a monocyclic structure or a polycyclic structure.

The ring in the divalent cyclic group may be a skeleton of the ring formed of hetero atoms in addition to carbon atoms. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like, and an oxygen atom is preferable. The number of heteroatoms in the ring may be 1 or more, and may be 2 or more.

Specific examples of the divalent cyclic group include the following divalent groups (i) or (ii),

[ chemical formula 26]

(in the divalent groups (i), (ii), R⁵¹、R⁵²、R⁵⁵、R⁵⁶、R⁵⁷、R⁶¹And R⁶²Each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R⁵³、R⁵⁴、R⁵⁸、R⁵⁹And R⁶⁰Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. ).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is preferred. As R⁵¹、R⁵²、R⁵⁵、R⁵⁶、R⁵⁷、R⁶¹And R⁶²Preferably, it represents a methyl group. R⁵³、R⁵⁴、R⁵⁸、R⁵⁹And R⁶⁰Preferably a hydrogen atom or a methyl group.

In addition, the divalent cyclic group may combine a plurality of divalent cyclic groups. Specific examples of the case of combining divalent cyclic groups include divalent cyclic groups represented by the following formula (D4),

[ chemical formula 27]

(in the formula (D4), R⁷¹、R⁷²、R⁷⁵、R⁷⁶、R⁷⁷、R⁸¹、R⁸²、R⁸⁵And R⁸⁶Each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R⁷³、R⁷⁴、R⁷⁸、R⁷⁹、R⁸⁰、R⁸³And R⁸⁴Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. d1 and d2 each represents an integer of 0 to 300. Note that the case where one of d1 and d2 is 0 is excluded. ).

R⁷¹、R⁷²、R⁸⁵And R⁸⁶And R in formula (i)⁵¹The meaning is the same. R⁷³、R⁷⁴、R⁸³And R⁸⁴And R in formula (i)⁵³The meaning is the same. R⁷⁵、R⁷⁶、R⁷⁷、R⁸¹And R⁸²And R in the formula (ii)⁵⁵The meaning is the same. R⁷⁸、R⁷⁹And R⁸⁰And R in the formula (ii)⁵⁸The meaning is the same.

d1 and d2 each represents an integer of 0 to 300. Note that the case where one of d1 and d2 is 0 is excluded. D1 and d2 preferably represent an integer of 1 to 100, more preferably an integer of 1 to 50, and still more preferably an integer of 1 to 10. d1 and d2 may be the same or different.

The divalent cyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, an oxo group and the like, and an alkyl group is preferable.

The vinylphenyl group may be bound directly to the divalent cyclic group or via a divalent linking group. Examples of the divalent linking group include alkylene, alkenylene, arylene, heteroarylene, -C (═ O) O-, -NHC (═ O) -, -NC (═ O) N-, -NHC (═ O) O-, -C (═ O) -, -S-, -SO-, -NH-, and a plurality of these groups may be combined. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms. The alkylene group may be any of linear, branched, and cyclic. Examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1, 1-dimethylethylene, and methylene, ethylene, and 1, 1-dimethylethylene are preferable. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and still more preferably an alkenylene group having 2 to 5 carbon atoms. The arylene group or heteroarylene group is preferably an arylene group or heteroarylene group having 6 to 20 carbon atoms, more preferably an arylene group or heteroarylene group having 6 to 10 carbon atoms. As the divalent linking group, an alkylene group is preferable, and among them, a methylene group is preferable.

The polyphenylene ether-based curing agent is preferably represented by the following formula (D-10),

[ chemical formula 28]

(in the formula (D-10), R⁹¹And R⁹²Each independently represents a divalent linking group. Ring B1 represents a divalent cyclic group. ).

R⁹¹And R⁹²Each independently represents a divalent linking group. As the divalent linking group, the divalent linking group containingThe meaning is the same.

Ring B1 represents a divalent cyclic group. The ring B1 is the same as the above divalent cyclic group.

Ring B1 may have a substituent. The substituent is the same as the substituent that the above-mentioned divalent cyclic group may have.

Specific examples of the polyphenylene ether-based curing agent will be described below, but the present invention is not limited thereto,

[ chemical formula 29]

(q1 has the same meaning as D1 in formula (D4), and q1 has the same meaning as D2 in formula (D4)).

As the polyphenylene ether-based curing agent, commercially available products can be used, and examples thereof include "OPE-2 St" manufactured by Mitsubishi gas chemical corporation. The polyphenylene ether-based curing agent may be used alone or in combination of two or more.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the number average molecular weight of the polyphenylene ether-based curing agent is preferably 3000 or less, more preferably 2500 or less, further preferably 2000 or less and 1500 or less. The lower limit is preferably 100 or more, more preferably 300 or more, further preferably 500 or more and 1000 or more. The number average molecular weight is a number average molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC).

From the viewpoint of remarkably obtaining the effect of the present invention, the content of the (D) curing agent is preferably 1 mass% or more, more preferably 5 mass% or more, further preferably 10 mass% or more, preferably 25 mass% or less, further preferably 20 mass% or less, further preferably 15 mass% or less, with respect to 100 mass% of nonvolatile components in the resin composition.

