Resin composition

Abstract

The present invention provides a resin composition which provides a cured product having excellent dielectric properties (low dielectric loss tangent), excellent heat resistance (glass transition temperature), and excellent mechanical properties (puncture resistance). The present invention is a resin composition comprising: (A) an epoxy resin, (B) a binaphthol-type active ester compound or a bisnaphthol-type active ester compound, and (C) a maleimide resin.

Description

Technical Field

[0001] This invention relates to resin compositions. Furthermore, it relates to resin sheets, cured products, circuit boards, and semiconductor devices obtained using the resin compositions. Background Technology

[0002] Because epoxy resin compositions produce cured products with excellent insulation properties, they are widely used as insulating materials for circuit boards such as printed wiring boards or rewiring substrates for semiconductor packaging.

[0003] On the other hand, with the increasing speed of communication, in order to reduce transmission loss when operating in high-frequency environments, insulating materials with excellent dielectric properties (low dielectric loss tangent) are required for the insulating materials of circuit boards. As insulating materials with excellent dielectric properties, insulating materials using specific curing agents such as reactive ester resins that can reduce or suppress the formation of polar groups such as secondary hydroxyl groups in the curing reaction of epoxy resins have been reported (for example, Patent Document 1).

[0004] Existing technical documents Patent documents Patent document 1: Japanese Patent Application Publication No. 2019-157027. Summary of the Invention

[0005] The problem that the invention aims to solve With the development of high-speed communication, and considering that signal frequencies will further increase in the future, the dielectric properties required of insulating materials will become more stringent. Furthermore, with the increasing size and multilayering of semiconductor packaging, the mechanical properties and heat resistance requirements for insulating materials will also become more stringent, while also balancing dielectric properties.

[0006] Here, the inventors have discovered that in resin compositions containing epoxy resin and reactive ester resin, if the resin composition is modified in order to improve heat resistance (glass transition temperature), the mechanical properties (puncture resistance) and dielectric properties (low dielectric loss tangent) sometimes deteriorate.

[0007] The present invention was made in view of the above-mentioned problems, and its object is to provide a resin composition that simultaneously achieves excellent dielectric properties (low dielectric loss tangent), excellent heat resistance (glass transition temperature) and excellent mechanical properties (puncture resistance).

[0008] Methods for solving problems The inventors conducted in-depth research and found that the above-mentioned problems could be solved by a resin composition containing (A) epoxy resin, (B) a binaphthol-type active ester compound or a bisnaphthol-type active ester compound, and (C) maleimide resin, thereby completing the present invention.

[0009] That is, the present invention includes the following: <1> A resin composition comprising: (A) Epoxy resin, (B) Binaphthol-type active ester compounds or bisnaphthol-type active ester compounds, and (C) Maleimide resin; <2> according to <1> The resin composition wherein component (B) is an ester compound represented by formula (1-1) or formula (1-2) below. [Chemical Formula 1] (in the formula, X A1 and X A2 Each independently represents a monovalent organic group containing at least one aromatic ring (a). X B Each independently represents a divalent organic group containing at least one aromatic ring (b). X C Each independently represents a divalent organic group containing at least one aromatic ring (c). At least one X C It is a divalent group as shown in the following formula (C-1), n represents an integer greater than or equal to 1. [Chemical Formula 2] (in the formula, R C1 Indicates a divalent organic group or a single bond. R C2 Each can independently represent a halogen atom or an alkyl group. nc1 and nc2 each independently represent integers from 0 to 6. * indicates a connection key. <3> according to <1> or <2> The resin composition wherein the mass ratio of component (B) to component (A) [component (B) / component (A)] is 1.5 or more; <4> according to <1> ~ <3> The resin composition according to any one of the following, wherein component (C) comprises an aromatic maleimide resin; <5> according to <1> or <4> The resin composition according to any one of the following methods, wherein it further comprises (D) an inorganic filler material; <6> according to <5> The resin composition wherein, when the non-volatile component in the resin composition is set to 100% by mass, the content of component (D) is 50% by mass or more. <7> according to <1> ~ <6> The resin composition according to any one of the following, wherein it further comprises (E) an organic filler material; <8> according to <1> ~ <7> The resin composition according to any one of the following methods, wherein it further comprises (F) a thermoplastic resin; <9> according to <8> The resin composition wherein component (F) comprises a phenoxy resin; <10> according to <1> ~ <9> The resin composition according to any one of the following methods, wherein it further comprises (G) a curing accelerator; <11> according to <1> ~ <10> The resin composition described in any one of the above statements is used as an insulating layer on a circuit board. <12> A resin sheet comprising a support and disposed on the support. <1> ~ <11> The layer of the resin composition described in any one of the following; <13> according to <12> The resin sheet wherein the support is a thermoplastic resin film or a metal foil; <14> <1> ~ <11> The cured product of the resin composition described in any one of the above statements; <15> A circuit board, comprising an insulating layer, the insulating layer containing <1> ~ <11> The cured product of the resin composition described in any one of the above statements; <16> A semiconductor device, wherein, includes <15> The circuit board mentioned above.

[0010] The effects of the invention According to the present invention, a resin composition can be provided that simultaneously achieves excellent dielectric properties (low dielectric loss tangent), excellent heat resistance (glass transition temperature), and excellent mechanical properties (puncture resistance); resin sheets, cured products, circuit boards, and semiconductor devices obtained using the resin composition. Detailed Implementation

[0011] The present invention will now be described in detail with reference to the embodiments and examples shown below. However, the present invention is not limited to the embodiments and examples listed below, and may be implemented in any way without departing from the scope of the claims and their equivalents.

[0012] [Explanation of Terminology] In the following explanation, the descriptions of numerical ranges as "above XX and below YY" or "XX to YY" refer to the numerical range including both the lower and upper limits as endpoints, unless otherwise specified. When the numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily.

[0013] In the following description, "non-volatile component" refers to the component constituting the resin composition other than the organic solvents described later. Additionally, "resin component" refers to the non-volatile component constituting the resin composition after removing the inorganic filler materials described later.

[0014] In the following description, the term "optionally having substituents" used to refer to compounds or groups, unless otherwise stated, refers to both the case where the hydrogen atoms of the compound or group are not substituted by substituents and the case where some or all of the hydrogen atoms of the compound or group are substituted by substituents. Furthermore, when the number of constituent atoms and carbon atoms of the compound or group are stated, unless otherwise specified, this number of constituent atoms and carbon atoms does not include the number of constituent atoms and carbon atoms of substituents.

[0015] In this specification, the term "substituent" refers, unless otherwise specified, to halogen atoms, alkyl, alkenyl, alkynyl, polyalkenyl, cycloalkyl, cycloalkenyl, alkoxy, cycloalkoxy, aryl, aryloxy, arylalkyl, arylalkoxy, monovalent heterocyclic, alkylidene, amino, silyl, acyl, acyloxy, (meth)acryloyl, carboxyl, sulfonyl, cyano, nitro, hydroxyl, mercapto, and oxo. It should be noted that groups containing only carbon and hydrogen, such as alkyl, alkenyl, alkynyl, polyalkenyl, cycloalkyl, cycloalkenyl, aryl, arylalkyl, and alkylidene, are also collectively referred to as "hydrocarbon groups." Furthermore, groups containing unsaturated bonds, such as alkenyl, alkynyl, polyalkenyl, cycloalkenyl, and (meth)acryloyl, are also collectively referred to as "groups containing unsaturated bonds." Here, "(meth)acryloyl" refers to both acryloyl and methacryloyl.

[0016] Examples of halogen atoms used as substituents include fluorine, chlorine, bromine, and iodine atoms.

[0017] The alkyl group used as a substituent can be either straight-chain or branched. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 14, even more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.

[0018] The alkenyl group used as a substituent can be either linear or branched. The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 14, even more preferably 2 to 12, even more preferably 2 to 6, and particularly preferably 2 or 3. Examples of such alkenyl groups include vinyl, allyl, 1-propenyl, butenyl, sec-butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl.

[0019] The alkynyl group used as a substituent can be either straight-chain or branched. The number of carbon atoms in the alkynyl group is preferably 2 to 20, more preferably 2 to 14, even more preferably 2 to 12, even more preferably 2 to 6, and particularly preferably 2 or 3. Examples of such alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl, hepynyl, octyynyl, nonynyl, and decynyl.

[0020] The polyene group used as a substituent can be either linear or branched, and 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. The number of carbon atoms in the polyene group is preferably 3 to 20, more preferably 3 to 14, even more preferably 3 to 12, and even more preferably 3 to 6.

[0021] The cycloalkyl group used as a substituent preferably has 3 to 20 carbon atoms, more preferably 3 to 12, and even more preferably 3 to 6. Examples of such cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0022] The number of carbon atoms in the cycloalkenyl group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. Examples of such cycloalkenyl groups include cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

[0023] The alkoxy group used as a substituent can be either straight-chain or branched. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 6. Examples of such alkoxy groups include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, and decoxy.

[0024] The number of carbon atoms in the cycloalkoxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. Examples of such cycloalkoxy groups include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, and cyclohexyloxy.

[0025] The aryl group used as a substituent is a group formed by removing one hydrogen atom from the aromatic ring of an aromatic hydrocarbon. The number of carbon atoms in the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. Examples of such aryl groups include phenyl, naphthyl, and anthracene.

[0026] The number of carbon atoms in the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. Examples of aryloxy groups used as substituents include phenoxy, 1-naphthyloxy, and 2-naphthyloxy.

[0027] The aralkyl group used as a substituent preferably has 7 to 25 carbon atoms, more preferably 7 to 19, even more preferably 7 to 15, and even more preferably 7 to 11. Examples of such aralkyl groups include phenyl-C1 to C1-C2. 12 Alkyl, naphthyl-C1~C 12 Alkyl and anthracene-C1~C 12 alkyl.

[0028] The arylalkoxy group used as a substituent preferably has 7 to 25 carbon atoms, more preferably 7 to 19, even more preferably 7 to 15, and even more preferably 7 to 11. Examples of such arylalkoxy groups include phenyl-C1 to C1-C24. 12 Alkoxy and naphthyl-C1~C 12 Alkyl group.

[0029] A monovalent heterocyclic group used as a substituent is a group formed by removing one hydrogen atom from the heterocycle of a heterocyclic compound. The monovalent heterocyclic group preferably has 3 to 21 carbon atoms, more preferably 3 to 15, and even more preferably 3 to 9. This monovalent heterocyclic group also includes monovalent aromatic heterocyclic groups (heteroaryl). Examples of such monovalent heterocyclic groups include: thiophene, pyrrole, furanyl, furyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolidinyl, piperidinyl, quinolinyl, and isoquinolinyl.

[0030] An alkylidene group used as a substituent refers to a group formed by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms in this alkylidene group is preferably 1 to 20, more preferably 1 to 14, even more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3. Examples of such alkylidene groups include: methylidene, ethylidene, propylidene, isopropylidene, butylidene, sec-butylidene, isobutylidene, pentylidene, hexylidene, heptylidene, octylidene, nonylidene, and decylidene.

[0031] The acyl group used as a substituent refers to a group represented by the formula -C(=O)-R (where R is an alkyl or aryl group). The alkyl group represented by R can be either straight-chain or branched. Examples of aryl groups represented by R include phenyl, naphthyl, and anthracene. The number of carbon atoms in the acyl group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. Examples of acyl groups include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, and benzoyl.

[0032] The acyloxy group used as a substituent refers to a group represented by the formula -OC(=O)-R (where R is an alkyl or aryl group). The alkyl group represented by R can be either straight-chain or branched. Examples of aryl groups represented by R include phenyl, naphthyl, and anthracene. The number of carbon atoms in this acyloxy group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. Examples of acyloxy groups include acetoxy, propionyloxy, butyryloxy, isobutyryloxy, pivaloyloxy, and benzoyloxy.

[0033] The substituents described above may further have substituents (hereinafter sometimes referred to as "secondary substituents"). As secondary substituents, the same group as the substituents described above may be used unless otherwise specified.

[0034] In this specification, the term "organic group" refers to a group containing at least a carbon atom as a skeleton atom, and can be linear, branched, or cyclic. Unless otherwise specified, the number of skeleton atoms in an organic group is preferably 1 to 3000, more preferably 1 to 1000, even more preferably 1 to 100, even more preferably 1 to 50, and particularly preferably 1 to 30 or 1 to 20. Examples of organic groups include those containing one or more skeleton atoms selected from carbon, oxygen, nitrogen, and sulfur (containing at least a carbon atom).

[0035] In this specification, the term "hydrocarbon group" refers to a group formed by removing one or more hydrogen atoms from a hydrocarbon compound. Specifically, a monovalent hydrocarbon group is a group formed by removing one hydrogen atom from a hydrocarbon compound, and a divalent hydrocarbon group is a group formed by removing two hydrogen atoms from a hydrocarbon compound. Examples of hydrocarbon groups include aliphatic or aromatic groups containing only carbon and hydrogen atoms, as described later. In this specification, aliphatic groups containing only carbon and hydrogen atoms are also referred to as "aliphatic hydrocarbon groups," and aromatic groups containing only carbon and hydrogen atoms are also referred to as "aromatic hydrocarbon groups."

[0036] In this specification, the term "aliphatic group" refers to a group formed by removing one or more hydrogen atoms bonded to an aliphatic carbon atom of an aliphatic compound. Specifically, a monovalent aliphatic group is a group formed by removing one hydrogen atom bonded to an aliphatic carbon atom of an aliphatic compound, and a divalent aliphatic group is a group formed by removing two hydrogen atoms bonded to an aliphatic carbon atom of an aliphatic compound. Examples of divalent aliphatic groups include: optionally alkylene groups with substituents, optionally cycloalkylene groups with substituents, optionally alkenyl groups with substituents, optionally cycloalkenyl groups with substituents, and optionally polyalkenyl groups with substituents (preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and even more preferably 2). In this specification, unless otherwise specified, the number of carbon atoms in the aliphatic group is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, 4 or more, 5 or more, or 6 or more, preferably 50 or less, more preferably 40 or less, and further preferably 30 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less. This number of carbon atoms does not include the number of carbon atoms of the substituents.

[0037] In this specification, the term "aromatic group" refers to a group formed by removing one or more hydrogen atoms from the aromatic ring of an aromatic compound. Specifically, a monovalent aromatic group is a group formed by removing one hydrogen atom from the aromatic ring of an aromatic compound, and a divalent aromatic group is a group formed by removing two hydrogen atoms from the aromatic ring of an aromatic compound. Examples of monovalent aromatic groups include aryl groups optionally having substituents and heteroaryl groups optionally having substituents; examples of divalent aromatic groups include arylene groups optionally having substituents and heteroarylene groups optionally having substituents. 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, further preferably 6 or more, and preferably up to 24 or less, more preferably 18 or less or 14 or less, and further preferably 10 or less. This number of carbon atoms does not include the number of carbon atoms from the substituents.

[0038] In this specification, the term "aromatic ring" refers to a ring that obeys Hückel's law and has 4p+2 electrons (p being a natural number) in its π-electron system. This includes monocyclic aromatic rings and fused polycyclic aromatic rings formed by the condensation of two or more monocyclic aromatic rings. The aromatic ring can be an aromatic carbon ring having only carbon atoms as cyclic atoms, or an aromatic heterocycle having oxygen, nitrogen, sulfur, or other heteroatoms in addition to carbon atoms as cyclic atoms. In this specification, unless otherwise specified, the number of carbon atoms in the aromatic ring is preferably 3 or more, more preferably 4 or more or 5 or more, further preferably 6 or more, and preferably up to 24 or less, more preferably 18 or less or 14 or less, and further preferably 10 or less. This number of carbon atoms does not include the number of carbon atoms of substituents. Examples of aromatic rings include: monocyclic aromatic rings such as benzene rings, furan rings, thiophene rings, pyrrole rings, pyrazole rings, oxazole rings, isoxazole rings, thiazole rings, imidazole rings, pyridine rings, pyridazine rings, pyrimidine rings, and pyrazine rings; and fused polycyclic aromatic rings formed by the condensation of two or more monocyclic aromatic rings such as naphthalene rings, anthracene rings, phenanthrene rings, benzofuran rings, isobenzofuran rings, indole rings, isoindole rings, benzothiophene rings, benzoimidazolium rings, indazole rings, benzooxazole rings, benzoisooxazole rings, benzothiazole rings, quinoline rings, isoquinoline rings, quinoxaline rings, acridine rings, quinazoline rings, borazine rings, and phthalazine rings. It should be noted that in this specification, the carbon atoms constituting the aromatic ring are referred to as "aromatic carbons".

[0039] [Resin Composition] The resin composition of the present invention contains (A) an epoxy resin, (B) a binaphthol-type active ester compound or a bisnaphthol-type active ester compound, and (C) a maleimide resin. By combining components (A), (B), and (C) in the resin composition, a cured product can be obtained that simultaneously achieves excellent dielectric properties (low dielectric loss tangent), excellent heat resistance (glass transition temperature), and excellent mechanical properties (puncture resistance). Furthermore, the inventors have confirmed that the cured product obtained by the present invention exhibits a low dielectric loss tangent even at high temperatures (90°C), and the resin composition of the present invention also exhibits excellent film stability.

[0040] The resin composition of the present invention may further contain any other components by combining it with components (A), (B), and (C). Examples of such optional components include: an active ester compound other than component (B) (hereinafter referred to as "component (B')"), (D) an inorganic filler, (E) an organic filler, (F) a thermoplastic resin, (G) a curing accelerator, (H) an organic solvent, and (I) other additives. The components contained in the resin composition of the present invention will be described in detail below.

[0041] <(A) Epoxy Resin> The resin composition of the present invention contains (A) an epoxy resin. The epoxy resin is a curable resin having an epoxy equivalent of 5000 g / eq. or less. By containing (A) an epoxy resin in the resin composition, the glass transition temperature of the cured product can be effectively increased. One type of (A) epoxy resin can be used alone, or two or more types can be used in combination. In one embodiment, two or more types of (A) epoxy resin are preferably used in combination.

[0042] (A) The type of epoxy resin is not particularly limited as long as it has one or more (preferably two or more) epoxy groups in one molecule. Examples of epoxy resins (A) include: xylenol-type epoxy resins, bisphenol-type epoxy resins (bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol C type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, etc.), dicyclopentadiene-type epoxy resins, triphenol-type epoxy resins, naphthol phenolic varnish-type epoxy resins, phenolic phenolic varnish-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol phenolic varnish-type epoxy resins, phenol aralkyl-type epoxy resins, biphenyl-type epoxy resins, biphenyl aralkyl-type epoxy resins, linear aliphatic epoxy resins, and epoxy resins with a butadiene structure. The resins include alicyclic epoxy resins, heterocyclic epoxy resins, epoxy resins containing spirocyclic rings, cyclohexane-type epoxy resins, cyclohexane-diethanol-type epoxy resins, naphthyl ether-type epoxy resins, trihydroxymethyl-type epoxy resins, tetraphenylethane-type epoxy resins, isocyanurate-type epoxy resins, phenol benzopyrrolidone-type epoxy resins, Glycirol-type epoxy resins, epoxy resins containing alkylene oxide skeletons, epoxy resins containing fluorene structures, halogenated epoxy resins, and resorcinol-type epoxy resins, preferably bisphenol-type epoxy resins, naphthyl-type epoxy resins, or biphenyl-type epoxy resins, and more preferably bisphenol C-type epoxy resins, naphthyl-type epoxy resins, or biphenyl-type epoxy resins. In one embodiment, component (A) preferably comprises an epoxy resin having an aromatic backbone, more preferably bisphenol-type epoxy resin, naphthalene-type epoxy resin, or biphenyl-type epoxy resin, and even more preferably bisphenol C-type epoxy resin, naphthalene-type epoxy resin, or biphenyl-type epoxy resin. Furthermore, from the viewpoint of further improving film stability, component (A) particularly preferably comprises bisphenol C-type epoxy resin.

[0043] For the resin composition of the present invention, as component (A), it is preferable to include an epoxy resin having two or more epoxy groups per molecule. From the viewpoint of significantly obtaining the desired effect of the present invention, the proportion of epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of epoxy resin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0044] (A) The epoxy resin includes an epoxy resin that is liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at 20°C (hereinafter sometimes referred to as "solid epoxy resin"). For the resin composition of the present invention, as component (A), it may contain only liquid epoxy resin, only solid epoxy resin, or a combination of both. In one embodiment, the resin composition of the present invention preferably contains a combination of liquid epoxy resin and solid epoxy resin.

[0045] As a liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0046] Examples of liquid epoxy resins include: Glycirol type epoxy resins, bisphenol type epoxy resins (bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol C type epoxy resin, bisphenol AF type epoxy resin, etc.), naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, phenolic varnish type epoxy resins, alicyclic epoxy resins with ester skeletons, cyclohexanediol type epoxy resins, cyclic aliphatic glycidyl ethers, epoxy resins with butadiene structures, dicyclopentadiene type epoxy resins, epoxy resins containing alkylene oxide skeletons, epoxy resins containing fluorene structures, resorcinol type epoxy resins, etc., preferably bisphenol type epoxy resins or naphthalene type epoxy resins, more preferably bisphenol C type epoxy resins or naphthalene type epoxy resins. In one embodiment, from the viewpoints of further reducing the dielectric loss tangent, further increasing the glass transition temperature, and further improving puncture resistance, a naphthalene-type epoxy resin is further preferred as the liquid epoxy resin. In another embodiment, from the viewpoint of further improving film stability, a bisphenol C-type epoxy resin is further preferred as the liquid epoxy resin.

[0047] Specific examples of liquid epoxy resins include: Nagase ChemteX's "EX-992L", Mitsubishi Chemical's "YX7400", DIC's "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin); and Mitsubishi Chemical's "828US", "jER828EL", "828EL", "825", and "EPIKOTE". 828EL, DIC's "850S" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenolic varnish type epoxy resin); Mitsubishi Chemical's "630", "630LSD", and "604" (glycidylamine type epoxy resin); ADEKA's "ED-523T" (glycirol type epoxy resin); ADEKA's "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin); ADEKA's "EP-4088S" (dicyclopentadiene type epoxy resin); Nippon Steel Chemical Materials Co., Ltd.'s "ZX-1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase The following epoxy resins are available: ChemteX's "EX-721" (glycidyl ester type epoxy resin); Nagase ChemteX's "EX-991L" (epoxy resin containing an alkylene oxide backbone); Daicel's "CELLOXIDE 2021P" (alicyclohexane epoxy resin with an ester backbone); Daicel's "PB-3600"; Nippon Soda's "JP-100" and "JP-200" (epoxy resins with butadiene structures); Nippon Steel Chemical Materials' "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin); Osaka Gas Chemical's "EG-280" (epoxy resin containing a fluorene structure); and Nagase ChemteX's "EX-201" (resorcinol type epoxy resin). These can be used individually or in combination of two or more.

[0048] As a solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0049] Examples of solid epoxy resins include: xylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, naphthol phenolic varnish-type epoxy resins, cresol phenolic varnish-type epoxy resins, dicyclopentadiene-type epoxy resins, triphenol-type epoxy resins, triphenylmethane-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, biphenyl aralkyl-type epoxy resins, naphthyl ether-type epoxy resins, anthracene-type epoxy resins, bisphenol-type epoxy resins (bisphenol A type epoxy resin, bisphenol AF type epoxy resin, etc.), phenol aralkyl-type epoxy resins, tetraphenylethane-type epoxy resins, phenol benzopyrrolidone type epoxy resins, and epoxy resins containing fluorene structures. Preferably, biphenyl aralkyl-type epoxy resins or biphenyl-type epoxy resins are preferred, and more preferably, biphenyl-type epoxy resins are preferred.

[0050] Specific examples of solid epoxy resins include: DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" and "N-695" (cresol phenolic varnish type epoxy resins); DIC's "HP-7200," "HP-7200HH," "HP-7200H," and "HP-7200L" (dicyclopentadiene type epoxy resins); and DIC's "EXA-7311" and "EXA-7311- G3, EXA-7311-G4, EXA-7311-G4S, HP-6000, HP-6000L (naphthalene ether type epoxy resin); EPPN-502H (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NC-7000L (naphthalene phenolic varnish type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NC-3000, NC-3000L, NC-3000FH, NC-3100 (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NC-3000H (biphenyl aryl type) manufactured by Nippon Kayaku Co., Ltd. Epoxy resins; Nippon Steel Chemical Materials Co., Ltd.'s "ESN475V" and "ESN4100V" (naphthalene-type epoxy resins); Nippon Steel Chemical Materials Co., Ltd.'s "ESN485" (naphthol-type epoxy resins); Nippon Steel Chemical Materials Co., Ltd.'s "ESN375" (dihydroxynaphthalene-type epoxy resins); Mitsubishi Chemical Corporation's "YX4000H", "YX4000", "YX4000HK", and "YL7890" (bi-xylenol-type epoxy resins); Mitsubishi Chemical Corporation's "YL6121" (biphenyl-type epoxy resins); Mitsubishi Chemical Corporation's "YX8800" (anthracite-type epoxy resins). These include: epoxy resins such as Mitsubishi Chemical's "YX7700" (phenolic aralkyl type epoxy resin); Osaka Gas Chemical's "PG-100" and "CG-500"; Mitsubishi Chemical's "YL7760" (bisphenol AF type epoxy resin); Mitsubishi Chemical's "YL7800" (fluorene-containing epoxy resin); Mitsubishi Chemical's "jER1010" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER1031S" (tetraphenylethane type epoxy resin); and Nippon Kayaku Co., Ltd.'s "WHR991S" (phenolic benzopyrrolidone type epoxy resin). These can be used individually or in combination of two or more.

