Resin composition

Abstract

To provide a resin composition capable of forming a cured product that exhibits favorable dielectric properties, demonstrates excellent smear removing capability, and ensures excellent adhesive strength with a conductor layer; a resin sheet comprising the resin composition; a circuit board comprising a cured product of the resin composition; and a semiconductor device comprising the circuit board.SOLUTION: A resin composition comprises (A) an epoxy resin and (B) an active ester resin, where the component (B) includes (B1) an active ester resin containing a specific structural unit, and (B2) an active ester resin containing an allyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition, a resin sheet, a circuit board, and a semiconductor device. [Background technology]

[0002] Resin compositions containing epoxy resins and their curing agents produce cured products with excellent insulation properties, heat resistance, adhesion, and other properties, and therefore have been widely used as insulating materials for circuit boards such as printed wiring boards and rewiring boards for semiconductor chip packages.

[0003] On the other hand, with the recent increase in communication speed, insulating materials for circuit boards are required to have excellent dielectric properties (low dielectric tangent) in order to reduce transmission loss when they are operated in a high-frequency environment. As insulating materials with excellent dielectric properties, those that use specific curing agents such as active ester resins that can reduce or suppress the generation of polar groups such as secondary hydroxyl groups in the curing reaction of epoxy resins have been reported (for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6205692 [Patent Document 2] Patent No. 7259783 Summary of the Invention [Problem to be solved by the invention]

[0005] In this regard, when an active ester resin is blended to such an extent that good dielectric properties are achieved, the smear removability during desmearing tends to deteriorate.In addition, since the insulating layer of a circuit board contacts a conductor layer, it is required to have good adhesive strength with the conductor layer (e.g., copper foil or plated copper as a base layer).

[0006] Therefore, an object of the present invention is to provide a resin composition that exhibits good dielectric properties, is excellent in smear removal properties, and is capable of forming a cured product having excellent adhesion strength with a conductor layer; a resin sheet containing the resin composition; a circuit board containing a cured product of the resin composition; and a semiconductor device containing the circuit board. [Means for solving the problem]

[0007] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that, in a resin composition containing (A) an epoxy resin and (B) an active ester-based resin, the component (B) contains (B1) an active ester-based resin containing a specific structural unit, and (B2) an active ester-based resin containing an allyl group, thereby solving the above-mentioned problems and completing the present invention. That is, the present invention includes the following.

[0008] <1> (A) an epoxy resin; and (B) an active ester resin, A resin composition, wherein the component (B) comprises (B1) an active ester resin containing a structural unit represented by the following formula (B1-1), and (B2) an active ester resin containing an allyl group: [ka] (In formula (B1-1), Ar 1 each independently represents a divalent aromatic group which may have a substituent; At least one Ar 1 is a naphthylene group which may have a substituent; L B each independently represents a single bond or a divalent linking group; R B1 represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof; m1 is an integer of 0 to 5; "*" represents a bond.) <2> the ratio of the amount of the component (A) to the amount of the component (B) is in the range of 1:0.3 to 1:2, in terms of the ratio of [total number of epoxy groups in the component (A)]:[total number of active ester groups in the component (B)]; <1> The resin composition according to claim 1. <3> The content of the (A) component is 20% by mass or more and 50% by mass or less, when the resin component in the resin composition is 100% by mass. <1> or <2> The resin composition according to claim 1. <4> The content of the (B1) component is 10% by mass or more and 60% by mass or less, when the resin component in the resin composition is 100% by mass. <1> ~ <3> The resin composition according to any one of claims 1 to 10. <5> The content of the (B2) component is 10% by mass or more and 60% by mass or less, when the resin component in the resin composition is 100% by mass. <1> ~ <4> The resin composition according to any one of claims 1 to 10. <6> Further, (C) containing an inorganic filler, <1> ~ <5> The resin composition according to any one of claims 1 to 10. <7> The content of the (C) component is 50% by mass or more and 90% by mass or less, when the non-volatile components in the resin composition are 100% by mass. <6> The resin composition according to claim 1. <8> For forming an insulating layer. <1> ~ <7> The resin composition according to any one of claims 1 to 10. <9> A support and a resin composition layer provided on the support, The resin composition layer is <1> ~ <8> A resin sheet comprising the resin composition according to any one of claims 1 to 7. <10> <1> ~ <8> 13. A circuit board comprising a cured product of the resin composition according to claim 12. <11> <10> A semiconductor device comprising the circuit board according to claim 1. Effect of the Invention

[0009] According to the present invention, there can be provided a resin composition capable of forming a cured product that exhibits good dielectric properties, is excellent in smear removal properties, and has excellent adhesive strength with a conductor layer; a resin sheet containing the resin composition; a circuit board containing a cured product of the resin composition; and a semiconductor device containing the circuit board. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] <Terminology explanation> As used herein, the term "optionally substituted" in reference to a compound or group means both the case where none of the hydrogen atoms of the compound or group are substituted with a substituent, and the case where some or all of the hydrogen atoms of the compound or group are substituted with a substituent.

[0011] In this specification, unless otherwise specified, the term "substituent" means a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a monovalent heterocyclic group, an alkylidene group, an amino group, a silyl group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group.

[0012] Examples of halogen atoms used as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The alkenyl group used as a substituent may be either linear or branched. The number of carbon atoms in the alkenyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 or 3. The number of carbon atoms in the cycloalkyl group used as a substituent is preferably 3 to 12, more preferably 3 to 6. The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 12, more preferably 1 to 6. The number of carbon atoms in the cycloalkyloxy group used as a substituent is preferably 3 to 12, more preferably 3 to 6. The aryl group used as a substituent is a group obtained by removing one hydrogen atom on the aromatic ring from an aromatic hydrocarbon. The number of carbon atoms in the aryl group used as a substituent is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms of the arylalkyl group used as a substituent is preferably 7 to 15, more preferably 7 to 11. The number of carbon atoms of the arylalkoxy group used as a substituent is preferably 7 to 15, more preferably 7 to 11. The monovalent heterocyclic group used as a substituent refers to a group in which one hydrogen atom is removed from the heterocycle of a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3 to 15, more preferably 3 to 9. The alkylidene group used as a substituent refers to a group in which two hydrogen atoms are removed from the same carbon atom of an alkane. The number of carbon atoms of the alkylidene group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The above-mentioned substituent may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). Unless otherwise specified, the same one as the above-mentioned substituent may be used as the secondary substituent.

[0013] In this specification, the term "aromatic group" refers to a group in which one or more hydrogen atoms have been removed from an aromatic ring of an aromatic compound. In detail, a monovalent aromatic group refers to a group in which one hydrogen atom has been removed from an aromatic ring of an aromatic compound, and a divalent aromatic group refers to a group in which two hydrogen atoms have been removed from an aromatic ring of an aromatic compound. In addition, the term "aromatic ring" refers to a ring that follows the Huckel rule in which the number of electrons contained in the π electron system on the ring is 4n+2 (n is a natural number), and includes a monocyclic aromatic ring and a fused aromatic ring in which two or more monocyclic aromatic rings are fused. The aromatic ring may be a carbocyclic ring or a heterocyclic ring. Examples of the monovalent aromatic group include an aryl group that may have a substituent and a heteroaryl group that may have a substituent, and examples of the divalent aromatic group include an arylene group that may have a substituent and a heteroarylene group that may have a substituent. In this specification, unless otherwise specified, the number of carbon atoms in an aromatic group is preferably 3 or more, more preferably 4 or more or 5 or more, and even more preferably 6 or more, and the upper limit is preferably 24 or less, more preferably 18 or less or 14 or less, and even more preferably 10 or less. The number of carbon atoms does not include the number of carbon atoms of substituents.

[0014] In this specification, the term "aliphatic group" refers to a group in which one or more hydrogen atoms bonded to an aliphatic carbon of an aliphatic compound have been removed. In particular, a divalent aliphatic group refers to a group in which two hydrogen atoms bonded to an aliphatic carbon of an aliphatic compound have been removed. Examples of divalent aliphatic groups include an alkylene group which may have a substituent, a cycloalkylene group which may have a substituent, an alkenylene group which may have a substituent, a cycloalkenylene group which may have a substituent, and an alkapolyenylene group which may have a substituent (the number of double bonds is preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2). In this specification, unless otherwise specified, the number of carbon atoms of an aliphatic group is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0015] In this specification, the term "non-volatile components" in the resin composition refers to components other than the organic solvent, which will be described later, among the components constituting the resin composition. Also, the term "resin components" in the resin composition refers to components other than the inorganic filler, which will be described later, among the non-volatile components constituting the resin composition.

[0016] Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and may be modified and implemented as desired without departing from the scope of the claims of the present invention and their equivalents.

[0017] [Resin composition] The resin composition of the present invention is characterized in that it comprises (A) an epoxy resin and (B) an active ester-based resin, in which component (B) comprises (B1) an active ester-based resin containing a structural unit represented by formula (B1-1), and (B2) an active ester-based resin containing an allyl group.

[0018] As described above, insulating materials for circuit boards are required to exhibit good dielectric properties in order to reduce transmission loss when they are operated in a high-frequency environment. In this regard, the present inventors have found that when an active ester resin is blended to an extent that good dielectric properties are achieved, the resulting insulating material tends to have poor smear removability during desmear treatment.

[0019] In contrast, the present invention uses an active ester resin containing a structural unit represented by formula (B1-1) and an active ester resin containing an allyl group in a combination of an epoxy resin and an active ester resin, and exhibits good dielectric properties and good smear removal. In addition, a cured product having excellent adhesion strength with a conductor layer can be formed. Thus, the present invention can provide a cured product that exhibits good dielectric properties, good smear removal, and excellent adhesion strength with a conductor layer, and significantly contributes to realizing a circuit board equipped with a circuit that advantageously reduces transmission loss when operating in a high-frequency environment and exhibits desired characteristics.

[0020] Each component will be described below.

[0021] <(A) Epoxy resin> The resin composition of the present invention contains an epoxy resin as component (A).

[0022] Examples of epoxy resins include bisphenol type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. Bisphenol type epoxy resins refer to epoxy resins having a bisphenol structure, and examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AF type epoxy resins. Biphenyl type epoxy resin refers to an epoxy resin having a biphenyl structure, where the biphenyl structure may have a substituent such as an alkyl group, an alkoxy group, or an aryl group. Therefore, bixylenol type epoxy resin and biphenyl aralkyl type epoxy resin are also included in biphenyl type epoxy resin. The epoxy resin may be used alone or in combination of two or more kinds.

[0023] The epoxy resin is preferably an aromatic epoxy resin, where the aromatic epoxy resin means an epoxy resin having an aromatic ring in the molecule.

[0024] The epoxy resin preferably has two or more epoxy groups in one molecule. When the epoxy resin is taken as 100% by mass, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, and is usually 100% by mass or less.

[0025] Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resins").

[0026] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0027] Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins such as alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, and epoxy resins having a butadiene structure.

[0028] Specific examples of liquid epoxy resins include "HP-4032", "HP-4032-D", and "HP-4032-SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epikote 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "630" and "630LSD" (glycidylamine type epoxy resins) manufactured by Mitsubishi Chemical Corporation. resin); "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Material Corporation; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin with an ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin with a butadiene structure) manufactured by Daicel Corporation; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Corporation.