When the number of epoxy groups of the component (A) is 1, the number of active groups of the curing agent (D) is preferably at least 0.1, more preferably at least 0.2, still more preferably at least 0.3, yet more preferably at most 2, yet more preferably at most 1.8, yet more preferably at most 1.6, particularly preferably at most 1.4. The term "the number of active groups of the (D) curing agent" means a total of all the values obtained by dividing the mass of nonvolatile components of the (D) curing agent present in the resin composition by the active group equivalent. When the number of epoxy groups of the component (a) is 1, the number of active groups of the curing agent (D) falls within the above range, and the desired effects of the present invention can be remarkably obtained.

(E) curing Accelerator

The resin composition may contain, as optional components, a curing accelerator as the component (E) in addition to the above components.

Examples of the component (E) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. (E) One of the components may be used alone, or two or more of the components may be used in combination.

Examples of the phosphorus-based curing accelerator include: triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

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

Examples of the imidazole-based curing accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, tris (meth) acrylate ester, or a mixture thereof, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi chemical corporation.

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

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 the organometallic complex include: organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the component (E) is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, further preferably 0.03 mass% or more, preferably 1 mass% or less, further preferably 0.5 mass% or less, further preferably 0.1 mass% or less, with respect to 100 mass% of nonvolatile components in the resin composition.

< (F) other additives

The resin composition may further contain other additives as optional components in addition to the above components. Examples of such additives include resin additives such as thermoplastic resins, flame retardants, thickeners, defoaming agents, leveling agents, and adhesion imparting agents. These additives may be used alone or in combination of two or more. The content of each additive can be appropriately set by those skilled in the art.

The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include: and a method of adding the compounding ingredients, adding a solvent if necessary, and mixing and dispersing the mixture by using a rotary mixer or the like.

< Properties and uses of resin composition >

The resin composition comprises a component (A) and a component (B). This can suppress the occurrence of unevenness generated when laminating the resin composition layer containing the resin composition. In the present invention, a cured product having excellent plating peel strength, copper foil adhesion, and copper foil adhesion after HAST, low dielectric characteristics, and low arithmetic mean roughness (Ra) can be obtained.

The resin composition exhibits such a characteristic that occurrence of unevenness at the time of laminating a resin composition layer containing the resin composition can be suppressed. Specifically, the procedure was carried out in accordance with the method described in examples described later. In this case, unevenness was not observed at all, and the surface was completely uniform. The details of the evaluation of unevenness after lamination can be measured by the methods described in the examples described later.

The roughened surface obtained by roughening the surface of a cured product obtained by heat-curing a resin composition at 130 ℃ for 30 minutes and then at 170 ℃ for 30 minutes generally exhibits a low arithmetic average roughness (Ra). Therefore, the cured product brings about an insulating layer having low arithmetic mean roughness. The arithmetic average roughness is preferably 300nm or less, more preferably 250nm or less, and still more preferably 200nm or less. On the other hand, the lower limit of the arithmetic average roughness may be 30nm or more. The arithmetic average roughness (Ra) can be measured by the method described in the examples described later.

A cured product obtained by thermally curing the resin composition at 190 ℃ for 90 minutes generally exhibits low dielectric characteristics (dielectric loss tangent). Therefore, the cured product brings about an insulating layer having a low dielectric loss tangent. The dielectric loss tangent is preferably 0.005 or less, more preferably 0.004 or less, further preferably 0.003 or less. The lower limit value of the dielectric loss tangent may be 0.0001 or higher. The dielectric loss tangent can be measured by the method described in the examples described below.

A cured product obtained by heat-curing the resin composition at 130 ℃ for 30 minutes, then at 170 ℃ for 30 minutes, and then at 200 ℃ for 90 minutes, generally exhibits excellent peel strength with a conductor layer (plated conductor layer) formed by plating. Therefore, the cured product provides an insulating layer having excellent peel strength with respect to the plated conductor layer. The peel strength is preferably 0.3kgf/cm or more, more preferably 0.35kgf/cm or more, still more preferably 0.4kgf/cm or more. The upper limit of the peel strength may be 10kgf/cm or less. The peel strength of the plated conductor layer can be measured by the method described in the examples described below.

A cured product obtained by heat-curing the resin composition at 130 ℃ for 30 minutes, subsequently at 170 ℃ for 30 minutes, and then at 200 ℃ for 90 minutes shows characteristics of excellent peel strength (copper foil adhesiveness) with a copper foil. Therefore, the cured product provides an insulating layer having excellent peel strength with the copper foil. The peel strength is preferably 0.3kgf/cm or more, more preferably 0.4kgf/cm or more, still more preferably 0.5kgf/cm or more. The upper limit of the peel strength may be 10kgf/cm or less. The adhesion of the copper foil can be measured by the method described in the examples described below.