[0051] (A) The epoxy equivalent of the epoxy resin is preferably 50 to 5000 g / eq. The lower limit of the epoxy equivalent is more preferably 60 g / eq. or more, further preferably 80 g / eq. or more, and particularly preferably 110 g / eq. or more. The upper limit of the epoxy equivalent is preferably 3000 g / eq. or less, more preferably 2000 g / eq. or less, further preferably 1000 g / eq. or less, and particularly preferably 500 g / eq. or less, 400 g / eq. or less, or 300 g / eq. or less. The epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy groups, and can be determined according to JIS K 7236.

[0052] (A) The weight-average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. The weight-average molecular weight (Mw) of the epoxy resin can be determined by using the GPC method as a value converted from polystyrene.

[0053] From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition is set to 100% by mass, the content of (A) epoxy resin in the resin composition is preferably 0.1% by mass or more or 0.5% by mass or more, more preferably 1% by mass or more or 2% by mass or more, further preferably 3% by mass or more or 4% by mass or more, particularly preferably 5% by mass or more, 6% by mass or more, or 7% by mass or more. The upper limit is preferably 40% by mass or less or 35% by mass or less, more preferably 30% by mass or less or 25% by mass or less, further preferably 20% by mass or less, 15% by mass or less or 12% by mass or less, particularly preferably 10% by mass or less, 9% by mass or less or 8% by mass or less.

[0054] From the viewpoint of significantly obtaining the effects of the present invention, when the resin component in the resin composition is set to 100% by mass, the content of (A) epoxy resin in the resin composition is preferably 1% by mass or more or 3% by mass or more, more preferably 5% by mass or more or 8% by mass or more, further preferably 10% by mass or more, 12% by mass or more or 15% by mass or more, and particularly preferably 18% by mass or more, 20% by mass or more or 22% by mass or more. In one embodiment, it can be 24% by mass or more, 25% by mass or more, 26% by mass or more, etc. The upper limit is preferably 70% by mass or less or 65% by mass or less, more preferably 60% by mass or less or 55% by mass or less, further preferably 50% by mass or less, 45% by mass or less or 40% by mass or less, and particularly preferably 35% by mass or less, 30% by mass or less or 28% by mass or less.

[0055] <(B) Binaphthol-type active ester compounds or bisnaphthol-type active ester compounds> The resin composition of the present invention contains (B) a binaphthol-type active ester compound or a bisnaphthol-type active ester compound. By including component (B) in the resin composition, the glass transition temperature of the cured product can be increased while the dielectric loss tangent can be effectively reduced. The increase in the glass transition temperature of the cured product due to the inclusion of component (B) in the resin composition is believed to be caused by the stacking of naphthalene rings in the binaphthol or bisnaphthol backbone. Component (B) can be used alone or in combination of two or more.

[0056] (B) Component is a compound having one or more active ester groups in one molecule, and having a binatrol skeleton or a bisnatrol skeleton. In this invention, a "binatrol skeleton" refers to a skeleton formed by two naphthol skeletons linked by a single bond. Conversely, a "bisnatrol skeleton" refers to a skeleton formed by two naphthol skeletons linked by a divalent linking group. In one embodiment, the binatrol skeleton is preferably the skeleton shown in formula (B-1), and the bisnatrol skeleton is preferably the skeleton shown in formula (B-2). It should be noted that the naphthalene rings specified in formulas (B-1) and (B-2) below may optionally have substituents.

[0057] [Chemical Formula 3] (where R is in the formula) C (This indicates a divalent linker; * indicates a linker bond).

[0058] In one embodiment, component (B) is preferably an ester compound represented by formula (1-1) or formula (1-2).

[0059] [Chemical Formula 4] (in the formula, X A1 and X A2 Each independently represents a monovalent organic group containing at least one aromatic ring (a). X B Each independently represents a divalent organic group containing at least one aromatic ring (b). X C Each independently represents a divalent organic group containing at least one aromatic ring (c). At least one X C It is a divalent group as shown in the following formula (C-1), n represents an integer greater than or equal to 1.

[0060] [Chemical Formula 5] (in the formula, R C1Indicates a divalent organic group or a single bond. R C2 Each can independently represent a halogen atom or an alkyl group. nc1 and nc2 each independently represent integers from 0 to 6. * indicates a connection key.

[0061] The manufacturing method of component (B) is described later, but in relation to divalent aromatic hydroxyl compounds (HO-X) C -OH), divalent aromatic carboxylic acid compounds or divalent aromatic carboxyl halides (YC(=O)-X B -C(=O)-Y; where Y represents a hydroxyl or halogen atom) combination, in which a monovalent aromatic hydroxyl compound (X) is formed. A1 Under the reaction of -OH), the active ester compound shown in formula (1-1) is obtained. This is achieved by reacting a monovalent aromatic carboxylic acid compound or a monovalent aromatic carboxyl halide compound (X). A2 -C(=O)-Y; where Y represents the same meaning as above) under the reaction, the active ester compound shown in formula (1-2) is obtained. Additionally, component (B) can be an ester compound shown in formula (1-1) or formula (1-2), and is X A1 X A2 X B X C Or a mixture of two or more different active ester compounds.

[0062] <<Monovalent organic group X A1 and X A2 >> In equation (1-1), X A1 Each of these independently represents a monovalent organic group containing at least one aromatic ring (a). Additionally, in formula (1-2), X... A2 Each of these groups independently represents a monovalent organic group containing at least one aromatic ring (a).

[0063] X A1 and X A2 The aromatic ring (a) contained in the monovalent organic group shown, as described in the [Explanation of Terms] section, can be any of a monocyclic aromatic ring or a fused polycyclic aromatic ring formed by the condensation of two or more monocyclic aromatic rings. Additionally, the aromatic ring can be any of an aromatic carbocyclic ring or an aromatic heterocyclic ring.

[0064] From the viewpoint of achieving a cured product exhibiting both better dielectric properties and heat resistance when combined with epoxy resin, the aromatic ring (a) is preferably an aromatic carbide ring. This aromatic carbide ring can be either a monocyclic aromatic carbide ring or a fused polycyclic aromatic carbide ring, and its carbon number is preferably 6 to 14, more preferably 6 to 10. Therefore, in a preferred embodiment, X A1 and X A2 The aromatic ring (a) contained in the monovalent organic group shown is an aromatic carbon ring with 6 to 14 carbon atoms.

[0065] From the perspective of achieving cured products with improved dielectric properties and heat resistance when combined with epoxy resins, X A1 and X A2 The number of aromatic rings (a) contained in the monovalent organic groups shown is relative to each X A1 or X A2 Preferably, there are 1 to 3 aromatic rings, more preferably 1 or 2. The number of aromatic rings (a) does not include the number of aromatic rings that are substituents.

[0066] The aromatic ring (a) may optionally have substituents. The substituents, as described in the [Explanation of Terms] section, are preferably selected from one or more of halogen atoms, hydrocarbon groups, and alkoxy groups, more preferably selected from one or more of halogen atoms, alkyl groups, aryl groups, and aralkyl groups, further preferably selected from one or more of fluorine atoms, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 12 carbon atoms, and particularly preferably aryl groups having 6 to 10 carbon atoms.

[0067] Therefore, in a preferred embodiment, X A1 and X A2 The aromatic ring (a) contained in the monovalent organic group shown is an aromatic carbon ring with 6 to 14 carbon atoms, optionally having one or more substituents selected from halogen atoms, alkyl, aryl and aralkyl.

[0068] X A1 and X A2 The monovalent organic group shown is not particularly limited as long as it contains at least one of the above-described aromatic rings (a). As mentioned above, it is a group that contains at least a carbon atom as a skeleton atom, but preferably a monovalent group that contains one or more skeleton atoms selected from carbon, oxygen, nitrogen, and sulfur atoms (preferably 1 to 100, 1 to 50, or 1 to 30). From the viewpoint of achieving a cured product exhibiting better dielectric properties and heat resistance when combined with epoxy resin, X... A1 and X A2The monovalent organic group shown is particularly preferred to contain only carbon atoms or only carbon and oxygen atoms as the skeleton atom. Furthermore, the preferred range for the number of skeleton atoms is as described above, wherein 6 to 30 or 10 to 30 is preferred.

[0069] From the viewpoint that combining with epoxy resin yields cured products exhibiting both good dielectric properties and good heat resistance, in general formula (1-1), with X... A1 The oxygen atom that is bonded is preferably with X. A1 The aromatic carbon atoms, that is, the carbon atoms that constitute the aromatic ring (a) mentioned above, are bonded together. From the same point of view, in general formula (1-2), with X... A2 The carbon atom of the carbonyl group is preferably bonded to X. A2 The aromatic carbon atoms, that is, the carbon atoms that make up the aromatic ring (a) mentioned above, are bonded together.

[0070] In a preferred embodiment, X A1 and X A2 Each is independently represented by the following formula (A-1) or (A-2).

[0071] [Chemical Formula 6] (in the formula, R A1 and R A2 Each substituent can be represented independently. nA1 represents an integer from 0 to 5. nA2 represents integers from 0 to 7. * indicates a connection key.

[0072] In formula (A-1), one benzene ring is explicitly shown. This benzene ring belongs to the group mentioned above for X. A1 and X A2 The aforementioned "aromatic ring (a)". That is, in X A1 and X A2 When represented by formula (A-1), it is a monovalent organic group containing one benzene ring. R A1 The preferred examples of the substituents shown are also as for X. A1 and X A2 As described by "aromatic ring (a)", it is more preferably selected from one or more of halogen atoms, alkyl groups, aryl groups, and aralkyl groups; more preferably selected from one or more of fluorine atoms, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 12 carbon atoms; and particularly preferably selected from aryl groups having 6 to 10 carbon atoms. nA1 represents an integer from 0 to 5, for example, it can represent an integer from 0 to 3, 0, or 1. In one embodiment, nA1 can be 0 or 1, but is preferably 1.

[0073] Equation (A-2) explicitly shows one naphthalene ring. This naphthalene ring belongs to the group mentioned above for X. A1 and X A2 The aforementioned "aromatic ring (a)". That is, in X A1 and X A2 When represented by formula (A-2), it is a monovalent organic group containing one naphthalene ring. R A2 Preferred examples of the substituents shown are also as for X. A1 and X A2 As described by "aromatic ring (a)", it is more preferably selected from one or more of halogen atoms, alkyl groups, aryl groups, and aralkyl groups; more preferably selected from one or more of fluorine atoms, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 12 carbon atoms; and particularly preferably selected from aryl groups having 6 to 10 carbon atoms. nA2 represents an integer from 0 to 7, for example, it can represent an integer from 0 to 4, an integer from 0 to 3, 0, or 1. In one embodiment, nA1 can be 0 or 1, but is preferably 0.

[0074] In equation (1-1), there are two X's. A1 They can be the same or different, but the same is preferred. Furthermore, in equation (1-2), the two X's... A2 They can be the same or different, but being the same is preferred.

[0075] <<Divalent organic group X B >> Whether it is equation (1-1) or equation (1-2), X B Each of them independently represents a divalent organic group containing at least one aromatic ring (b).

[0076] X B The aromatic ring (b) contained in the divalent organic group shown can be either a monocyclic aromatic ring or a fused polycyclic aromatic ring, as described above in the [Terminology Explanation] section. Additionally, the aromatic ring can be either an aromatic carbocyclic ring or an aromatic heterocyclic ring.

[0077] From the viewpoint of achieving a cured product exhibiting both better dielectric properties and heat resistance when combined with epoxy resin, the aromatic ring (b) is preferably an aromatic carbide ring. This aromatic carbide ring can be either a monocyclic aromatic carbide ring or a fused polycyclic aromatic carbide ring, and its carbon number is preferably 6 to 14, more preferably 6 to 10. Therefore, in a preferred embodiment, X B The aromatic ring (b) contained in the divalent organic group shown is an aromatic carbon ring with 6 to 14 carbon atoms.

[0078] From the perspective of achieving cured products with improved dielectric properties and heat resistance when combined with epoxy resins, XB The number of aromatic rings (b) contained in the divalent organic groups shown is relative to each X B Preferably, there are 1 to 3 aromatic rings, more preferably 1 or 2. The number of aromatic rings (b) does not include the number of aromatic rings that are substituents.

[0079] The aromatic ring (b) may optionally have substituents. The substituents are as described above in the [Explanation of Terms] section, wherein, from the viewpoint of producing a cured product exhibiting both better dielectric properties and heat resistance in combination with epoxy resin, they are preferably selected from one or more of halogen atoms, hydrocarbon groups, and alkoxy groups; more preferably from one or more of halogen atoms, alkyl groups, aryl groups, and aralkyl groups; and even more preferably from one or more of fluorine atoms, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 12 carbon atoms. Alternatively, in one embodiment, the aromatic ring (b) may also be without substituents.

[0080] Therefore, in a preferred embodiment, X B The aromatic ring (b) contained in the monovalent organic group shown is an aromatic carbon ring with 6 to 14 carbon atoms, optionally having one or more substituents selected from halogen atoms, alkyl, aryl and aralkyl.

[0081] X B The divalent organic group shown is not particularly limited as long as it contains at least one of the above-mentioned aromatic rings (b). As mentioned above, it is a group that contains at least a carbon atom as a skeleton atom, but preferably a divalent group that contains one or more skeleton atoms selected from carbon, oxygen, nitrogen, and sulfur atoms (preferably 1 to 100, 1 to 50, or 1 to 30). Among these, from the viewpoint of providing a cured product that simultaneously exhibits better dielectric properties and heat resistance when combined with epoxy resin, X is particularly preferred. B The divalent organic groups shown contain only carbon atoms or only carbon and oxygen atoms as skeletal atoms. Furthermore, the preferred range for the number of skeletal atoms is as described above, with 6–30 or 6–20 being preferred.

[0082] From the viewpoint of obtaining cured products exhibiting both good dielectric properties and good heat resistance when combined with epoxy resin, in formulas (1-1) and (1-2), with X B The two carbonyl groups that combine are preferably with X. B The aromatic carbon atoms, that is, the carbon atoms that constitute the aromatic ring (b) mentioned above, are bonded together.

[0083] In a preferred embodiment, X BEach is independently (i) a divalent group formed by removing two hydrogen atoms from a optionally substituent monocyclic aromatic carbide ring, or (ii) a divalent group formed by removing two hydrogen atoms from an optionally substituent fused polycyclic aromatic carbide ring. In the described embodiments, the monocyclic aromatic carbide ring or the fused polycyclic aromatic carbide ring belongs to the category of the above-described categories for X. B The aforementioned "aromatic ring (b)". In X B When X is a divalent group as described in (i) above, B It is a divalent organic group containing a single monocyclic aromatic carbon ring. In X B When X is a divalent group as described in (ii) above, B It is a divalent organic group containing one fused polycyclic aromatic carbocyclic ring. Preferred examples of substituents optionally present in the monocyclic or fused polycyclic aromatic carbocyclic rings, such as those for X. B As described in "aromatic ring (b)", it is more preferably selected from one or more of halogen atoms, alkyl, aryl and aralkyl, and even more preferably selected from one or more of fluorine atoms, alkyl with 1 to 6 carbon atoms, aryl with 6 to 10 carbon atoms and aralkyl with 7 to 12 carbon atoms.

[0084] From the perspective of achieving cured products that simultaneously provide better dielectric properties and heat resistance when combined with epoxy resin, X B The divalent organic group shown is preferably the divalent group of (i) above, and more preferably a divalent group formed by removing two hydrogen atoms from an unsubstituted monocyclic aromatic carbon ring.

[0085] <<Divalent organic group X C >> Whether it is equation (1-1) or equation (1-2), X C Each of them independently represents a divalent organic group containing at least one aromatic ring (c).

[0086] X C The aromatic ring (c) contained in the divalent organic group shown can be either a monocyclic aromatic ring or a fused polycyclic aromatic ring, as described above in the "Explanation of Terms" section. Alternatively, the aromatic ring can also be either an aromatic carbocyclic ring or an aromatic heterocyclic ring.

[0087] From the viewpoint of achieving a cured product exhibiting both better dielectric properties and heat resistance when combined with epoxy resin, the aromatic ring (c) is preferably an aromatic carbide ring. This aromatic carbide ring can be either a monocyclic aromatic carbide ring or a fused polycyclic aromatic carbide ring, and its carbon number is preferably 6 to 14, more preferably 6 to 10. Therefore, in a preferred embodiment, X CThe aromatic ring (c) contained in the divalent organic group shown is an aromatic carbon ring with 6 to 14 carbon atoms.

[0088] From the perspective of achieving cured products with improved dielectric properties and heat resistance when combined with epoxy resins, X C The number of aromatic rings (c) contained in the divalent organic groups shown is relative to each X C Preferably, there are 1 to 7 aromatic rings, more preferably 1 to 5 or 1 to 3. The number of aromatic rings (c) does not include the number of aromatic rings that are substituents.

[0089] From the perspective of producing cured products that simultaneously exhibit better dielectric properties and heat resistance, X C This refers to a divalent organic group containing two or more monocyclic aromatic carbon rings, or a divalent organic group containing at least one fused polycyclic aromatic carbon ring. Here, the number of carbon atoms in each monocyclic aromatic carbon ring is as described above, but preferably 6 (i.e., a benzene ring). The number of carbon atoms in each fused polycyclic aromatic carbon ring is as described above, but preferably 10 to 14 (e.g., a naphthalene ring, anthracene ring), more preferably 10.

[0090] As X C The divalent organic groups containing two or more monocyclic aromatic carbon rings shown can be exemplified by, for example, divalent groups obtained by removing two hydroxyl groups from a bisphenol compound optionally having substituents, or divalent groups obtained by removing two hydroxyl groups from a dihydroxybiphenyl compound optionally having substituents. These preferred embodiments are described below with reference to the following formula (C-3).

[0091] As X C The divalent organic group containing at least one fused polycyclic aromatic carbon ring shown can be exemplified by, for example: a divalent group obtained by removing two hydroxyl groups from a dihydroxynaphthalene compound that is optionally substituent (refer to formula (C-4) below), a divalent group obtained by removing two hydroxyl groups from a binaphthol compound that is optionally substituent (refer to formulas (C-1) and (C-2) below), and a divalent group obtained by removing two hydroxyl groups from a bisnaphthol compound that is optionally substituent (refer to formulas (C-1) and (C-2) below).

[0092] The aromatic ring (c) may optionally have substituents. The substituents are as described above in the "Explanation of Terms" section, wherein, from the viewpoint of producing a cured product exhibiting better dielectric properties and heat resistance in combination with epoxy resin, they are preferably selected from one or more of halogen atoms, hydrocarbon groups, and alkoxy groups; more preferably from one or more of halogen atoms, alkyl groups, aryl groups, and aralkyl groups; and even more preferably from one or more of fluorine atoms, alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 12 carbon atoms. Alternatively, in one embodiment, the aromatic ring (c) may not have substituents.

[0093] (B) The component is characterized by having at least one X C It is a divalent group as shown in the following formula (C-1). Therefore, in combination with epoxy resin, it is possible to obtain a cured product that simultaneously exhibits good dielectric properties and heat resistance.

[0094] [Chemical Formula 7] (in the formula, R C1 Indicates a divalent organic group or a single bond. R C2 Each substituent can be represented independently. nc1 and nc2 each independently represent integers from 0 to 6. * indicates a connection key.

[0095] Equation (C-1) explicitly shows two naphthalene rings. These two naphthalene rings belong to the group mentioned above for X. C The aforementioned "aromatic ring (c)". That is, X represented by formula (C-1) C It is a divalent organic group containing at least two naphthalene rings.

[0096] In equation (C-1), R C1 Represents a divalent organic group or a single bond. R C1 It can be a divalent organic group, R C1 It can also be a single key. In R C1 When the organic group is divalent, the ester compound represented by formula (1-1) or formula (1-2) is a bis(naphthol) type active ester compound. In R C1 In the case of a single bond, the ester compounds shown in formula (1-1) or formula (1-2) are binaphthol-type active ester compounds. In R C1In the case of a divalent organic group, as described above, the divalent organic group is a group that contains at least a carbon atom as a skeleton atom, but preferably a divalent group that contains one or more (preferably 1 to 30, 1 to 20, or 1 to 10) skeleton atoms selected from carbon, oxygen, nitrogen, and sulfur atoms. From the viewpoint of achieving a cured product exhibiting both better dielectric properties and heat resistance when combined with epoxy resin, R... C1 The divalent organic group in it is preferably a divalent hydrocarbon group with 1 to 10 carbon atoms, optionally having a substituent. That is, R C1 Preferably, it is a divalent hydrocarbon group or a single bond with 1 to 10 carbon atoms, optionally having a substituent. R C1 The number of carbon atoms in the divalent organic group is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 13, 1 to 10 or 1 to 8, even more preferably 1 to 6, 1 to 5, 1 to 4, 1 to 3 or 1 to 2, and particularly preferably 1.

[0097] As R C1 The divalent hydrocarbon group in R can be exemplified by divalent aliphatic hydrocarbon groups or divalent aromatic hydrocarbon groups, and can be exemplified by: alkylene, cycloalkylene, alkenylene, cycloalkenylene, polyalkenylene (preferably with 2 to 10 double bonds, more preferably 2 to 6, further preferably 2 to 4, even more preferably 2), arylene, etc., preferably alkylene, cycloalkylene, alkenylene, cycloalkenylene, or arylene, more preferably alkylene, cycloalkylene, or arylene, and even more preferably alkylene. That is, R C1 Preferably, it is an alkylene group or a single bond.

[0098] R C1 The alkylene group can be either straight-chain or branched, and its carbon number is more preferably 1 to 6, further preferably 1 to 4 or 1 to 3, even more preferably 1 to 2, and particularly preferably 1. This carbon number does not include the number of carbon atoms of substituents. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, and hexylene.

[0099] R C1 The number of carbon atoms in the cycloalkyl group is more preferably 3 to 10, 4 to 10, or 6 to 10. This number of carbon atoms does not include the number of carbon atoms of the substituents. Examples of cycloalkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, decahydronaphthyl, norbornyl, dicyclopentanylene, and adamantylene.

[0100] R C1The number of carbon atoms in the arylene group is more preferably 6 to 10. This number of carbon atoms does not include the number of carbon atoms of the substituents. Examples of arylene groups include phenylene, naphthylene, and indanediyl.

[0101] R C1 The substituents optionally present in the divalent hydrocarbon group are as described above in the [Explanation of Terms] section. Preferably, such substituents are selected from one or more alkyl and aryl groups, more preferably from one or more alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 10 carbon atoms. If these substituents optionally have secondary substituents, as previously described, preferably, such secondary substituents are selected from one or more alkyl and aryl groups, more preferably from one or more alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 10 carbon atoms.

[0102] In equation (C-1), R C2 Preferred examples of the substituents shown are also as for X. C As explained in “aromatic ring (c)”, from the viewpoint of bringing about a cured product that simultaneously exhibits better dielectric properties and heat resistance in combination with epoxy resin, it is preferably selected from one or more of halogen atoms, hydrocarbon groups and alkoxy groups, more preferably selected from one or more of halogen atoms, alkyl groups, aryl groups and aralkyl groups, even more preferably halogen atoms or alkyl groups, and even more preferably fluorine atoms or alkyl groups having 1 to 6 carbon atoms.

[0103] In equation (C-1), nc1 and nc2 each independently represent an integer from 0 to 6, for example, an integer from 0 to 4, an integer from 0 to 3, 0, or 1. In one embodiment, nc1 and nc2 can also be 0.

[0104] In formula (C-1), the linking bond* can extend from the carbon at position 1 or position 2 of the naphthalene ring as explicitly shown, but from the viewpoint of bringing about a cured product that simultaneously exhibits better dielectric properties and heat resistance in combination with epoxy resin, it is preferable to extend from the carbon at position 2 of the naphthalene ring as explicitly shown.

[0105] In equation (C-1), R C1 The relationship with the linking bond* can be either adjacent or para, wherein the linking bond* is bonded to the carbon at position 2 of the naphthalene ring, and R C1 The effect of the invention is better achieved when the carbon bond is attached to the carbon at the 1-position of the naphthalene ring, which is adjacent to the linker bond*. Therefore, this is preferred.

[0106] From the viewpoint of achieving a cured product that simultaneously exhibits better dielectric properties and heat resistance when combined with epoxy resin, in a particularly preferred embodiment, the divalent group represented by formula (C-1) is the divalent group represented by formula (C-2) below.

[0107] [Chemical Formula 8] (in the formula, R C2 nc1 and nc2 have the same meaning as described above. R C3 Represents a hydrogen atom or a monovalent organic group. * indicates a connection key.