[0029] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0030] As the solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferred.

[0031] Specific examples of solid epoxy resins include "HP-4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200HH", "HP-7200H", and "HP-7200" (dicyclopentadiene epoxy resins) manufactured by DIC Corporation. type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC; "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku; "NC-7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku; "NC-3000H", "NC-3000", "NC-3000" manufactured by Nippon Kayaku L, "NC-3100" (biphenyl type epoxy resin); "ESN-475V" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN-485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. "YX8800" (anthracene type epoxy resin) manufactured by Osaka Gas Chemicals; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical; and "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical.

[0032] The resin composition of the present invention may contain only a liquid epoxy resin as an epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. When a liquid epoxy resin and a solid epoxy resin are used in combination, the ratio of the amounts (liquid epoxy resin:solid epoxy resin) is preferably 1:0.01 to 1:50, more preferably 1:0.05 to 1:20, and even more preferably 1:0.1 to 1:10, by mass.

[0033] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of an epoxy group. This epoxy equivalent can be measured according to JIS K7236.

[0034] The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, and further preferably from 400 to 1500. The Mw of the epoxy resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0035] The content of the (A) component in the resin composition, relative to 100 mass% of the total of the (A) component and the (B) component in the resin composition, is preferably 10 mass% or more, more preferably 20 mass% or more, even more preferably 25 mass% or more, or 30 mass% or more, and is preferably 60 mass% or less, more preferably 50 mass% or less, and even more preferably 45 mass% or less or 40 mass% or less.

[0036] When the resin composition contains components other than the (A) component and the (B) component, the content of the (A) component in the resin composition, relative to 100 mass% of the non-volatile components in the resin composition, is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more or 6 mass% or more, and is preferably 50 mass% or less, more preferably 40 mass% or less, even more preferably 30 mass% or less, 20 mass% or less, or 10 mass% or less.

[0037] When the resin composition contains components other than the (A) component and the (B) component, the content of the (A) component in the resin composition, relative to the resin components in the resin composition being 100% by mass, is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less or 35% by mass.

[0038] <(B) Active ester resin> The resin composition of the present invention contains an active ester resin as component (B).

[0039] The active ester moiety contained in the (B) component is preferably an aromatic ester skeleton. The aromatic ester skeleton represents a skeleton having an ester bond and an aromatic ring bonded to one end or both ends of the ester bond. Among them, the aromatic ester skeleton is preferably one having an aromatic ring at both ends of the ester bond. Examples of groups having such a skeleton include an arylcarbonyloxy group, an aryloxycarbonyl group, an arylenecarbonyloxy group, an aryleneoxycarbonyl group, an arylcarbonyloxyarylene group, an aryloxycarbonylarylene group, an arylenecarbonyloxyarylene group, and an aryleneoxycarbonylarylene group. The number of carbon atoms of the group having such a skeleton is preferably 7 to 20, more preferably 7 to 15, and even more preferably 7 to 11. The aromatic group such as an aryl group and an arylene group may have a substituent.

[0040] 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, and even more preferably an aryl group having 6 to 10 carbon atoms. Examples of such aryl groups include those obtained by removing one hydrogen atom from a monocyclic aromatic compound such as a phenyl group, a furanyl group, a pyrrolyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a pyridinyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, or a triazinyl group; and those obtained by removing one hydrogen atom from a condensed ring aromatic compound such as a naphthyl group, anthracenyl group, a phenalenyl group, a phenanthrenyl group, a quinolinyl group, an isoquinolinyl group, a quinazolyl group, a phthalazinyl group, a pteridinyl group, a coumarinyl group, an indole group, a benzimidazolyl group, a benzofuranyl group, or an acridinyl group.

[0041] 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 further preferably an arylene group having 6 to 10 carbon atoms. Examples of such an arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group (-C 6 H 4 -C 6 H 4 -) etc.

[0042] The aromatic ester skeleton may have a substituent. The substituent is not particularly limited, and examples of the substituent include a halogen atom, -OH, -OC 1-6 Alkyl group, -N(C 1-10 (alkyl group) 2 , an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aryl group having 6 to 10 carbon atoms, -NH 2 , -CN, -C(O)OC 1-10 Alkyl groups, -COOH, -C(O)H, -NO 2 Here, "C p-qThe term "(where p and q are positive integers and p < q)" indicates that the number of carbon atoms in the organic group described immediately after this term is from p to q. For example, 1-10 the expression "C

[0043] alkyl group" indicates 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 includes spiro rings and fused rings. In the resin composition of the present invention, the (B) active ester resin includes, as the (B1) component, an active ester resin containing a structural unit represented by the following formula (B1-1) (hereinafter sometimes referred to as "(B1) specific structural unit-containing active ester resin"). The specific structural unit-containing active ester resin as the (B1) component may be used alone or in combination of two or more.

[0044] [Chemical formula]

[0045] (In formula (B1-1), Ar 1 each independently represents a divalent aromatic group which may have a substituent; at least one of the Ar 1 is a naphthylene group which may have a substituent; L B each independently represents a single bond or a divalent linking group; R B1 represents a divalent group composed of a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a combination thereof; m1 is an integer from 0 to 5; "*" represents a bond.)

[0046] As the component (B1), a compound containing an active ester moiety that reacts with the component (A) and a structural unit represented by formula (B1-1) can be used. The component (B1) may have a structural unit represented by formula (B1-1) as the active ester moiety. Among them, the active ester moiety contained in the component (B1) is preferably an aromatic ester skeleton.

[0047] In formula (B1-1), Ar 1 Each independently represents a divalent aromatic group which may have a substituent. 1 is a naphthylene group which may have a substituent. Ar other than a naphthylene group which may have a substituent 1 From the viewpoint of better enjoying the effects of the present invention, is preferably an arylene group which may have a substituent (excluding a naphthylene group which may have a substituent), and more preferably a phenylene group which may have a substituent.

[0048] In formula (B1-1), Ar 1 When there are a plurality of Ar (i.e., when m is an integer of 1 to 5), at least one Ar 1 In formula (B1-1), Ar may be a naphthylene group which may have a substituent, and there is no particular limitation on the number of naphthylene groups which may have a substituent. 1 If there are multiple Ar 1 may be a naphthylene group which may have a substituent, and all of Ar 1 may be a naphthylene group which may have a substituent.

[0049] Ar 1 The substituents which may be possessed by the aromatic ester skeleton are the same as those which may be possessed by the aromatic ester skeleton, and among these, the substituent is more preferably one or more selected from the group consisting of a fluorine atom, -OH, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0050] In formula (B1-1), L Brepresents a single bond or a divalent linking group. B Examples of the divalent linking group represented by the formula (I) include a divalent organic group having one or more (for example, 1 to 3000, 1 to 1000, 1 to 100, or 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. B is preferably a single bond, a divalent aromatic group which may have a substituent, or a divalent aliphatic group which may have a substituent. The divalent aromatic group and the divalent aliphatic group are as described above.

[0051] L B From the viewpoint of obtaining the effects of the present invention more effectively, the divalent aromatic group represented by the following formula (I) is preferably an arylene group. B The number of carbon atoms in the arylene group is preferably 6 to 24, more preferably 6 to 18, and further preferably 6 to 14. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a fluorenediyl group (for example, a 9H-fluorene-9,9-diyl group), a phenanthrenediyl group, an indanediyl group, and a pyrenediyl group.

[0052] L B From the viewpoint of obtaining the effects of the present invention, the divalent aliphatic group represented by the formula (I) is preferably one or more divalent aliphatic groups consisting of an alkylene group, a cycloalkylene group, an alkenylene group, and a cycloalkenylene group, more preferably one or more divalent aliphatic groups consisting of an alkylene group and a cycloalkylene group, and further preferably a cycloalkylene group. B The alkylene group in may be either linear or branched, and the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 4. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. BThe number of carbon atoms in the cycloalkylene group in the formula (I) is preferably 3 to 15, more preferably 3 to 12, and further preferably 3 to 10. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a decahydronaphthalene group, a norbornanylene group, a dicyclopentanylene group, and an adamantanylene group. B The alkenylene group in may be either linear or branched, and the number of carbon atoms is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. Examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, and a hexenylene group. B The number of carbon atoms in the cycloalkenylene group is preferably 3 to 15, more preferably 3 to 12, and further preferably 3 to 10. Examples of the cycloalkenylene group include a cyclopropenylene group, a cyclobutenylene group, a cyclopentenylene group, a cyclohexenylene group, and a norbornenylene group.

[0053] L B The substituents which may be possessed by the aromatic ester skeleton are the same as those which may be possessed by the aromatic ester skeleton, and among these, the substituent is more preferably one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0054] In formula (B1-1), R B1 represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. B1 is preferably a divalent aromatic group, a divalent aliphatic group, or a divalent group consisting of a combination thereof. The divalent aromatic group and the divalent aliphatic group are as described above.

[0055] R B1 From the viewpoint of obtaining the effects of the present invention, the divalent aromatic group represented by the following formula (I) is preferably an arylene group which may have a substituent. BThe number of carbon atoms in the arylene group in the formula (I) is preferably 6 to 18, more preferably 6 to 14, and further preferably 6 to 10. The number of carbon atoms does not include the number of carbon atoms of the substituent. B The divalent aromatic group represented by the following formula (I) is a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and more preferably a phenylene group which may have a substituent.

[0056] R B1 From the viewpoint of obtaining the effects of the present invention more effectively, the divalent aliphatic group represented by the following formula (I) is preferably an alkylene group which may have a substituent, or an alkenylene group which may have a substituent. B1 The alkylene group in may be either linear or branched, and the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. R B1 The alkenylene group in may be either linear or branched, and the number of carbon atoms is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, and a hexenylene group.

[0057] R B1 The substituents which may be possessed by the aromatic ester skeleton are the same as those which may be possessed by the aromatic ester skeleton. Among them, the substituent is preferably at least one selected from a halogen atom, an alkyl group, an alkenyl group, and an aryl group, and more preferably at least one selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0058] In formula (B1-1), m is an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably an integer of 0 to 2.

[0059] The terminal of the component (B1) is preferably a monovalent aromatic group. Examples of the monovalent aromatic group include aryl groups, and the aryl groups are as described above. The monovalent aromatic group at the terminal of the component (B1) is preferably a phenyl group.

[0060] The terminal of the component (B1) is more preferably an aromatic oxycarbonyl group. The terminal aromatic oxycarbonyl group is more preferably a structure represented by aromatic carbon -O-C(=O)-, and even more preferably a structure represented by the following formula (B1-2).

[0061] [ka]

[0062] (In formula (B1-2), Ar 2 represents a monovalent aromatic group which may have a substituent; "*" represents a bond.)

[0063] In formula (B1-2), Ar 2 represents a monovalent aromatic group which may have a substituent. The monovalent aromatic group is as described above. Ar 2 From the viewpoint of obtaining the effects of the present invention, Ar is preferably an aryl group which may have a substituent. 2 The number of carbon atoms of the aryl group in the formula (I) is preferably 6 to 18, more preferably 6 to 14, and further preferably 6 to 10. The number of carbon atoms does not include the number of carbon atoms of the substituent. 2 The monovalent aromatic group represented by the following formula (I) is a phenyl group which may have a substituent, or a naphthyl group which may have a substituent.