A cured product obtained by heat-curing the resin composition at 130 ℃ for 30 minutes and then at 170 ℃ for 30 minutes generally exhibits excellent peel strength with a copper foil after a HAST test (130 ℃, humidity 85% RH, 100 hours) (copper foil adhesion after HAST). Therefore, the cured product provides an insulating layer having excellent peel strength after HAST with the copper foil. The adhesiveness of the copper foil after HAST is preferably at least 0.15kgf/cm, more preferably at least 0.2kgf/cm, still more preferably at least 0.25 kgf/cm. The upper limit of the adhesiveness of the copper foil after HAST can be 10kgf/cm or less. The adhesion of the copper foil after HAST can be measured by the method described in the examples described below.

The resin composition of the present invention can suppress the occurrence of unevenness at the time of laminating a resin composition layer containing the resin composition. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation applications. Specifically, it can be suitably used as a resin composition for forming an insulating layer (insulating layer forming resin composition for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer(s).

In addition, in a multilayer printed wiring board described later, it can be suitably used as: the resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board), and the resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board).

In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as: a resin composition for a rewiring-forming layer (a resin composition for forming a rewiring-forming layer) as an insulating layer for forming a rewiring layer; and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). In manufacturing the semiconductor chip package, a re-wiring layer may be further formed on the sealing layer,

(1) a step of laminating a temporary fixing film on the substrate,

(2) A step of temporarily fixing the semiconductor chip to the temporary fixing film,

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

(4) A step of peeling the base material and the temporary fixing film from the semiconductor chip,

(5) A step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled, and

(6) and forming a rewiring layer as a conductor layer on the rewiring-forming layer.

[ resin sheet ]

The resin sheet of the present invention comprises a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

From the viewpoint of making the printed wiring board thin and providing a cured product of the resin composition having excellent insulation even when the cured product is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 5 μm or more.

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

When a film made of a plastic material is used as the support, examples of the plastic material include: polyester such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), acrylic polymer such as polycarbonate (hereinafter sometimes abbreviated as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and particularly, inexpensive polyethylene terephthalate is preferable.

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

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

Further, as the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support with a release layer, commercially available products can be used, and examples thereof include "SK-1", "AL-5" and "AL-7" manufactured by Linderaceae, which are PET films having a release layer containing an alkyd resin-based release agent as a main component, "LUMIRROR T60" manufactured by Toray, manufactured by Ditika, and "Unipel" manufactured by Unitika.

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

In one embodiment, the resin sheet may further include other layers as necessary. Examples of the other layer include a protective film selected depending on the support and provided on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust or the like to the surface of the resin composition layer and formation of scratches can be suppressed.

The resin sheet can be produced, for example, as follows: a resin varnish obtained by dissolving a resin composition in an organic solvent is prepared, and the resin varnish is applied to a support by a die coater or the like, and dried to form a resin composition layer.

Examples of the organic solvent include: ketones such as acetone, Methyl Ethyl Ketone (MEK) and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate (cellosolve acetate), propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. One kind of the organic solvent may be used alone, or two or more kinds may be used in combination.

The drying can be carried out by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, and the drying is performed under conditions such that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. The drying conditions also vary depending on the boiling point of the organic solvent in the resin varnish, and for example, in the case of using a resin varnish containing 30 to 60 mass% of an organic solvent, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes.

The resin sheet can be stored in a roll form. When the resin sheet has a protective film, the protective film can be peeled off and used.

[ printed Wiring Board ]

The printed wiring board of the present invention comprises an insulating layer formed from a cured product of the resin composition of the present invention.

The printed wiring board can be produced, for example, by a method including the following steps (I) and (II) using the above resin sheet:

(I) laminating the resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate;

(II) a step of forming an insulating layer by thermally curing the resin composition layer.

The "inner layer substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductive layer on one or both surfaces thereof, and the conductive layer may be subjected to patterning. An inner layer substrate having a conductor layer (circuit) formed on one surface or both surfaces of a substrate is also referred to as an "inner layer circuit substrate". In addition, an intermediate product in which an insulating layer and/or a conductor layer is further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate in which components are embedded may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-crimping the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressure bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "heat-pressure bonding member") include a heated metal plate (SUS end plate (or other plate)) and a metal roll (SUS roll). It is preferable that the heating and pressure-bonding member is not directly pressed against the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The lamination of the inner substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heating and pressure-bonding temperature is preferably in the range of 60 to 160 ℃, more preferably 80 to 140 ℃, the heating and pressure-bonding pressure is preferably in the range of 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the heating and pressure-bonding time is preferably in the range of 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably carried out under a reduced pressure of 26.7hPa or less.

The lamination can be carried out by means of a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Kabushiki Kaisha, a vacuum applicator manufactured by Nikko-Materials, and a batch vacuum pressure laminator.

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

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

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

For example, the conditions for heat curing the resin composition layer may vary depending on the kind of the resin composition, and the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, and still more preferably 170 to 210 ℃. The curing time may be preferably from 5 minutes to 120 minutes, more preferably from 10 minutes to 100 minutes, and still more preferably from 15 minutes to 100 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, further preferably 15 minutes to 100 minutes) at a temperature of 50 ℃ or more and less than 120 ℃ (preferably 60 ℃ or more and 115 ℃ or less, further preferably 70 ℃ or more and 110 ℃ or less) before the resin composition layer is thermally cured.

