Resin composition, cured product, prepreg, copper-clad laminate, and interlayer insulating film

Abstract

Disclosed is a resin composition which contains: a polymer (A) that has an ethylenically unsaturated double bond, and has a weight average molecular weight (Mw) of 1,500-500,000; and a compound (B) that has two or more groups represented by formula (Y) and satisfies conditions (α1), (α2), and (α3). In formula (Y), R31 represents a hydrogen atom or an alkyl group having 1-5 carbon atoms, and * represents a bond with another moiety in the compound (B). (α1) The molecular weight is 1,000 or less. (α2) The solubility in toluene at 25°C is 20 mass% or more. (α3) The 1% weight loss temperature is more than 130°C as determined by simultaneous thermogravimetric-differential thermal analysis (TG / DTA).

Description

Resin compositions, cured products, prepregs, copper-clad laminates, and interlayer insulating films

[0001] The present invention relates to a resin composition, a cured product, a prepreg, a copper-clad laminate, and an interlayer insulating film.

[0002] In recent years, in the field of information and communications, the signal bandwidth of information and communications devices has been increasing in frequency in order to achieve high-speed, large-capacity transmission. To accommodate this increase in frequency, there is an increasing demand for low-dielectric and low-dielectric-tangent materials for insulators used in printed wiring boards and semiconductor packages. Furthermore, since the insulators are in contact with metal wiring such as copper, it is desirable for the insulator material to have a coefficient of thermal expansion (linear expansion coefficient) due to heat generation during conduction that is close to that of the metal type of the wiring.

[0003] As materials that can accommodate this trend toward higher frequencies, polyolefin resin, styrene resin, fluororesin, polyphenylene ether resin, vinylbenzyl ether resin, or compositions using polyphenylene ether resin have been proposed (see, for example, Patent Documents 1 to 6).

[0004] Japanese Patent Application Laid-Open No. 7-188362 Japanese Patent Application Laid-Open No. 2004-83680 Japanese Patent No. 3414556 Japanese Patent Application Laid-Open No. 2003-306591 Japanese Patent No. 5649773 Japanese Patent Application Laid-Open No. 2017-200997

[0005] However, while research has been conducted on reducing the dielectric constant and dielectric loss tangent of resins contained in large proportions of conventional materials, such as the compositions described in Patent Documents 1 to 6, research has not been sufficient on reducing the dielectric constant and dielectric loss tangent of other components contained in large proportions, particularly crosslinkers. In this technical field, the performance required of such compositions is not only low dielectric constant and dielectric loss tangent of the resulting cured product, but also heat resistance, adhesion, and a small difference in the elongation of the cured product and the elongation of inorganic materials such as metal wiring when heat is generated during electrical conduction (hereinafter also referred to as "low elongation"). However, simply improving the resin's performance has not been sufficient to meet all of these requirements. For example, cured products obtained from compositions using polyphenylene ether resins or fluororesins have excellent low dielectric constants, low dielectric loss tangents, and heat resistance, but lack sufficient adhesion to low-roughened copper foil, and there is a large difference between the elongation of the cured film due to heat generated during electrical conduction and the elongation of the copper in the wiring, etc. Furthermore, if the elongation due to heat generated during electrical conduction is greater than the elongation of copper, etc., this can cause cracks in the cured product, peeling from the copper interface, disconnection, poor connection, etc. Therefore, in order to reduce the difference in elongation rate with metal species such as copper wiring, a method of using an inorganic filler in combination is generally used, but if the amount added is too large, there is a problem that adhesion with copper wiring is reduced. As such, it is difficult to balance various physical properties with compositions using polyphenylene ether resins and fluororesins. Furthermore, the composition described in Patent Document 6 has room for improvement in terms of low dielectric properties.

[0006] The problem to be solved by one embodiment of the present invention is to provide a resin composition which produces a cured product having a low dielectric constant, a low dielectric dissipation factor, and a low elongation percentage, as well as excellent heat resistance and compatibility with solvents. The problem to be solved by another embodiment of the present invention is to provide a cured product, a prepreg, a copper-clad laminate, and an interlayer insulating film which have a low dielectric constant, a low dielectric dissipation factor, a low elongation percentage, and excellent heat resistance.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration examples. Means for solving the above problems include the following aspects.