[0064] Ar 2The substituents which may be possessed by the aromatic ester skeleton are the same as those which may be possessed by the aromatic ester skeleton. Among them, the substituent is preferably at least one selected from a halogen atom, an alkyl group, an alkenyl group, and an aryl group, and more preferably at least one selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0065] The component (B1) preferably contains a compound represented by the following formula (B1-3).

[0066] [ka]

[0067] (In formula (B1-3), Ar 1 , Ar 2 , L B , R B1 and m1 is the same as above; and m2 is an integer from 1 to 10.

[0068] In formula (B1-3), Ar 1 , Ar 2 , L B , R B1 and m1, including preferred examples and the range thereof, are as explained above for formula (B1-1) and formula (B1-2).

[0069] (B1) The active ester resin containing a specific structural unit may be a commercially available product. Examples of the commercially available product include "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", and "HPC-8150-62T" (manufactured by DIC Corporation), and "PC1300-02-65MA" (manufactured by Air Water Corporation).

[0070] The content of the (B1) component in the resin composition, relative to the total amount of the (B) components in the resin composition being 100% by mass, is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 13% by mass or more or 14% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, 83% by mass or less, or 81% by mass or less.

[0071] The content of the (B1) component in the resin composition, relative to 100 mass% of the total of the (A) component and the (B) component in the resin composition, is preferably 5 mass% or more, more preferably 7 mass% or more, and even more preferably 9 mass% or more, and is preferably 70 mass% or less, more preferably 60 mass% or less, and even more preferably 55 mass% or less, 53 mass% or less, or 51 mass% or less.

[0072] When the resin composition contains components other than the (A) component and the (B) component, the content of the (B1) component in the resin composition, relative to 100 mass% of the non-volatile components in the resin composition, is preferably 0.1 mass% or more, more preferably 1 mass% or more, even more preferably 1.5 mass% or more or 2 mass% or more, and is preferably 20 mass% or less, more preferably 15 mass% or less, even more preferably 13 mass% or less, 12 mass% or less, or 11 mass% or less.

[0073] When the resin composition contains components other than the (A) component and the (B) component, the content of the (B1) component in the resin composition, relative to the resin components in the resin composition taken as 100 mass%, is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more or 7 mass% or more, and is preferably 60 mass% or less, more preferably 50 mass% or less, even more preferably 45 mass% or less, 43 mass% or less, or 42 mass% or less.

[0074] <(B2) Active ester resin containing allyl group> In the resin composition of the present invention, the (B) active ester resin contains, as the (B2) component, an active ester resin containing an allyl group (hereinafter, sometimes referred to as "(B2) allyl group-containing active ester resin"). The (B2) component may be used as one type of allyl group-containing active ester resin alone or in combination of two or more types. In this specification, an active ester resin containing a structural unit represented by formula (B1-1) and an allyl group is classified as the (B2) component.

[0075] As the component (B2), a compound containing an active ester moiety that reacts with the component (A) and an allyl group can be used. In particular, the active ester moiety contained in the component (B2) is preferably an aromatic ester skeleton.

[0076] The terminal of the component (B2) is preferably a monovalent aromatic group. Examples of the monovalent aromatic group include aryl groups, and the aryl groups are as described above. The monovalent aromatic group at the terminal of the component (B2) is preferably a phenyl group.

[0077] The component (B2) may have, in addition to the allyl group and aromatic ester skeleton, an aromatic group, an aliphatic group, or a group consisting of a combination thereof.

[0078] The aromatic group that the component (B2) may have is preferably a divalent aromatic group, more preferably an arylene group or an aralkylene group, and even more preferably an arylene group. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group. The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and even more preferably an aralkylene group having 7 to 15 carbon atoms. Among these, a phenylene group is preferable.

[0079] The aliphatic group that the (B2) component may have is preferably a divalent aliphatic group, more preferably a divalent saturated aliphatic group, and even more preferably an alkylene group or a cycloalkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, and a hexylene group, and the 1,1-dimethylmethylene group is preferred.

[0080] The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and even more preferably a cycloalkylene group having 5 to 10 carbon atoms. The cycloalkylene group may have a monocyclic structure or a polycyclic structure. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and cycloalkylene groups represented by the following formulas (a) to (d). In the formulas (a) to (d), "*" represents a bond.

[0081] [ka]

[0082] The group consisting of these combinations is preferably a divalent group, and examples thereof include a group consisting of a combination of an aliphatic group and an aromatic group, a group consisting of a combination of an aromatic group, an aliphatic group and an aromatic group, etc. One embodiment of the group consisting of these combinations is a group consisting of a combination of arylene-alkylene-arylene, and a group consisting of a combination of phenylene-1,1-dimethylmethylene-phenylene is preferred.

[0083] The component (B2) contains an allyl group. From the viewpoint of significantly obtaining the desired effects of the present invention, the number of allyl groups per molecule of the component (B2) is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less.

[0084] The allyl group contained in the (B2) component may be present as a substituent on a terminal monovalent aromatic group, or as a substituent on an aromatic group or an aliphatic group. When the (B2) component contains an allyl group as a substituent on a terminal monovalent aromatic group, the (B2) component preferably contains allyl groups as substituents on aromatic groups at both ends.

[0085] The aromatic group and aliphatic group that may be contained in the component (B2) may further have a substituent. The substituent is not particularly limited, and examples of the substituent include a halogen atom, -OH, -OC 1-6 Alkyl group, -N(C 1-10 (alkyl group) 2 , an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aryl group having 6 to 10 carbon atoms, -NH 2 , -CN, -C(O)OC 1-10 Alkyl groups, -COOH, -C(O)H, -NO 2 etc.

[0086] The component (B2) is preferably either a compound represented by the following formula (B2-1) or a compound represented by the following formula (B2-2).

[0087] [ka]

[0088] (In formula (B2-1), Ar 11 each independently represents a monovalent aromatic group which may have a substituent; Ar 12 each independently represents a divalent aromatic group which may have a substituent; R B2 each independently represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof; Ar 11 , Ar 12 and R B2 At least one of the above has an allyl group as a substituent; n a represents an integer between 0 and 10.)

[0089] [ka]

[0090] (In formula (B2-2), Ar 21 each independently represents a monovalent aromatic group which may have a substituent; Ar 22 each independently represents a divalent aromatic group which may have a substituent; R B3 each independently represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof; Ar 21 , Ar 22 and R B3 At least one of the above has an allyl group as a substituent; n b represents an integer from 0 to 10.)

[0091] In formula (B2-1), Ar 11Each of the groups independently represents a monovalent aromatic group which may have a substituent. Examples of the monovalent aromatic group include monocyclic aromatic compounds such as phenyl, furanyl, pyrrolyl, thiophene, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, and triazinyl groups from which one hydrogen atom has been removed; and condensed ring aromatic compounds such as naphthyl, anthracenyl, phenalenyl, phenanthrenyl, quinolinyl, isoquinolinyl, quinazolyl, phthalazinyl, pteridinyl, coumarinyl, indole, benzimidazolyl, benzofuranyl, and acridinyl groups from which one hydrogen atom has been removed. In addition, Ar in formula (B2-1) 11 may be different from each other, but are preferably the same. 11 is preferably a phenyl group, from the viewpoint of obtaining the effects of the present invention significantly.

[0092] Ar 11 The substituents which the aromatic ester skeleton may have are the same as those which the aromatic ester skeleton may have.

[0093] In formula (B2-1), Ar 12 each independently represents a divalent aromatic group which may have a substituent. The divalent aromatic group is as described above.

[0094] Ar 12 The substituents which the aromatic ester skeleton may have are the same as those which the aromatic ester skeleton may have.

[0095] In formula (B2-1), R B2 each independently represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. Examples of the divalent hydrocarbon group include a divalent aromatic group, a divalent aliphatic group, or a divalent group consisting of a combination thereof.

[0096] In formula (B2-1), RB2 is preferably a divalent group combining an optionally substituted divalent aromatic group, an optionally substituted divalent aliphatic group, and an oxygen atom, and more preferably a divalent group combining multiple optionally substituted divalent aromatic groups and multiple optionally substituted divalent aliphatic groups alternately. The divalent aromatic group and the divalent aliphatic group are as described above. Specific examples of these combined divalent groups include divalent groups represented by the following formulae (B2-1-1) to (B2-1-9). In the formulae, b1 to b7 represent integers of 0 to 10, preferably integers of 0 to 5. "*" represents a bond, and the wavy line represents a structure obtained by reaction of an aromatic compound, an acid halide of an aromatic compound, or an ester of an aromatic compound used in synthesizing the (B2) component.

[0097] [ka]

[0098] [ka]

[0099] R B2 The substituents which the aromatic ester skeleton may have are the same as those which the aromatic ester skeleton may have.

[0100] In formula (B2-1), Ar 11 , Ar 12 and R B2 At least one of the groups has an allyl group as a substituent. 11 It is preferable that at least one of Ar has an allyl group as a substituent. 11 However, it is more preferable that the aryl group be an allyl group as a substituent.

[0101] In formula (B2-1), n a represents an integer from 0 to 10. ais preferably an integer of 0 to 5, and more preferably an integer of 0 to 3. When the compound represented by formula (B2-1) is an oligomer or a polymer, n a represents the average value.

[0102] The compound represented by formula (B2-1) is preferably a compound represented by the following formula (B2-3).

[0103] [ka]

[0104] (In formula (B2-3), Ar 31 each independently represents a monovalent aromatic group having an allyl group as a substituent; Ar 32 each independently represents a divalent aromatic group which may have a substituent; R B4 each independently represents a divalent aromatic group which may have a substituent, a divalent aliphatic group which may have a substituent, and a divalent group formed by combining an oxygen atom; n a1 represents an integer from 0 to 10.)

[0105] In formula (B2-3), Ar 31 Each of the groups independently represents a monovalent aromatic group having an allyl group as a substituent. The monovalent aromatic group is as described above. Among them, Ar 31 is preferably a phenyl group having an allyl group as a substituent, from the viewpoint of achieving a remarkable effect of the present invention.

[0106] Ar 31 may have a substituent other than an allyl group. The substituent is the same as the substituent that the aromatic ester skeleton may have.

[0107] In formula (B2-3), Ar 32each independently represents a divalent aromatic group which may have a substituent, and Ar 12 is the same as:

[0108] In formula (B2-3), R B4 each independently represents a divalent aromatic group which may have a substituent, a divalent aliphatic group which may have a substituent, and a divalent group which is a combination of an oxygen atom. B4 R is preferably a divalent group formed by alternating a plurality of divalent aromatic groups which may have a substituent and a plurality of divalent aliphatic groups which may have a substituent. B4 Specific examples of the divalent groups include the divalent groups represented by the above formulas (B2-1-1) to (B2-1-6).

[0109] R B4 The substituents which the aromatic ester skeleton may have are the same as those which the aromatic ester skeleton may have.