[0108] In equation (C-2), R C2 nc1 and nc2 are the same as described above, and their preferred types and ranges are also as described above with respect to formula (C-1). From the viewpoint that the effects of the present invention can be particularly enjoyed, nc1 and nc2 are preferably 0.

[0109] In equation (C-2), R C3 Represents a hydrogen atom or a monovalent organic group. R C3 The monovalent organic group shown, as described above in the [Explanation of Terms] section, is a group that contains at least a carbon atom as a skeleton atom, but preferably a monovalent group containing one or more (preferably 1 to 30, 1 to 20, or 1 to 15) skeleton atoms selected from carbon, oxygen, nitrogen, and sulfur atoms. From the viewpoint of achieving a cured product exhibiting both better dielectric properties and heat resistance when combined with epoxy resin, R... C3 The monovalent organic group shown is preferably a monovalent aliphatic group or a monovalent aromatic group optionally having a substituent, more preferably a monovalent aromatic group optionally having a substituent, even more preferably an aryl group optionally having a substituent, and even more preferably an aryl group optionally having a substituent with 6 to 10 carbon atoms. R C3 The substituents optionally present in the monovalent organic group are as described above, but from the viewpoint of better enjoying the effects of the present invention, it is preferable to have one or more substituents selected from alkyl and aryl groups, and more preferably one or more substituents selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 10 carbon atoms. Therefore, in a preferred embodiment, R C3 It represents a hydrogen atom or an optional monovalent aromatic group with substituents, more preferably a hydrogen atom.

[0110] From the perspective of achieving cured products that simultaneously exhibit better dielectric properties and heat resistance when combined with epoxy resins, at least one X C The divalent group represented by any of the following formulas (C-2-1) to (C-2-8) is preferred, especially if X C From the viewpoint that the divalent group represented by formula (C-2-1) is particularly preferred, it is especially desirable to enjoy the effects of the present invention more fully.

[0111] [Chemical Formula 9] .

[0112] As stated above, for component (B), as long as at least one X C If the divalent group represented by formula (C-1) above is present, then other divalent organic groups may also be included as X. C Regarding the other divalent organic groups, as described above, however, from the viewpoint that the effects of the invention can be better enjoyed in combination with the divalent group shown in formula (C-1), the divalent groups shown in formula (C-3) or formula (C-4) are preferred.

[0113] [Chemical Formula 10] (in the formula, R C4 It represents a single bond, or a divalent linking group selected from 1 to 10 divalent hydrocarbon groups, oxygen atoms, sulfonyl groups, carbonyl groups, carbonate groups, and combinations thereof, having any number of carbon atoms and having optional substituents. R C5 and R C6 Each substituent can be represented independently. nc3, nc4, and nc5 each independently represent integers from 0 to 4. * indicates a connection key.

[0114] Equation (C-3) explicitly shows two benzene rings. These two benzene rings belong to the group mentioned above concerning X. C The aforementioned "aromatic ring (c)". That is, X represented by formula (C-3) C It is a divalent organic group containing at least two benzene rings. R C5 Preferred examples of the substituents shown are also as for X. C As described in "aromatic ring (c)", more preferably, it is selected from one or more of halogen atoms, alkyl, aryl and aralkyl, and even more preferably, it is selected from one or more of fluorine atoms, alkyl with 1 to 6 carbon atoms, aryl with 6 to 10 carbon atoms and aralkyl with 7 to 12 carbon atoms.

[0115] In formula (C-3), nc3 and nc4 each independently represent integers from 0 to 4, preferably from 0 to 3, more preferably from 0 to 2, and even more preferably from 0 or 1.

[0116] In equation (C-3), R C4 R represents a single bond, or a divalent linking group selected from 1 to 10 divalent hydrocarbon groups, oxygen atoms, sulfonyl groups, carbonyl groups, carbonate groups, and combinations thereof, having any number of carbon atoms and having optional substituents. C4The number of carbon atoms in the divalent linker shown is preferably 1 to 30, more preferably 1 to 20 or 1 to 15.

[0117] R C4 The divalent hydrocarbon group in, including its preferred examples, with R C1 The divalent hydrocarbon group in the group is the same, wherein preferably it is an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms. Here, as a preferred example of a divalent group formed by a combination of hydrocarbon groups, the following can be cited: C1 to C6 alkylene group - C6 to C6 alkylene group. 10 arylene-C1~C6 alkylene, C1~C6 alkylene-C6~C 10 Aspartic-C6~C 10 Arylene-C1 to C6 alkylene, etc. In the divalent groups formed by combinations of these, the preferred range of the number of carbon atoms of the constituting alkylene or arylene, or the optional presence of substituents, is as described above. Preferred examples of substituents are also related to R. C1 The divalent hydrocarbon groups in them are the same.

[0118] From the viewpoint that the effects of the present invention can be better enjoyed in combination with the divalent group shown in formula (C-1), the following shows a particularly preferred X represented by formula (C-3). C Examples.

[0119] In a preferred embodiment, in formula (C-3), R C4 This refers to a single bond, or, optionally, an alkylene group having 1 to 6 carbon atoms with substituents, a cycloalkylene group having 6 to 10 carbon atoms with substituents, an aryl group having 6 to 10 carbon atoms with substituents, or a divalent group formed by a combination of these. R C5 Each can independently represent a halogen atom, alkyl group, aryl group, or aralkyl group. nc3 and nc4 are each independently 0 or 1.

[0120] In a more preferred embodiment, in formula (C-3), R C4 This indicates a single bond, an alkylene group with 1 to 3 carbon atoms optionally having a substituent, or a cycloalkylene group with 6 to 10 carbon atoms optionally having a substituent. R C5 Each can independently represent a fluorine atom, an alkyl group with 1 to 6 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an aralkyl group with 7 to 12 carbon atoms. nc3 and nc4 are each independently 0 or 1.

[0121] Equation (C-4) explicitly shows one naphthalene ring. This single naphthalene ring belongs to the group mentioned above for X. C The aforementioned "aromatic ring (c)". That is, X shown in formula (C-4) C It is a divalent organic group containing one naphthalene ring. R C6 Preferred examples of the substituents shown are also as for X. C As described in "aromatic ring (c)", more preferably, it is selected from one or more of halogen atoms, alkyl, aryl and aralkyl, and even more preferably, it is selected from one or more of fluorine atoms, alkyl with 1 to 6 carbon atoms, aryl with 6 to 10 carbon atoms and aralkyl with 7 to 12 carbon atoms.

[0122] In formula (C-4), each nc5 independently represents an integer from 0 to 4, preferably from 0 to 3, and more preferably from 0 to 2.

[0123] From the viewpoint that the effects of the present invention can be better enjoyed in combination with the divalent group shown in formula (C-1), the following shows a particularly preferred X represented by formula (C-4). C Examples.

[0124] In a preferred embodiment, in formula (C-4), R C6 Each can independently represent a halogen atom, alkyl group, aryl group, or aralkyl group. Each nc5 is an integer from 0 to 4.

[0125] In a more preferred embodiment, in formula (C-4), R C6 Each of these can independently represent a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Each nc5 is an integer from 0 to 4.

[0126] In both general formula (1-1) and general formula (1-2), n represents an integer greater than or equal to 1. As described above, X, through component (B) containing at least the divalent group shown in formula (C-1), C and as X BThe oligomer units form the structural units, thus enabling the production of cured products with excellent dielectric properties and good heat resistance when combined with epoxy resin. From the viewpoint of maximizing the effects of the present invention, the upper limit of n is preferably 10 or less or 8 or less, more preferably 6 or less, further preferably 5 or less or 4 or less, and particularly preferably 3 or less. Therefore, in a preferred embodiment, n represents an integer of 1 or more and 6 or less. In the case of mixtures of ester compounds represented by formula (1-1) or formula (1-2) with different n values ​​in component (B), the average value of n exceeds 0, preferably 0.25 or more, 0.50 or more, or 0.75 or more, and more preferably 1 or more. From the viewpoint of maximizing the effects of the present invention, the upper limit of the average value of n is preferably 10 or less or 8 or less, more preferably 6 or less, further preferably 5 or less or 4 or less, and particularly preferably 3 or less. Therefore, in a preferred embodiment, the average value of n is 1 or more and 6 or less.

[0127] From the viewpoint of better enjoying the effects of the present invention, when X of each molecule (B) component is... C When the quantity of X is set to nC and the quantity of divalent groups shown in formula (C-1) is set to nC1, the ratio of nC1 to nC [nC1 / nC] is preferably 0.2 or more, more preferably 0.3 or more or 0.4 or more, and even more preferably 0.5 or more, 0.6 or more, 0.7 or more or 0.8 or more. There is no particular upper limit to this ratio, and it can be 1 (i.e., all X...). C It can be a divalent group as shown in formula (C-1), but it can also be less than 0.95, less than 0.9, etc.

[0128] From the viewpoint of better enjoying the effects of the present invention, when X of each molecule (B) component is... C When the quantity of X is set to nC and the quantity of divalent groups shown in formula (C-2) is set to nC2, the ratio of nC2 to nC [nC2 / nC] is preferably 0.2 or more, more preferably 0.3 or more or 0.4 or more, and even more preferably 0.5 or more, 0.6 or more, 0.7 or more or 0.8 or more. There is no particular upper limit to this ratio, and it can be 1 (i.e., all X...). C It can be a divalent group as shown in formula (C-2), but it can also be less than 0.95, less than 0.9, etc.

[0129] From the viewpoint of better enjoying the effects of the present invention, the X of each molecule (B) component is... A1 or X A2 Let the quantity be nA, and let X B Let the quantity be nB, and let X C The quantity is set to nC, and X is... A1 X A2 X Band X C When the number of groups containing fused polycyclic aromatic rings is set as n', the ratio of n' to the total of nA, nB, and nC [n' / (nA+nB+nC)] is preferably greater than 0.2, more preferably greater than 0.3, greater than 0.4, or greater than 0.5, and even more preferably greater than 0.5, greater than 0.52, or greater than 0.53. There is no particular upper limit to this ratio; it can be 1, for example, less than 0.9, less than 0.8, or less than 0.8.

[0130] (B) In component B, the active ester equivalent is preferably 180 g / eq. or more, more preferably 190 g / eq. or more, and even more preferably 200 g / eq. or more or 210 g / eq. or more. The upper limit of this active ester equivalent may be, for example, 1000 g / eq. or less, 750 g / eq. or less, 700 g / eq. or less, 600 g / eq. or less, 500 g / eq. or less, 400 g / eq. or less, or 300 g / eq. or less.

[0131] From the viewpoint of using it as a curing agent for epoxy resin in a resin composition, the number average molecular weight (Mn) of component (B) is preferably 5000 or less, more preferably 4000 or less, and even more preferably 3500 or less or 3000 or less. This lower limit of Mn is not particularly limited as long as it has the desired structure containing the divalent group shown in formula (C-1) above, and can be, for example, 400 or more, 500 or more, 600 or more, etc. The Mn of component (B) can be determined by gel permeation chromatography (GPC) as a polystyrene equivalent. The above-mentioned preferred range of Mn is based on values ​​determined according to the method described in the (GPC determination conditions) column below.

[0132] From the viewpoint of producing cured products that simultaneously exhibit better dielectric properties and heat resistance when combined with epoxy resin, component (B) is a compound represented by general formula (1-1).

[0133] From the viewpoint of producing cured products that simultaneously exhibit better dielectric properties and heat resistance when combined with epoxy resins, examples of compounds represented by particularly preferred general formula (1-1) are shown below.

[0134] In a particularly preferred embodiment, in general formula (1-1), X A1 Each independently represents the monovalent group shown in formula (A-1) or (A-2) above (R in each formula). A1 R A2 nA1, nA2 (including preferred methods and ranges, all of which are the same as described above), X BEach of these terms independently represents a divalent group formed by removing two hydrogen atoms from a monocyclic aromatic carbon ring having one or more substituents selected from halogen atoms, alkyl groups, aryl groups, and aralkyl groups. X C Each of these terms independently represents a divalent organic group containing two or more monocyclic aromatic carbon rings, or a divalent organic group containing at least one fused polycyclic aromatic carbon ring, wherein at least one X represents a divalent organic group. C The divalent group represented by formula (C-2) above (R in the formula) C2 R C3 nc1 and nc2, including preferred methods and ranges, are the same as described above. n represents an integer greater than 1 and less than 6.

[0135] In a more preferred embodiment, in general formula (1-1), X A1 Each independently represents the monovalent group shown in formula (A-1) or (A-2) above (where R is a monovalent group). A1 R is selected from one or more of the following: fluorine atom, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, and aralkyl group having 7 to 12 carbon atoms. A2 It is selected from one of the following: fluorine atom, alkyl group having 1 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, and aralkyl group having 7 to 12 carbon atoms (nA1 is 0 or 1, nA2 is 0 or 1). X B This indicates a divalent group formed by removing two hydrogen atoms from a monocyclic aromatic carbon ring that has never been substituted. X C Each of these terms independently represents a divalent organic group containing two or more benzene rings (preferably a divalent group obtained by removing two hydroxyl groups from a bisphenol compound having one or more substituents selected from halogen atoms, alkyl, aryl, and aralkyl, or a divalent group obtained by removing two hydroxyl groups from a dihydroxybiphenyl compound having one or more substituents selected from halogen atoms, alkyl, aryl, and aralkyl), or a divalent organic group containing at least one naphthalene ring (preferably a divalent group obtained by removing two hydroxyl groups from a dihydroxynaphthalene compound having one or more substituents selected from halogen atoms, alkyl, aryl, and aralkyl, or a divalent group obtained by removing two hydroxyl groups from a bis(naphthol) compound having one or more substituents selected from halogen atoms, alkyl, aryl, and aralkyl), wherein at least one X C The divalent group shown in the above formula (C-2) (where R is a divalent group) C3 It is a hydrogen atom, or a monovalent aromatic group optionally having one or more substituents selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 10 carbon atoms (nc1 and nc2 are 0). n represents an integer greater than 1 and less than 6.

[0136] <(B) Manufacturing Method of Component> The following is an example of the synthesis steps for component (B).

[0137] In one implementation, component (B) is (x1) is a divalent aromatic hydroxyl compound that contains at least the compound represented by the general formula (x1) below. (x2) Divalent aromatic carboxylic acid compounds or divalent aromatic carboxyl halides, and (x3) Monovalent aromatic hydroxyl compounds, or monovalent aromatic carboxylic acid compounds, or monovalent carboxyl halides The condensation reaction products.

[0138] [Chemical Formula 11] (where R is in the formula) C1 R C2 nc1 and nc2 have the same meaning as above).

[0139] <<(x1) Divalent aromatic hydroxyl compounds>> Component (x1) is a divalent aromatic hydroxy compound comprising at least the compound shown in the general formula (x1) above. By using component (x1), active ester compounds comprising a binaphthol skeleton or a bisnaphthol skeleton can be synthesized.

[0140] When synthesizing an aromatic oxycarbonyl compound containing the preferred bis-naphthol skeleton shown in formula (C-2), as component (x1), any divalent aromatic hydroxy compound containing at least the compound shown in general formula (x1-1) may be used.

[0141] [Chemical Formula 12] (where R is in the formula) C2 R C3 nc1 and nc2 have the same meaning as above).

[0142] In R C1 When the organic group is divalent, the compound represented by the above general formula (x1) is (x1a) Naphthol with substituents, and (x1b) Aldehyde compounds Addition condensation reactants.

[0143] Therefore, in one embodiment, the method for manufacturing the active ester compound (bisnaphthol-type active ester compound) containing the bisnaphthol skeleton in component (B) includes the following steps: (1) The step of obtaining the divalent aromatic hydroxyl compound of general formula (x1) by condensation reaction of (x1a) a naphthol with optional substituents with (x1b) an aldehyde compound, and (2) A step of condensing the obtained divalent aromatic hydroxyl compound, (x2) divalent aromatic carboxylic acid compound or divalent aromatic carboxyl halide compound, and (x3) monovalent aromatic hydroxyl compound, or monovalent aromatic carboxylic acid compound or monovalent carboxyl halide compound.

[0144] As an optional substituted naphthol (x1a), in order to achieve the target bis-naphthol-type active ester compound, X C The structure allows the use of any naphthol compound. X C Preferred examples are described above. For example, regarding such naphthol compounds, as X bringing forth the above formula (C-2) C Compounds with the structure can use 2-naphthol, optionally with substituents. X is represented by formula (C-2) with nc1 and nc2 equal to 0. C For compounds with the structure described, unsubstituted 2-naphthol can be used. Additionally, as a source of R... C2 X is represented by formula (C-2) where alkyl group, nC1, and nC2 are 1. C For compounds with the structure described above, 2-naphthol with monoalkyl substitution can be used.

[0145] As an aldehyde compound (x1b), in order to achieve X in the target bis(naphthol) type active ester compound. C The structure can use any aldehyde compound. For example, regarding such aldehyde compounds, as bringing R... C1 X is an alkylene group of formula (C-1) with optional substituents. C For compounds with the structure described above, alkyl aldehyde compounds with optional substituents may be used. Specifically, for example, X as the compound with the structure shown in formula (C-2-1) above. C Compounds with the structure shown in formula (C-2-2) can be obtained using formaldehyde; as the compound that brings about the structure shown in formula (C-2-2) above, X C Compounds with the structure shown in formula (C-2-3) can be obtained using benzaldehyde; as the X that brings about the structure shown in formula (C-2-3) above. C Compounds with the structure described above, such as 4-phenylbenzaldehyde, are readily available; as the compound that brings about the structure shown in formula (C-2-4) X C Compounds with the structure described above, such as 4-methylbenzaldehyde, are readily available; as the compound that brings about the structure shown in formula (C-2-5) X C Compounds with the structure described above, such as 4-propylbenzaldehyde, are readily available; as the compound that brings about the structure shown in formula (C-2-6) X CCompounds with the structure described above, such as 1,4,6-trimethylbenzaldehyde, are readily available; as the compound bringing forth the structure shown in formula (C-2-7) X C Compounds with the structure described above, such as 1-naphthaldehyde, are readily available; as the source of X as shown in formula (C-2-8) C For compounds with the structure of , 2-naphthaldehyde can be used.

[0146] Through the addition condensation reaction of components (x1a) and (x1b), a compound of general formula (x1) (hereinafter also referred to as "divalent aromatic hydroxyl compound (x1)") can be synthesized, R C1 For compounds with divalent organic groups (bisnaphthol-type active ester compounds), depending on whether the component (x1a) used is a 1-naphthol compound or a 2-naphthol compound, the R in this divalent aromatic hydroxyl compound (x1) can be adjusted. C1 The binding site with the naphthalene ring. That is, if a 2-naphthol compound is used, R can be achieved. C1 The structure is linked to the carbon at position 1 of the naphthalene ring (even the structure shown in formula (C-2)). Alternatively, if a 1-naphthol compound is used, R can be achieved. C1 In structures bonded to the 2- and / or 4-carbon positions of the naphthalene ring, the divalent aromatic hydroxyl compound (x1) can undergo oligomerization. As described above, from the viewpoint of better enjoying the effects of the present invention, X C Preferably, the compound has the structure shown in formula (C-2). As a divalent aromatic hydroxyl compound (x1), the compound shown in formula (x1-1) above is preferred. Therefore, as component (x1a), 2-naphthol compound is more preferably used.

[0147] The hydroxyl equivalent of the divalent aromatic hydroxyl compound (x1) synthesized in this way is preferably 400 g / eq. or less, more preferably 350 g / eq. or less, 300 g / eq. or less, 250 g / eq. or less, 240 g / eq. or less, 220 g / eq. or less, or 200 g / eq. or less. The lower limit of this hydroxyl equivalent can be, for example, 150 g / eq. or more.

[0148] After the reaction, the divalent aromatic hydroxyl compound (x1) can be purified and dried. For example, after the condensation reaction, in order to remove byproduct salts or excess starting materials from the system, purification treatments such as washing with water or fine filtration can be performed. In detail, after the condensation reaction, the precipitated (x1) component is filtered and separated, washed multiple times with organic solvents such as water or toluene, and then purified by filtration again. Then, the organic solvents such as water or toluene can be removed by drying under vacuum, and the (x1) component is obtained as a solid. However, the inventors have found that, from the viewpoint of obtaining a cured product that simultaneously exhibits better dielectric properties and heat resistance in combination with epoxy resin, it is preferable to provide the product containing the divalent aromatic hydroxyl compound (x1) obtained by the addition condensation reaction of components (x1a) and (x1b) for the condensation reaction with components (x2) and (x3) without performing the above-described purification and drying treatments. This is presumably because purification and drying can lead to oxidation of the divalent aromatic hydroxyl compound (x1), resulting in a deterioration in the structure and properties of the obtained divalent aromatic hydroxyl compound (x1) and even component (B). In a preferred embodiment, the product comprising the divalent aromatic hydroxyl compound (x1) obtained by an addition condensation reaction of naphthol (x1a) optionally having a substituent with an aldehyde compound (x1b) in the presence of an organic solvent is provided for the condensation reaction with components (x2) and (x3) without purification or drying (i.e., keeping it in a liquid state). Regarding the type of organic solvent, the same organic solvents described below for the condensation reactions with components (x1), (x2), and (x3) can be cited.

[0149] Component (x1) may also contain other divalent aromatic hydroxyl compounds, provided that it contains at least the compound shown in the general formula (x1) above. To achieve the target component (B) X C The structure can be achieved using any other divalent aromatic hydroxyl compound. For example, regarding the aforementioned other divalent aromatic hydroxyl compound, as X bringing the above formula (C-3) to the position... C Compounds with the structure X can be exemplified by: biphenyl compounds, various bisphenol compounds, etc. Examples of bisphenol compounds include: bisphenol A, bisphenol F, bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol M, etc. Furthermore, regarding divalent aromatic hydroxyl compounds, as compounds that bring about the structure X shown in formula (C-4) above... C Compounds with this structure include diols (2,7-naphthodiol, 1,4-naphthodiol, 1,5-naphthodiol, 1,6-naphthodiol, 2,6-naphthodiol, etc.) in which two hydroxyl groups are bonded to the carbon atom on the naphthalene ring. For these divalent aromatic hydroxyl compounds, the target aromatic oxycarbonyl compound contains X... CIf a substituent is present, a divalent aromatic hydroxyl compound having that substituent can be used.

[0150] <<(x2) Divalent aromatic carboxylic acid (halides) compounds>> (x2) is a divalent aromatic carboxylic acid compound or a divalent aromatic carboxyl halide compound, represented by the following formula (x2).

[0151] [Chemical Formula 13] (where X) B As above, Y represents a hydroxyl group or a halogen atom.

[0152] As component (x2), X is determined based on the aromatic oxycarbonyl compound as the target. B Any divalent aromatic carboxylic acid (halide) compound can be used. X B Preferred examples are as described above. For example, X in the target aromatic oxycarbonyl compound. B If the phenylene oxide is optionally substituted, then isophthalic acid (chloride) or terephthalic acid (chloride) optionally substituted may be used.

[0153] <<(x3) Monovalent aromatic hydroxyl compounds or monovalent aromatic carboxylic acid (halides) compounds>> (x3) is a monovalent aromatic hydroxy compound, represented by the following formula (x3-1), or a monovalent aromatic carboxylic acid compound or a monovalent aromatic carboxyl halide compound, represented by the following formula (x3-2).

[0154] [Chemical Formula 14] (where X) A1 X A2 And Y is the same as above).

[0155] In the case of manufacturing component (B) as shown in formula (1-1), the monovalent aromatic hydroxyl compound (x3-1) is reacted in combination with components (x1) and (x2).

[0156] As a component (x3-1), based on X in component (B) as the objective. A1 Any aromatic monool can be used. X A1 Preferred examples are as described above. For example, X in component (B) as the target is such an aromatic monool. A1 If the naphthyl group is optionally substituted, naphthol optionally substituted may be used; in component (B) as the target, X A1If the phenyl group is optionally substituted, then phenol optionally substituted may be used.

[0157] In the case of manufacturing component (B) as shown in formula (1-2), a monovalent aromatic carboxylic acid compound or a monovalent aromatic carboxyl halide compound (x3-2) is reacted in combination with components (x1) and (x2).

[0158] As a component of (x3-2), X is based on the target component (B). A2 Any aromatic monocarboxylic acid (halide) compound can be used. X A2 Preferred examples are as described above. For example, as such an aromatic monocarboxylic acid (halide) compound, X in component (B) as the target... A2 If the naphthyl group is optionally substituted, naphthoic acid (halide) optionally substituted can be used, in component (B) X as the target. A2 If the phenyl group is optionally substituted, then benzoic acid (halide) optionally substituted can be used.

[0159] In the condensation reaction of components (x1), (x2), and (x3), in addition to condensation (esterification) between components (x1) and (x2), when component (x3-1) is used as component (x3), condensation also occurs between components (x3) and (x2); and when component (x3-2) is used as component (x3), condensation also occurs between components (x3) and (x1). In such a reaction, by changing the molar ratios of the components and other conditions, the degree of condensation between components (x1) and (x2) can be adjusted, and the structure of the resulting component (B) (average of the number of repetitions n) can also be adjusted.