[0008] <1> A resin composition comprising: a polymer (A) having an ethylenically unsaturated double bond and having a weight average molecular weight (Mw) of 1,500 or more and 500,000 or less; and a compound (B) having two or more groups represented by the following formula (Y) and satisfying the following conditions (α1), (α2), and (α3):

[0009]

[0010] In formula (Y), R ３１ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * represents a bonding site to another moiety in compound (B). <Conditions> (α1) Molecular weight is 1,000 or less; (α2) Solubility in toluene at 25°C and 1 atmosphere is 20% by mass or more; (α3) 1% weight loss temperature measured by simultaneous differential thermal analysis-thermogravimetric analysis (TG / DTA) exceeds 130°C. <2> The resin composition according to <1>, wherein the polymer (A) is at least one resin selected from the group consisting of polyphenylene ether resins, polyfunctional vinyl aromatic copolymers, and heteroaromatic-aromatic ether resins. <3> The resin composition according to <1>, wherein the compound (B) is at least one compound selected from the group consisting of compounds represented by the following formula (1A), formula (1B), or formula (2), or compounds containing structural units represented by formulas (4a), (4b), and (4c):

[0011]

[0012] In formula (1A), R １１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; １２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R １３ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. １３n12 is an integer of 2 to 4, n13 is an integer of 0 to 6, n14 is an integer of 1 to 12, and n15 is 1 or 2; when n15 is 1, R １０ is a hydrogen atom, and when n15 is 2, R １０ is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms.

[0013]

[0014] In formula (1B), R １１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; １２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R １０ is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms; R ３１ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0015]

[0016] In formula (2), A １ and A ２ represent groups represented by the following formula (A-1) and formula (A-2), respectively, n22 is an integer of 2 to 4, n25 is an integer of 1 to 4, R ２０ is a hydrogen atom when n25 is 1, and is a single bond, a substituted or unsubstituted methylene group, or an n25-valent hydrocarbon group having 2 to 10 carbon atoms when n25 is an integer of 2 to 4.

[0017]

[0018] In formula (A-1), R ２１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 1 to 5 carbon atoms substituted with an aryl group; R ２２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ２４is a single bond, a substituted or unsubstituted methylene group, or an alkanediyl group having 2 to 10 carbon atoms, and # in formula (A-1) represents the bonding site with ## in formula (A-2). ２Ｘ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; R ２３ are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom, n23 is an integer of 0 to 4, n24 is 0 or 1, ## in formula (A-2) represents a bonding site with # in formula (A-1), * represents R in formula (2), ２０ where n25 in formula (2) is 1, n23+n22 is a number equal to or less than the maximum number of substituents on the aromatic ring included in formula (A-2), and where n25 in formula (2) is 2 to 4, n22+n23+1 is a number equal to or less than the maximum number of substituents on the aromatic ring included in formula (A-2).

[0019]

[0020] In formulas (4a), (4b) and (4c), Ar ４１ and Ar ４２ each independently represents a divalent aromatic hydrocarbon group; ４１ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms; R ４２ each independently represents a vinyl group or a monovalent organic group having a vinyl group; R ４３ represents a group derived from a chain diene hydrocarbon compound, * represents a bonding site with another structural unit, n41 is 1 or 2, and a is 0.1 to 0.8, b is 0.1 to 0.8, and c is 0 to 0.8, relative to 1, which is the total number of the structural units a, b, and c. <4> The resin composition according to <3>, wherein compound (B) is a compound represented by formula (1A) or formula (1B), and the compound represented by formula (1A) or formula (1B) is a compound represented by the following formula (1-1) or formula (1-2):

[0021]

[0022] In formula (1-1), R １１are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; １２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, １３ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. １３ n12 is an integer of 2 to 4, n13 is an integer of 0 to 6, and n14 is an integer of 1 to 12.