[0110] In formula (B2-3), n a1 represents an integer of 0 to 10, and n in formula (B2-1) a is the same as:

[0111] In formula (B2-2), Ar 21 Each of the groups independently represents a monovalent aromatic group which may have a substituent. The monovalent aromatic group is as described above. 21 may be different from each other, but are preferably the same. 21 is preferably a phenyl group, from the viewpoint of obtaining the effects of the present invention significantly.

[0112] Ar 21 The substituents which the aromatic ester skeleton may have are the same as those which the aromatic ester skeleton may have.

[0113] In formula (B2-2), Ar 22each independently represents a divalent aromatic group which may have a substituent. The divalent aromatic group is as described above.

[0114] Ar 22 The substituents which the aromatic ester skeleton may have are the same as those which the aromatic ester skeleton may have.

[0115] In formula (B2-2), R B3 Each of R independently represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof. The divalent hydrocarbon group is as described above. B3 is preferably a divalent group combining a divalent aromatic group which may have a substituent and a divalent aliphatic group which may have a substituent, more preferably a divalent group combining a divalent aromatic group which may have a substituent-a divalent aliphatic group which may have a substituent-a divalent aromatic group which may have a substituent in this order, and even more preferably a divalent group having the order phenylene-1,1-dimethylmethylene-phenylene. The divalent group having the order phenylene-1,1-dimethylmethylene-phenylene is a group excluding the allyl group in the above formula (B2-1-9), and is specifically represented by the following formula (B2-1-10). In the formula, "*" represents a bond.

[0116] [ka]

[0117] R B3 The substituents which the aromatic ester skeleton may have are the same as those which the aromatic ester skeleton may have.

[0118] In formula (B2-2), Ar 21 , Ar 22 and R B3 At least one of R has an allyl group as a substituent. B3 It is preferable that at least one of R has an allyl group as a substituent. B3More preferably, the divalent aromatic group has an allyl group as a substituent.

[0119] In formula (B2-2), n b represents an integer of 0 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1. When the compound represented by formula (B2-2) is an oligomer or polymer, n b represents the average value.

[0120] The compound represented by formula (B2-2) is preferably a compound represented by the following formula (B2-4).

[0121] [ka]

[0122] (In formula (B2-4), Ar 41 each independently represents a monovalent aromatic group which may have a substituent; Ar 42 each independently represents a divalent aromatic group having an allyl group as a substituent; Ar 43 each independently represents a divalent aromatic group which may have a substituent; R B5 each independently represents a divalent aliphatic hydrocarbon group which may have a substituent; n b1 represents an integer from 0 to 10.)

[0123] In formula (B2-4), Ar 41 each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, and Ar 21 The same applies to Ar in formula (B2-4). 41 may be different from each other, but are preferably the same.

[0124] Ar 41The substituents which the aromatic ester skeleton may have are the same as those which the aromatic ester skeleton may have.

[0125] In formula (B2-4), Ar 42 Each of the groups independently represents a divalent aromatic group having an allyl group as a substituent. The divalent aromatic group is as described above. Among them, Ar 42 is preferably a phenylene group having an allyl group as a substituent, from the viewpoint of achieving a remarkable effect of the present invention.

[0126] Ar 42 may have a substituent other than an allyl group. The substituent is the same as the substituent that the aromatic ester skeleton may have.

[0127] In formula (B2-4), Ar 43 Each of the groups independently represents a divalent aromatic group which may have a substituent. The divalent aromatic group is as described above. Among them, Ar 43 is preferably a phenylene group which may have a substituent, from the viewpoint of achieving the effects of the present invention remarkably.

[0128] In formula (B2-4), R B5 Each of R independently represents a divalent aliphatic hydrocarbon group which may have a substituent. B5 is preferably a 1,1-dimethylmethylene group, from the viewpoint of achieving the remarkable effects of the present invention.

[0129] In formula (B2-4), n b1 represents an integer of 0 to 10, and n in formula (B2-2) b is the same as:

[0130] Specific examples of the (B2) component include compounds represented by the following formula (B2-5), (B2-6), or (B2-7). Specific examples of the (B2) component include the compounds described in paragraphs 0068 to 0071 of International Publication No. 2018 / 235424 and paragraphs 0113 to 0115 of International Publication No. 2018 / 235425. However, the (B2) component is not limited to these specific examples. In formula (B2-5), s represents an integer of 0 or 1 or more, and r represents an integer of 1 to 10. In formula (B2-6), n b2 The average value of is 1. In formula (B2-7), n and m each independently represent 0 or an integer of 1 or more.

[0131] [ka]

[0132] The component (B2) may be synthesized by a known method. The component (B2) can be synthesized by, for example, the method described in WO 2018 / 235424 or WO 2018 / 235425.

[0133] From the viewpoint of significantly obtaining the effects of the present invention, the weight average molecular weight of the component (B2) is preferably at least 150, more preferably at least 200, and even more preferably at least 250, and is preferably at most 5000, more preferably at most 3000, and even more preferably at most 2000. The weight average molecular weight of the component (B2) is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0134] From the viewpoint of obtaining the effects of the present invention significantly, the allyl group equivalent of the (B2) component is preferably 50 g / eq or more, more preferably 100 g / eq or more, even more preferably 150 g / eq, and is preferably 2000 g / eq or less, more preferably 1000 g / eq or less, even more preferably 500 g / eq or less. The allyl group equivalent is the mass of the (B2) component containing one equivalent of an allyl group.

[0135] The content of the (B2) component in the resin composition, relative to the total amount of the (B) components in the resin composition being 100% by mass, is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, 17% by mass or more, or 19% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 88% by mass or less, or 86% by mass or less.

[0136] The content of the (B2) component in the resin composition, relative to 100 mass% of the total of the (A) component and the (B) component in the resin composition, is preferably 5 mass% or more, more preferably 8 mass% or more, even more preferably 10 mass% or more or 11 mass% or more, and is preferably 70 mass% or less, more preferably 65 mass% or less, even more preferably 60 mass% or less or 59 mass% or less.

[0137] The mass ratio of the content of the (B2) component to the content of the (B1) component in the resin composition ((B2) component / (B1) component) is preferably 0.1 or more, more preferably 0.15 or more, even more preferably 0.2 or more, 0.23 or more, or 0.24 or more, and is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

[0138] When the resin composition contains components other than the (A) component and the (B) component, the content of the (B2) component in the resin composition, relative to 100 mass% of the non-volatile components in the resin composition, is preferably 0.1 mass% or more, more preferably 1 mass% or more, even more preferably 1.5 mass% or more, 2 mass% or more, or 2.5 mass% or more, and is preferably 25 mass% or less, more preferably 20 mass% or less, even more preferably 15 mass% or less, or 14 mass% or less.

[0139] When the resin composition contains components other than the (A) component and the (B) component, the content of the (B2) component in the resin composition, relative to the resin components in the resin composition taken as 100 mass%, is preferably 1 mass% or more, more preferably 5 mass% or more, even more preferably 7 mass% or more, 9 mass% or more, or 10 mass% or more, and is preferably 60 mass% or less, more preferably 55 mass% or less, and even more preferably 50 mass% or less.

[0140] <(B3) Other active ester resins> In the resin composition of the present invention, the (B) active ester resin may further contain (B3) other active ester resin as an optional component in addition to the (B1) and (B2) components. The (B3) other active ester resin as the (B3) component does not include those corresponding to the above-mentioned (A), (B1) and (B2) components. The (B3) other active ester resin may be used alone or in combination of two or more.

[0141] The (B3) component is not particularly limited, but generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. The (B3) component is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound is more preferred. 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 phenol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0142] Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferred, and among them, an active ester compound containing a dicyclopentadiene-type diphenol structure is more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0143] Commercially available products of the component (B3) include active ester compounds containing a dicyclopentadiene-type diphenol structure such as "EXB-9451", "EXB-9460", "EXB-9460S", "HPC-8000-65T", and "HPC-8000L-65TM" (manufactured by DIC Corporation), active ester compounds containing acetylated phenol novolac such as "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester compounds containing benzoylated phenol novolac such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation), active ester curing agents which are acetylated phenol novolac such as "DC808" (manufactured by Mitsubishi Chemical Corporation), and active ester curing agents which are benzoylated phenol novolac such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

[0144] When the resin composition of the present invention contains the (B3) component, the content of the (B3) component in the resin composition, relative to the total of the (B) components in the resin composition being 100 mass%, is, for example, 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and even more preferably 1 mass% or more, and for example, 15 mass% or less, preferably 10 mass% or less, more preferably 7 mass% or less, and even more preferably 5 mass% or less, 4 mass% or less, or 3 mass% or less.

[0145] When the resin composition of the present invention contains the (B3) component, the content of the (B3) component in the resin composition, relative to 100 mass% of the non-volatile components in the resin composition, is, for example, 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 1 mass% or more, and even more preferably 2 mass% or more, and for example, 15 mass% or less, preferably 10 mass% or less, more preferably 7 mass% or less, and even more preferably 5 mass% or less, 4 mass% or less, or 3 mass% or less.

[0146] When the resin composition of the present invention contains the (B3) component, the content of the (B3) component in the resin composition, relative to the resin component in the resin composition being 100% by mass, is, for example, 0.1% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, 9% by mass or more, or 10% by mass or more, and is, for example, 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 13% by mass or less, 12% by mass or less, or 11% by mass or less.

[0147] The ratio of the amount of the (A) component to the (B) component is the ratio of [total number of epoxy groups in the (A) component]:[total number of active ester groups in the (B) component], and is preferably in the range of 1:0.01 to 1:10, more preferably in the range of 1:0.1 to 1:5, even more preferably in the range of 1:0.2 to 1:3, even more preferably in the range of 1:0.3 to 1:2, even more preferably in the range of 1:0.8 to 1:2, even more preferably in the range of 1:1 to 1:1.8, especially preferably in the range of 1:1.2 to 1:1.6, and especially preferably in the range of 1:1.3 to 1:1.5. Here, the "total number of epoxy groups in the (A) component" refers to the total value of all values ​​obtained by dividing the mass of the (A) component present in the resin composition by the epoxy equivalent. In addition, the "total number of active ester groups in the (B) component" refers to the total value of all values ​​obtained by dividing the mass of the (B) component present in the resin composition by the active ester group equivalent. By adjusting the ratio of the amount of the component (B) to the amount of the component (A) within the above range, the effects of the present invention can be significantly achieved.

[0148] The content of the (B) component in the resin composition, relative to 100 mass% of the total of the (A) component and the (B) component in the resin composition, is preferably 30 mass% or more, more preferably 40 mass% or more, even more preferably 50 mass% or more, 55 mass% or more, or 60 mass% or more, and is preferably 80 mass% or less, more preferably 75 mass% or less, and even more preferably 70 mass% or less.

[0149] When the resin composition contains components other than the (A) component and the (B) component, the content of the (B) component in the resin composition, relative to 100 mass% of the non-volatile components in the resin composition, is preferably 5 mass% or more, more preferably 8 mass% or more, even more preferably 10 mass% or more, 12 mass% or more, or 13 mass% or more, and is preferably 30 mass% or less, more preferably 25 mass% or less, even more preferably 20 mass% or less, 18 mass% or less, or 16 mass%.