[0160] Condensation reactions can be carried out in solvent-free systems without the use of a solvent, or in organic solvent systems. Examples of organic solvents used in condensation reactions include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosol acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosol and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. One organic solvent can be used alone, or two or more can be used in combination.

[0161] In condensation reactions, bases can be used. Examples of bases include alkali metal hydroxides such as sodium hydroxide (caustic soda) or potassium hydroxide; and tertiary amines such as triethylamine, pyridine, and N,N-dimethyl-4-aminopyridine (DMAP). A single base can be used, or two or more bases can be used in combination.

[0162] In condensation reactions, condensing agents or phase transfer catalysts can also be used. These can be any substances previously known to be used in esterification reactions.

[0163] The reaction temperature in the condensation reaction is not particularly limited as long as the condensation reaction proceeds; for example, it can be in the range of 0 to 80°C. Furthermore, the reaction time in the condensation reaction is not particularly limited as long as the structure of the target component (B) is achieved; for example, it can be in the range of 30 minutes to 8 hours.

[0164] The active ester compound can be purified after the condensation reaction. For example, after the condensation reaction, purification steps such as water washing or fine filtration can be performed to remove byproduct salts or excess starting materials from the system. Specifically, after the condensation reaction, the amount of water required to dissolve the byproduct salts is added, the mixture is allowed to stand and separate, and the aqueous layer is discarded. Then, acid is added as needed for neutralization and repeated water washing is performed. After removing impurities and purifying the compound through a reagent-based or azeotropic dehydration process, the organic solvent is removed by distillation as needed to obtain component (B). Alternatively, the organic solvent can be used directly as a solvent in the resin composition without complete removal.

[0165] <(B) Content of Component> When the non-volatile component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, and particularly from the viewpoint of obtaining a cured product exhibiting superior dielectric properties (low dielectric loss tangent) even at high temperatures (90°C), the content of component (B) in the resin composition is preferably 1% by mass or more or 2% by mass or more, more preferably 3% by mass or more or 4% by mass or more, further preferably 5% by mass or more or 6% by mass or more, and particularly preferably 7% by mass or more or 8% by mass or more. In one embodiment, it can be 9% by mass or more, 10% by mass or more, 11% by mass or more, 12% by mass or more, 13% by mass or more, 14% by mass or more, 15% by mass or more, 16% by mass or more, etc. The upper limit is preferably 50% by mass or less or 45% by mass or less, more preferably 40% by mass or less or 35% by mass or less, further preferably 30% by mass or less or 25% by mass or less, and particularly preferably 22% by mass or less, 20% by mass or less or 18% by mass or less.

[0166] When the non-volatile component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, and particularly from the viewpoint of obtaining a cured product exhibiting superior dielectric properties (low dielectric loss tangent) even at high temperatures (90°C), the content of the active ester compound (i.e., the total of component (B) and component (B') described later) in the resin composition is preferably 1% by mass or more or 2% by mass or more, more preferably 3% by mass or more or 4% by mass or more, further preferably 5% by mass or more or 6% by mass or more, particularly preferably 7% by mass or more, 8% by mass or more, 9% by mass or more, 10% by mass or more, 11% by mass or more, 12% by mass or more, 13% by mass or more, 14% by mass or more, 15% by mass or more, or 16% by mass or more. The upper limit is preferably 50% by mass or less or 45% by mass or less, more preferably 40% by mass or less or 35% by mass or less, further preferably 30% by mass or less or 25% by mass or less, and particularly preferably 22% by mass or less, 20% by mass or less, or 18% by mass or less.

[0167] When the resin component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, and particularly from the viewpoint of obtaining a cured product exhibiting superior dielectric properties (low dielectric loss tangent) even at high temperatures (90°C), the content of component (B) in the resin composition is preferably 2% by mass or more, more preferably 5% by mass or more or 8% by mass or more, further preferably 10% by mass or more or 15% by mass or more, and particularly preferably 20% by mass or more, 25% by mass or more, 30% by mass or more, or 35% by mass or more. In one embodiment, it can be 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, etc. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less or 80% by mass or less, further preferably 75% by mass or less or 70% by mass or less, and particularly preferably 65% ​​by mass or less or 60% by mass or less.

[0168] When the resin component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, and particularly from the viewpoint of obtaining a cured product exhibiting superior dielectric properties (low dielectric loss tangent) even at high temperatures (90°C), the content of the active ester compound (i.e., the total of component (B) and component (B') described later) in the resin composition is preferably 2% by mass or more, more preferably 5% by mass or more or 8% by mass or more, further preferably 10% by mass or more or 15% by mass or more, particularly preferably 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more or 55% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less or 80% by mass or less, further preferably 75% by mass or less or 70% by mass or less, and particularly preferably 65% ​​by mass or less or 60% by mass or less.

[0169] When the non-volatile component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the total content of component (A) and component (B) in the resin composition is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more or 10% by mass or more, and particularly preferably 12% by mass or more or 15% by mass or more. Alternatively, in one embodiment, it can be 18% by mass or more, 20% by mass or more, 22% by mass or more, 24% by mass or more, etc. The upper limit is preferably 60% by mass or less or 55% by mass or less, more preferably 50% by mass or less or 45% by mass or less, further preferably 40% by mass or less or 35% by mass or less, and particularly preferably 30% by mass or less or 25% by mass or less.

[0170] When the non-volatile component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the total content of component (A) and the active ester compound (i.e., the sum of component (B) and component (B') described later) in the resin composition is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more or 10% by mass or more, particularly preferably 12% by mass or more, 15% by mass or more, 18% by mass or more, 20% by mass or more, 22% by mass or more, or 24% by mass or more. The upper limit is preferably 60% by mass or less or 55% by mass or less, more preferably 50% by mass or less or 45% by mass or less, further preferably 40% by mass or less or 35% by mass or less, particularly preferably 30% by mass or less or 25% by mass or less.

[0171] When the resin component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the total content of component (A) and component (B) in the resin composition is preferably 5% by mass or more or 10% by mass or more, more preferably 15% by mass or more or 20% by mass or more, further preferably 25% by mass or more, 30% by mass or more or 35% by mass or more, particularly preferably 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more or 60% by mass or more. In one embodiment, it can be 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, etc. The upper limit is preferably 95% by mass or less, more preferably 92% by mass or less, further preferably 90% by mass or less, particularly preferably 88% by mass or less or 85% by mass or less.

[0172] When the resin component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the total content of component (A) and the active ester compound (i.e., the sum of component (B) and component (B') described later) in the resin composition is preferably 5% by mass or more or 10% by mass or more, more preferably 15% by mass or more or 20% by mass or more, further preferably 25% by mass or more, 30% by mass or more or 35% by mass or more, particularly preferably 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more or 80% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 92% by mass or less, further preferably 90% by mass or less, and particularly preferably 88% by mass or less or 85% by mass or less.

[0173] From the viewpoint of significantly obtaining the effects of the present invention, the mass ratio of component (B) to component (A) in the resin composition [component (B) / (A)] is preferably 0.1 or more or 0.3 or more, more preferably 0.5 or more or 0.8 or more, further preferably 1.0 or more, 1.1 or more or 1.2 or more, 1.3 or more or 1.4 or more, and particularly preferably 1.5 or more. In one embodiment, it can be 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, 2.0 or more, more than 2.0, 2.1 or more, etc. The upper limit is preferably 10 or less or 8 or less, more preferably 6 or less or 5 or less, further preferably 4 or less or 3.0 or less, and particularly preferably 2.8 or less, 2.5 or less or 2.2 or less.

[0174] From the viewpoint of significantly obtaining the effects of the present invention, the mass ratio of the active ester compound (i.e., the total of component (B) and component (B') described later) to component (A) in the resin composition [active ester compound / (A) component] is preferably 0.1 or more or 0.3 or more, more preferably 0.5 or more or 0.8 or more, further preferably 1.0 or more, 1.1 or more or 1.2 or more, 1.3 or more or 1.4 or more, particularly preferably 1.5 or more, 1.6 or more, 1.7 or more, 1.8 or more, 1.9 or more, 2.0 or more, more than 2.0, or 2.1 or more. The upper limit is preferably 10 or less or 8 or less, more preferably 6 or less or 5 or less, further preferably 4 or less or 3.0 or less, particularly preferably 2.8 or less, 2.5 or less or 2.2 or less.

[0175] <Active ester compounds other than component (B)> The resin composition of the present invention may further contain an active ester compound ((B') component) other than component (B) as an optional component. Component (B') may be used alone or in combination of two or more.

[0176] As component (B'), compounds that are not part of component (B) and have one or more active ester groups per molecule can be used. Among these, components that are (B') preferably phenolic esters, thiophenolic esters, N-hydroxylamine esters, heterocyclic hydroxyl esters, or other compounds having two or more highly reactive ester groups per molecule are preferred. This active ester resin is preferably a resin obtained through a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenolic compound and / or a naphthol compound is more preferred.

[0177] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0178] Examples of phenolic or naphthol compounds include: hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, phenylphenol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadiene-type diphenol compounds, linear phenolic resins, etc. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0179] Preferred examples of component (B') include: active ester resins containing a cyclopentadiene-type diphenol structure (hereinafter also referred to as "dicyclopentadiene-type active ester resins"), active ester resins containing a naphthalene structure, active ester resins containing phosphorus, active ester resins containing acetylated linear phenolic resins, active ester resins containing benzoylated linear phenolic resins, and active ester resins containing a butadiene structure. Among these, active ester resins containing a naphthalene structure, active ester resins containing a dicyclopentadiene-type diphenol structure, or active ester resins containing a butadiene structure are preferred; more preferably, active ester resins containing a naphthalene structure or active ester resins containing a dicyclopentadiene-type diphenol structure are preferred; and even more preferably, active ester resins containing a dicyclopentadiene-type diphenol structure are preferred. "Dicyclopentadiene-type diphenol structure" refers to a divalent structural unit containing a phenylene-dicyclopentylene-phenylene group.

[0180] The active ester equivalent (functional group equivalent) of component (B') is preferably 180 g / eq. or more, more preferably 190 g / eq. or more, and even more preferably 200 g / eq. or more or 210 g / eq. or more. The upper limit of this active ester equivalent (functional group equivalent) may be, for example, 1000 g / eq. or less, 750 g / eq. or less, 700 g / eq. or less, 600 g / eq. or less, 500 g / eq. or less, 400 g / eq. or less, or 300 g / eq. or less.

[0181] Regarding commercially available products containing component (B'), examples of reactive ester resins containing a dicyclopentadiene-type diphenol structure include: "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "EXB-8000H", "HPC-8000L-65MT", and "EXB-8000L-65TM" (manufactured by DIC Corporation); examples of naphthalene-type reactive ester resins containing a naphthalene structure include: "EXB-9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "HPC-8150-62T", "EXB-8100L-65T", "EXB-8" (manufactured by DIC Corporation), "PC1300-02-65T", and "PC1300-02-65MA" (Air Water Corporation (manufactured); as a phosphorus-containing reactive ester resin, "EXB-9401" (manufactured by DIC Corporation) can be cited; as a reactive ester resin containing an acetylated linear phenolic resin, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; as a reactive ester resin containing a benzoylated linear phenolic resin, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), "EXB-8500-65T" (manufactured by DIC Corporation) can be cited, etc.

[0182] When the non-volatile component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the content of component (B') in the resin composition is preferably 1% by mass or more or 2% by mass or more, more preferably 3% by mass or more or 4% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less or 15% by mass or less, and particularly preferably 12% by mass or less, 10% by mass or less, 8% by mass or less, 7% by mass or less or 6% by mass or less.

[0183] When the resin component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the content of component (B') in the resin composition is preferably 2% by mass or more, more preferably 5% by mass or more or 8% by mass or more, and even more preferably 10% by mass or more or 15% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 55% by mass or less or 50% by mass or less, even more preferably 45% by mass or less or 40% by mass or less, and particularly preferably 35% by mass or less, 30% by mass or less, 25% by mass or less or 20% by mass or less.

[0184] <(C) Maleimide Resin> The resin composition of the present invention contains (C) maleimide resin. By containing (C) maleimide resin in the resin composition, the puncture resistance can be effectively improved while reducing the dielectric loss tangent of the cured product. (C) maleimide resin can be used alone or in combination of two or more types.

[0185] As for (C) maleimide resin, there is no particular limitation on the type as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl) in one molecule. Examples of maleimide resins include: "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", and "BMI-689" (all by Designer Molecules). Maleimide resins containing an aliphatic backbone of 36 carbon atoms derived from dimeric diamine, etc.; aliphatic maleimide resins such as "SLK-1500-T80" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), "SLK-6895" (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and "BMI-TMH" (manufactured by Daiwa Chemical Co., Ltd.); maleimide resins containing an indene backbone as described in Japan Invention Association Publication No. 2020-500211; maleimide resins containing an aromatic ring backbone directly bonded to the nitrogen atom of the maleimide group, such as "MIR-3000-70MT", "MIR-5000-60T" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000", "BMI-2300" (manufactured by Daiwa Chemical Co., Ltd.), "BMI-80", and "BMI-70" (manufactured by KI Chemical Co., Ltd.); "BMI-4200" (Designer Molecules... Maleimide resins, etc., having both an aliphatic backbone of 36 carbon atoms derived from dimeric diamine and an aromatic ring backbone directly bonded to the nitrogen atoms of maleimide groups; etc. Among these, aromatic maleimide resins are preferred as (C). That is, in one embodiment, component (C) preferably comprises an aromatic maleimide resin.

[0186] In one embodiment, (C) maleimide resin is preferably (C1) maleimide resin having a trimethylindane backbone. That is, (C) maleimide resin preferably comprises (C1) maleimide resin having a trimethylindane backbone. In another embodiment, (C) maleimide resin is preferably (C2) maleimide resin represented by formula (3) below. That is, (C) maleimide resin preferably comprises (C2) maleimide resin represented by formula (3) below.

[0187] <<(C1) Maleimide resin with a trimethylindene backbone>> Component (C1) is a maleimide resin having a trimethyl indane skeleton. The trimethyl indane skeleton represents the skeleton shown in the following formula (C1-1).

[0188] [Chemical Formula 15] .

[0189] The benzene ring in the trimethylindene skeleton optionally has substituents. When the benzene ring in the trimethylindene skeleton has substituents, the number of substituents can be one or more. The upper limit for the number of substituents on the benzene ring in the trimethylindene skeleton is generally three or less. When the number of substituents is two or more, they can be the same or different from each other. Preferably, the benzene ring in the trimethylindene skeleton is unsubstituent.

[0190] The number of trimethylindene skeletons contained in one molecule of component (C1) can be 1 or more. The upper limit can be, for example, less than 10, less than 8, less than 7, or less than 6.

[0191] From the viewpoint of better enjoying the effects of the present invention, component (C1) preferably comprises the structure shown in formula (C1-2) below. Component (C1) as a whole may have the structure shown in formula (C1-2), and a portion of component (C1) may have the structure shown in formula (C1-2).

[0192] [Chemical Formula 16] .

[0193] In formula (C1-2), Ar a1 This indicates an optional divalent aromatic group with substituents. R a1 and R a2 Each substituent can be represented independently. R a3 It represents a divalent aliphatic hydrocarbon group. n a1 Represents positive integers. n a2 Each can independently represent an integer from 0 to 4. n a3 Each can independently represent an integer from 0 to 3. In R... a1 In multiple cases, they can be the same or different, in R a2 In the case of multiple cases, they can be the same or different; there are multiple Rs. a3 They can be the same or different.

[0194] Ara1 This refers to a divalent aromatic group optionally having substituents. The divalent aromatic group preferably has 6 or more carbon atoms, more preferably 20 or less, and more preferably 16 or less, 14 or less, or 10 or less. Examples of divalent aromatic groups include phenylene and naphthylene. Examples of substituents optionally present in the divalent aromatic group include the aforementioned substituents, preferably alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, arylthio groups with 6 to 10 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, halogen atoms, hydroxyl groups, and mercapto groups. The hydrogen atoms of each substituent may also be replaced by halogen atoms. When the divalent aromatic group has substituents, the number of substituents is preferably 1 to 4. When the divalent aromatic group has 2 or more substituents, these 2 or more substituents may be the same or different from each other. Ar a1 Preferably, it is a divalent aromatic group without substituents.

[0195] R a1 Indicates a substituent. As R a1 The substituents shown may include those described in the [Explanation of Terms] section above, preferably alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, arylthio groups with 6 to 10 carbon atoms, cycloalkyl groups with 3 to 10 carbon atoms, halogen atoms, nitro groups, hydroxyl groups, and mercapto groups. The hydrogen atoms of each substituent may also be further substituted with halogen atoms. Wherein, R a1 More preferably, it is one or more groups selected from alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 10 carbon atoms, and even more preferably, it is an alkyl group having 1 to 4 carbon atoms.

[0196] R a2 Indicates a substituent. As R a2 The substituents shown can be exemplified by those described above, and are preferably alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, arylthio groups having 6 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, halogen atoms, hydroxyl groups, and mercapto groups. The hydrogen atoms of each substituent may also be further substituted with halogen atoms. Wherein, R... a2 More preferably, it is one or more groups selected from alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 10 carbon atoms.

[0197] R a3This indicates a divalent aliphatic hydrocarbon group. Examples of divalent aliphatic hydrocarbon groups include alkylene groups and alkenylene groups, with alkylene groups being preferred. R a3 The alkylene group in the alkylene group preferably has 1 to 20 or 1 to 15 carbon atoms, more preferably 1 to 10, further preferably 1 to 5, and particularly preferably 3. As R a3 Examples of alkylene compounds include methylene, ethylene, ethylidene, 1,2-propylene, 1,3-propylene, 1,1-propylidene, 2,2-propylidene, etc., preferably methylene or 2,2-propylidene, more preferably 2,2-propylidene.

[0198] n a1 Represents a positive integer. n a1 Preferably, it is 1 or more, more preferably 10 or less, and even more preferably 8 or less.

[0199] n a2 Each of the n integers from 0 to 4 can be represented independently. a2 Preferably 2 or 3, more preferably 2. Multiple n a2 They can also be different, but it is preferred that they are the same. In n a2 When the value is 2 or higher, multiple R values a1 They can be the same or different.

[0200] n a3 Represents integers from 0 to 3. In n a3 In the case of multiple instances, they can be different, but it is preferable that they are the same as each other. a3 The preferred value is 0.

[0201] From the viewpoint of better enjoying the effects of the present invention, component (C1) is further preferably composed of the structure shown in formula (C1-3). Component (C1) as a whole may have the structure shown in formula (C1-3), and a portion of component (C1) may have the structure shown in formula (C1-3).

[0202] [Chemical Formula 17] .

[0203] In equation (C1-3), R a1 R a2 n a1 n a2 and n a3 As illustrated in equation (C1-2).

[0204] The (C1) component may further include the structure shown in the following formula (C1-4).

[0205] [Chemical Formula 18] .

[0206] In equation (C1-4), R a1 R a2 n a2 and n a3 As explained in equation (C1-2). Additionally, n c This is the number of repeating units, representing an integer from 1 to 20. * indicates a linker.

[0207] For example, for component (C1), when n in equation (C1-2) a2 The number of unbound R groups is 3 or less, and there are more than two unbound R groups in the ortho and para positions of the benzene ring to which the maleimide group is attached relative to the maleimide group binding position. a1 In this case, it can be combined with the structure shown in equation (C1-2) to include the structure shown in equation (C1-4) above.

[0208] Additionally, for example, regarding component (C1), when n in equation (C1-3) a2 The number of unbound R groups is 3 or less, and there are more than two unbound R groups in the ortho and para positions of the benzene ring to which the maleimide group is attached relative to the maleimide group binding position. a1 In the case of [the structure shown in equation (C1-3)], it can be combined with the structure shown in equation (C1-4) above to include the structure shown in equation (C1-4).

[0209] The manufacturing method of component (C1) is not particularly limited, and can be manufactured by, for example, by the method described in Japanese Invention Publication No. 2020-500211. According to the manufacturing method described in Japanese Invention Publication No. 2020-500211, a maleimide resin having a distribution in the number of repeating units of the trimethylindene backbone can be obtained. The maleimide resin obtained by this method comprises the structure shown in formula (C1-5) below. Therefore, component (C1) can also comprise a maleimide resin containing the structure shown in formula (C1-5); [Chemical Formula 19] (In formula (C1-5), R) a1 R a2 n a2 and n a3 Each with R in equation (C1-2) a1 R a2 n a2 and n a3 The meanings are the same, and the preferred types and ranges are also the same. t'' represents the average number of repeating units from 0.95 to 10.0.

[0210] In formula (C1-5), t'' represents the average number of repeating units, which ranges from 0.95 to 10.0. According to the manufacturing method described in Japanese Invention Publication No. 2020-500211, a group of maleimide resins containing the structure shown in formula (C1-5) can be obtained. Since the average number of repeating units t'' in formula (C1-5) can be less than 1.00, the maleimide resin containing the structure shown in formula (C1-5) obtained in this way can contain maleimide resins with a repeating unit number of 0 for the trimethylindene backbone. Therefore, by purifying a maleimide resin containing the structure shown in formula (C1-5) to obtain a maleimide resin with zero repeating units of the trimethylindane backbone, the resulting maleimide resin can be included solely in the resin composition, or the maleimide resin containing the structure shown in formula (C1-5) can be included in the resin composition without removing the maleimide resin with zero repeating units of the trimethylindane backbone. In one embodiment, it is preferred that the maleimide resin containing the structure shown in formula (C1-5) is included in the resin composition without removing the maleimide resin with zero repeating units of the trimethylindane backbone.

[0211] In formula (C1-5), the average number of repeating units t'' is preferably 0.95 or more, more preferably 0.98 or more, even more preferably 1.0 or more, and particularly preferably 1.1 or more. The upper limit of the average number of repeating units t'' is preferably 10.0 or less, more preferably 8.0 or less, even more preferably 7.0 or less, and particularly preferably 6.0 or less. When the average number of repeating units t'' is within this range, the effects of the present invention can be significantly obtained.

[0212] Among the above, as specific examples of maleimide resins having a trimethylindene skeleton (C1), maleimide resins shown in formulas (C1-6) to (C1-8) can be cited. [Chemical Formula 20] .

[0213] The molecular weight distribution (Mw / Mn) of component (C1) is preferably within a specific range as determined by gel permeation chromatography (GPC). Specifically, the molecular weight distribution (Mw / Mn) of component (C1) is preferably 1.0 to 4.0, more preferably 1.1 to 3.8, even more preferably 1.2 to 3.6, and particularly preferably 1.3 to 3.4.

[0214] For component (C1), the functional group equivalent of maleimide is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, even more preferably 200 g / eq. or more, preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, and even more preferably 800 g / eq. or less.

[0215] <<(C2) Formula (3) shows the maleimide resin>> (C2) is the maleimide resin shown in formula (3) below.

[0216] [Chemical Formula 21] .

[0217] [Chemical Formula 22] .

[0218] [Chemical Formula 23] .

[0219] [Chemical Formula 24] .

[0220] [Chemical Formula 25] In equations (3), (4), (5), (6), and (7), R 11 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 16 Each independently represents a monovalent organic group. R 17 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 18 This refers to a hydrocarbon group containing 1 to 18 hydrogen or carbon atoms. 1 Each represents an integer from 0 to 2 independently, m 6 Each represents an integer from 0 to 2 independently, m 5 Each element independently represents an integer from 0 to 3, satisfying m 1 +m 6 ≤2 and m 1 +m 5 ≤3. m 2 Each represents an integer from 0 to 4 independently, m 7 Each represents an integer from 0 to 4 independently, m 4 Each represents an integer from 0 to 5 independently, n 1 and n 2Each element independently represents the number of repeating units, where n represents an integer greater than or equal to 1. 1 r 2 r 3 r 4 and r 5 Each represents an integer greater than or equal to 0 independently. X M1 Represents a hydrogen atom, a monovalent group as shown in formula (4), or a monovalent group as shown in formula (6). X M2 Represents a hydrogen atom, a hydroxyl group, an alkoxy group with 1 to 18 carbon atoms, a monovalent group as shown in formula (5), or a monovalent group as shown in formula (7). * Represents a linking bond.

[0221] In equations (3) and (5), R 11 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. In m 1 Or, in the case where n is an integer greater than 2, multiple existing R 11 They can be the same or different, but it is preferable that they are the same. R 11 The preferred method and R described later 13 same.

[0222] In equations (3) and (5), R 12 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 12 They can be the same as or different from each other, but are preferably the same. Examples of hydrocarbon groups include alkyl, alkenyl, and aromatic hydrocarbon groups, with alkyl being preferred. The upper limit of the number of carbon atoms in the hydrocarbon group is preferably 12 or less or 10 or less, more preferably 6 or less, and even more preferably 5 or less, 4 or less, or 3 or less. The lower limit of the number of carbon atoms in the hydrocarbon group is preferably 2 or more. In one embodiment, R... 12 The number of carbon atoms in the hydrocarbon group is particularly preferred to be 2.