[0023]

[0024] In formula (1-2), R １１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; １２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R １３ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. １３ n12 is an integer of 2 to 4, n13 is an integer of 0 to 6, and n14 is an integer of 1 to 12; R １０ is a single bond, a substituted or unsubstituted methylene group, or an alkanediyl group having 2 to 20 carbon atoms. <5> The resin composition according to <3>, wherein the compound (B) is a compound represented by formula (2), and the compound represented by formula (2) is a compound represented by formula (2-1):

[0025]

[0026] In formula (2-1), A １ and A ２represent groups represented by the following formula (A-1) and formula (A-3), respectively, and n22 is an integer of 2 to 4.

[0027]

[0028] In formula (A-1), R ２１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; R ２２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ２４ is a single bond, a substituted or unsubstituted methylene group, or an alkanediyl group having 2 to 10 carbon atoms, and # in formula (A-1) represents the bonding site with ## in formula (A-3). ２Ｘ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; R ２３ represents an alkyl group having 1 to 5 carbon atoms or a halogen atom, n22 is an integer of 2 to 4, n23 is an integer of 0 to 4, n24 is 0 or 1, and ## in Formula (A-3) represents a bonding site with # in Formula (A-1). Here, n23 + n22 is a number equal to or less than the maximum number of substituents on the aromatic ring contained in Formula (A-3). <6> The resin composition according to any one of <1> to <5>, further containing a polymerization initiator (C). <7> The resin composition according to any one of <1> to <6>, further containing an organic solvent (D). <8> The resin composition according to any one of <1> to <7>, further containing a thermoplastic resin (E) different from the polymer (A) and the compound (B). <9> The resin composition according to any one of <1> to <8>, further containing a filler (F). <10> A cured product comprising the resin composition according to any one of <1> to <9>. <11> A prepreg obtained by impregnating a fibrous base material with the resin composition according to any one of <1> to <9>. <12> A copper-clad laminate obtained by laminating the prepreg according to <11> and a copper substrate. <13> An interlayer insulating film made of the cured product according to <10>.

[0029] According to one embodiment of the present invention, there is provided a resin composition which produces a cured product having a low dielectric constant, a low dielectric dissipation factor, and a low elongation percentage, as well as excellent heat resistance and compatibility with solvents. Also, according to one embodiment of the present invention, there are provided a cured product, a prepreg, a copper-clad laminate, and an interlayer insulating film which have a low dielectric constant, a low dielectric dissipation factor, a low elongation percentage, and excellent heat resistance.

[0030] Preferred embodiments of the present invention will be described in detail below. It should be understood that the present invention is not limited to the embodiments described below, but also includes various modifications that are implemented within the scope of the present invention. In this specification, a numerical range described using "to" means that the numerical values ​​before and after "to" are included as the lower and upper limits.

[0031] [Resin Composition] The resin composition according to the present invention contains a polymer (A) having an ethylenically unsaturated double bond and having a weight average molecular weight (Mw) of 1,500 or more and 500,000 or less, and a compound (B) having two or more groups represented by the following formula (Y) and satisfying the following conditions (α1) to (α3):

[0032] <Polymer (A)> The resin composition of the present invention contains a polymer (A) (hereinafter also simply referred to as "polymer (A)") having a group having an ethylenically unsaturated double bond and having a weight average molecular weight (Mw) of 1,500 or more and 500,000 or less. The weight average molecular weight (Mw) of the polymer (A) is 1,500 or more and 500,000 or less in terms of polystyrene. The lower limit of the weight average molecular weight (Mw) of the polymer (A) is preferably 2,000, more preferably 3,000, and even more preferably 5,000. The upper limit of the weight average molecular weight (Mw) of the polymer (A) is preferably 100,000, more preferably 30,000, and even more preferably 15,000. When the weight average molecular weight (Mw) of the polymer (A) is within the above range, the polymer (A) has an excellent balance of adhesion, heat resistance, impregnation into glass cloth, moldability such as resin flow, and the like. The weight average molecular weight (Mw) can be determined by measuring by gel permeation chromatography (GPC) under the conditions described in the examples below.