In the production of the printed wiring board, (III) a step of forming a hole in 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) can be carried out by various methods known to those skilled in the art used for the production of printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). The formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated as necessary to form a multilayer wiring board.

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

The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), removal of smear is also performed. The roughening treatment step and conditions are not particularly limited, and known steps and conditions generally used for forming an insulating layer of a printed wiring board can be used. For example, the roughening treatment may be performed on the insulating layer by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid. The swelling solution used in the roughening treatment is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and an alkali solution is preferred, and a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available Swelling liquids include "spinning Dip securigant P", "spinning Dip securigant SBU", "spinning Dip securigant P (スウェリングディップ · セキュリガント P)" manufactured by atmet JAPAN (ato ech JAPAN). The swelling treatment with the swelling solution is not particularly limited, and for example, the swelling treatment can be performed by immersing the insulating layer in the swelling solution at 30 to 90 ℃ for 1 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 solution at 40 to 80 ℃ for 5 to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid 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 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution securigant P" manufactured by amett japan. The neutralizing Solution used for the roughening treatment is preferably an acidic aqueous Solution, and examples of commercially available products include "Reduction Solution securigant P" manufactured by amatt japan. The treatment with the neutralizing solution can be performed by immersing the treated surface having been subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ℃ for 1 to 30 minutes. From the viewpoint of handling and the like, it is preferable to immerse the object subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.

In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300nm or less, more preferably 250nm or less, and still more preferably 200nm or less. The lower limit is not particularly limited, but is preferably 30nm or more, more preferably 40nm or more, and still more preferably 50nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include layers formed of an alloy of two or more metals selected from the above metals (e.g., a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoint of versatility of forming a conductor layer, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper is even more preferable.

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

The thickness of the conductor layer depends on the design of the desired 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, the conductive layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, and is preferably formed by the semi-additive method from the viewpoint of ease of manufacturing. An example of forming a conductor layer by a semi-additive method is shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer corresponding to a desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.

[ semiconductor device ]

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

Examples of the semiconductor device include various semiconductor devices used for electric products (for example, a computer, a mobile phone, a digital camera, a television, and the like), vehicles (for example, a motorcycle, an automobile, a train, a ship, an aircraft, and the like), and the like.

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a portion of the printed wiring board that conducts an electrical signal, and may be located on the surface or embedded in the printed wiring board. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting a semiconductor chip in the manufacture of a semiconductor device is not particularly limited as long as the semiconductor chip can function effectively, and specific examples thereof include a wire bonding mounting method, a flip chip mounting method, a mounting method using a build-up solderless layer (BBUL), a mounting method using an Anisotropic Conductive Film (ACF), a mounting method using a nonconductive film (NCF), and the like. Here, the "mounting method using a build-up layer without solder (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip is connected to a wiring on the printed wiring board".

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "part" and "%" mean "part by mass" and "% by mass", respectively, unless otherwise stated.

< Synthesis example 1: synthesis of active ester Compound (B-1)

A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer was charged with 320g (2.0 mol) of 2, 7-dihydroxynaphthalene, 184g (1.7 mol) of benzyl alcohol, and 5.0g of p-toluenesulfonic acid monohydrate, and stirred at room temperature while blowing nitrogen gas. Then, the temperature was raised to 150 ℃ and the resulting water was distilled out of the system while stirring for 4 hours. After completion of the reaction, 900g of methyl isobutyl ketone and 5.4g of a 20% aqueous solution of sodium hydroxide were added thereto, and after neutralization, the aqueous layer was removed by liquid separation, and then washed with 280g of water for 3 times, and methyl isobutyl ketone was removed under reduced pressure to obtain 460g of a benzyl-modified naphthalene compound (A-1). The benzyl-modified naphthalene compound (A-1) was obtained as a black solid, and the hydroxyl group equivalent was 180 g/equivalent.

A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 203.0g of isophthaloyl dichloride (the number of moles of acid chloride groups: 2.0 moles) and 1400g of toluene, and the system was dissolved by replacing the atmosphere with nitrogen under reduced pressure. Then, 72.4g (0.67 mol) of o-cresol and 240g (mol number of phenolic hydroxyl group: 1.33 mol) of benzyl-modified naphthalene compound (A-1) were charged, and the inside of the system was replaced with nitrogen gas under reduced pressure to dissolve them. Then, 0.70g of tetrabutylammonium bromide was dissolved, the temperature in the system was controlled to 60 ℃ or lower while purging with nitrogen gas, and 400g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Subsequently, stirring was continued under these conditions for 1.0 hour. After the reaction, the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactant was dissolved, and the mixture was stirred and mixed for 15 minutes, and then the mixture was allowed to stand for liquid separation to remove the water layer. This operation was repeated until the pH of the aqueous layer became 7. Then, the reaction mixture was dehydrated by a decanter to remove water, thereby obtaining an active ester compound (B-1) in the form of a toluene solution containing 65 mass% of nonvolatile matter. The active ester equivalent of the obtained active ester compound (B-1) was 238g/eq.