[0223] R 12 The alkyl group is a chain (straight-chain or branched) alkyl or a cyclic alkyl group, preferably a chain alkyl group, more preferably a straight-chain alkyl group. The upper limit for the number of carbon atoms in the alkyl group is 18 or less, preferably 12 or less or 10 or less, more preferably 6 or less, and even more preferably 5 or less, 4 or less or 3 or less. The lower limit for the number of carbon atoms in the alkyl group is preferably 2 or more. In one embodiment, R... 12 and R 14 The alkyl group in the form of the alkyl group preferably has 2 carbon atoms. Examples of chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, 2-ethylhexyl, octyl, decyl, etc., with methyl, ethyl, n-propyl, isopropyl, or tert-butyl being preferred, methyl or ethyl being more preferred, and ethyl being even more preferred. Additionally, examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, cyclooctyl, etc., with cyclohexyl being preferred.

[0224] R 12 The alkenyl group is a straight-chain, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one non-aromatic carbon-carbon double bond. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 12 or 2 to 10, more preferably 2 to 6, further preferably 2 to 5, 2 to 4, or 2 to 3, and particularly preferably 2. Examples of alkenyl groups include: vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotonyl, methyl allyl (metallyl), isocrotonyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octenyl, etc.), cyclopentenyl (2-cyclopentenyl, etc.), cyclohexenyl (3-cyclohexenyl), etc.

[0225] R 12 The aromatic hydrocarbon group is a group formed by removing one hydrogen atom from an aromatic carbon ring. The aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 to 12 or 6 to 10, and more preferably 6. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthracene, etc., preferably phenyl or naphthyl, and more preferably phenyl.

[0226] In equation (3), R 13 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. In m 2 n 1 Or, in the case where n is an integer greater than 2, multiple existing R 13 They can be the same or different, but being the same is preferred. Examples of hydrocarbon groups include alkyl, alkenyl, and aromatic hydrocarbon groups, with alkyl being preferred. That is, R 13 Preferably, it is an alkyl group having 1 to 18 carbon atoms. The upper limit for the number of carbon atoms in the hydrocarbon group is preferably 12 or less or 10 or less, more preferably 6 or less, and even more preferably 5 or less, 4 or less, 3 or less, or 2 or less. In one embodiment, R 13 The number of carbon atoms in the hydrocarbon group is particularly preferably 1.

[0227] R 13The alkyl group is a chain (straight-chain or branched) alkyl or a cyclic alkyl group, preferably a chain alkyl group, more preferably a straight-chain alkyl group. The alkyl group has 1 to 18 carbon atoms, preferably 1 to 12 or 1 to 10, more preferably 1 to 6, further preferably 1 to 5, 1 to 4, 1 to 3 or 1 to 2, and particularly preferably 1. Examples of chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, 2-ethylhexyl, octyl, decyl, etc., preferably methyl, ethyl, n-propyl, isopropyl or tert-butyl, more preferably methyl or ethyl, and further preferably methyl. Examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, cyclooctyl, etc., preferably cyclohexyl.

[0228] R 13 The alkenyl group is a straight-chain, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one non-aromatic carbon-carbon double bond. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 12 or 2 to 10, more preferably 2 to 6, further preferably 2 to 5, 2 to 4, or 2 to 3, and particularly preferably 2. Examples of alkenyl groups include: vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotonyl, methylallyl, isocrotonyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octenyl, etc.), cyclopentenyl (2-cyclopentenyl, etc.), cyclohexenyl (3-cyclohexenyl), etc.

[0229] R 13 The aromatic hydrocarbon group is a group formed by removing one hydrogen atom from an aromatic carbon ring. The aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 to 12 or 6 to 10, and more preferably 6. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthracene, etc., preferably phenyl or naphthyl, and more preferably phenyl.

[0230] In equations (3) and (5), R 16 Each independently represents a monovalent organic group. R 16 Preferably, it is a hydrocarbon group, more preferably a hydrocarbon group having 1 to 18 carbon atoms. R 16 The preferred method and R 13 same.

[0231] In equations (4), (6), and (7), R 17 Each group independently represents a hydrocarbon group with 1 to 18 carbon atoms. R 17 The preferred method and R 13 Same. In m 7 or n 2 In the case of integers greater than 2, multiple existing R 17They can be the same or different, but being the same is preferred.

[0232] In equation (4), R 18 A hydrocarbon group representing 1 to 18 hydrogen or carbon atoms. Examples of hydrocarbon groups include alkyl, alkenyl, and aromatic hydrocarbon groups, with alkyl being preferred. That is, R 18 Preferably, it is an alkyl group having 1 to 18 hydrogen atoms or carbon atoms. The upper limit for the number of carbon atoms in the hydrocarbon group is preferably 12 or less or 10 or less, more preferably 6 or less, and even more preferably 5 or less, 4 or less, 3 or less, or 2 or less. In one embodiment, R 18 The hydrocarbon group in R preferably has 1 carbon atom. 18 Preferably, it contains hydrogen atoms or methyl groups.

[0233] R 18 The alkyl group is a chain (straight-chain or branched) alkyl or a cyclic alkyl group, preferably a chain alkyl group, more preferably a straight-chain alkyl group. The alkyl group has 1 to 18 carbon atoms, preferably 1 to 12 or 1 to 10, more preferably 1 to 6, further preferably 1 to 5, 1 to 4, 1 to 3 or 1 to 2, and particularly preferably 1. Examples of chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, 2-ethylhexyl, octyl, decyl, etc., preferably methyl, ethyl, n-propyl, isopropyl or tert-butyl, more preferably methyl or ethyl, and further preferably methyl. In addition, examples of cyclic alkyl groups include cyclopentyl, cyclohexyl, cyclooctyl, etc., preferably cyclohexyl.

[0234] R 18 The alkenyl group is a straight-chain, branched, and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one non-aromatic carbon-carbon double bond. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 12 or 2 to 10, more preferably 2 to 6, further preferably 2 to 5, 2 to 4, or 2 to 3, and particularly preferably 2. Examples of alkenyl groups include: vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotonyl, methylallyl, isocrotonyl, etc.), pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octenyl, etc.), cyclopentenyl (2-cyclopentenyl, etc.), cyclohexenyl (3-cyclohexenyl), etc.

[0235] R 18 The aromatic hydrocarbon group is a group formed by removing one hydrogen atom from an aromatic carbon ring. The aromatic hydrocarbon group has 6 to 18 carbon atoms, preferably 6 to 12 or 6 to 10, and more preferably 6. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, anthracene, etc., preferably phenyl or naphthyl, and more preferably phenyl.

[0236] In equations (3) and (5), m 1 Each represents an integer from 0 to 2 independently, m 6 Each represents an integer from 0 to 2 independently, m 5 Each element independently represents an integer from 0 to 3, satisfying m 1 +m 6 ≤2 and m 1 +m 5 ≤3. m 1 Preferably 0 or 1, more preferably 0. m 6 Preferably 0 or 1, more preferably 0. m 5 Preferably, it is an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0237] In equation (3), m 2 Each element independently represents an integer from 0 to 4. In n 1 Or, in the case where n is an integer greater than 2, multiple existing m 2 They can be the same as or different from each other, but are preferably the same. In one embodiment, m 2 The lower limit is preferably 1 or higher. 2 The upper limit is preferably 3 or less, more preferably 2 or less. Additionally, m 2 A further preferred value is 2. In another embodiment, m 2 It can also be 0.

[0238] In equations (4), (6), and (7), m 7 Each represents an integer from 0 to 4 independently. m 7 The preferred method and m 2 Same. In n 2 In the case of integers greater than 2, multiple existing m 7 They can be the same or different, but it is preferable that they are the same.

[0239] In equation (3), m 4 Each element independently represents an integer from 0 to 5. In m 6 When the value is 2, multiple existing m 4 They can be the same as or different from each other, but are preferably the same. In one embodiment, m 4 The lower limit is preferably 1 or higher. 4 The upper limit is preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. Additionally, m 4 A particularly preferred value is 2. In another embodiment, m 4 It can also be 0.

[0240] In equations (3), (4), and (6), n 1 and n2 Each represents the number of repeating units independently. From the viewpoint of adjusting the viscosity of the resin composition, n 1 and n 2 The upper limit is preferably 50 or less, more preferably 30 or less, and even more preferably 15 or less. 1 and n 2 The lower limit is 0 or higher, preferably 1 or higher. Furthermore, in one embodiment, n 1 and n 2 It can also be 1. The number of repeating units n 1 and n 2 Calculations can be made based on the feed ratio, NMR, etc.

[0241] In equation (3), n represents an integer greater than or equal to 1. The upper limit of n is preferably 20 or less or 15 or less, more preferably 10 or less or 9 or less, further preferably 8 or less, 7 or less or 6 or less, and particularly preferably 5 or less, 4 or less or 3 or less.

[0242] In equations (3), (4), (5), and (6), r 1 r 2 r 3 r 4 and r 5 Each represents an integer greater than 0 independently. When there are multiple r... 1 r 2 r 3 r 4 or r 5 In the case of multiple existing r 1 r 2 r 3 r 4 or r 5 They can be the same or different. 1 r 2 r 3 r 4 and r 5 Each of the following is preferably 10 or less, more preferably 8 or less or 6 or less, further preferably 4 or less or 3 or less, and particularly preferably 2 or less or 1 or less. In one embodiment, r 1 r 2 r 3 r 4 and r 5 Each can be 0, 1, or 2 independently.

[0243] In equation (3), X M1 This represents a hydrogen atom, a monovalent group as shown in formula (4), or a monovalent group as shown in formula (6). In one embodiment, X M1 Hydrogen atoms are preferred.

[0244] In equation (3), X M2 The group represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 18 carbon atoms, a monovalent group represented by formula (5), or a monovalent group represented by formula (7). In one embodiment, X M2 Preferably, it is a monovalent group as shown in formula (5).

[0245] X M2 The alkoxy group in the alkoxy group has 1 to 18 carbon atoms, preferably 12 or less or 10 or less, more preferably 6 or less, and even more preferably 5 or less, 4 or less, 3 or less, or 2 or less. In one embodiment, X M2 The number of carbon atoms in the alkoxy group is particularly preferably 1.

[0246] X M2 The alkoxy group in the form is a chain (straight-chain or branched) alkoxy group or a cyclic alkoxy group, preferably a chain alkoxy group, and more preferably a straight-chain alkoxy group. Examples of chain alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, neopentoxy, hexylalkoxy, 2-ethylhexylalkoxy, octylalkoxy, decylalkoxy, etc., preferably methoxy, ethoxy, n-propoxy, isopropoxy, or tert-butoxy, more preferably methoxy or ethoxy, and even more preferably methoxy. Examples of cyclic alkoxy groups include: cyclopentylalkoxy, cyclohexylalkoxy, cyclooctylalkoxy, etc., preferably cyclohexylalkoxy.

[0247] Specific examples of component (C2) include maleimide resins as shown in formulas (3-1) to (3-13) below.

[0248] [Chemical Formula 26] .

[0249] [Chemical Formula 27] .

[0250] [Chemical Formula 28] .

[0251] [Chemical Formula 29] .

[0252] [Chemical Formula 30] .

[0253] [Chemical Formula 31] .

[0254] [Chemical Formula 32] .

[0255] [Chemical Formula 33] .

[0256] [Chemical Formula 34] .

[0257] [Chemical Formula 35] .

[0258] [Chemical Formula 36] .

[0259] [Chemical Formula 37] .

[0260] [Chemical Formula 38] .

[0261] The number-average molecular weight (Mn) of component (C2) is preferably 200 or more, more preferably 250 or more, and even more preferably 300 or more. The upper limit of the number-average molecular weight (Mn) of component (C2) is preferably 1500 or less or 1200 or less, more preferably 1000 or less or 800 or less, and even more preferably 600 or less, 500 or less, or 400 or less. In one embodiment, the number-average molecular weight (Mn) of component (C2) is preferably in the range of 200 to 1500, more preferably in the range of 300 to 800. Furthermore, the weight-average molecular weight (Mw) of component (C2) is preferably 280 or more, more preferably 300 or more or 330 or more, even more preferably 350 or more or 400 or more, and particularly preferably 450 or more or 500 or more. The upper limit of the weight-average molecular weight (Mw) of component (C2) is preferably 2000 or less or 1500 or less, more preferably 1200 or less or 1000 or less, and even more preferably 800 or less, 700 or less, or 600 or less. In one embodiment, the weight-average molecular weight (Mw) of component (C2) is preferably in the range of 280 to 2000, more preferably in the range of 330 to 1200.

[0262] For component (C2), from the viewpoint of obtaining a resin composition with excellent solvent solubility and a cured product with superior heat resistance and dielectric properties (low dielectric loss tangent), the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) calculated by gel permeation chromatography (GPC) is preferably in the range of 1.01 to 4.0, more preferably 1.05 to 2.0, and even more preferably 1.10 to 1.8. It should be noted that in the GPC plot obtained by GPC, when the molecular weight distribution is in a wide range and there is a high proportion of high molecular weight components, the proportion of high molecular weight components that contribute to flexibility increases. Therefore, compared with cured products using maleimide resins other than component (C2), it is possible to obtain cured products with suppressed brittleness and excellent flexibility, which is a preferred approach.

[0263] It should be noted that the number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of component (C2) can be determined by gel permeation chromatography (GPC).

[0264] From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition is set to 100% by mass, the content of (C) maleimide resin in the resin composition is preferably 0.01% by mass or more or 0.05% by mass or more, more preferably 0.1% by mass or more, 0.3% by mass or more or 0.5% by mass or more, further preferably 0.8% by mass or more, 1.0% by mass or more or 1.5% by mass or more, particularly preferably 2.0% by mass or more, 2.5% by mass or more or 3.0% by mass or more. In one embodiment, it can be 3.5% by mass or more, 4.0% by mass or more, 4.5% by mass or more, etc. The upper limit is preferably 30% by mass or less or 25% by mass or less, more preferably 20% by mass or less or 15% by mass or less, further preferably 12% by mass or less or 10% by mass or less, particularly preferably 9% by mass or less, 8% by mass or less or 7% by mass or less. In another embodiment, it can be 6.5% by mass or less, 6.0% by mass or less, 5.5% by mass or less, etc.

[0265] From the viewpoint of significantly obtaining the effects of the present invention, when the resin component in the resin composition is set to 100% by mass, the content of (C) maleimide resin in the resin composition is preferably 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, more preferably 2% by mass or more, 3% by mass or more, or 4% by mass or more, further preferably 5% by mass or more, 6% by mass or more, or 7% by mass or more, particularly preferably 8% by mass or more, 9% by mass or more, 10% by mass or more, or 11% by mass or more. In one embodiment, it can be 12% by mass or more, 13% by mass or more, 14% by mass or more, 15% by mass or more, etc. The upper limit is preferably 70% by mass or less or 65% by mass or less, more preferably 60% by mass or less, 55% by mass or less, or 50% by mass or less, further preferably 45% by mass or less, 40% by mass or less, or 35% by mass or less, particularly preferably 30% by mass or less, 25% by mass or less, or 22% by mass or less. In another embodiment, the content can be 20% or less by mass, 19% or less by mass, 18% or less by mass, 17% or less by mass, etc.

[0266] When the non-volatile component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the total content of component (A), component (B), and component (C) in the resin composition is preferably 2% by mass or more, more preferably 5% by mass or more or 8% by mass or more, further preferably 10% by mass or more or 12% by mass or more, and particularly preferably 15% by mass or more or 18% by mass or more. In one embodiment, the content can be 20% by mass or more, 22% by mass or more, 25% by mass or more, 28% by mass or more, etc. There is no particular upper limit; it can be 100% by mass, or less than 90% by mass, less than 80% by mass, less than 70% by mass, less than 60% by mass, less than 50% by mass, less than 40% by mass, less than 35% by mass, etc.

[0267] When the non-volatile component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the total content of component (A), the active ester compound (i.e., the sum of component (B) and component (B')) and component (C) in the resin composition is preferably 2% by mass or more, more preferably 5% by mass or more or 8% by mass or more, further preferably 10% by mass or more or 12% by mass or more, particularly preferably 15% by mass or more, 18% by mass or more, 20% by mass or more, 22% by mass or more, 25% by mass or more, or 28% by mass or more. There is no particular upper limit; it can be 100% by mass, or less than 90% by mass, less than 80% by mass, less than 70% by mass, less than 60% by mass, less than 50% by mass, less than 40% by mass, less than 35% by mass, etc.

[0268] When the resin component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the total content of component (A), component (B), and component (C) in the resin composition is preferably 30% by mass or more or 35% by mass or more, more preferably 40% by mass or more or 45% by mass or more, further preferably 50% by mass or more or 55% by mass or more, and particularly preferably 60% by mass or more, 65% by mass or more, 70% by mass or more, or 75% by mass or more. In one embodiment, it can be 80% by mass or more, 85% by mass or more, 90% by mass or more, etc. There is no particular upper limit; it can be 100% by mass, or 99.9% by mass or less, 99.5% by mass or less, 99% by mass or less, 98% by mass or less, 97% by mass or less, 96% by mass or less, 95% by mass or less, etc.

[0269] When the resin component in the resin composition is set to 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention, the total content of component (A), the active ester compound (i.e., the sum of component (B) and component (B')), and component (C) in the resin composition is preferably 30% by mass or more or 35% by mass or more, more preferably 40% by mass or more or 45% by mass or more, further preferably 50% by mass or more or 55% by mass or more, and particularly preferably 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more. There is no particular upper limit; it can be 100% by mass or less, or it can be 99.9% by mass or less, 99.5% by mass or less, 99% by mass or less, 98% by mass or less, 97% by mass or less, 96% by mass or less, 95% by mass or less, etc.

[0270] From the viewpoint of significantly obtaining the effects of the present invention, the mass ratio of component (C) to component (A) in the resin composition [(C) component / (A) component] is preferably 0.001 or more or 0.005 or more, more preferably 0.01 or more or 0.03 or more, further preferably 0.05 or more, 0.08 or more or 0.1 or more, and particularly preferably 0.2 or more, 0.3 or more or 0.4 or more. In one embodiment, it can be 0.5 or more, 0.6 or more, etc. The upper limit is preferably 50 or less, 20 or less, or 15 or less, more preferably 10 or less, 8 or less, or 6 or less, further preferably 5 or less, 4 or less, or 3 or less, and particularly preferably 2 or less, 1.0 or less, or 0.9 or less. In one embodiment, it can be 0.8 or less, 0.7 or less, etc.

[0271] From the viewpoint of significantly obtaining the effects of the present invention, the mass ratio of component (C) to component (B) in the resin composition [(C) component / (B) component] is preferably 0.001 or more, 0.003 or more, or 0.005 or more, more preferably 0.008 or more, 0.01 or more, or 0.03 or more, even more preferably 0.05 or more, 0.08 or more, or 0.1 or more, and particularly preferably 0.12 or more, 0.15 or more, or 0.18 or more. In one embodiment, it can be 0.20 or more, 0.25 or more, etc. The upper limit is preferably 20 or less, 15 or less, or 10 or less, more preferably 8 or less, 5 or less, or 4 or less, even more preferably 3 or less, 2 or less, or 1.0 or less, and particularly preferably 0.8 or less, 0.5 or less, or 0.4 or less. In one embodiment, it can be 0.35 or less, 0.30 or less, etc.

[0272] From the viewpoint of significantly obtaining the effects of the present invention, the mass ratio of component (C) to the active ester compound (i.e., the total of components (B) and (B')) in the resin composition [(C) component / active ester compound] is preferably 0.001 or more, 0.003 or more, or 0.005 or more, more preferably 0.008 or more, 0.01 or more, or 0.03 or more, further preferably 0.05 or more, 0.08 or more, or 0.1 or more, and particularly preferably 0.12 or more, 0.15 or more, or 0.18 or more. In one embodiment, it can be 0.20 or more, 0.25 or more, etc. The upper limit is preferably 20 or less, 15 or less, or 10 or less, more preferably 8 or less, 5 or less, or 4 or less, further preferably 3 or less, 2 or less, or 1.0 or less, and particularly preferably 0.8 or less, 0.5 or less, or 0.4 or less. In another embodiment, it can be 0.35 or less, 0.30 or less, etc.

[0273] <(D) Inorganic filler materials> The resin composition of the present invention may contain (D) inorganic filler as an optional component, but is preferably containing (D) inorganic filler. By containing (D) inorganic filler, the linear thermal expansion coefficient and dielectric loss tangent of the cured product can be reduced more effectively.

[0274] Inorganic compounds can be used as the inorganic filler material (D). Examples of inorganic filler materials (D) include: silicon dioxide, alumina, aluminosilicates, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, 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 zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silicon dioxide is preferred. Examples of silicon dioxide include: amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, etc. Furthermore, spherical silicon dioxide is preferred as the shape of the silicon dioxide. (D) Inorganic filler materials can be used alone or in combination of two or more in any ratio.

[0275] Commercially available products as (D) inorganic filler materials include: "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SC2300-SVJ", "SC2050-SXF", and "180nmSX-C1" manufactured by Yatuma 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 Co., Ltd.; "CellSpheres" and "MGH-005" manufactured by Pacific Cement Co., Ltd.; and "LHP-208" manufactured by Ube Exsymo Co., Ltd., etc.

[0276] From the viewpoint that the surface of the cured material (insulating layer) has low roughness and is easy to form fine wiring, the average particle size of the inorganic filler material (D) is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less or 0.6 μm or less. The lower limit of the average particle size of the inorganic filler material (D) is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, and particularly preferably 0.15 μm or more, 0.2 μm or more, 0.3 μm or more, or 0.4 μm or more. The average particle size of the inorganic filler (D) can be determined by laser diffraction-scattering based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler material can be prepared using a laser diffraction-scattering particle size distribution measuring device with a volume reference, and the median diameter can be used as the average particle size for measurement. For the sample to be measured, a sample obtained by weighing 100 mg of inorganic filler material and 10 g of methyl ethyl ketone into a vial and dispersing it ultrasonically for 10 minutes can be used. The light source wavelength used in the laser diffraction particle size distribution measuring device can be set to blue or red, and the measurement is performed in a flow cell. Examples of laser diffraction particle size distribution measuring devices include, for example, the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0277] (D) The specific surface area of ​​the inorganic filler material is not particularly limited, but is preferably 0.1 m². 2 / g or more, preferably 0.5m 2 / g or more, further preferably 1m 2 / g or more or 3m 2 / g or more. (D) There is no particular limit to the upper limit of the specific surface area of ​​the inorganic filler material, but it is preferably 100m². 2 / g or less, preferably 70m 2 / g or less, more preferably 50m 2 / g or less, especially preferably 40m 2 / g or less, 30m 2 / g or less, 20m 2 / g or less or 10m 2 / g or less. The specific surface area of ​​inorganic fillers can be calculated using the BET method, which involves using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen onto the sample surface and then using the BET multi-point method.

[0278] (D) Inorganic filler materials are preferably surface-treated with surface treatment agents. Surface treatment improves the moisture resistance and dispersibility of the (D) inorganic filler materials. Examples of surface treatment agents include: vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, and 3-epoxypropoxypropyltriethoxysilane; styrene-based silane coupling agents such as p-styrenetrimethoxysilane; and 3-methylpropene. Methacrylic acid-based silane coupling agents such as acyloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic acid-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane and other amino-based silane coupling agents; tris(trimethoxysilylpropyl)isocyanurate and other isocyanurate-based silane coupling agents; 3-ureopropyltrialkoxysilane and other ureoyl-based silane coupling agents; 3-mercapto... Thiol-based silane coupling agents such as propylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanate-propyltriethoxysilane; anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide; other silane coupling agents; non-silane coupling-alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane, organosilane compounds, titanate-based coupling agents, etc. Furthermore, the surface treatment agent can be used alone or in combination of two or more in any ratio. In one embodiment, (D) the inorganic filler material is preferably surface-treated with an amino-based silane coupling agent, more preferably with N-phenyl-3-aminopropyltrimethoxysilane.

[0279] From the viewpoint of improving the dispersibility of inorganic filler materials, the degree of surface treatment using a surface treatment agent is preferably within a specified range. Specifically, 100 parts by weight of the inorganic filler material is preferably surface treated with 0.2 to 5 parts by weight of a surface treatment agent, more preferably with 0.2 to 3 parts by weight, and even more preferably with 0.3 to 2 parts by weight.

[0280] The degree of surface treatment using surface treatment agents can be evaluated by the carbon content per unit surface area of ​​the inorganic filler material. From the viewpoint of improving the dispersibility of the inorganic filler material, the carbon content per unit surface area of ​​the inorganic filler material is preferably 0.02 mg / m². 2 The above, more preferably 0.1 mg / m 2 The above is further preferred to be 0.2 mg / m³. 2 The above. The preferred upper limit is 1 mg / m³. 2 The following is more preferably 0.8 mg / m³ 2 The following is a further preferred value: 0.5 mg / m³ 2 the following.

[0281] (D) The carbon content per unit surface area of ​​inorganic filler materials can be determined after cleaning the surface-treated inorganic filler materials with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK is added as a solvent to the surface-treated inorganic filler materials, and the materials are ultrasonically cleaned at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler materials can be determined using a carbon analyzer. A suitable carbon analyzer is the "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd.