[0150] When the resin composition contains components other than the (A) component and the (B) component, the content of the (B) component in the resin composition, relative to the resin components in the resin composition taken as 100 mass%, is preferably 30 mass% or more, more preferably 40 mass% or more, even more preferably 45 mass% or more, 48 mass% or more, or 50 mass% or more, and is preferably 80 mass% or less, more preferably 70 mass% or less, even more preferably 60 mass% or less, or 59 mass% or less.

[0151] <(C) Inorganic filler> The resin composition of the present invention may further contain an inorganic filler as component (C). By including component (C), the thermal expansion coefficient and dielectric tangent tend to be further reduced.

[0152] Examples of materials for the component (C) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum silicate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferred as the silica. The component (C) may be used alone or in combination of two or more.

[0153] Examples of commercially available products of component (C) include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Corporation; and "Cellspheres" and "MGH-005" manufactured by Taiheiyo Cement Corporation.

[0154] The average particle size of component (C) is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, 2 μm or less, 1 μm or less, or 0.7 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more. The average particle size of component (C) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction / scattering type particle size distribution measuring device, and the median diameter is taken as the average particle size. The measurement sample can be prepared by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing the mixture by ultrasonic waves for 10 minutes. The measurement sample was measured using a laser diffraction type particle size distribution measuring device with blue and red light source wavelengths, and the particle size distribution of the inorganic filler on a volume basis was measured using a flow cell method, and the average particle size was calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction type particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

[0155] The specific surface area of ​​component (C) is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, 3m 2 / g or more or 5m 2 The upper limit of the specific surface area is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 80m 2 / g or less, more preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 The specific surface area of ​​component (C) is obtained by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method, and calculating the specific surface area using the BET multipoint method.

[0156] The (C) component is preferably surface-treated with a suitable surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the (C) component can be improved. Examples of the surface treatment agent include silane coupling agents such as vinyl silane coupling agents, epoxy silane coupling agents, styryl silane coupling agents, (meth)acrylic silane coupling agents, amino silane coupling agents, isocyanurate silane coupling agents, ureido silane coupling agents, mercapto silane coupling agents, isocyanate silane coupling agents, and acid anhydride silane coupling agents; non-silane coupling-alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane; and silazane compounds. The surface treatment agent may be used alone or in combination of two or more.

[0157] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), and Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane).

[0158] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, it is preferable that 100% by mass of the inorganic filler is surface-treated with 0.2 to 5% by mass of the surface treatment agent.

[0159] 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 amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, the carbon amount per unit surface area of ​​the inorganic filler is preferably 1 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is more preferable. The carbon amount per unit surface area of ​​component (C) can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, an "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used.

[0160] When the resin composition of the present invention contains the (C) component, the content of the (C) component in the resin composition is, for example, 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, 65% by mass or more, or 70% by mass or more, when the non-volatile components in the resin composition are 100% by mass, from the viewpoint of easily realizing a resin composition that provides a lower dielectric tangent and thermal expansion coefficient. The upper limit of the content of the (C) component is not particularly limited, but may be, for example, 90% by mass or less, 85% by mass or less, 80% by mass or less, 77% by mass or less, or 75% by mass or less. Even when the (C) component is blended at a high content in order to further reduce the dielectric tangent and thermal expansion coefficient of the cured product of the resin composition, the resin composition of the present invention can obtain a cured product that has excellent smear removability and excellent adhesion strength with the conductor layer.

[0161] <(D) Other thermosetting resins> The resin composition of the present invention may further contain, as component (D), a thermosetting resin other than components (A) and (B) (also referred to as "other thermosetting resins").

[0162] Examples of the component (D) include phenol-based resins, naphthol-based resins, acid anhydride-based resins, cyanate ester-based resins, carbodiimide-based resins, amine-based resins, etc. The component (D) may be used alone or in combination of two or more.

[0163] As the phenolic resin and naphtholic resin, those having a novolac structure are preferred from the viewpoint of heat resistance and water resistance, and from the viewpoint of adhesion to the conductor layer, nitrogen-containing phenolic resins and nitrogen-containing naphtholic resins are preferred, and triazine skeleton-containing phenolic resins and triazine skeleton-containing naphtholic resins are more preferred.

[0164] Specific examples of phenol-based resins and naphthol-based resins include, for example, "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", and "SN-375" manufactured by Nippon Steel Chemical & Material Co., Ltd. and "SN-395" manufactured by DIC Corporation; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", and "KA-1165" manufactured by Gun-ei Chemical Co., Ltd.; and "GDP-6115L", "GDP-6115H", and "ELPC75" manufactured by Gun-ei Chemical Co., Ltd.

[0165] Examples of the acid anhydride resin include those having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. Examples of acid anhydrides include polymeric acid anhydrides such as anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and styrene-maleic acid resins, which are copolymers of styrene and maleic acid. Commercially available acid anhydride resins include "MH-700" manufactured by New Japan Chemical Co., Ltd.

[0166] Examples of cyanate ester resins include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester resins include arxada's "PT30" and "PT60" (phenol novolac type multifunctional cyanate ester resins), "ULL-950S" (multifunctional cyanate ester resin), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine-converted into a trimer).

[0167] Specific examples of carbodiimide resins include Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216 g / eq.), V-05 (carbodiimide group equivalent: 262 g / eq.), V-07 (carbodiimide group equivalent: 200 g / eq.), V-09 (carbodiimide group equivalent: 200 g / eq.), and Stavaxol (registered trademark) P (carbodiimide group equivalent: 302 g / eq.), all manufactured by Nisshinbo Chemical Inc.

[0168] Examples of the amine resin include resins having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Specific examples of the amine resin include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)- ... phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. As the amine-based resin, commercially available products may be used, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0169] When the resin composition of the present invention contains the (D) component, the ratio of the amounts of the (A) component, the (B) component and the (D) component is preferably in the range of 1:0.01 to 1:10, more preferably in the range of 1:0.05 to 1:8, even more preferably in the range of 1:0.1 to 1:5, even more preferably in the range of 1:0.5 to 1:3, even more preferably in the range of 1:1 to 1:2.5, even more preferably in the range of 1:1.3 to 1:2, and particularly preferably in the range of 1:1.5 to 1:1.8. The "total number of epoxy groups in the (A) component" is as described above. In addition, the "total number of active groups in the (B) component and the (D) component" is the total value of the mass of the (B) component present in the resin composition divided by the active ester group equivalent and the mass of the (D) component divided by the active group equivalent. When the resin composition of the present invention contains the component (D), the effects of the present invention can be significantly achieved by setting the quantitative ratio of the components (B) and (D) to the component (A) within the above range.

[0170] When the resin composition of the present invention contains the (D) component, the content of the (D) component in the resin composition, relative to 100 mass% of the non-volatile components in the resin composition, is, for example, 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 1 mass% or more, and even more preferably 2 mass% or more, and for example, 15 mass% or less, preferably 10 mass% or less, more preferably 7 mass% or less, and even more preferably 5 mass% or less or 4 mass% or less.

[0171] When the resin composition of the present invention contains the (D) component, the content of the (D) component in the resin composition, relative to 100 mass% of the resin components in the resin composition, is, for example, 0.1 mass% or more, preferably 1 mass% or more, more preferably 5 mass% or more, and even more preferably 7 mass% or more, and for example, 25 mass% or less, preferably 20 mass% or less, more preferably 15 mass% or less, and even more preferably 13 mass% or less or 12 mass% or less.

[0172] <(E) Organic filler> The resin composition of the present invention may further contain an organic filler as component (E). The organic filler (E) may be used alone or in combination of two or more kinds.

[0173] As the organic filler, organic fillers containing a rubber component can be widely used. Examples of the rubber component contained in the organic filler include silicone-based elastomers such as polydimethylsiloxane; olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, and ethylene-propylene-butene terpolymer; and thermoplastic elastomers such as acrylic thermoplastic elastomers such as polypropyl(meth)acrylate, polybutyl(meth)acrylate, polycyclohexyl(meth)acrylate, and polyoctyl(meth)acrylate. Furthermore, silicone-based rubbers such as polyorganosiloxane rubber may be mixed into the rubber component. The glass transition temperature (Tg) of the rubber component contained in the rubber particles is, for example, 0° C. or lower, preferably −10° C. or lower, more preferably −20° C. or lower, and even more preferably −30° C. or lower.

[0174] In one embodiment, the organic filler is a core-shell type rubber particle consisting of a core particle containing the above-mentioned rubber component and a shell part obtained by graft copolymerization of a monomer component copolymerizable with the rubber component contained in the core particle. Here, the core-shell type does not necessarily refer only to those in which the core particle and the shell part are clearly distinguishable, but also includes those in which the boundary between the core particle and the shell part is unclear, and the core particle does not necessarily have to be completely covered with the shell part.

[0175] Specific examples of organic fillers containing a rubber component include "CHT" manufactured by Samsung SDI; "B602" manufactured by Techno UMG; "Paraloid EXL-2602", "Paraloid EXL-2603", "Paraloid EXL-2655", "Paraloid EXL-2311", "Paraloid-EXL2313", "Paraloid EXL-2315", "Paraloid KM-330", "Paraloid KM-336P", "Paraloid KCZ-201" manufactured by Dow; and "Metabrene C-223A" manufactured by Mitsubishi Rayon. ", "Metablen E-901", "Metablen S-2001", "Metablen W-450A", "Metablen SRK-200", "Kane Ace M-511", "Kane Ace M-600", "Kane Ace M-400", "Kane Ace M-580", "Kane Ace MR-01" manufactured by Kaneka Corporation, "Staphyloid AC3355", "Staphyloid AC3816", "Staphyloid AC3832", "Staphyloid AC4030", "Staphyloid AC3364" manufactured by Aica Kogyo Co., Ltd. These are core-shell type rubber particles.

[0176] When the resin composition of the present invention contains the (E) component, the content of the (E) component in the resin composition, relative to 100 mass% of the non-volatile components in the resin composition, is, for example, 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1 mass% or more, and for example, 15 mass% or less, preferably 10 mass% or less, more preferably 7 mass% or less, and even more preferably 5 mass% or less, 4 mass% or less, or 3 mass% or less.

[0177] When the resin composition of the present invention contains the (E) component, the content of the (E) component in the resin composition, relative to 100 mass% of the resin components in the resin composition, is, for example, 0.1 mass% or more, preferably 1 mass% or more, more preferably 3 mass% or more, and even more preferably 4 mass% or more, and for example, 20 mass% or less, preferably 15 mass% or less, more preferably 10 mass% or less, and even more preferably 8 mass% or less.

[0178] <(F) Curing accelerator> The resin composition of the present invention may contain a curing accelerator as the component (F).

[0179] Examples of the (F) component include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, peroxide-based curing accelerators, etc. The curing accelerators may be used alone or in combination of two or more.

[0180] When the resin composition of the present invention contains the (F) component, the content of the (F) component in the resin composition, relative to 100 mass% of the non-volatile components in the resin composition, is, for example, 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 0.2 mass% or more, and still more preferably 0.25 mass% or more, and for example, 5 mass% or less, preferably 3 mass% or less, more preferably 2 mass% or less, and still more preferably 1 mass% or less.