[0033] As used herein, the term "ethylenically unsaturated double bond" refers to a double bond formed between carbon atoms excluding those forming an aromatic ring. The group containing the ethylenically unsaturated double bond is preferably a group capable of crosslinking with the polymer (B) described below, from the viewpoint of providing a cured product with a low dielectric constant and a low dielectric dissipation factor. Examples of groups capable of crosslinking with the polymer (B) include vinyl groups, allyl groups, and (meth)acryloyl groups. The polymer (A) containing an ethylenically unsaturated double bond is not particularly limited, but suitable examples include polyphenylene ether polymers, polyfunctional vinyl aromatic copolymers, and heteroaromatic-aromatic ether polymers having one or more groups selected from vinyl groups, allyl groups, and (meth)acryloyl groups at the main chain terminal or side chain of the polymer (A). Hereinafter, these terms may be abbreviated as "modified polyphenylene ether polymer," "modified polyfunctional vinyl aromatic copolymer," and "modified heteroaromatic-aromatic ether polymer," respectively.

[0034] The polymer (A) has a group having an ethylenically unsaturated double bond and a specific weight-average molecular weight (Mw), resulting in a polymer with excellent low dielectric constant and low dielectric dissipation factor. Because the polymer (A) has a weight-average molecular weight (Mw) of 1,500 or more and 500,000 or less, when used in combination with the compound (B) having the specific structure described below, crosslinking proceeds efficiently, and the resulting cured product maintains a low dielectric constant and low dielectric dissipation factor while also ensuring heat resistance. Furthermore, because the polymer (A) has a weight-average molecular weight (Mw) of 1,500 or more and 500,000 or less, a composition with an excellent balance of these properties can be obtained without impairing flowability or adhesion to the substrate. From this perspective, the polymer (A) is preferably at least one resin selected from the group consisting of polyphenylene ether polymer (A2), polyfunctional vinyl aromatic copolymer (A3), and heteroaromatic-aromatic ether polymer (A1).

[0035] [Modified Heteroaromatic-Aromatic Ether Polymer (A1)] The heteroaromatic-aromatic ether polymer (A1) (hereinafter also referred to as "polymer (A1)") may be, for example, a polymer (A1) having a structural unit represented by formula (A1-1).

[0036]

[0037] In formula (A1-1), R ａ１ is a divalent group represented by the following formula (A2), and R ａ２ is expressed by the following formula (R ａ２ −1), (R ａ２ −2) and (R ａ２ -3) is a divalent group represented by one selected from the following:

[0038]

[0039] In formula (A2), Ar ａ１ and Ar ａ２ are each independently an unsubstituted or substituted aromatic hydrocarbon group, and L is a single bond, —O—, —S—, —N(R ８ )-, -C(O)-, -C(O)-O-, -C(O)-NH-, -S(O)-, -S(O) ２ -, -P(O)- or a divalent organic group, ８ represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, y represents an integer of 0 to 5, and when y is 2 or more, a plurality of Ar ａ１ and L are the same or different, R ａ６ and R ａ７ are each independently a single bond, a methylene group, or an alkanediyl group having 2 to 4 carbon atoms.

[0040] [Ar ａ１ and Ar ａ２ 〕 Ar ａ１ and Ar ａ２ The unsubstituted or substituted aromatic hydrocarbon group represented by the formula (I) is more preferably a phenylene group, a naphthalenediyl group or an anthracenediyl group, and particularly preferably a phenylene group or a naphthalenediyl group.

[0041] The substituent on the aromatic hydrocarbon group is not particularly limited and examples thereof include groups having an ethylenically unsaturated double bond such as an allyl group or a (meth)acryloyloxy group; a halogen atom; an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group; an alkenyl group such as an ethenyl group, a propenyl group, a butenyl group or a pentenyl group; an alkynyl group having 2 to 10 carbon atoms such as an ethynyl group, a propynyl group, a butynyl group or a pentynyl group; a cycloalkyl group having 5 to 10 carbon atoms such as a cyclopentyl group, a cyclohexyl group or a norbornyl group; and an aryl group such as a phenyl group or a naphthyl group. Of these, an alkyl group is preferred as the substituent on the aromatic hydrocarbon group.