[0282] When the non-volatile component in the resin composition is set to 100% by mass, the content of (D) inorganic filler material in the resin composition is 0% by mass or more. From the viewpoint of significantly obtaining the effects of the present invention, it is preferably 10% by mass or more, more preferably 20% by mass or more, 30% by mass or more, or 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. In addition, in one embodiment, it can be 70% by mass or more, etc. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, and particularly preferably 80% by mass or less.

[0283] When the resin composition of the present invention contains inorganic filler material (D), from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition is set to 100% by mass, the total content of components (A), (B), (C), and (D) in the resin composition is preferably 10% by mass or more or 20% by mass or more, more preferably 30% by mass or more or 40% by mass or more, further preferably 50% by mass or more or 60% by mass or more, and particularly preferably 70% by mass or more or 80% by mass or more. In one embodiment, it can be 90% by mass or more, 95% by mass or more, 98% by mass or more, etc. There is no particular upper limit; it can also be 100% by mass, or 99.9% by mass or less, 99.5% by mass or less, 99% by mass or less, 98.5% by mass or less, etc.

[0284] When the resin composition of the present invention contains inorganic filler material (D), from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile component in the resin composition is set to 100% by mass, the total content of component (A), active ester compound (i.e., the sum of component (B) and component (B'), component (C), and component (D) in the resin composition is preferably 10% by mass or more or 20% by mass or more, more preferably 30% by mass or more or 40% by mass or more, further preferably 50% by mass or more or 60% by mass or more, and particularly preferably 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 98% by mass or more. There is no particular upper limit; it can be 100% by mass or less, or 99.9% by mass or less, 99.5% by mass or less, 99% by mass or less, 98.5% by mass or less, etc.

[0285] <(E) Organic Filler Materials> The resin composition of the present invention may contain (E) organic filler as an optional component, preferably containing (E) organic filler. One type of (E) organic filler may be used alone, or two or more may be used in combination.

[0286] (E) The organic filler material exists in the resin composition in a particulate form. Examples of the (E) organic filler material include rubber particles, polyamide microparticles, silicone particles, core-shell particles, etc. In this invention, from the viewpoint of significantly obtaining the desired effect of this invention, the (E) organic filler material preferably includes either rubber particles or core-shell particles, more preferably rubber particles, and even more preferably core-shell rubber particles.

[0287] Examples of rubber components contained in rubber particles include olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, 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 acrylic thermoplastic elastomers such as poly(meth)acrylate, poly(meth)acrylate, poly(cyclohexyl methacrylate), and poly(octyl methacrylate), preferably acrylic thermoplastic elastomers. Rubber particles containing acrylic thermoplastic elastomers as rubber components are called "acrylic rubber particles." Core-shell particles containing acrylic thermoplastic elastomers as rubber components are called "acrylic core-shell particles." Core-shell rubber particles containing acrylic thermoplastic elastomers as rubber components are referred to as "acrylic core-shell rubber particles". That is, (E) the organic filler material preferably contains either acrylic rubber particles or acrylic core-shell particles, more preferably acrylic rubber particles, and even more preferably acrylic core-shell rubber particles. Furthermore, silicone rubbers such as polysiloxane rubbers may also be mixed into the rubber component. The glass transition temperature of the rubber component contained in the rubber particles is preferably below 0°C, more preferably below -10°C, even more preferably below -20°C, and particularly preferably below -30°C.

[0288] Commercially available products can be used as rubber particles, such as Dow Chemical Japan's "EXL-2655" and AICA Industries' "STAPHYLOID AC3401N" and "STAPHYLOID AC3816N". "STAPHYLOID AC3816N" also belongs to the core-shell type of rubber particles.

[0289] Core-shell particles are particulate organic filler materials comprising "core particles containing rubber components as listed above" and "one or more shell layers covering them". Furthermore, core-shell particles are preferably core-shell graft copolymer particles comprising "core particles containing rubber components as listed above" and "shell layers formed by graft copolymerization of monomer components that can copolymerize with the rubber components contained in the core particles". Here, "core-shell" does not necessarily refer only to those where the core particles and shell layers can be clearly distinguished; it also includes those where the boundary between the core particles and shell layers is unclear, and the core particles may not be completely covered by the shell layer.

[0290] The rubber component preferably contains 40% by mass or more in the core-shell graft copolymer particles, more preferably 50% by mass or more, and even more preferably 60% by mass or more. There is no particular upper limit to the content of the rubber component in the core-shell graft copolymer particles, but from the viewpoint of ensuring sufficient coverage of the core particles by the shell, it is preferably, for example, 95% by mass or less, or 90% by mass or less.

[0291] Examples of monomer components that form the shell portion of core-shell graft copolymer particles include: methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, glycidyl methacrylate, and other methacrylates; methacrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimides; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; and methacrylonitrile, preferably methacrylates, and more preferably methyl methacrylate.

[0292] Commercially available products containing core-shell graft copolymer particles include: Samsung SDI's "CHT"; Techno UMG's "B602"; Dow Chemical Japan's "PARALOID EXL2602", "PARALOID EXL2603", "PARALOID EXL-2655", "PARALOID EXL2311", "PARALOID EXL2313", "PARALOID EXL2315", "PARALOID KM330", "PARALOID KM336P", "PARALOID KCZ201"; Mitsubishi Chemical's "METABLEN C-223A", "METABLEN E-901", "METABLENS-2001", "METABLEN W-450A", "METABLEN SRK-200"; and Kaneka's "Kane Ace M-511", "Kane Ace M-600", "Kane Ace M-400", "Kane Ace M-400", etc. Brands such as "Ace M-580" and "KaneAce MR-01" can be used individually or in combination.

[0293] The average particle size (average primary particle size) of the core-shell graft copolymer particles is not particularly limited, but is preferably 20 nm or more, more preferably 50 nm or more, further preferably 80 nm or more, and particularly preferably 100 nm or more. The upper limit is preferably 5000 nm or less, more preferably 2000 nm or less, further preferably 1000 nm or less, and particularly preferably 500 nm or less. The average particle size (average primary particle size) of the core-shell graft copolymer particles can be measured using a zeta potential particle size distribution measuring device or the like.

[0294] When the non-volatile component in the resin composition is set to 100% by mass, the content of (E) organic filler material in the resin composition is 0% by mass or more. From the viewpoint of significantly obtaining the effects of the present invention, it is preferably 0.01% by mass or more or 0.03% by mass or more, more preferably 0.05% by mass or more or 0.08% by mass or more, further preferably 0.1% by mass or more or 0.3% by mass or more, and particularly preferably 0.5% by mass or more or 0.7% by mass or more. The upper limit is preferably 15% by mass or less or 10% by mass or less, more preferably 8% by mass or less or 5% by mass or less, further preferably 4% by mass or less or 3% by mass or less, and particularly preferably 2% by mass or less, 1.0% by mass or less or 0.8% by mass or less.

[0295] When the resin component in the resin composition is set to 100% by mass, the content of the (E) organic filler material in the resin composition is 0% by mass or more. From the viewpoint of significantly obtaining the effects of the present invention, it is preferably 0.05% by mass or more or 0.1% by mass or more, more preferably 0.3% by mass or more, 0.5% by mass or more or 0.8% by mass or more, further preferably 1.0% by mass or more, 1.2% by mass or more or 1.5% by mass or more, particularly preferably 1.8% by mass or more, 2.0% by mass or more or 2.2% by mass or more. The upper limit is preferably 30% by mass or less or 25% by mass or less, more preferably 20% by mass or less, 15% by mass or less or 10% by mass or less, further preferably 8% by mass or less, 6% by mass or less or 5% by mass or less, particularly preferably 4% by mass or less, 3.0% by mass or less or 2.8% by mass or less.

[0296] When the resin composition of the present invention contains (D) inorganic filler and (E) organic filler, from the viewpoint of significantly obtaining the effects of the present invention, the mass ratio of component (E) to component (D) in the resin composition [(E) component / (D) component] is preferably 1×10⁻⁶. -4 The above is preferred to be 3×10 -4 Above or 5×10 -4 The above is further optimized to 8×10 -4 Above or 1×10 -3The above is particularly preferred, with 3×10 -3 Above, 5×10 -3 Above or 8×10 -3 The above. The upper limit is preferably below 1 or 8 × 10. -1 The following is more preferably 5×10 -1 Below or 3×10 -1 Hereinafter, 1×10 is further preferred. -1 Below or 8×10 -2 The following is particularly preferred: 5×10 -2 Below or 3×10 -2 the following.

[0297] <(F) Thermoplastic Resins> The resin composition of the present invention may further contain (F) thermoplastic resin as an optional component. Preferably, it contains (F) thermoplastic resin.

[0298] Examples of thermoplastic resins include: phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamide-imide resins, polyether-imide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, polyester resins, etc. From the viewpoint of significantly obtaining the effects of the present invention, phenoxy resins are preferred. That is, component (F) preferably includes a phenoxy resin. The phenoxy resin described herein refers to a component other than those belonging to the epoxy resin family. Furthermore, one thermoplastic resin may be used alone, or two or more may be used in combination.

[0299] Examples of phenoxy resins include those having one or more skeletons selected from the following: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal group of the phenoxy resin can be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0300] Specific examples of phenoxy resins include: Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing a bisphenol A backbone); Mitsubishi Chemical's "YX8100" (phenoxy resin containing a bisphenol S backbone); Mitsubishi Chemical's "YX6954" (phenoxy resin containing a bisphenol acetophenone backbone); Nippon Steel Chemical Materials' "FX280" and "FX293"; and Mitsubishi Chemical's "YL6954BH30", "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30", etc.

[0301] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred. Specific examples of polyvinyl acetal resins include the S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemicals Co., Ltd.

[0302] Examples of polyolefin resins include: low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, and other ethylene-based copolymers; polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

[0303] Specific examples of polyimide resins include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Rikka Co., Ltd.

[0304] Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Other specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane backbone) manufactured by Resonac Co., Ltd.

[0305] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0306] Specific examples of polysulfone resins include polysulfones such as "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0307] Examples of polyester resins include: polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, and polycyclohexanedimethyl terephthalate resin.

[0308] From the viewpoint of achieving significant effects of the present invention, the weight-average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

[0309] When the non-volatile component in the resin composition is set to 100% by mass, the content of (F) thermoplastic resin in the resin composition is 0% by mass or more. From the viewpoint of significantly obtaining the effects of the present invention, it is preferably 0.01% by mass or more or 0.03% by mass or more, more preferably 0.05% by mass or more or 0.8% by mass or more, further preferably 0.1% by mass or more or 0.3% by mass or more, and particularly preferably 0.5% by mass or more or 0.6% by mass or more. The upper limit is preferably 10% by mass or less or 8% by mass or less, more preferably 6% by mass or less or 5% by mass or less, further preferably 4% by mass or less or 3% by mass or less, and particularly preferably 2% by mass or less, 1.0% by mass or less or 0.8% by mass or less.

[0310] When the resin component in the resin composition is set to 100% by mass, the content of (F) thermoplastic resin in the resin composition is 0% by mass or more. From the viewpoint of significantly obtaining the effects of the present invention, it is preferably 0.05% by mass or more or 0.1% by mass or more, more preferably 0.3% by mass or more or 0.5% by mass or more, further preferably 0.8% by mass or more, 1.0% by mass or more or 1.2% by mass or more, particularly preferably 1.5% by mass or more, 1.8% by mass or more or 2.0% by mass or more. The upper limit is preferably 30% by mass or less, 25% by mass or less or 20% by mass or less, more preferably 15% by mass or less, 12% by mass or less or 10% by mass or less, further preferably 8% by mass or less, 6% by mass or less or 5% by mass or less, particularly preferably 4% by mass or less, 3.0% by mass or less or 2.5% by mass or less.

[0311] <(G) Curing Accelerator> The resin composition of the present invention may contain (G) curing accelerator as an optional component, preferably containing (G) curing accelerator. By containing (G) curing accelerator, the curability of the resin composition can be improved while obtaining a cured product exhibiting superior dielectric properties (low dielectric loss tangent). One (G) curing accelerator may be used alone, or two or more may be used in combination.

[0312] Examples of (G) curing accelerators include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. A single (G) curing accelerator may be used alone, or two or more may be used in combination. Preferably, the (G) curing accelerator includes an amine-based curing accelerator or an imidazole-based curing accelerator, and more preferably, it includes an imidazole-based curing accelerator.

[0313] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine; pyridines such as 4-dimethylaminopyridine; benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with pyridines being preferred, and 4-dimethylaminopyridine being more preferred. One of these accelerators may be used alone, or two or more may be used in combination.

[0314] As an amine-based curing accelerator, commercially available products can be used, such as "MY-25" manufactured by Ajinomoto Fine Technology Co., Ltd., and "DMAP" manufactured by Kwangei Chemical Industry Co., Ltd.

[0315] Examples of phosphorus-based curing accelerators include: tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic phthalate, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate, and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, and p-toluene. Aromatic phosphonium salts including triphenylphosphonium tetratolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetratolylborate, triphenylethylphosphonium tetraphenylborate, tri(3-methylphenyl)ethylphosphonium tetraphenylborate, tri(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc.; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-benzoquinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butylphosphine, etc. Aliphatic phosphines such as 2-butenylphosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine; and tributylphenylphosphine, di-tert-butylphenylphosphine, methyl diphenylphosphine, ethyl diphenylphosphine, butyl diphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine, etc. Aromatic phosphines include tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether. They can be used alone or in combination of two or more.

[0316] Examples of urea-based curing accelerators include: 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. Aromatic dimethylureas include 1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea)[toluenebisdimethylurea], etc. These can be used alone or in combination of two or more.

[0317] Examples of guanidine-based curing accelerators include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine. They can be used alone or in combination of two or more.

[0318] Examples of imidazole-based curing accelerators include: 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[ [2'-Undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds, as well as adducts of imidazole compounds and epoxy resins, preferably 1-benzyl-2-phenylimidazolium.

[0319] Commercially available imidazole-based curing accelerators include, for example, those manufactured by Shikoku Chemical Industry Co., Ltd. such as "1B2PZ", "2P4MZ", "2M4MZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A"; and "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd. These can be used individually or in combination of two or more.

[0320] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) and cobalt(III) acetylacetone, organocopper complexes such as copper(II) acetylacetone, organozinc complexes such as zinc(II) acetylacetone, organoiron complexes such as iron(III) acetylacetone, organonickel complexes such as nickel(II) acetylacetone, and organomanganese complexes such as manganese(II) acetylacetone. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. They can be used alone or in combination of two or more.

[0321] When the non-volatile component in the resin composition is set to 100% by mass, the content of the (G) curing accelerator in the resin composition is 0% by mass or more. From the viewpoint of significantly obtaining the effects of the present invention, it is preferably 0.001% by mass or more or 0.005% by mass or more, more preferably 0.01% by mass or more or 0.03% by mass or more, further preferably 0.05% by mass or more or 0.08% by mass or more, particularly preferably 0.10% by mass or more, 0.15% by mass or more, 0.18% by mass or more, or 0.20% by mass or more. The upper limit is preferably 10% by mass or less or 8% by mass or less, more preferably 5% by mass or less or 2% by mass or less, further preferably 1% by mass or less, 0.8% by mass or less or 0.5% by mass or less, particularly preferably 0.4% by mass or less, 0.3% by mass or less or 0.25% by mass or less.

[0322] When the resin component in the resin composition is set to 100% by mass, the content of (G) curing accelerator in the resin composition is 0% by mass or more. From the viewpoint of significantly obtaining the effects of the present invention, it is preferably 0.01% by mass or more or 0.03% by mass or more, more preferably 0.05% by mass or more or 0.08% by mass or more, further preferably 0.1% by mass or more or 0.3% by mass or more, and particularly preferably 0.5% by mass or more or 0.7% by mass or more. The upper limit is preferably 20% by mass or less or 15% by mass or less, more preferably 10% by mass or less or 8% by mass or less, further preferably 5% by mass or less, 4% by mass or less or 3% by mass or less, and particularly preferably 2% by mass or less, 1.5% by mass or less, 1.0% by mass or less or 0.8% by mass or less.

[0323] <(H) Organic solvents> The resin composition of the present invention may contain (H) organic solvent as an optional component. One (H) organic solvent may be used alone, or two or more may be used in combination. In one embodiment, two or more (H) organic solvents are preferably used in combination.

[0324] Examples of (H) organic solvents include organic solvents composed of atoms selected from carbon, oxygen, nitrogen, phosphorus, sulfur, halogen, and hydrogen atoms. From a safety point of view, (H) organic solvents are preferably organic solvents composed of atoms selected from carbon, oxygen, and hydrogen atoms, and more preferably organic solvents composed of carbon, oxygen, and hydrogen atoms.

[0325] Examples of (H) organic solvents include: glycol-based organic solvents, glycol ether-based organic solvents, glycol ether ester-based organic solvents, ketone-based organic solvents, ester-based organic solvents, ether-based organic solvents, alcohol-based organic solvents, aliphatic hydrocarbon-based organic solvents, aromatic organic solvents, nitrogen-based organic solvents, sulfur-based organic solvents, and halogen-based organic solvents. Examples of nitrogen-based organic solvents include: amide-based organic solvents, urea-based organic solvents, and nitrile-based organic solvents. From a safety perspective, ester-based organic solvents, ketone-based organic solvents, glycol-based organic solvents, glycol ether-based organic solvents, glycol ether ester-based organic solvents, or aromatic organic solvents are preferred as (H) organic solvents; more preferably, ester-based organic solvents, glycol ether ester-based organic solvents, ketone-based organic solvents, or aromatic organic solvents are even more preferred; ketone-based organic solvents or aromatic organic solvents are particularly preferred.

[0326] Examples of diol-based organic solvents include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and 1,3-propanediol.

[0327] Examples of glycol ether-based organic solvents include: ethylene glycol monomethyl ether (also known as methyl cellosolve), ethylene glycol monoethyl ether (also known as cellosolve), ethylene glycol monopropyl ether (also known as propyl cellosolve), ethylene glycol monobutyl ether (also known as butyl cellosolve), ethylene glycol monoisobutyl ether (also known as isobutyl cellosolve), ethylene glycol monotert-butyl ether (also known as tert-butyl cellosolve), ethylene glycol monohexyl ether, etc.; diethylene glycol monomethyl ether (also known as methyl carbitol), diethylene glycol monomethyl ether, etc. Carbitol derivatives include monoethyl ether (also known as carbitol), diethylene glycol monopropyl ether (also known as propyl carbitol), and diethylene glycol monobutyl ether (DB) (also known as butyl carbitol); propylene glycol ethers include monomethyl ether (PGM, also known as 1-methoxy-2-propanol), monoethyl ether, monopropyl ether, and monobutyl ether; and dipropylene glycol ethers include dimethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether. Propylene glycol ethers are preferred, and monomethyl ether (1-methoxy-2-propanol) is more preferred.

[0328] Examples of glycol ether ester-based organic solvents include: ethylene glycol monomethyl ether acetate (also known as methyl cellosolve acetate), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate), ethylene glycol monobutyl ether acetate (also known as butyl cellosolve acetate), and other cellosolve esters; carbitol esters such as diethylene glycol monoethyl ether acetate (EDGAc) (also known as carbitol acetate) and diethylene glycol monobutyl ether acetate (also known as butyl carbitol acetate); propylene glycol ether esters such as propylene glycol monomethyl ether acetate (PGMEAc) and propylene glycol monoethyl ether acetate; and dipropylene glycol ether esters such as dipropylene glycol monomethyl ether acetate, preferably carbitol esters, and more preferably diethylene glycol monoethyl ether acetate.

[0329] Examples of ketone-based organic solvents include: aliphatic acyclic ketones such as acetone, methyl ethyl ketone (MEK), diethyl ketone, 2-pentanone, methyl isobutyl ketone, 2-hexanone, 2-heptanone (MAK), and diisobutyl ketone; aliphatic cyclic ketones such as cyclopentanone, cyclohexanone (Anone), and 2-methylcyclohexanone; and aromatic ketones such as acetophenone, with methyl ethyl ketone (MEK) or cyclohexanone being preferred. The lower limit of the number of carbon atoms in the ketone-based organic solvent is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The upper limit of the number of carbon atoms in the ketone-based organic solvent is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

[0330] Ester-based organic solvents are organic solvents with an ester structure that do not belong to the glycol ether ester system. Examples include: alkyl esters of fatty acids such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, isopentyl acetate, ethyl propionate, propyl propionate, and isopropyl propionate; alkyl esters of hydroxy acids such as methyl lactate, ethyl lactate, and butyl lactate; alkyl esters of keto acids such as methyl acetoacetate and ethyl acetoacetate; lactones such as γ-butyrolactone and α-acetyl-γ-butyrolactone; and aromatic esters such as methyl benzoate and ethyl benzoate. Lactones are preferred as ester-based organic solvents. Furthermore, the number of carbon atoms in ester-based organic solvents is preferably 3 to 9.

[0331] Ether-based organic solvents are organic solvents with ether structures that do not belong to the glycol ether system or the glycol ether ester system. Examples include: aliphatic acyclic ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; aliphatic cyclic ethers such as tetrahydrofuran, 1,4-dioxane, and 1,3-dioxolane; and aromatic ethers such as anisole and phenethyl ether. The preferred number of carbon atoms in ether-based organic solvents is 2 to 9.

[0332] Alcohol-based organic solvents are organic solvents with an alcohol structure that do not belong to the diol-based or diol ether-based organic solvents. Examples include: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, sec-pentanol, tert-pentanol, neopentanol, n-hexanol, n-heptanol, isoheptanol, n-octanol, 2-ethylhexanol, and other aliphatic noncyclic alcohols; cyclohexanol and other aliphatic cyclic alcohols; and benzyl alcohol, phenethyl alcohol, and other aromatic alcohols.

[0333] Examples of aliphatic hydrocarbon organic solvents include: n-pentane, n-hexane, 2-methylpentane (also known as isohexane), n-heptane, n-octane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, and decahydronaphthalene. The preferred number of carbon atoms in aliphatic hydrocarbon organic solvents is 5 to 10.

[0334] Examples of aromatic organic solvents include: benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, etc. 6-8 Aromatic hydrocarbons; C9 aromatic hydrocarbons including 1,2,3-trimethylbenzene, 1,3,5-trimethylbenzene (also known as mesitylene), 1,2,4-trimethylbenzene, 4-ethyltoluene, 3-ethyltoluene, 2-ethyltoluene, etc.; C9 aromatic hydrocarbons including 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 3-ethyl-o-xylene, 4-ethyl-o-xylene, 2-ethyl-p-xylene, 1,2,3,5-tetramethylbenzene, tetrahydronaphthalene, etc. 10 Aromatic hydrocarbons; aromatic heterocyclic compounds such as pyridine, furan, and thiophene, preferably toluene. The aromatic organic solvent preferably has 6 to 10 carbon atoms.

[0335] Examples of amide-based organic solvents include: aliphatic acyclic amides such as N,N-dimethylacetamide and N,N-dimethylformamide; lactams such as N-methyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone; and phosphoramides such as hexamethylphosphoramide. The preferred number of carbon atoms in amide-based organic solvents is 2 to 10.

[0336] Examples of urea-based organic solvents include tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0337] Examples of nitrile organic solvents include acetonitrile, propionitrile, and benzonitrile. The preferred number of carbon atoms in nitrile organic solvents is 2 to 10.

[0338] Examples of sulfur-based organic solvents include dimethyl sulfoxide.

[0339] Examples of halogenated organic solvents include chloroform, dichloromethane, carbon tetrachloride, and 1,2-dichloroethane. The preferred number of carbon atoms in halogenated organic solvents is 1 to 10.

[0340] The organic solvent used in (H) is preferably γ-butyrolactone, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, propylene glycol, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or toluene; more preferably methyl ethyl ketone (MEK), cyclohexanone, diethylene glycol monoethyl ether acetate, γ-butyrolactone, propylene glycol monomethyl ether, or toluene; even more preferably methyl ethyl ketone (MEK), cyclohexanone, propylene glycol monomethyl ether, or toluene; and particularly preferably methyl ethyl ketone (MEK), cyclohexanone, or toluene.

[0341] When all components in the resin composition are set at 100% by mass, the content of (H) organic solvent in the resin composition is 0% by mass or more. From the viewpoint of obtaining a varnish with appropriate viscosity, this can be 1% by mass or more, 3% by mass or more, 5% by mass or more, 8% by mass or more, 10% by mass or more, 12% by mass or more, 15% by mass or more, 18% by mass or more, 20% by mass or more, etc. The upper limit can be 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, etc.