[0181] When the resin composition of the present invention contains the (F) component, the content of the (F) component in the resin composition, relative to the resin component in the resin composition being 100 mass%, is, for example, 0.1 mass% or more, preferably 0.5 mass% or more, more preferably 1 mass% or more, and still more preferably 1.1 mass% or more, and for example, 10 mass% or less, preferably 7 mass% or less, more preferably 5 mass% or less, and still more preferably 3 mass% or less.

[0182] <(G) Optional Additives> The resin composition of the present invention may further contain (G) any additive. Examples of such additives include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, and polyester resins; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as bentone and montmorillonite; defoamers such as silicone defoamers, acrylic defoamers, fluorine defoamers, and vinyl resin defoamers; and ultraviolet absorbers such as benzotriazole ultraviolet absorbers. Examples of the suitable additives include ultraviolet ray absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers. The content of the component (G) may be determined depending on the properties required for the resin composition.

[0183] <(H) Organic Solvent> The resin composition of the present invention may further contain (H) an organic solvent as a volatile component. Examples of the organic solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate. Examples of the organic solvent include ether ester solvents such as ethyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The organic solvent may be used alone or in combination of two or more.

[0184] The resin composition of the present invention can be produced, for example, by adding and mixing the (A), (B1), and (B2) components, and, if necessary, the (B3), (C), (D), (E), (F), (G) or (H) components in any preparation vessel in any order and / or all or part of them at the same time. In the process of adding and mixing each component, the temperature can be appropriately set, and heating and / or cooling may be performed temporarily or throughout. In the process of adding and mixing or thereafter, the resin composition may be stirred or shaken using a stirring device or shaking device such as a mixer to disperse the resin composition uniformly. In addition, degassing may be performed under low pressure conditions such as under vacuum at the same time as stirring or shaking.

[0185] [Physical properties and applications of resin compositions] As described above, the resin composition of the present invention, which contains the components (A) and (B), wherein the component (B) contains the components (B1) and (B2), exhibits good dielectric properties and can provide a cured product that also exhibits good smear removal properties and excellent adhesive strength with a conductor layer.

[0186] The cured product of the resin composition of the present invention is characterized by a low relative dielectric constant (Dk). Therefore, the cured product provides an insulating layer with a low relative dielectric constant. For example, when measured at 5.8 GHz and 23°C as described in the section <Test Example 1: Measurement of relative dielectric constant (Dk) and dielectric loss tangent (Df)> below, the relative dielectric constant of the cured product obtained by thermally curing the resin composition at 190°C for 90 minutes is preferably 4.0 or less, more preferably 3.8 or less, and even more preferably 3.5 or less. The lower limit of the relative dielectric constant may be 0.001 or more.

[0187] The cured product of the resin composition of the present invention is characterized by a low dielectric loss tangent (Df). Therefore, the cured product provides an insulating layer with a low dielectric loss tangent. For example, when measured at 5.8 GHz and 23°C as described in the section <Test Example 1: Measurement of relative dielectric constant (Dk) and dielectric loss tangent (Df)> below, the dielectric loss tangent of the cured product obtained by thermally curing the resin composition at 190°C for 90 minutes is preferably 0.005 or less, more preferably 0.004 or less, and even more preferably 0.003 or less. The lower limit of the dielectric loss tangent may be 0.001 or more.

[0188] The cured product of the resin composition of the present invention exhibits a characteristic of excellent smear removability. The maximum smear length of the cured product is preferably less than 5 μm, more preferably less than 2 μm. The lower limit of the maximum smear length of the cured product may be 0 μm or may be greater than 0 μm. The "maximum smear length" refers to the maximum length of the smear from the circumference of the bottom surface of the via to the center of the circle. The evaluation of the above maximum smear length can be measured according to the method described in the section <Test Example 2: Evaluation of Smear Removability> below.

[0189] The insulating layer made of the cured product of the resin composition of the present invention exhibits a characteristic of excellent adhesion strength (peel strength) between the insulating layer and the conductor layer. The adhesion strength is preferably 0.55 kgf / cm or more, more preferably 0.60 kgf / cm or more, and even more preferably 0.65 kgf / cm or more. The upper limit of the adhesion strength is preferably as high as possible, and may be, for example, 10 kgf / cm or less. The adhesion strength (peel strength) can be measured according to the method described in the section <Test Example 3: Measurement of adhesion strength (peel strength) with conductor layer> below.

[0190] The resin composition of the present invention can exhibit the characteristic of excellent flexibility. Therefore, by using the resin composition of the present invention, a resin sheet with excellent flexibility can be manufactured. For example, a resin composition layer is formed on a plastic film as a support to obtain a resin sheet. When this resin sheet is folded 90° along an axis with a diameter of 3 mm so that the support is on the inside, cracking of the resin composition layer can be suppressed. Specifically, the flexibility can be measured according to the method described in the section <Test Example 4: Evaluation of Flexibility> below.

[0191] As described above, the resin composition of the present invention can provide a cured product that exhibits good dielectric properties, good smear removal properties, and excellent adhesion strength with a conductor layer. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for insulating layer of printed wiring board), and can be more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for interlayer insulating layer of printed wiring board). The resin composition of the present invention can also be suitably used when the printed wiring board is a circuit board with built-in components. The resin composition of the present invention can also be suitably used as a resin composition for forming an insulating layer of a rewiring board of a semiconductor package (resin composition for insulating layer of rewiring board). In the present invention, the printed wiring board and the rewiring board are collectively referred to as "circuit board", and therefore the resin composition of the present invention can be suitably used for the insulating layer of a circuit board.

[0192] The resin composition of the present invention can further be used in a wide range of applications requiring a resin composition, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, hole filling resins, sealing resins, and component embedding resins.

[0193] [Sheet-type laminated materials (resin sheets, prepregs)] The resin composition of the present invention can be used as it is, but it may also be used in the form of a sheet-like laminate material containing the resin composition.

[0194] As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

[0195] In one embodiment, the resin sheet includes a support and a layer of a resin composition (hereinafter simply referred to as a "resin composition layer") provided on the support, and is characterized in that the resin composition layer is formed from the resin composition of the present invention.

[0196] The thickness of the resin composition layer may vary depending on the application, and may be appropriately determined depending on the application. For example, the thickness of the resin composition layer is preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, or 30 μm or less from the viewpoint of thinning of printed wiring boards and semiconductor packages. The lower limit of the thickness of the resin composition layer is not particularly limited, but may usually be 1 μm or more, 5 μm or more, etc.

[0197] Examples of the support include a thermoplastic resin film, a metal foil, and a release paper, and a thermoplastic resin film and a metal foil are preferred. Thus, in a preferred embodiment, the support is a thermoplastic resin film or a metal foil.

[0198] When a thermoplastic resin film is used as the support, examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0199] When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0200] The support may be subjected to a matte treatment, a corona treatment, or an antistatic treatment on the surface to be bonded to the resin composition layer. In addition, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used as the support. The release agent used in the release layer of the support with a release layer may be, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available release agents include, for example, "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, which are alkyd resin-based release agents. In addition, commercially available supports with a release layer include, for example, "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Ltd., and "Unipeel" manufactured by Unitika Ltd., which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[0201] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the total thickness of the support with a release layer is in the above range.

[0202] When a metal foil is used as the support, a metal foil with a support substrate may be used, which is a thin metal foil with a peelable support substrate attached thereto. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When a metal foil with a support substrate is used as the support, the resin composition layer is provided on the metal foil.

[0203] In the metal foil with a supporting substrate, the material of the supporting substrate is not particularly limited, and examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. When copper foil is used as the supporting substrate, it may be electrolytic copper foil or rolled copper foil. In addition, the release layer is not particularly limited as long as it can release the metal foil from the supporting substrate, and examples thereof include an alloy layer of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic coating, etc.

[0204] In the metal foil with a supporting substrate, the material of the metal foil is preferably, for example, copper foil or copper alloy foil.

[0205] In the metal foil with a supporting substrate, the thickness of the supporting substrate is not particularly limited, but is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm, and the thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

[0206] In one embodiment, the resin sheet may further include an optional layer as necessary. For example, such an optional layer may be a protective film provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dirt and the like to the surface of the resin composition layer and scratches.

[0207] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving the liquid resin composition in an organic solvent or by applying the prepared resin varnish onto a support using a die coater or the like, and then drying the applied resin varnish to form a resin composition layer.

[0208] The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of two or more kinds.

[0209] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0210] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film.

[0211] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0212] The sheet-like fiber substrate used for the prepreg is not particularly limited, and can be a substrate commonly used for prepreg, such as glass cloth, aramid nonwoven fabric, or liquid crystal polymer nonwoven fabric. From the viewpoint of thinning of printed wiring boards and semiconductor chip packages, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is not particularly limited. It is usually 10 μm or more.

[0213] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0214] The thickness of the prepreg may be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

[0215] The sheet-like laminate material of the present invention can be suitably used to form an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used to form an interlayer insulating layer of a printed wiring board (for the insulating layer of a printed wiring board). The sheet-like laminate material of the present invention can also be suitably used to form an insulating layer of a rewiring board of a semiconductor package (for the insulating layer of a rewiring board). That is, the sheet-like laminate material of the present invention can be suitably used as an insulating layer of a circuit board.

[0216] [Circuit board] The resin composition of the present invention can be used to form an insulating layer for a circuit board. The present invention also provides such a circuit board, i.e., a circuit board including an insulating layer made of a cured product of the resin composition of the present invention.

[0217] <Printed wiring board> In one embodiment, the circuit board of the present invention is a printed wiring board.

[0218] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet, by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate such that a resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., heat curing) the resin composition layer to form an insulating layer.

[0219] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be called an "inner layer circuit substrate". In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be formed during the manufacture of a printed wiring board is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0220] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). The thermocompression bonding member may be pressed directly onto the resin sheet, or may be pressed via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate.

[0221] The lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination may be performed under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0222] The lamination can be performed by a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch type vacuum pressure laminator.

[0223] After lamination, the laminated resin sheet may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. The lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0224] The support may be removed between step (I) and step (II), or after step (II). When a metal foil is used as the support, the conductor layer may be formed using the metal foil without peeling off the support. When a metal foil with a support substrate is used as the support, the support substrate (and the peel layer) may be peeled off. Then, the conductor layer can be formed using the metal foil.

[0225] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions that are usually adopted when forming an insulating layer for a printed wiring board may be used.

[0226] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, etc., but in one embodiment, the curing temperature is preferably 140° C. to 250° C., more preferably 150° C. to 240° C., and even more preferably 160° C. to 230° C. The curing time is preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

[0227] Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50° C. to 140° C., preferably 60° C. to 135° C., more preferably 70° C. to 130° C. for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0228] In manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in manufacturing printed wiring boards. When the support is removed after step (II), the removal of the support may be carried out between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0229] In another embodiment, the printed wiring board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when a resin sheet is used.

[0230] Step (III) is a step of drilling holes in the insulating layer, which allows holes such as via holes and through holes to be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined depending on the design of the printed wiring board.