< Synthesis example 2: synthesis of active ester Compound (B-2)

A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 203.0g of isophthaloyl dichloride (the number of moles of acid chloride groups: 2.0 moles) and 1400g of toluene, and the system was dissolved by replacing the atmosphere with nitrogen under reduced pressure. Then, 113.9g (0.67 mol) of o-phenylphenol and 240g (mol number of phenolic hydroxyl groups: 1.33 mol) of the benzyl-modified naphthalene compound (A-1) were charged, and the inside of the system was replaced with nitrogen gas under reduced pressure to dissolve the compound. Then, 0.70g of tetrabutylammonium bromide was dissolved, the temperature in the system was controlled to 60 ℃ or lower while purging with nitrogen gas, and 400g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Subsequently, stirring was continued under these conditions for 1.0 hour. After the reaction, the mixture was allowed to stand for liquid separation to remove the water layer. Further, water was added to the toluene layer in which the reactant was dissolved, and the mixture was stirred and mixed for 15 minutes, and then the mixture was allowed to stand for liquid separation to remove the water layer. This operation was repeated until the pH of the aqueous layer became 7. Then, the reaction mixture was dewatered by a decanter to remove water, whereby an active ester compound (B-2) was obtained in the form of a toluene solution containing 65 mass% of nonvolatile matter. The active ester equivalent of the obtained active ester compound (B-2) was 206g/eq.

< Synthesis example 3: synthesis of active ester Compound (B-3)

A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with 203.0g of isophthaloyl dichloride (the number of moles of acid chloride groups: 2.0 moles) and 1400g of toluene, and the system was dissolved by replacing the atmosphere with nitrogen under reduced pressure. Then, 132.7g (0.67 mol) of styrenated phenol and 240g (mol number of phenolic hydroxyl group: 1.33 mol) of benzyl-modified naphthalene compound (A-1) were charged, and the inside of the system was replaced with nitrogen gas under reduced pressure to dissolve them. Then, 0.70g of tetrabutylammonium bromide was dissolved, the temperature in the system was controlled to 60 ℃ or lower while purging with nitrogen gas, and 400g of a 20% aqueous solution of sodium hydroxide was added dropwise over 3 hours. Subsequently, stirring was continued under these conditions for 1.0 hour. After the reaction, the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactant was dissolved, and the mixture was stirred and mixed for 15 minutes, and then the mixture was allowed to stand for liquid separation to remove the water layer. This operation was repeated until the pH of the aqueous layer became 7. Then, water was removed by dehydration with a decanter to obtain an active ester compound (B-3) in the form of a toluene solution containing 65 mass% of nonvolatile matter. The active ester equivalent of the obtained active ester compound (B-3) was 259g/eq.

The active ester compounds (B-1) to (B-3) were identified as follows. As a result of the identification, it was found that Ar in the general formula (B-3) was contained in the active ester compound (B-1)³¹Having a group represented by the formula (1), Ar in the general formula (B-3) for the active ester compound (B-2)³¹Having a group represented by the formula (2), Ar in the general formula (B-3) for the active ester compound (B-3)³¹Has a group represented by formula (3) (n is 1-5).

< example 1: preparation of resin composition 1

3 parts of an epoxy resin "ESN 475V" (manufactured by Nippon iron chemical Co., Ltd., epoxy equivalent: about 330g/eq.) as a component (A) and 7 parts of an epoxy resin "HP-4032-SS" (manufactured by DIC Co., Ltd., epoxy equivalent: about 144g/eq.) as a component (A) were dissolved in 10 parts of Methyl Ethyl Ketone (MEK) to obtain an epoxy resin solution A;

to this epoxy resin solution A were added 25 parts of an active ester compound (B-1) as a component (B), 65 parts of spherical silica (average particle diameter 0.77 μm, SO-C2 "manufactured by Yatoma corporation) (hereinafter also referred to as" inorganic filler A ") surface-treated with an amine-based alkoxysilane compound (" KBM573 "manufactured by shin-Etsu chemical Co., Ltd.) as a component (C), and 0.2 parts of an imidazole compound" 1B2PZ "(manufactured by Sikko chemical Co., Ltd.) as a component (E), and the mixture was uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish A;

the inorganic filler A had an average particle diameter of 0.5 μm and a specific surface area of 5.9m²/g。

< example 2: preparation of resin composition 2

In example 1, 25 parts of the active ester compound (B-1) was changed to 25 parts of the active ester compound (B-2). In the same manner as in example 1 except for the above matters, resin composition 2 was prepared.

< example 3: preparation of resin composition 3

In example 1, 25 parts of the active ester compound (B-1) was changed to 25 parts of the active ester compound (B-3). In the same manner as in example 1 except for the above matters, resin composition 3 was prepared.