[0342] <(I) Other Additives> Without prejudice to the purpose of the invention, the resin composition of the present invention may further contain (I) other additives as optional components. Examples of such additives include: epoxy resin curing agents other than components (B) and (B') of phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents; free radical polymerizable resins such as (meth)acrylic resins and styrene resins; free radical polymerization initiators such as peroxide-based free radical polymerization initiators and azo-based free radical polymerization initiators; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as organosilicon-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; and defoamers such as organosilicon-based defoamers, acrylic defoamers, fluorine-based defoamers, and vinyl resin-based defoamers. Defoamers; ultraviolet absorbers such as benzotriazole-based UV absorbers; adhesive enhancers such as ureasilanes; adhesive enhancers such as triazole-based, tetraazole-based, and triazine-based adhesive enhancers; antioxidants such as hindered phenolic antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based and organosilicon-based surfactants; flame retardants such as phosphorus-based (e.g., phosphate ester compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based (e.g., melamine sulfate), halogen-based, and inorganic-based (e.g., antimony trioxide); dispersants such as phosphate ester-based, polyoxyethylene-based, acetylene-based, organosilicon-based, anionic, and cationic dispersants; stabilizers such as borate ester-based, titanate ester-based, aluminate ester-based, zirconate ester-based, isocyanate-based, carboxylic acid-based, and carboxylic anhydride-based stabilizers. The content of the additive can be determined according to the required properties of the resin composition. Furthermore, the components (A) to (H) above may also function as epoxy resin curing agents, free radical polymerizing resins, free radical polymerization initiators, organometallic compounds, colorants, polymerization inhibitors, leveling agents, thickeners, defoamers, ultraviolet absorbers, adhesion enhancers, bonding agents, antioxidants, fluorescent whitening agents, surfactants, flame retardants, dispersants, and stabilizers. In this case, the component is not component (I), but is considered as each component of (A) to (H).

[0343] <Method for manufacturing resin composition> The resin composition of the present invention can be prepared by appropriately mixing the required components in components (A) to (I) above, and by mixing or blending as needed using a mixing means such as a three-roll mill, ball mill, bead mill, sand mill, or by stirring means such as a super mixer, planetary mixer, or high-speed rotary mixer.

[0344] <Properties and Uses of Resin Compositions> In one embodiment, the cured resin composition of the present invention exhibits a low dielectric loss tangent (Df) even at high temperatures. For example, as described in the section "Experimental Example 1: Determination of Dielectric Loss Tangent Df" below, when the measurement was performed at a measurement frequency of 10 GHz and a measurement temperature of 90°C, the dielectric loss tangent (Df) of the cured resin composition of the present invention is preferably less than 0.0100, more preferably less than 0.0080 or less than 0.0060, further preferably less than 0.0050 or less than 0.0040, and particularly preferably less than 0.0035 or less than 0.0030. The lower limit is not particularly limited and can be 0.0001 or more, 0.0010 or more, etc.

[0345] In one embodiment, the cured resin composition of the present invention exhibits a low dielectric loss tangent (Df) at room temperature. For example, as described in the section "Experimental Example 1: Determination of Dielectric Loss Tangent Df" below, when the measurement is performed at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C, the dielectric loss tangent (Df) of the cured resin composition of the present invention is preferably less than 0.0100 or less than 0.0080, more preferably less than 0.0060 or less than 0.0050, further preferably less than 0.0040 or less than 0.0035, and particularly preferably less than 0.0030, less than 0.0028, or less than 0.0026. The lower limit is not particularly limited and can be 0.0001 or more, 0.0010 or more, etc.

[0346] In one embodiment, the cured resin composition of the present invention exhibits a high glass transition temperature. For example, as described in the section "Experimental Example 2: Determination of Glass Transition Temperature Tg" below, when measured using a thermomechanical analysis apparatus, the glass transition temperature of the cured resin composition of the present invention is preferably 130°C or higher, more preferably 135°C or higher or 140°C or higher, even more preferably 145°C or higher or 150°C or higher, and particularly preferably 155°C or higher or 160°C or higher. The upper limit is not particularly limited and can be 400°C or lower, 300°C or lower, etc.

[0347] In one embodiment, the cured resin composition of the present invention exhibits high puncture resistance. For example, as described in the section "Test Example 3: Stab Test" described later, the maximum point load when tested using a universal testing machine is preferably 0.5 N or more, 0.6 N or more, 0.7 N or more, 0.8 N or more, or 0.9 N or more, more preferably 1.0 N or more, further preferably 1.1 N or more, or 1.2 N or more, and particularly preferably 1.3 N or more. The upper limit is not particularly limited and can be 100 N or less, 50 N or less, 10 N or less, 5 N or less, etc.

[0348] In one embodiment, the resin composition of the present invention exhibits high film stability. For example, as described in the <Experimental Example 4: Evaluation of Film Stability> section below, the lowest melt viscosity (MV) of the resin composition layer immediately after the resin sheet was manufactured was measured. 0h The lowest melt viscosity (MV) of the resin composition layer after the resin sheet has been left to stand at 23°C for 72 hours. 72h In the case of ), it is preferable to satisfy 1.00≤MV 72h / MV 0h A relationship less than 1.80 is preferred, and more preferably, 1.00 ≤ MV is preferred. 72h / MV 0h The relationship is less than 1.50. This can be achieved by setting 1.00 ≤ MV. 72h / MV 0h This can reduce leakage during lamination on the circuit board and suppress uneven film thickness within the plane. By setting it to 1.80 > MV... 72h / MV 0h This can improve the embedding properties into the circuit board. Therefore, this range is preferred.

[0349] As described above, the resin composition of the present invention can produce a cured product that simultaneously achieves excellent dielectric properties (low dielectric loss tangent), excellent heat resistance (glass transition temperature), and excellent mechanical properties (puncture resistance). Therefore, the resin composition of the present invention is suitable for use as a resin composition for forming an insulating layer of a printed wiring board (resin composition for insulating layer of printed wiring board), and is more suitable for use 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 is also suitable for use in cases where the printed wiring board is a component-integrated circuit board. The resin composition of the present invention is also suitable for use as a resin composition for forming an insulating layer of a redistribution substrate for semiconductor packaging (resin composition for insulating layer of redistribution substrate). It should be noted that in the present invention, printed wiring boards or redistribution substrates are collectively referred to as "circuit boards," therefore, the resin composition of the present invention is suitable for use as an insulating layer for circuit boards.

[0350] The resin composition of the present invention can also be widely used in applications requiring resin compositions, such as resin sheets, prepregs and other sheet-like laminated materials, solder resists, underfill materials, chip bonding materials, hole-filling resins, sealing resins, and component embedding resins.

[0351] [Sheet-like laminated materials (resin sheets, prepregs)] The resin composition of the present invention can be used directly or in the form of a sheet-like laminate containing the resin composition.

[0352] As sheet-like laminated materials, resin sheets and prepregs as shown below are preferred.

[0353] In one embodiment, the resin sheet is characterized by comprising a support and a layer of resin composition disposed on the support (hereinafter referred to as "resin composition layer"), the resin composition layer being formed from the resin composition of the present invention.

[0354] The preferred thickness of the resin composition layer varies depending on the application and can be appropriately determined according to the application. For example, from the viewpoint of thinning printed wiring boards or semiconductor packages, 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. There is no particular limitation on the lower limit of the thickness of the resin composition layer, and it can usually be 1 μm or more, 5 μm or more, etc.

[0355] Examples of supports include thermoplastic resin films, metal foils, and release paper, with thermoplastic resin films and metal foils being preferred. Therefore, in a preferred embodiment, the support is a thermoplastic resin film or a metal foil.

[0356] When using a thermoplastic resin film as a support, examples of thermoplastic resins include: polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); acrylic resins such as polycarbonate (PC); polymethyl methacrylate (PMMA); cyclic polyolefins; triacetyl cellulose (TAC); polyether sulfide (PES); polyether ketone; and polyimide. Polyester resins are preferred, polyethylene terephthalate or polyethylene naphthalate are more preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0357] When using metal foil as a support, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. As copper foil, foil containing a single metal such as copper can be used, or foil containing an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0358] For the support body, the surface bonded to the resin composition layer can be treated with matte finish, corona treatment, or antistatic treatment. Furthermore, a support body with a release layer on the surface bonded to the resin composition layer can be used. Examples of release agents used in the release layer of the support body with a release layer include, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Commercially available release agents include, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation. Additionally, commercially available products can be used as supports with a release layer, such as PET films having a release layer with an alkyd resin-based or polyolefin resin-based release agent as the main component, such as "Purex" manufactured by Toyobo Corporation and "Unipeel" manufactured by Unitika Corporation.

[0359] 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. It should be noted that when using a support with a release layer, the overall thickness of the support with the release layer is preferably within the above-mentioned range.

[0360] When using a metal foil as a support, a metal foil with a peelable support substrate can be used, which is a thin metal foil bonded to a metal substrate. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer disposed on the support substrate, and a metal foil disposed on the release layer. When using a metal foil with a support substrate as a support, a resin composition layer is disposed on the metal foil.

[0361] In metal foils with a supporting substrate, the material of the supporting substrate is not particularly limited, and examples include copper foil, aluminum foil, stainless steel foil, titanium foil, and copper alloy foil. When copper foil is used as the supporting substrate, it can be electrolytic copper foil or rolled copper foil. Furthermore, for the release layer, there are no particular limitations as long as the metal foil can be peeled off from the supporting substrate; examples include alloy layers selected from elements such as Cr, Ni, Co, Fe, Mo, Ti, W, and P; and organic films.

[0362] In metal foils with a supporting substrate, the preferred material for the metal foil is, for example, copper foil or copper alloy foil.

[0363] 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. Alternatively, the thickness of the metal foil can be, for example, in the range of 0.1 μm to 10 μm.

[0364] In one embodiment, the resin sheet may further comprise any layer as needed. Examples of such arbitrary layers include, for instance, a protective film disposed on the side of the resin composition layer not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, and can be, for example, 1 μm to 75 μm, preferably 1 μm to 40 μm. By laminating the protective film, the adhesion of debris and other contaminants to the surface of the resin composition layer and the generation of damage can be suppressed.

[0365] Resin sheets can be manufactured, for example, by directly coating a liquid resin composition onto a support using a die-casting machine, or by preparing a resin varnish made by dissolving the resin composition in an organic solvent, coating the prepared resin varnish onto the support, and then drying it to form a resin composition layer.

[0366] As an organic solvent, examples can be made of the same organic solvents described as components of the resin composition. One organic solvent may be used alone, or two or more may be used in combination.

[0367] Drying can be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out such that the content of organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Drying conditions also vary depending on the boiling point of the organic solvent in the resin composition or resin varnish. For example, when using a resin composition or resin varnish containing 30% to 60% by mass of organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0368] Resin sheets can be stored in rolls. If the resin sheet has a protective film, it can be used by peeling off the protective film.

[0369] In one embodiment, the prepreg is formed by impregnating the resin composition of the present invention into a sheet fiber substrate.

[0370] There are no particular limitations on the sheet fiber substrate used for prepregs; materials commonly used as prepreg substrates, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning printed wiring boards or semiconductor packaging, the thickness of the sheet fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. There is no particular limitation on the lower limit of the thickness of the sheet fiber substrate; for example, it can be 10 μm or more.

[0371] Prepregs can be manufactured using known methods such as hot-melt methods and solvent methods.

[0372] The thickness of the prepreg can be the same range as the resin composition layer in the resin sheet described above.

[0373] The sheet-like laminate material of the present invention is suitable for use as an insulating layer in printed wiring boards (for insulating layers of printed wiring boards), and is more suitable for use as an interlayer insulating layer in printed wiring boards (for interlayer insulating layers of printed wiring boards). The sheet-like laminate material of the present invention is also suitable for use as an insulating layer in a redistribution substrate of a semiconductor package (for insulating layers of a redistribution substrate). That is, the sheet-like laminate material of the present invention is suitable for use as an insulating layer in a circuit board.

[0374] [Circuit board] Using the resin composition of the present invention, an insulating layer of a circuit board can be formed. The present invention also provides a circuit board comprising an insulating layer containing a cured product of the resin composition of the present invention.

[0375] Printed wiring boards In one embodiment, the circuit board of the present invention is a printed wiring board.

[0376] Printed wiring boards can be manufactured, for example, using the resin sheets described above, by a method comprising the following steps (I) and (II): (I) The process of laminating a resin sheet onto an inner substrate by bonding a resin composition layer of the resin sheet to the inner substrate. (II) The process of curing the resin composition layer (e.g., heat curing) to form an insulating layer.

[0377] The "inner layer substrate" used in step (I) is a component that becomes the substrate of a printed wiring board, and examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. Additionally, this substrate may optionally have a conductor layer on one or both sides, and this conductor layer may also be patterned. An inner layer substrate with a conductor layer (circuit) formed on one or both sides of the substrate is sometimes called an "inner layer circuit substrate." Furthermore, intermediate products for which an insulating layer and / or conductor layer are to be further formed during the manufacture of a printed wiring board are also included in the "inner layer substrate" as described in this invention. In cases where the printed wiring board is a component-integrated circuit board, an inner layer substrate with integrated components may also be used.

[0378] The lamination of the inner substrate and the resin sheet can be achieved, for example, by heating and pressing the resin sheet onto the inner substrate from the support side. Examples of components for heating and pressing the resin sheet onto the inner substrate (hereinafter also referred to as "heat-pressing components") include, for example, heated metal plates (SUS end plates, etc.) or metal rollers (SUS rollers). It should be noted that the heat-pressing components can be pressed directly onto the resin sheet, or they can be pressed using an elastic material such as heat-resistant rubber, so that the resin sheet fully conforms to the surface irregularities of the inner substrate.

[0379] The lamination of the inner substrate and the resin sheet can be performed by vacuum lamination. In vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C; the heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa; and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination can preferably be performed under reduced pressure conditions below 26.7 hPa.

[0380] Lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include: vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., vacuum dressing machines manufactured by Nikko-Materials Co., Ltd., and batch vacuum pressure laminators.

[0381] After lamination, the laminated resin sheets can be smoothed by pressing them under normal pressure (atmospheric pressure), for example, by pressing the heated pressing member from the support side. The pressing conditions for smoothing can be the same as the heating and pressing conditions for lamination described above. Smoothing can be performed using a commercially available laminator. It should be noted that lamination and smoothing can also be performed continuously using the aforementioned commercially available vacuum laminator.

[0382] The support can be removed between steps (I) and (II), or after step (II). It should be noted that when using a metal foil as the support, the conductor layer can be formed using the metal foil without peeling off the support. Alternatively, when using a metal foil with a support substrate as the support, the support substrate (and release layer) can be peeled off. Furthermore, the conductor layer can be formed using a metal foil.

[0383] In step (II), the resin composition layer is cured (e.g., heat-cured) to form an insulating layer comprising the cured resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions typically used when forming insulating layers for printed wiring boards can be used.

[0384] For example, the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, etc. In one embodiment, the curing temperature is preferably 140°C to 250°C, more preferably 150°C to 240°C, and even more preferably 180°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.

[0385] Before heat curing the resin composition layer, the resin composition layer can be preheated at a temperature lower than the curing temperature. For example, before heat curing the resin composition layer, the resin composition layer can 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.

[0386] In manufacturing a printed wiring board, steps (III) of opening holes in the insulating layer, (IV) of roughening the insulating layer, and (V) of forming a conductor layer can be further performed. These steps (III) to (V) can be performed according to various methods known to those skilled in the art in the manufacture of printed wiring boards. It should be noted that if the support is removed after step (II), the removal of the support can be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). In addition, as needed, the formation of the insulating layer and conductor layer in steps (I) to (V) can be repeated to form a multilayer wiring board.

[0387] In other embodiments, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is essentially the same as that used with resin sheets.

[0388] Process (III) is the process of creating openings in the insulating layer, thereby forming through holes, vias, and other holes in the insulating layer. Process (III) can be performed using, for example, a drill bit, a laser, or plasma, depending on the composition of the resin composition used in the formation of the insulating layer. The size and shape of the holes can be appropriately determined according to the design of the printed circuit board.

[0389] Step (IV) is a roughening process for the insulating layer. Typically, in step (IV), contamination removal (decontamination) is also performed. The steps and conditions for the roughening process are not particularly limited; known steps and conditions commonly used in forming the insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened sequentially by performing a swelling treatment using a swelling solution, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing solution.

[0390] The swelling solution used in the roughening treatment is not particularly limited, and examples include alkaline solutions and surfactant solutions, with alkaline solutions being preferred, and sodium hydroxide solutions and potassium hydroxide solutions being more preferred. Commercially available swelling solutions include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Ammet Japan Co., Ltd. The swelling treatment using the swelling solution is not particularly limited; for example, it can be performed by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of controlling the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0391] The oxidant used in the roughening treatment is not particularly limited, and examples include, for instance, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. For roughening treatment using an oxidant such as an alkaline permanganate solution, it is preferable to immerse the insulating layer in an oxidant solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Commercially available oxidants include, for example, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Ammet Japan Co., Ltd.

[0392] Furthermore, an acidic aqueous solution is preferred as the neutralizing liquid used in the roughening process. Commercially available examples include, for instance, "Reduction Solution Securiganth P" manufactured by Ammet Japan Co., Ltd.

[0393] The treatment using the neutralizing solution can be performed by immersing the roughened surface treated with an oxidant in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From an operational perspective, it is preferable to immerse the roughened surface treated with an oxidant in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0394] Step (V) is the step of forming a conductor layer, which is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer can be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above-mentioned metals (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). From the viewpoints of versatility, cost, and ease of patterning in conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium, copper-nickel, or copper-titanium alloys, is preferred. More preferably, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloys, is even more preferred. A single metal layer of copper is even more preferred.

[0395] The conductor layer can be a single-layer structure or a multi-layer structure obtained by stacking two or more single-metal layers or alloy layers containing different types of metals or alloys. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0396] The thickness of the conductor layer depends on the desired printed wiring board design, but is generally 3μm to 35μm, preferably 5μm to 30μm.

[0397] In one embodiment, the conductor layer can be formed by plating. From the viewpoint of facilitating the formation of fine wiring, it is preferable to form it using a semi-additive method. An example of forming the conductor layer using a semi-additive method is shown below.

[0398] First, a seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed seed layer, corresponding to the desired wiring pattern, exposing a portion of the seed layer. After forming a metal layer on the exposed seed layer using electrolytic plating, the mask pattern is removed. Then, the unwanted seed layer is removed using etching or the like, forming a conductor layer with the desired wiring pattern.

[0399] In other embodiments, the conductor layer can be formed using metal foil. When using metal foil to form the conductor layer, step (V) is preferably performed between steps (I) and (II). For example, after step (I), the support is removed, and metal foil is laminated onto the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be performed using vacuum lamination. The lamination conditions can be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer with the desired wiring pattern can be formed using existing known techniques such as a modified semi-additive method.

[0400] Metal foils can be manufactured using known methods such as electrolysis and rolling. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Minerals & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Metals Corporation.

[0401] Alternatively, as described above, when using a metal foil or a metal foil with a supporting substrate, the metal foil can be used to form a conductor layer as a support for the resin sheet.

[0402] <Rewiring substrate for semiconductor packaging> In one embodiment, the circuit board of the present invention is a redistribution substrate (redistribution layer) for semiconductor packaging. Hereinafter, a method for manufacturing a semiconductor package will be described.

[0403] A semiconductor package, serving as an insulating layer for a redistribution substrate, comprises an insulating layer containing a cured resin composition of the present invention. It should be noted that the semiconductor package may also comprise a sealing layer containing a cured resin composition of the present invention.

[0404] Semiconductor packages can be manufactured, for example, using the resin composition and resin sheet of the present invention, by a method comprising the steps (1) to (6) described below. The resin composition and resin sheet of the present invention can be used to form the redistribution layer (an insulating layer for forming the redistribution substrate) of step (5) or the sealing layer of step (3). An example of forming the redistribution layer or sealing layer using the resin composition or resin sheet is shown below, but the techniques for forming the redistribution layer or sealing layer of a semiconductor package are well known. Those skilled in the art can use the resin composition or resin sheet of the present invention to manufacture a semiconductor package according to known techniques. (1) The process of laminating a temporary fixing film on a substrate. (2) The process of temporarily fixing the semiconductor chip onto the temporary fixing film. (3) The process of forming a sealing layer on a semiconductor chip. (4) The process of peeling the substrate and temporary fixing film from the semiconductor chip. (5) The process of forming a rewiring layer as an insulating layer on the surface of a semiconductor chip where the substrate and temporary fixing film have been stripped, and (6) The process of forming a redistribution layer as a conductor layer on the redistribution forming layer.

[0405] <<Process (1)>> There are no particular limitations on the materials used for the substrate. Examples of substrates include: semiconductor wafers such as silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates obtained by permeating glass fibers with epoxy resin or the like and then performing a thermosetting process (e.g., FR-4 substrates); substrates containing bismaleimide triazine resin (BT resin); and so on.

[0406] For temporary fixing films, there are no particular limitations on the material, as long as they can be peeled off from the semiconductor chip in process (4) and temporarily fixed at the same time. Commercially available products can be used for temporary fixing films. Examples of commercially available products include REVALPHA manufactured by Nitto Denko Corporation.

[0407] <<Process (2)>> Temporary fixation of semiconductor chips can be performed using known devices such as flip chip bonders and die bonders. The layout and number of semiconductor chips can be appropriately set according to the shape and size of the temporary fixation film, the production quantity of the target semiconductor package, etc. For example, they can be arranged in a matrix with multiple rows and columns for temporary fixation.

[0408] <<Process (3)>> The resin composition of the resin sheet of the present invention is laminated onto a semiconductor chip, or the resin composition of the present invention is coated onto a semiconductor chip and cured (e.g., thermosetting) to form a sealing layer.

[0409] For example, the stacking of a semiconductor chip and a resin sheet can be performed by heating and pressing the resin sheet onto the semiconductor chip from the support side after removing the protective film from the resin sheet. Examples of components for heating and pressing the resin sheet onto the semiconductor chip (hereinafter also referred to as "heat-pressing components") include, for example, heated metal plates (SUS end plates, etc.) or metal rollers (SUS rollers). It should be noted that, preferably, the heat-pressing component is not directly pressed onto the resin sheet, but rather pressed using an elastic material such as heat-resistant rubber, so that the resin sheet fully conforms to the surface irregularities of the semiconductor chip. The stacking of the semiconductor chip and the resin sheet can be performed by vacuum lamination, with the same lamination conditions as described in the method for manufacturing printed wiring boards, and the preferred range is also the same.

[0410] After lamination, the resin composition is thermo-cured to form a sealing layer. The thermo-curing conditions are the same as those described in the method for manufacturing printed wiring boards.

[0411] The support for the resin sheet can be peeled off after the resin sheet is laminated onto the semiconductor chip and thermo-cured, or it can be peeled off before the resin sheet is laminated onto the semiconductor chip.

[0412] When the resin composition of the present invention is coated to form a sealing layer, the coating conditions are the same as those described for forming a resin composition layer with respect to the resin sheet of the present invention, and the preferred range is also the same.

[0413] <<Process (4)>> The method for peeling the substrate and the temporary fixing film can be appropriately changed depending on the material of the temporary fixing film. Examples include: heating the temporary fixing film to make it foam (or expand) for peeling; and irradiating the substrate side with ultraviolet light to reduce the adhesion of the temporary fixing film for peeling.

[0414] In methods involving heating the temporary fixing film to cause it to foam (or expand) for peeling, the heating conditions are typically 100–250°C for 1–90 seconds or 5–15 minutes. Alternatively, in methods involving irradiating the temporary fixing film with ultraviolet light from the substrate side to reduce its adhesion and thus peeling, the ultraviolet irradiation dose is typically 10 mJ / cm². 2 ~1000mJ / cm 2 .

[0415] <<Process (5)>> The resin composition and resin sheet of the present invention are used to form a redistribution layer (an insulating layer of a redistribution substrate).

[0416] After the redistribution layer is formed, vias can be formed in the redistribution layer to enable interlayer interconnection between the semiconductor chip and the conductor layer described later. The vias can be formed using known methods, depending on the material of the redistribution layer.

[0417] <<Process (6)>> The formation of the conductor layer on the redistribution layer can be performed in the same manner as step (V) described in the method for manufacturing printed wiring boards. It should be noted that steps (5) and (6) can be performed repeatedly, alternately stacking (laminating) the conductor layer (rewiring layer) and the redistribution layer (insulating layer).

[0418] In the manufacture of semiconductor packages, the following steps may be further performed: (7) forming a solder mask layer on the conductor layer (rewiring layer), (8) forming bumps, and (9) dicing multiple semiconductor packages into individual semiconductor packages for monolithic assembly. These steps may be performed in accordance with various methods known to those skilled in the art in the manufacture of semiconductor packages.

[0419] By using the resin composition and resin sheet of the present invention, which produce a cured product with low dielectric loss tangent and simultaneously exhibit excellent contamination removal and high heat resistance (glass transition temperature), a redistribution layer (insulating layer) is formed, thereby enabling semiconductor packages, whether fan-in or fan-out, to achieve minimal transmission loss without concern for cracking or circuit deformation. In one embodiment, the semiconductor package of the present invention is a fan-out package. The resin composition and resin sheet of the present invention are applicable to both fan-out panel-level packages (FOPLP) and fan-out wafer-level packages (FOWLP). In one embodiment, the semiconductor package of the present invention is either a fan-out panel-level package (FOPLP) or a fan-out wafer-level package (FOWLP).

[0420] [Semiconductor Devices] The semiconductor device of the present invention comprises an insulating layer of a cured product containing the resin composition of the present invention. That is, the semiconductor device of the present invention comprises the circuit board of the present invention. The semiconductor device of the present invention can be manufactured using the circuit board of the present invention.