[0231] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear removal (desmear) is also performed. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0232] The swelling liquid used in the roughening treatment is not particularly limited, but includes an alkaline solution, a surfactant solution, etc., and is preferably an alkaline solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes, for example. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 to 15 minutes.

[0233] The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP", "Concentrate Compact P", and "Dosing Solution Securigans P" manufactured by Atotech Japan.

[0234] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be mentioned.

[0235] The treatment with the neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method in which the object that has been roughened with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0236] 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 from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among these, from the viewpoints of versatility in forming the 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 preferred, 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 preferred, and a single metal layer of copper is even more preferred.

[0237] The conductor layer may be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

[0238] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

[0239] In one embodiment, the conductor layer may be formed by plating. From the viewpoint of facilitating the formation of fine wiring, it is preferable to form the conductor layer by a semi-additive method. An example of forming the conductor layer by the semi-additive method will be described below.

[0240] First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the 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. Thereafter, unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0241] In another embodiment, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, it is preferable to carry out the step (V) between the steps (I) and (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for the step (I). Then, the step (II) is carried out to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a modified semi-additive method, using the metal foil on the insulating layer.

[0242] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Metal Mining Co., Ltd.

[0243] Alternatively, when a metal foil or a metal foil with a supporting substrate is used as the support for the resin sheet, the conductor layer may be formed using the metal foil, as described above.

[0244] <Rewiring substrate for semiconductor packages> In one embodiment, the circuit board of the present invention is a rewiring board (rewiring layer) of a semiconductor package. Hereinafter, a method for manufacturing a semiconductor package will be described.

[0245] The semiconductor package includes an insulating layer made of the cured product of the resin composition of the present invention as an insulating layer of a rewiring board. The semiconductor package may also include a sealing layer made of the cured product of the resin composition of the present invention.

[0246] A semiconductor package can be manufactured, for example, by a method including the following steps (1) to (6) using the resin composition and resin sheet of the present invention. The resin composition and resin sheet of the present invention may be used to form a rewiring formation layer (insulating layer for forming a rewiring board) in step (5) or a sealing layer in step (3). An example of forming a rewiring formation layer or a sealing layer using a resin composition or a resin sheet is shown below, but the technology for forming a rewiring formation layer or a sealing layer of a semiconductor package is publicly known, and a person skilled in the art can manufacture a semiconductor package using the resin composition and resin sheet of the present invention according to a publicly known technology. (1) A step of laminating a temporary fixing film onto a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) 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 have been peeled off; and (6) A process of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0247] -Process (1)- The material used for the substrate is not particularly limited. Examples of the substrate include semiconductor wafers such as silicon wafers, glass wafers, glass substrates, metal substrates such as copper, titanium, stainless steel, and cold-rolled steel (SPCC), substrates in which glass fibers are impregnated with epoxy resin or the like and subjected to a heat curing treatment (e.g., FR-4 substrates), and substrates made of bismaleimide triazine resin (BT resin).

[0248] The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in step (4) and can temporarily fix the semiconductor chip. A commercially available product can be used as the temporary fixing film. An example of the commercially available product is Riva Alpha manufactured by Nitto Denko Corporation.

[0249] -Process (2)- The semiconductor chips can be temporarily fixed using known devices such as a flip chip bonder, a die bonder, etc. The layout and number of semiconductor chips can be appropriately set depending on the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, etc., and for example, the semiconductor chips can be temporarily fixed by arranging them in a matrix shape of multiple rows and multiple columns.

[0250] -Process (3)- A resin composition layer of the resin sheet of the present invention is laminated on a semiconductor chip, or the resin composition of the present invention is applied onto a semiconductor chip and cured (for example, thermally cured) to form an encapsulating layer.

[0251] For example, the semiconductor chip and the resin sheet can be laminated by removing the protective film of the resin sheet and then heat-pressing the resin sheet to the semiconductor chip from the support side. Examples of the member for heat-pressing the resin sheet to the semiconductor chip (hereinafter also referred to as the "heat-pressing member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). It is preferable to press the heat-pressing member not directly onto the resin sheet but via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the semiconductor chip. The semiconductor chip and the resin sheet may be laminated by a vacuum lamination method, and the lamination conditions are the same as those described in relation to the manufacturing method of the printed wiring board, and the preferred ranges are also the same.

[0252] After lamination, the resin composition is thermally cured to form the encapsulating layer under the same conditions as those described in relation to the method for producing a printed wiring board.

[0253] The support of the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor chip and thermally cured, or the support may be peeled off before the resin sheet is laminated on the semiconductor chip.

[0254] When the resin composition of the present invention is applied to form a sealing layer, the application conditions are the same as the application conditions when forming the resin composition layer described in relation to the resin sheet of the present invention, and the preferred ranges are also the same.

[0255] -Process (4)- The method for peeling off the substrate and the temporary fixing film can be appropriately changed depending on the material of the temporary fixing film, and examples of the method include a method in which the temporary fixing film is heated and foamed (or expanded) to peel it off, and a method in which ultraviolet light is irradiated from the substrate side to reduce the adhesive strength of the temporary fixing film and then peeled off.

[0256] In the method of heating and foaming (or expanding) the temporary fixing film to peel it off, the heating conditions are usually 100 to 250° C. for 1 to 90 seconds or 5 to 15 minutes. In the method of irradiating ultraviolet light from the substrate side to reduce the adhesive strength of the temporary fixing film to peel it off, the irradiation dose of ultraviolet light is usually 10 mJ / cm. 2 ~1000mJ / cm 2 It is.

[0257] -Process (5)- The resin composition and resin sheet of the present invention are used to form a rewiring formation layer (insulating layer of a rewiring board).

[0258] After forming the redistribution layer, a via hole may be formed in the redistribution layer to connect the semiconductor chip to a conductor layer described later. The via hole may be formed by a known method depending on the material of the redistribution layer.

[0259] -Process (6)- The formation of the conductor layer on the rewiring formation layer may be carried out in the same manner as in step (V) described in relation to the method for producing a printed wiring board. Note that steps (5) and (6) may be repeated to alternately stack (build up) the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer).

[0260] In manufacturing the semiconductor package, the steps of (7) forming a solder resist layer on the conductor layer (rewiring layer), (8) forming bumps, and (9) dicing a plurality of semiconductor packages into individual semiconductor packages may be further carried out. These steps may be carried out according to various methods used in manufacturing semiconductor packages and known to those skilled in the art.

[0261] By forming a rewiring formation layer (insulating layer) using the resin composition and resin sheet of the present invention, which can provide a cured product exhibiting good dielectric properties, good smear removal properties, and excellent adhesive strength with a conductor layer, a semiconductor package with extremely low transmission loss can be realized regardless of whether the semiconductor package is a fan-in (Fan-In) type package or a fan-out (Fan-Out) type package. In one embodiment, the semiconductor package of the present invention is a fan-out (Fan-Out) type package. The resin composition and resin sheet of the present invention can be applied to any type of package, whether it is a fan-out type panel level package (FOPLP) or a fan-out type wafer level package (FOWLP). In one embodiment, the semiconductor package of the present invention is a fan-out type panel level package (FOPLP) or a fan-out type wafer level package (FOWLP).

[0262] [Semiconductor Devices] The semiconductor device of the present invention includes a layer made of a cured product of the resin composition layer of the present invention. The semiconductor device of the present invention can be produced by using the circuit board of the present invention.

[0263] Examples of the semiconductor device include various semiconductor devices used in electric appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). EXAMPLES

[0264] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the temperature and pressure conditions were room temperature (23°C) and atmospheric pressure (1 atm), unless otherwise specified.

[0265] <Synthesis Example 1: Synthesis of Active Ester Resin B (Active Ester Resin Containing a Specific Structural Unit)> In a flask equipped with a thermometer, dropping funnel, condenser, distillation tube, and stirrer, 320g (2.0 mol) of 2,7-dihydroxynaphthalene, 184g (1.7 mol) of benzyl alcohol, and 5.0g of paratoluenesulfonic acid monohydrate were charged and stirred at room temperature while blowing in nitrogen. The temperature was then raised to 150°C, and the mixture was stirred for 4 hours while distilling off the water produced. After the reaction was completed, 900g of methyl isobutyl ketone and 5.4g of 20% aqueous sodium hydroxide solution were added to neutralize the mixture, and the aqueous layer was removed by separation. The mixture was washed three times with 280g of water, and methyl isobutyl ketone was removed under reduced pressure to obtain 460g of benzyl-modified naphthalene compound A. The obtained benzyl-modified naphthalene compound A was a black solid, and the hydroxyl equivalent was 180g / equivalent.

[0266] In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 203.0 g of isophthalic acid chloride (molar number of acid chloride groups: 2.0 mol) and 1400 g of toluene were charged, and the system was purged with nitrogen under reduced pressure to dissolve. Next, 113.9 g (0.67 mol) of orthophenylphenol and 240 g of benzyl-modified naphthalene compound A (molar number of phenolic hydroxyl groups: 1.33 mol) were charged, and the system was purged with nitrogen under reduced pressure to dissolve. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the system was controlled to 60°C or less, and 400 g of 20% aqueous sodium hydroxide solution was dropped over 3 hours. Then, stirring was continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was left to stand for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for 15 minutes, and the mixture was allowed to stand and separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanting to obtain an active ester resin B in the form of a toluene solution with a non-volatile content of 65 mass %. The active ester equivalent of the obtained active ester resin B was 238 g / eq. The obtained active ester resin B is represented by the following formula (in the formula, it is mainly composed of compounds in which n is an integer of 0 to 5 and m is an integer of 0 to 15).

[0267] [ka]

[0268] <Synthesis Example 2: Synthesis example of active ester resin C (allyl group-containing active ester resin)> In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 165g of a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165g / eq., softening point 85°C), 134g (1.0mol) of orthoallylphenol, and 1200g of toluene were charged, and the system was purged with nitrogen under reduced pressure. Next, 203g (1.0mol) of isophthalic acid chloride was charged, and the system was purged with nitrogen under reduced pressure. 0.6g of tetrabutylammonium bromide was added, and while performing a nitrogen gas purging treatment, the system was controlled to 60°C or less, and 41.2g of a 20% aqueous sodium hydroxide solution was dropped over 3 hours, and after the dropwise addition, it was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and separating. Water was further added to the obtained toluene layer and stirred for 15 minutes, and the aqueous layer was removed by standing and separating. This operation was repeated until the pH of the aqueous layer became 7. The non-volatile content was adjusted to 70% by mass by heat drying, thereby obtaining an active ester resin C represented by the following chemical formula.

[0269] [ka]

[0270] In the above chemical formula, each s is independently an integer of 0 or 1 or more, and the average value of r calculated from the charge ratio is 1. The dashed line in the chemical formula is a structure obtained by reacting isophthalic acid chloride with a polyaddition reaction resin of phenol and / or ortho-allylphenol. The ester group equivalent of the obtained active ester resin C was calculated from the charge ratio to be 214 g / eq.