< example 4: preparation of resin composition 4

In the case of the example 1, the following,

the amount of the active ester compound (B-1) was changed from 25 parts to 22 parts, the amount of the imidazole compound (1B 2PZ, manufactured by Shikoku Kogyo Co., Ltd.) was changed from 0.2 part to 0.02 part,

2 parts of a triazine-containing cresol novolak resin ("LA-3018-50P" manufactured by DIC corporation and a methoxypropanol solution having a solid content of 50 mass%) and 1 part of a carbodiimide-based resin ("V-03" manufactured by Nisshinbo chemical corporation and having an active group equivalent of about 216 and a toluene solution having a solid content of 50 mass%);

in the same manner as in example 1 except for the above matters, a resin composition 4 was prepared.

< example 5: preparation of resin composition 5

In the case of the embodiment 2, the following,

the amount of the active ester compound (B-2) was changed from 25 parts to 22 parts, the amount of the imidazole compound (1B 2PZ, manufactured by Shikoku Kogyo Co., Ltd.) was changed from 0.2 part to 0.02 part,

in the same manner as in example 2 except for the above matters, resin composition 5 was prepared.

< example 6: preparation of resin composition 6

In the case of the embodiment 3, the following,

the amount of the active ester compound (B-3) was changed from 25 parts to 22 parts, the amount of the imidazole compound (1B 2PZ, manufactured by Shikoku Kogyo Co., Ltd.) was changed from 0.2 part to 0.02 part,

in the same manner as in example 3 except for the above matters, resin composition 6 was prepared.

< example 7: preparation of resin composition 7

In the case of the example 1, the following,

2 parts of a triazine-containing cresol novolak resin ("LA-3018-50P" manufactured by DIC corporation, a methoxypropanol solution having a solid content of 50 mass%) and 2 parts of a vinylbenzyl resin ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation, a toluene solution having a solid content of 65 mass%) were used;

in the same manner as in example 1 except for the above matters, a resin composition 7 was prepared.

< example 8: preparation of resin composition 8

In example 7, 2 parts of a vinylbenzyl resin ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation, a toluene solution having a solid content of 65 mass%) was changed to 2 parts of a maleimide resin ("MIR-3000-70 MT" manufactured by Nippon chemical corporation, a toluene/MEK solution having a solid content of 70 mass%). In the same manner as in example 7 except for the above matters, a resin composition 8 was prepared.

< example 9: preparation of resin composition 9

In example 7, 2 parts of a vinylbenzyl resin ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation, 65 mass% solid content in toluene solution) was changed to 1 part of a maleimide resin ("BMI-689" manufactured by DMI corporation). In the same manner as in example 7 except for the above matters, a resin composition 9 was prepared.

< example 10: preparation of resin composition 10

In example 7, 2 parts of a vinylbenzyl resin ("OPE-2 St" manufactured by Mitsubishi gas chemical corporation, 65 mass% solid content in toluene solution) was changed to 1 part of a maleimide resin ("BMI-1500" manufactured by DMI corporation). In the same manner as in example 7 except for the above matters, a resin composition 10 was prepared.

< comparative example 1: preparation of resin composition 11

In example 1, 25 parts of the active ester compound (B-1) was changed to 25 parts of another curing agent (an active ester curing agent, "HPC 8150-62T", available from DIC corporation, 62% solid content in toluene). In the same manner as in example 1 except for the above matters, a resin composition 11 was prepared.

Comparative example 2: preparation of resin composition 12

In example 1, 25 parts of the active ester compound (B-1) was changed to 23 parts of another curing agent (an active ester curing agent, "HPC 8000-65T", available from DIC corporation, a 65% solid toluene solution). In the same manner as in example 1 except for the above, a resin composition 12 was prepared.

< comparative example 3: preparation of resin composition 13

In example 4, 22 parts of the active ester compound (B-1) was changed to 22 parts of another curing agent (an active ester curing agent, "HPC 8150-62T" manufactured by DIC, Inc., 22 parts of a 62% solid toluene solution, and a resin composition 13 was prepared in the same manner as in example 4, except for the above matters.

< comparative example 4: preparation of resin composition 14

In example 3, 22 parts of the active ester compound (B-2) was changed to 21 parts of another curing agent (an active ester curing agent, "HPC 8000-65T", available from DIC corporation, a 65% solid toluene solution). In the same manner as in example 3 except for the above matters, a resin composition 14 was prepared.

< evaluation of unevenness after lamination, measurement of arithmetic average roughness, and peeling Strength of plated conductor layer >

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

As a support, a polyethylene terephthalate film (AL 5, manufactured by Linekekaceae) having a release layer was prepared (thickness: 38 μm). The resin compositions obtained in examples and comparative examples were uniformly applied to the release layer of the support so that the thickness of the resin composition layer after drying became 40 μm. Then, the resin composition was dried at 80 to 100 ℃ (average 90 ℃) for 4 minutes to obtain a resin sheet a including a support and a resin composition layer.

(2) Preparation of inner layer substrate

The both surfaces of the glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil 18 μm thick, substrate 0.4mm thick, "R1515A" manufactured by Sonar corporation) on which the inner layer circuit was formed were etched with a microetching agent ("CZ 8101" manufactured by Meige corporation) by 1 μm to roughen the copper surface.