[0421] Examples of semiconductor devices include various semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trams, ships, and airplanes). Example

[0422] The present invention will be specifically described below with reference to embodiments. However, the present invention is not limited to these embodiments. In the following description, the terms "parts" and "%" to indicate quantities refer to "parts by mass" and "% by mass," respectively, unless otherwise specified. In addition, the temperature and pressure conditions, unless otherwise specified, are room temperature (23°C) and atmospheric pressure (1 atm).

[0423] <Synthetic Example 1: Synthesis of Active Ester Compound 1> In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 320 g (2.0 mol) of 2,7-dihydroxynaphthalene, 184 g (1.7 mol) of benzyl alcohol, and 5.0 g of p-toluenesulfonic acid monohydrate were added. The mixture was stirred while being purged with nitrogen at room temperature. Then, the temperature was raised to 150 °C, and the generated water was distilled off while stirring for 4 hours. After the reaction was complete, 900 g of methyl isobutyl ketone and 5.4 g of 20% sodium hydroxide aqueous solution were added for neutralization. The aqueous layer was then removed by separation, and the organic layer was washed three times with 280 g of water. The methyl isobutyl ketone was removed from the resulting organic layer under reduced pressure to obtain 460 g of benzyl-modified naphthalene compound (B-1'). The obtained benzyl-modified naphthalene compound (B-1') was a black solid with a hydroxyl equivalent of 180 g / eq.

[0424] In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 203.0 g of isophthaloyl chloride (2.0 mol of acyl chloride group) and 1400 g of toluene were added. The system was purged with nitrogen under reduced pressure and dissolved. Next, 113.9 g (0.67 mol) of o-phenylphenol and 240 g of benzyl-modified naphthalene compound (B-1') (1.33 mol of phenolic hydroxyl group) were added, and the system was purged with nitrogen under reduced pressure and dissolved. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen, the system was kept below 60°C. 400 g of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. The mixture was then stirred for another 1 hour under these conditions. After the reaction was complete, the mixture was allowed to stand and separated to remove the aqueous layer. Water was then added to the toluene layer containing the dissolved product, and the mixture was stirred for 15 minutes. The mixture was then allowed to stand and separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, water was removed from the toluene layer by decanting to obtain active ester compound 1 in a toluene solution containing 62% by mass of non-volatile components. The active ester equivalent of the obtained active ester compound 1 was 238 g / eq. (where n≥0, m≥0).

[0425] [Chemical Formula 39] Active ester compound 1 .

[0426] <Synthetic Example 2: Synthesis of Active Ester Compound 2> [Chemical Formula 40] .

[0427] In a four-necked round flask equipped with a stirrer, thermometer, and condenser, 69.12 g (0.48 mol, reagent) of 2-naphthol, 400 g of toluene, and 3.92 g (0.05 mol, reagent) of 49% sodium hydroxide aqueous solution were added, and the mixture was heated to 50 °C to dissolve the naphthol. While maintaining the temperature at 50 °C, 19.46 g (0.24 mol, reagent) of 37% formaldehyde aqueous solution was added dropwise over 30 minutes, and the reaction was maintained at 80 °C for 2 hours. After neutralization with an appropriate amount of hydrochloric acid, the mixture was heated and the toluene and water were distilled off until no more water was distilled off. Then, azeotropic dehydration was performed to completely remove the water. The product was then used directly in liquid form for the condensation reaction without purification or drying. That is, in this product, with a composition ratio of n=1.0 and active ester equivalent of 212 g / eq. in the theoretical structure shown in formula (1a) above, 97.44 g (0.48 mol, reagent) of isophthaloyl chloride, 69.12 g (0.48 mol, reagent) of 1-naphthol, 2.39 g (reagent) of tetrabutylammonium bromide, and 100 g (reagent) of toluene were added and stirred while blowing nitrogen gas until completely dissolved. 156.7 g (0.98 mol) of a 25% sodium hydroxide aqueous solution was added dropwise over 2 hours at 30°C while maintaining heat, gradually increasing the temperature to 60°C. Then, after stirring at 60°C for another 2 hours, 100 g of distilled water was added and the mixture was allowed to stand and separate, discarding the lower brine layer. Then, an equal volume of distilled water was added to the organic layer, and after two water washes for purification, the mixture was heated and subjected to azeotropic dehydration. After the obtained solution was precisely filtered to remove impurities, toluene was distilled under reduced pressure at a maximum temperature of 200℃ to obtain 185g of solid.

[0428] After measuring the mass spectrum of the obtained solid, peaks were detected corresponding to m / z = 849 for the proton adduct with n = 1 and m / z = 1279 for the proton adduct with n = 2. Furthermore, based on GPC and IR analysis results, the obtained solid was confirmed to possess the target molecular structure, namely, the structure of the active ester compound containing the bis-naphthol skeleton involved in the theoretical structure shown in formula (1a) above (where the average value of n is > 0). The obtained active ester compound is referred to as "active ester compound 2". The obtained active ester compound 2 was dissolved in a toluene:cyclohexanone = 1:1 mixed solvent to prepare a solution with 50% by mass of non-volatile components, which was used in the manufacture of the resin composition described later.

[0429] (Mass spectrometry determination conditions) Dilute the sample to 1 mg / mL with THF and determine the LC / MS under the following conditions: HPLC: ACQUITY UPLC (manufactured by Waters Corporation, Japan) MS: SQ Detector2 (manufactured by Waters Corporation, Japan) Column: ACQUITY UPLC BEH C8 1.7μm, 2.1mm × 50mm (manufactured by Waters Corporation, Japan) Mobile phase A: 2 mmol / L ammonium acetate aqueous solution Mobile phase B: 2-propanol / THF (80:20) Mobile phase mixing time and mixing ratio (A%): 0 minutes (50%) → 5 minutes (5%) → 12 minutes (5%) → 12.1 minutes (50%) → 14 minutes (50%) Flow rate: 0.25 mL / min Analysis time: 14 minutes Column temperature: 40℃ Ion mode: ESI (electrospray ionization) positive or negative Ion polarity: Positive detection mode or Negative detection mode Desolventizing gas flow rate: 700 L / hr, 250 °C Cone gas: 70L / hr Ion source heater: 150℃.

[0430] (GPC measurement conditions) Measuring device: Tosoh Corporation "HLC-8420GPC" Columns: Tosoh Corporation "HXL-L" protective column + Tosoh Corporation "TSK-GEL SuperHZ2000" + Tosoh Corporation "TSK-GEL SuperHZ2000" + Tosoh Corporation "TSK-GEL SuperHZ3000" + Tosoh Corporation "TSK-GEL SuperHZ4000" Detector: RI (Differential Refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Column temperature: 40℃ Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL / min Standard: According to the above-mentioned "GPC Workstation EcoSEC-WorkStation" test manual, use the following monodisperse polystyrene with a known molecular weight. TSKgel F-10, F-4, F-1, A-5000, A-1000, A-500 (manufactured by Tosoh Corporation) Sample: 10 μL of a tetrahydrofuran solution obtained by filtering it through a microfilter, with the resin solids content calculated as 0.2% by mass.

[0431] (IR measurement conditions) Measuring device: JASCO Corporation "FT / IR-4600".

[0432] <Synthesis Example 3: Synthesis of Active Ester Compound 3> [Chemical Formula 41] .

[0433] In a four-necked round flask equipped with a stirrer, thermometer, and condenser, 68.72 g (0.24 mol) of 1,1'-bi-2-naphthol, 97.44 g (0.48 mol, reagent) of isophthaloyl chloride, 81.60 g (0.48 mol, reagent) of 2-phenylphenol, 2.39 g (reagent) of tetrabutylammonium bromide, and 350 g (reagent) of toluene were added while blowing nitrogen gas and stirring until completely dissolved. 156.7 g (0.98 mol) of a 25% sodium hydroxide aqueous solution was added dropwise over 2 hours at 30°C, gradually increasing the temperature to 60°C while maintaining heat generation. Then, after stirring for another 2 hours at 60°C, 100 g of distilled water was added, and the mixture was allowed to stand and separate, discarding the lower brine layer. Then, an equal amount of distilled water was added to the organic layer, and the mixture was washed twice for purification. The solution was then heated and subjected to azeotropic dehydration. After precise filtration to remove impurities, toluene was distilled under reduced pressure at a maximum temperature of 200°C to obtain 180g of solid.

[0434] After measuring the mass spectrum of the obtained solid, peaks were detected at m / z = 835 for the proton adduct with n = 1 and m / z = 1251 for the proton adduct with n = 2. Furthermore, based on GPC and IR analyses, the obtained solid was confirmed to possess the target molecular structure, namely, the structure of the active ester compound containing the binaphthol skeleton involved in the theoretical structure shown in formula (c1a) above (where the average value of n is > 0). The obtained active ester compound is designated as "active ester compound 3". Active ester compound 3 was dissolved in toluene to prepare a solution with 62% by mass of non-volatile components, which was used in the manufacture of the resin composition described later.

[0435] <Synthetic Example 4: Synthesis of Active Ester Compound 4> [Chemical Formula 42] .

[0436] In a four-necked round flask equipped with a stirrer, thermometer, and condenser, 68.72 g (0.24 mol) of 1,1'-bi-2-naphthol, 73.08 g (0.36 mol, reagent) of isophthaloyl chloride, 40.8 g (0.24 mol, reagent) of 2-phenylphenol, 2.39 g (reagent) of tetrabutylammonium bromide, and 350 g (reagent) of toluene were added while blowing nitrogen gas and stirring until completely dissolved. 156.7 g (0.98 mol) of a 25% sodium hydroxide aqueous solution was added dropwise over 2 hours at 30°C, gradually increasing the temperature to 60°C until it reached 60°C. Then, after stirring for another 2 hours at 60°C, 100 g of distilled water was added, and the mixture was allowed to stand and separate, discarding the lower brine layer. Then, an equal amount of distilled water was added to the organic layer, and the mixture was washed twice for purification. The solution was then heated and subjected to azeotropic dehydration. After precise filtration to remove impurities, toluene was distilled under reduced pressure at a maximum temperature of 200°C to obtain 180g of solid.

[0437] After measuring the mass spectrum of the obtained solid, peaks were detected at m / z = 835 for the proton adduct with n = 1 and m / z = 1251 for the proton adduct with n = 2. Furthermore, based on GPC and IR analyses, the obtained solid was confirmed to possess the target molecular structure, namely, the structure of the active ester compound containing the binaphthol skeleton involved in the theoretical structure shown in formula (c1a) above (where the average value of n is > 0). The obtained active ester compound was designated "active ester compound 4". Active ester compound 4 was dissolved in toluene to prepare a solution with 62% by mass of non-volatile components, which was used in the manufacture of the resin composition described later.

[0438] <Synthetic Example 5: Synthesis of Active Ester Compound 5> [Chemical Formula 43] .

[0439] In the synthesis step (2-2) of active ester compound 2, 81.60 g (0.48 mol, reagent) of 2-phenylphenol was used instead of 69.12 g (0.48 mol, reagent) of 1-naphthol. Otherwise, the procedure was the same as in synthesis example 2, and 195 g of solid was obtained.

[0440] After measuring the mass spectrum of the obtained solid, peaks were detected at m / z = 902 for the proton adduct with n = 1 and m / z = 1331 for the proton adduct with n = 2. Furthermore, based on GPC and IR analysis results, the obtained solid was confirmed to possess the target molecular structure, namely, the structure of the active ester compound containing the bis-naphthol skeleton involved in the theoretical structure shown in formula (2a) above (where the average value of n is > 0). The obtained active ester compound was designated "active ester compound 5". Active ester compound 5 was dissolved in toluene to prepare a solution with 62% by mass of non-volatile components, which was used in the manufacture of the resin composition described later.

[0441] <Synthesis Example 6: Synthesis of Liquid Epoxy Resin 1> 100g of 2,2-bis(4-hydroxy-3-methylphenyl)propane was dissolved in 1050g of epichlorohydrin, and 0.25g of benzyltriethylammonium chloride was added. 90g of a 48% sodium hydroxide aqueous solution was added dropwise over 5 hours at 70°C under reduced pressure. The generated water was removed from the system by azeotropic mixing with the epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the addition was complete, the reaction was continued at 70°C for 2 hours. The generated salt was then removed by filtration, followed by washing with water and distillation to remove the epichlorohydrin. The resulting epoxy resin was dissolved in 400g of methyl isobutyl ketone, and 10g of a 10% sodium hydroxide aqueous solution was added at 85°C and the reaction was allowed to proceed for 2 hours. After the reaction was complete, the methyl isobutyl ketone was removed by filtration, washing with water, and distillation to obtain 129g of a single-yellow liquid, "Liquid Epoxy Resin 1". The liquid epoxy resin 1 has the structure shown in formula (A) (where n is 0 to 5), and its epoxy equivalent is 193 g / eq. Furthermore, the viscosity (25°C) of the liquid epoxy resin 1 is 43,870 mPa·s.

[0442] [Chemical Formula 44] .

[0443] <Synthesis Example 7: Synthesis of Maleimide Resin 1> A MEK solution (62% by mass) of maleimide resin 1 (Mw / Mn = 1.81, t'' = 1.47 (mainly 1, 2 or 3)) synthesized using the method described in Synthesis Example 1 of Japan Invention Patent Publication No. 2020-500211 was prepared. This maleimide resin 1 has the structure shown in the following formula (C1).

[0444] [Chemical Formula 45] .

[0445] <Synthesis Example 8: Synthesis of Maleimide Resin 2> (I) Synthesis of intermediate amine compound C' In a flask equipped with a thermometer, cooling tubes, a Dean-Stark trap, and a stirrer, 400 g (3.3 mol) of 2-ethylaniline, 127 g of a compound with a benzyl ether skeleton ("NIKANOLL" from Fudow), 193 g of toluene, and 53 g of activated clay were added. The mixture was heated to 120 °C while stirring and held at this temperature for 30 minutes. The temperature was then increased to 150 °C and held at this temperature for 3 hours. Next, the temperature was increased to 200 °C over 30 minutes and held for 10 hours. The mixture was then diluted with 193 g of toluene, and the activated clay was separated by filtration. The solvent and excess 2-ethylaniline were removed from the filtrate by distillation under reduced pressure to obtain the intermediate amine compound C' (amine equivalent 209 g / eq.).

[0446] (II) Synthesis of maleimide resin 2 (maleimidization) In a 2L flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer, 127.5 g (1.3 equivalents) of maleic anhydride and 461 g of toluene were added and stirred at room temperature. Then, a mixed solution of 209 g (1 equivalent) of intermediate amine compound C' and 57.7 g of N,N-dimethylformamide was added dropwise over 1 hour, and the reaction was allowed to proceed for 2 hours. 9.72 g of p-toluenesulfonic acid monohydrate was added to the reaction solution. The reaction solution was heated to 115°C, and the azeotropic water and toluene, which were under reflux, were cooled and separated. Only the toluene was returned to the system for a dehydration reaction over 5 hours. After the reaction solution was cooled to room temperature under air, it was concentrated under reduced pressure, and the resulting brown solution was dissolved in 600 g of ethyl acetate. The solution was washed three times with 200 g of deionized water and three times with 150 g of 2% sodium bicarbonate aqueous solution. Next, after adding sodium sulfate and drying, the product obtained by vacuum concentration was dried at 80°C for 4 hours to obtain maleimide resin 2. Maleimide resin 2 contains the maleimide compound shown in formula (C2) as its main component. In formula (C2), n represents an integer greater than or equal to 1. 1 Each of the following independently represents the number of repeating units, and Et represents ethyl. The resulting maleimide resin 2 is dissolved in MEK (methyl ethyl ketone) to prepare a solution with 62% by mass of non-volatile components, which is used in the manufacture of the resin composition described later.

[0447] [Chemical Formula 46] .

[0448] <Examples 1-9 and Comparative Examples 1-5: Preparation of Resin Compositions and Fabrication of Resin Sheets> (1) Preparation of resin composition Weigh each component according to the mass parts listed in Table 1 below, then mix 20 parts by mass of methyl ethyl ketone, and disperse evenly using a high-speed rotary mixer to obtain a varnish-like resin composition.

[0449] [Table 1-1] [Table 1-2] .

[0450] In addition, the details of each component recorded in Table 1 are as follows: (A) Epoxy resin • "NC-3000L": Biphenyl-type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 270g / eq. • "HP-4032SS": A naphthalene-type epoxy resin that is liquid at 20°C, manufactured by DIC Corporation, with an epoxy equivalent of 144 g / eq.

[0451] (B') Active ester compounds other than component (B) • "HPC-8000L-65MT": An active ester resin containing a dicyclopentadiene-type diphenol structure, manufactured by DIC Corporation, with an active ester equivalent of 223 g / eq.

[0452] (D) Inorganic filler materials • "SO-C2": Spherical silica (manufactured by Yaduma Corporation, "SO-C2", average particle size 0.5μm, specific surface area 5.8m²). 2 / g) The material obtained by surface treatment with an amino-based silane coupling agent (Shin-Etsu Chemical Industry Co., Ltd. "KBM-573", N-phenyl-3-aminopropyltrimethoxysilane).

[0453] (E) Organic filler materials • “EXL-2655”: Core-shell type rubber particles, manufactured by Dow Chemical Company, “PARALOID EXL-2655”.

[0454] (F) Thermoplastic resin YX7553BH30: A mixed solution of phenoxy resin, 30% non-volatile MEK and cyclohexanone, manufactured by Mitsubishi Chemical Corporation.

[0455] (G) Curing Accelerator • "1B2PZ": Imidazole-based curing accelerator (1-benzyl-2-phenylimidazole), manufactured by Shikoku Chemical Industry Co., Ltd.

[0456] (H) Organic solvents • "MEK": Methyl ethyl ketone.

[0457] (2) Fabrication of resin sheet A As a support, a polyethylene terephthalate film (thickness 38 μm) that had been released with an alkyd resin-based release agent (Lintec "AL-5") was prepared.

[0458] The resin composition obtained in (1) above is uniformly coated onto the release layer of the support so that the thickness of the dried resin composition layer is 40 μm. Then, the resin composition is dried at 80°C to 100°C (average 90°C) for 3 minutes to obtain a resin sheet A with a resin composition layer / support layer structure having a thickness of 40 μm.

[0459] <Experimental Example 1: Determination of the dielectric loss tangent Df> Resin sheet A was heated in an oven at 190°C for 90 minutes to cure the resin composition layer. Then, the support was peeled off to obtain the cured resin composition layer A.

[0460] The cured material A was cut into pieces with a length of 30 mm and a width of 40 mm to obtain sample A1. For sample A1, the dielectric loss tangent Df was measured using a measuring apparatus (Agilent Technologies HP8362B) at a measurement frequency of 10 GHz and a measurement temperature of 90 °C via the split-cylinder method. Measurements were performed on two samples, and the average value was calculated and evaluated according to the following criteria: (Evaluation criteria for dielectric loss tangent Df at a measurement frequency of 10 GHz and a measurement temperature of 90 °C) “○”: The dielectric loss tangent is less than 0.0030°. "×": The dielectric loss tangent is above 0.0030°.

[0461] In addition, the cured material A was cut into pieces 2 mm wide and 80 mm long to serve as test pieces for measuring the dielectric loss tangent Df. For these test pieces, an Agilent Technologies HP8362B was used, and the dielectric loss tangent Df was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C using the resonant cavity perturbation method. Measurements were performed on three test pieces, and the average value was calculated.

[0462] <Experimental Example 2: Determination of Glass Transition Temperature Tg> Cured material A was cut into pieces with a length of 20 mm and a width of 6 mm to obtain specimen A2. Specimen A2 was subjected to thermomechanical analysis using a thermomechanical analysis apparatus (Rigaku Thermo Plus TMA8310) employing the tensile loading method. Specifically, specimen A2 was mounted on the aforementioned thermomechanical analysis apparatus, and two consecutive thermomechanical analyses were performed under the following conditions: a load of 1 g, a heating rate of 5 °C / min, and a temperature range from 25 °C to 220 °C. The glass transition temperature (Tg; °C) was then calculated in the second measurement and evaluated according to the following criteria: “○”: Tg is above 150℃ "×": Tg is less than 150℃.

[0463] <Experimental Example 3: Stab Test> The cured material A obtained in Test Example 1 was cut into test pieces with a side length of approximately 30 mm, and its puncture resistance was tested using a universal testing machine (manufactured by AND Corporation, "Tensiron RTC1250A"). After the test piece was installed in the above-mentioned device, a needle with a load of 50 N and a diameter of 1 mm was brought into contact with the test piece at a speed of 50 mm / min, and the maximum point load at the point of fracture was measured.

[0464] <Experimental Example 4: Evaluation of Membrane Stability> The resin sheet A obtained from the examples and comparative examples was obtained by peeling off only the resin composition layer and compressing it with a mold to obtain test pellets (18 mm in diameter, 1.3 g).

[0465] Using a dynamic viscoelasticity measuring apparatus (UBM Rheosol-G3000), for 1.3g of test particles, a parallel plate with a diameter of 18mm was used. The temperature was increased from an initial temperature of 80℃ to 200℃ at a rate of 5℃ / min. The dynamic viscoelastic modulus was measured under the following conditions: temperature interval of 2.5℃, vibration frequency of 1Hz, and strain of 5deg. After measuring the dynamic viscoelastic modulus, a graph was plotted with temperature on the horizontal axis and melt viscosity on the vertical axis, and the minimum melt viscosity (MV) was calculated. 0h ).

[0466] Next, under conditions of 23°C and 40-45% humidity, the resin sheet A obtained in the examples and comparative examples was left to stand for 72 hours from the moment T0 when the temperature of the resin composition layer reached 23°C. Only the resin composition layer was peeled off from the stood resin sheet, and it was compressed using a mold to obtain test particles (18 mm in diameter, 1.3 g). Similarly, after measuring the dynamic viscoelastic modulus, a graph was plotted with temperature on the horizontal axis and melt viscosity on the vertical axis to calculate the minimum melt viscosity (MV). 72h ).

[0467] Based on the MV obtained from the above measurements 0h and MV 72h The value of is used to evaluate the stability of the melt viscosity according to the following criteria. Based on the stability of this melt viscosity, the stability of the film can be evaluated; (Evaluation criteria for the stability of melt viscosity) "◎": Satisfies 1.00≤MV 72h / MV 0h <1.50 relationship “○”: satisfies 1.50≤MV 72h / MV 0h <1.80 relationship "×": for MV 72h / MV 0h <1.00 or MV 72h / MV 0h ≥1.80.

[0468] As shown in Table 1, Examples 1-9, containing (A) epoxy resin, (B) a binaphthol-type active ester compound or a bisnaphthol-type active ester compound, and (C) maleimide resin, simultaneously achieved excellent dielectric properties (low dielectric loss tangent), excellent heat resistance (glass transition temperature), and excellent mechanical properties (puncture resistance). On the other hand, Comparative Example 1, which did not contain components (B) and (C), did not meet the required levels of heat resistance (glass transition temperature) and mechanical properties (puncture resistance). Comparative Examples 2-5, which contained component (C) but not component (B), did not meet the required levels of heat resistance (glass transition temperature).

Claims

1. A resin composition, wherein, contain: (A) Epoxy resin, (B) Binaphthol-type active ester compounds or bisnaphthol-type active ester compounds, and (C) Maleimide resin.

2. The resin composition according to claim 1, wherein, (B) The component is an ester compound represented by formula (1-1) or formula (1-2) below. In the formula, X A1 and X A2 Each independently represents a monovalent organic group containing at least one aromatic ring (a). X B Each independently represents a divalent organic group containing at least one aromatic ring (b). X C Each independently represents a divalent organic group containing at least one aromatic ring (c). At least one X C It is a divalent group as shown in the following formula (C-1), n represents an integer greater than or equal to 1; In the formula, R C1 Indicates a divalent organic group or a single bond. R C2 Each can independently represent a halogen atom or an alkyl group. nc1 and nc2 each independently represent integers from 0 to 6. * indicates a connection key.

3. The resin composition according to claim 1, wherein, The mass ratio of component (B) to component (A), i.e., component (B) / component (A), is 1.5 or more.

4. The resin composition according to claim 1, wherein, (C) Components include aromatic maleimide resins.

5. The resin composition according to claim 1, wherein, It further contains (D) inorganic filler materials.

6. The resin composition according to claim 5, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (D) is 50% by mass or more.

7. The resin composition according to claim 1, wherein, It further contains (E) organic filler material.

8. The resin composition according to claim 1, wherein, It further contains (F) thermoplastic resin.

9. The resin composition according to claim 8, wherein, (F) Component contains phenoxy resin.

10. The resin composition according to claim 1, wherein, It further contains (G) curing accelerator.

11. The resin composition according to any one of claims 1 to 10, used as an insulating layer of a circuit board.

12. A resin sheet comprising a support and a layer of the resin composition of any one of claims 1 to 10 disposed on the support.

13. The resin sheet according to claim 12, wherein, The support is a thermoplastic resin film or metal foil.

14. The cured product of the resin composition according to any one of claims 1 to 10.

15. A circuit board, wherein, It includes an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 10.

16. A semiconductor device, wherein, It includes the circuit board as described in claim 15.

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