[0271] <Examples 1 to 10 and Comparative Examples 1 to 5. Preparation of Resin Varnish> Each component was weighed and mixed in the amount (parts by mass) shown in Tables 1 and 2 below, and then 10 parts by mass of methyl ethyl ketone and 10 parts by mass of cyclohexanone were mixed and uniformly dispersed using a high-speed rotating mixer to obtain a varnish-like resin composition (resin varnish). Details of each component shown in Tables 1 and 2 below are as follows.

[0272] (A) Epoxy resin: "HP-4032-SS": DIC Corporation, naphthalene type liquid epoxy resin, epoxy equivalent 144g / eq. - "NC-3000L": Manufactured by Nippon Kayaku Co., Ltd., naphthol novolac type solid epoxy resin, epoxy equivalent 272g / eq.

[0273] (B1) Active ester resin containing specific structural units: "HPC-8150-62T": Manufactured by DIC Corporation, an active ester resin containing a structural unit represented by formula (B1-1), which is an active ester resin represented by formula (B1-3) (in formula (B1-3), Ar 1 is a naphthylene group having two benzyl groups as substituents, Ar 2 is a naphthyl group, R B is a phenylene group, m1 is 0, and m2 is 1.) A toluene solution containing 61.5% nonvolatile matter by mass, and an active ester group equivalent of 223 g / eq. "Active ester B": an active ester resin containing a structural unit represented by formula (B1-1), synthesized in Synthesis Example 1

[0274] (B2) Allyl group-containing active ester resin: "Active ester C": an active ester resin containing an allyl group, synthesized in Synthesis Example 2 "Active ester D": an active ester resin containing an allyl group, which is represented by the following formula (wherein the formula is mainly composed of compounds in which n is an integer from 0 to 6 and m is an integer from 0 to 6), a toluene solution of 70% non-volatile components, and an active ester group equivalent of 250 g / eq.

[0275] [ka]

[0276] (B3) Other active ester resins: "HPC-8000L-65TM": DIC Corporation, active ester resin containing dicyclopentadiene-type diphenol structure, toluene: methyl ethyl ketone = 1: 1 solution with 65% non-volatile content by mass

[0277] (C) Inorganic filler: "SO-C2": Spherical silica (manufactured by Admatechs) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)

[0278] (D) Other thermosetting resins: "LA-3018-50P": DIC Corporation, phenol-based hardener, 1-methoxy-2-propanol solution with 50% non-volatile content by mass, phenol group equivalent 151g / eq. "LA-1356": DIC Corporation, phenol-based hardener, methyl ethyl ketone solution with 60% non-volatile content, phenol equivalent 146g / eq.

[0279] (E) Organic filler: "EXL-2655": Rubber particles manufactured by Dow Chemical Japan

[0280] (F) Curing accelerator: "1B2PZ": Imidazole-based curing accelerator manufactured by Shikoku Chemical Industry Co., Ltd.

[0281] [Table 1]

[0282] [Table 2]

[0283] <Preparation of resin sheet A> A polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. On the release layer of this support, the resin varnish obtained in the examples and comparative examples was uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain a resin sheet A including a support and a resin composition layer.

[0284] <Test Example 1: Measurement of relative dielectric constant (Dk) and dielectric loss tangent (Df)> The resin sheet A obtained in each of the examples and comparative examples was cured in an oven at 190° C. for 90 minutes. The support was peeled off from the resin sheet A taken out of the oven to obtain a cured product of the resin composition layer. The cured product was cut into a length of 80 mm and a width of 2 mm to be used as a cured product for evaluation.

[0285] For each of the cured evaluation products, the dielectric constant and dielectric tangent (Dk value and Df value) were measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C using an Agilent Technologies "HP8362B." Measurements were performed on two test pieces, and the average was calculated.

[0286] <Test Example 2: Evaluation of smear removal ability> (1) Surface preparation for inner layer circuit boards Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") with an inner layer circuit formed were etched 1 μm with a microetching agent (Mec "CZ8101") to roughen the copper surface.

[0287] (2) Lamination of resin sheets Using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"), resin sheet A was laminated on both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. This lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, heat pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0288] (3) Thermal curing of the resin composition layer The inner layer substrate laminated with the resin sheet A was placed in an oven at 130°C and heated for 30 minutes, then transferred to an oven at 170°C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. The support was then peeled off to obtain a cured substrate A1 having an insulating layer / inner layer substrate / insulating layer in this order.

[0289] (4) Formation of via holes The insulating layer of the cured substrate A1 was processed using a Via Mechanics CO2 laser processing machine (LK-2K212 / 2C) under conditions of a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and 3 shots, forming a via hole with a top diameter of 50 μm on the surface of the insulating layer and a diameter of 50 μm on the bottom surface of the insulating layer, thereby obtaining a circuit substrate A2.

[0290] (5) Roughening treatment The insulating layer surface of the circuit board A2 was immersed in a swelling liquid, Swelling Dip Securiganth P, manufactured by Atotech Japan, at 60°C for 10 minutes. Next, the insulating layer surface of the circuit board was immersed in a roughening liquid, Concentrate Compact P, manufactured by Atotech Japan (aqueous solution of KMnO4: 60g / L, NaOH: 40g / L), at 80°C for 15 minutes. Finally, the insulating layer surface of the circuit board was immersed in a neutralizing liquid, Reduction Solution Securiganth P, manufactured by Atotech Japan, at 40°C for 5 minutes.

[0291] (6) Evaluation of smear removal In the roughening-treated circuit board A2, the periphery of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image and evaluated according to the following criteria. [Evaluation criteria for smear removal] ◎: Maximum smear length is less than 2 μm ○: Maximum smear length is 2 μm or more and less than 5 μm ×: Maximum smear length is 5 μm or more

[0292] <Test Example 3: Measurement of adhesion strength (peel strength) with conductor layer> (1) Surface preparation of the substrate for adhesion strength evaluation A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic "R1515A") with copper foil on the surface was prepared as an inner layer substrate. The copper foil on the surface of this inner layer substrate was completely removed by etching. It was then dried at 190°C for 30 minutes.

[0293] (2) Lamination of resin sheets Using a batch-type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), resin sheet A was laminated on both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. This lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressing at 100°C and a pressure of 0.74 MPa for 30 seconds. Next, a heat press was performed at 100°C and a pressure of 0.5 MPa for 60 seconds. Thereafter, the support was peeled off to obtain an intermediate laminate I including a resin composition layer / inner layer substrate / resin composition layer in this order.

[0294] (3) Copper foil preparation The shiny side of an electrolytic copper foil (Mitsui Mining & Smelting Co., Ltd. "3EC-III", thickness 35 μm) was etched by 1 μm with a micro-etching agent (Mech Co., Ltd. "CZ8101") to roughen the copper surface, and then anti-rust treatment (CL8300) was performed. The copper foil whose surface was etched with the micro-etching agent in this way may be referred to as "CZ copper foil" hereinafter. Furthermore, this copper foil was heat-treated in an oven at 130°C for 30 minutes to obtain copper foil I having a roughened treated surface.

[0295] (4) Copper foil lamination Copper foil I was laminated on both sides of intermediate laminate I so that the treated surface of copper foil I was bonded to the resin composition layer of intermediate laminate I. This lamination was performed under the same conditions as in "(2) Lamination of resin sheets" above. As a result, intermediate laminate II including copper foil I / resin composition layer / inner layer substrate / resin composition layer / copper foil I in this order was obtained.

[0296] (5) Thermal curing of the resin composition layer The intermediate laminate II was placed in a 100°C oven and heated for 30 minutes, then transferred to a 170°C oven and heated for 30 minutes. The intermediate laminate II was then removed from the oven under room temperature atmosphere, and placed in a 200°C oven and heated for an additional 90 minutes. This resulted in thermal curing of the resin composition layer, and an evaluation substrate III was obtained that included the roughened copper foil / insulating layer (cured product of the resin composition layer) / inner layer substrate / insulating layer (cured product of the resin composition layer) / roughened copper foil in this order. In this evaluation substrate III, the roughened copper foil corresponds to the conductor layer.

[0297] (6) Measurement of adhesion strength (peel strength) with the conductor layer The peel strength between the roughened copper foil and the insulating layer was measured using the evaluation board III. This peel strength measurement was performed in accordance with JIS C6481. Specifically, the peel strength measurement was performed by the following procedure.

[0298] A cut was made in the roughened copper foil of evaluation board III to surround a rectangular portion 10 mm wide and 100 mm long. One end of this rectangular portion was peeled off and held with a gripper (Autocom type tester "AC-50C-SL" manufactured by TSE Corporation). A range of 35 mm long of the rectangular portion was peeled off in the vertical direction, and the load (kgf / cm) at the time of peeling was measured as the peel strength. The peeling was performed at room temperature at a speed of 50 mm / min. From the measured values, the adhesion strength with the conductor layer was evaluated according to the following criteria. [Evaluation criteria for adhesion strength with conductor layer] ○: Peel strength is 0.65kgf / cm or more △: Peel strength value is 0.55kgf / cm or more and less than 0.65kgf / cm ×: Peel strength value is less than 0.55kgf / cm

[0299] <Test Example 4: Evaluation of flexibility> Resin sheet A was folded 90° along a shaft having a diameter of 3 mm so that the support was on the inside, and flexibility was confirmed and evaluated according to the following criteria. [Flexibility evaluation criteria] ○: No cracks in the resin composition layer ×: The resin composition layer is cracked.

[0300] <Result> The results of the Examples and Comparative Examples are shown in Tables 3 and 4 below.

[0301] [Table 3]

[0302] [Table 4]

Claims

1. (A) an epoxy resin; and (B) an active ester resin, The component (B) comprises (B1) an active ester resin containing a structural unit represented by the following formula (B1-1), and (B2) an active ester resin containing an allyl group: 【Chemistry 1】 (In formula (B1-1), Ar １ each independently represents a divalent aromatic group which may have a substituent; At least one Ar １ is a naphthylene group which may have a substituent; L Ｂ each independently represents a single bond or a divalent linking group; R Ｂ１ represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof; m1 is an integer from 0 to 5; "*" represents a bond.)

2. 2. The resin composition according to claim 1, wherein the ratio of the amount of the component (A) to the amount of the component (B) is in the range of 1:0.3 to 1:2, expressed as the ratio of [total number of epoxy groups in the component (A)]:[total number of active ester groups in the component (B)].

3. The resin composition according to claim 1 , wherein the content of the component (A) is 20% by mass or more and 50% by mass or less, when the resin components in the resin composition are taken as 100% by mass.

4. The resin composition according to claim 1, wherein the content of the component (B1) is 10% by mass or more and 60% by mass or less, when the resin components in the resin composition are taken as 100% by mass.

5. The resin composition according to claim 1, wherein the content of the component (B2) is 10% by mass or more and 60% by mass or less, when the resin component in the resin composition is 100% by mass.

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

7. The resin composition according to claim 6, wherein the content of the component (C) is 50% by mass or more and 90% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass.

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

9. A support and a resin composition layer provided on the support, A resin sheet, wherein the resin composition layer comprises the resin composition according to any one of claims 1 to 8.

10. A circuit board comprising a cured product of the resin composition according to any one of claims 1 to 8.

11. A semiconductor device comprising the circuit board according to claim 10.

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