(3) Lamination of resin sheet A

A batch type vacuum pressure Laminator (2-Stage build up Laminator (CVP 700), manufactured by Nikko Materials) was used to laminate both surfaces of the inner substrate so that the resin composition layer was in contact with the inner substrate. The lamination was carried out by: the pressure was reduced for 30 seconds to 13hPa or less, and then the pressure was bonded at 120 ℃ and 0.74MPa for 30 seconds. Next, hot pressing was performed at 100 ℃ and a pressure of 0.5MPa for 60 seconds.

(4) Thermal curing of resin composition layers

Then, the inner substrate laminated with the resin sheet a was put into an oven at 130 ℃ and heated for 30 minutes, and then transferred to an oven at 170 ℃ and heated for 30 minutes to thermally cure the resin composition layer, thereby forming an insulating layer. Then, the support was peeled off to obtain a cured substrate a having the insulating layer, the interlayer substrate, and the insulating layer in this order.

(5) Evaluation of unevenness after lamination

The surface uniformity of the portion (surface opposite to the laminate) where the resin sheet a was laminated was visually observed on both sides of the cured substrate a, and evaluated as follows,

good: no unevenness was observed at all, and the surface was completely uniform;

x: in the portion where the resin sheet was laminated, uneven portions were observed.

(6) Roughening treatment

For the cured substrate a, desmear treatment as roughening treatment was performed. As the desmear treatment, the following wet desmear treatment was performed.

(Wet desmutting treatment)

The cured substrate a was immersed in a Swelling solution ("Swelling Dip securigant P", manufactured by amett japan corporation, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ℃ for 5 minutes, and then immersed in an oxidizing agent solution ("center Compact CP", manufactured by amett japan corporation, an aqueous solution having a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ℃ for 20 minutes. Next, the resultant was immersed in a neutralizing Solution ("Reduction Solution Securigith P" manufactured by Anmet Japan K.K., aqueous sulfuric acid Solution) at 40 ℃ for 5 minutes, and then dried at 80 ℃ for 15 minutes.

(7) Measurement of arithmetic average roughness (Ra) of roughened insulating layer surface

The arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment was determined from the obtained value using a non-contact surface roughness meter (WYKO NT3300 manufactured by Bruker Co., Ltd.) in a VSI mode with a measurement range of 121 μm × 92 μm using a 50-magnification lens. The average value of 10 points was determined.

(8) Formation of conductor layer

A conductor layer is formed on the roughened surface of the insulating layer by a semi-additive method. That is, the roughened substrate is made to contain PdCl₂The electroless copper plating solution of (3) was immersed at 40 ℃ for 5 minutes, and then immersed at 25 ℃ for 20 minutes in an electroless copper plating solution. Then, the resultant was heated at 150 ℃ for 30 minutes to perform annealingAfter that, a resist layer is formed, and patterning is performed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 25 μm, and annealing treatment was performed at 190 ℃ for 60 minutes. The resulting substrate was referred to as "evaluation substrate B".

(9) Measurement of peel Strength of plated conductor layer

The peel strength between the insulating layer and the conductive layer was measured in accordance with japanese industrial standards (JIS C6481). Specifically, a part of the conductor layer of the evaluation substrate B having a width of 10mm and a length of 100mm was cut, one end of the cut was peeled off and clamped by a jig, and the peel strength was determined by measuring the load (kgf/cm) when the test piece was peeled off at a speed of 50 mm/min in the vertical direction by 35mm at room temperature. A tensile tester (manufactured by T.S.E., Ltd. "AC-50C-SL") was used for the measurement.

< evaluation of dielectric Property >

The dielectric properties were evaluated by measuring the value of the dielectric loss tangent (Df). Specifically, a cured product B for evaluation was produced as follows, and the dielectric loss tangent (Df) was measured.

The resin sheets A obtained in examples and comparative examples were cured in an oven at 190 ℃ for 90 minutes. The resin sheet a was taken out of the oven, and the support was peeled from the resin sheet a taken out, whereby a cured product of the resin composition layer was obtained. The cured product was cut into a length of 80mm and a width of 2mm to obtain a cured product B for evaluation.

For each evaluation cured product B, a dielectric loss tangent value (Df value) was measured by a resonance cavity perturbation method using "HP 8362B" manufactured by Agilent Technologies at a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃. The measurement was carried out using 2 test pieces, and the average value was calculated.

< measurement of copper foil adhesion (peeling Strength) >

(1) Production of substrate for adhesion evaluation

As the inner layer substrate, a glass cloth substrate epoxy resin double-sided copper-clad laminate having a copper foil on the surface thereof was prepared (the thickness of the copper foil was 18 μm, the thickness of the substrate was 0.8mm, manufactured by Sonar corporation as "R1515A"). The copper foil on the surface of the inner layer substrate is entirely removed by etching. Then, drying was performed at 190 ℃ for 30 minutes.

The resin sheets a obtained in the above examples and comparative examples were laminated on both sides of the inner layer substrate using a batch type vacuum press laminator (CVP 700, 2-stage stacked laminator, manufactured by Nikko-Materials) so that the resin composition layer was bonded to the inner layer substrate. The lamination is carried out as follows: after the pressure was reduced for 30 seconds to 13hPa or less, the resultant was pressure-bonded at 100 ℃ under a pressure of 0.74MPa for 30 seconds.

Subsequently, the laminated resin sheet a was subjected to hot pressing under atmospheric pressure at 100 ℃ and a pressure of 0.5MPa for 60 seconds to smooth the sheet. Then, the support was peeled off to obtain an "intermediate multilayer body I" including the resin composition layer, the inner substrate, and the resin composition layer in this order.

On the other hand, a copper foil having a glossy surface (35 μm in thickness, "3 EC-III" manufactured by Mitsui metals Co., Ltd.) was prepared. The copper foil was roughened by etching with a copper etching amount of 1 μm using a microetching agent ("CZ 8101" by meige corporation). The thus obtained copper foil is referred to as "roughened copper foil".

The roughened copper foil is laminated on both surfaces of the intermediate multilayer body I so that the roughened surface of the roughened copper foil is bonded to the resin composition layer of the intermediate multilayer body I. This lamination was performed under the same conditions as the aforementioned lamination of the resin sheet to the inner layer substrate. Thus, an "intermediate multilayer body II" comprising the roughened copper foil, the resin composition layer, the inner substrate, the resin composition layer and the roughened copper foil in this order was obtained.

The intermediate multilayer body II was put into an oven at 100 ℃ and heated for 30 minutes, and then transferred to an oven at 170 ℃ and heated for 30 minutes. Next, the intermediate multilayer body II was taken out of the oven to room temperature atmosphere, and then put into an oven at 200 ℃ and additionally heated for 90 minutes. Thus, the resin composition layer was thermally cured to obtain an "evaluation substrate C" comprising, in order, the roughened copper foil, the insulating layer as a cured product of the resin composition layer, the inner substrate, the insulating layer as a cured product of the resin composition layer, and the roughened copper foil. In the evaluation substrate C, the roughened copper foil corresponds to a conductor layer.

(2) Measurement of copper foil adhesion (peeling Strength)

The peel strength between the roughened copper foil and the insulating layer was measured using the evaluation substrate C described above. The peel strength was measured according to JIS C6481. Specifically, the peel strength was measured by the following procedure.

A cut surrounding a rectangular portion having a width of 10mm and a length of 100mm was cut out from the roughened copper foil of the evaluation substrate C. One end of the rectangular portion was peeled off and held by a jig (AUTO COM model testing machine "AC-50C-SL", manufactured by T.S.E.). The rectangular portion was peeled in the vertical direction within a range of 35mm in length, and the load (kgf/cm) at the time of peeling was measured as the peel strength. The aforementioned tearing off was carried out at room temperature at a rate of 50 mm/min. Further, after the HAST test (130 ℃, humidity 85% RH, 100 hours), the copper foil adhesion (peel strength) was measured again.

[ Table 1]

In the table, "the content of the (C) component" represents the content of the (C) component when the nonvolatile component in the resin composition is 100 mass%.

It was confirmed that in examples 1 to 10, even when the components (C) to (E) were not contained, the results were similar to those in the above examples, although the differences were somewhat different.

Claims

1. A resin composition comprising:

(A) an epoxy resin, and

wherein, represents a connecting bond,

in the formula (3), n represents an integer of 1 to 5.

2. The resin composition according to claim 1, wherein the component (B) is an active ester compound represented by the following general formula (B-1),

in the general formula (b-1),

Ar¹³each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, a divalent aliphatic hydrocarbon group optionally having a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by combining these groups,

a represents an integer of 1 to 6,

b represents an integer of 0 to 10.

3. The resin composition according to claim 2, wherein Ar in the general formula (b-1)¹³Each independently represents a divalent group in which a divalent aromatic hydrocarbon group optionally having a substituent and an oxygen atom are combined.

4. The resin composition according to claim 1, wherein the component (B) is an active ester compound represented by the following general formula (B-3),

in the general formula (b-3),

Ar³¹each independently represents a group represented by the formula (1), a group represented by the formula (2), or a group represented by the formula (3)The group of (a) or (b),

a2 represents an integer of 1 to 6,

c2 represents an integer of 1 to 5,

d independently represents an integer of 0 to 6.

5. The resin composition according to claim 1, further comprising (C) an inorganic filler.

6. The resin composition according to claim 1, which is used for forming an insulating layer.

7. The resin composition according to claim 1, which is used for forming an insulating layer, the insulating layer being an insulating layer for forming a conductor layer.

8. A resin sheet, comprising:

a support, and

a resin composition layer comprising the resin composition according to any one of claims 1 to 7 provided on the support.

9. A printed wiring board comprising an insulating layer formed by using a cured product of the resin composition according to any one of claims 1 to 7.

10. A semiconductor device comprising the printed wiring board of claim 9.