[0042] [L] Examples of the divalent organic group for L include an unsubstituted or substituted methylene group, an alkanediyl group having 2 to 20 carbon atoms, an arylene group having 6 to 10 carbon atoms, a group comprising a combination of two or more selected from the group consisting of the methylene group, the alkanediyl group, and the arylene group, or a group represented by the following formula (L1):

[0043]

[0044] In formula (L1), R ｃ is a divalent group derived from an unsubstituted or substituted monocyclic or polycyclic divalent cyclic hydrocarbon group having 5 to 30 ring members, or a divalent group derived from a compound represented by the following formula (L2) to formula (L4) (i.e., a group obtained by removing two hydrogen atoms from the following compound):

[0045]

[0046] In formula (L2), R ８ and R ９ are each independently a hydrogen atom, a fluorine atom, or a monovalent chain hydrocarbon group having 1 to 20 carbon atoms; and k is independently an integer of 0 to 4.

[0047] -N(R ８ )-R in ８represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Examples of the monovalent organic group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, and n-butyl; alkenyl groups, such as ethenyl, propenyl, butenyl, and pentenyl; alkynyl groups having 2 to 10 carbon atoms, such as ethynyl, propynyl, butynyl, and pentynyl; cycloalkyl groups having 5 to 10 carbon atoms, such as cyclopentyl, cyclohexyl, and norbornyl; and aryl groups, such as phenyl and naphthyl.

[0048] From the viewpoint of the structural stability of the polymer (A1), L is preferably a single bond, —O—, —S—, —C(O)—, a substituted or unsubstituted methylene group, an alkanediyl group having 2 to 5 carbon atoms, or the formula (L1).

[0049] [y] In formula (A2), y is an integer of 0 to 5. From the viewpoint of the structural stability of the polymer (A1), y is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0050] R in formula (A1-1) ａ１ Examples of the monomer that serves as the raw material for the moiety containing (i.e., the divalent group represented by formula (A2)) include compounds represented by the following formulas, as well as diol compounds such as Priplast 1901, 1838, 3186, 3192, 3197, and 3199 (manufactured by Croda Japan Co., Ltd.). These monomers may be used alone or in combination of two or more. In addition, the R ａ１ The monomers that are raw materials for the moiety containing are not limited to the following exemplary compounds.

[0051]

[0052]

[0053]

[0054] <R ａ２ R in formula (A1-1) ａ２ is expressed by the following formula (R ａ２ −1), (R ａ２ −2) and (R ａ２-3) is a divalent group represented by one selected from the group consisting of:

[0055]

[0056] Formula (R ａ２ -1) to (R ａ２ -3) Medium, R １ are each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a nitro group, a cyano group, a primary amino group, a tertiary amino group, or a salt of a primary amino group, a tertiary amino group, and each n is independently an integer of 0 to 2. When n is 2, multiple R １ are the same or different and are part of a ring structure having 5 to 10 ring members that are joined together with the carbon atoms to which they are attached.

[0057] Formula (R ａ２ -1) to (R ａ２ -3) Medium, R １ From the viewpoint of improving the polymerization reactivity and the solubility of the resulting polymer, n is preferably a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably a fluorine atom, a chlorine atom, a methyl group, an ethyl group, or a phenyl group. From the same viewpoint, n is preferably 0 or 1, and more preferably 0.

[0058] Formula (R ａ２ −1), (R ａ２ −2) and (R ａ２ In the divalent group represented by one kind selected from the group consisting of aryl, aryloxy ...

[0059] In addition, from the viewpoint of improving the polymerization reactivity and improving the solubility in various organic solvents, R ａ２ As the compound, a compound having a pyrimidine skeleton represented by the above formula (R ａ２ -2) is preferred.

[0060] <<Group Crosslinkable with Compound (B)>> The heteroaromatic-aromatic ether polymer (A1) preferably has a group crosslinkable with the compound (B) described below at the end of the structural unit represented by the above formula (A1-1). The group crosslinkable with the compound (B) is preferably a terminal group Y represented by the following formula (a):

[0061]

[0062] In formula (a), Y is a group containing an ethylenically unsaturated double bond and having 3 to 50 carbon atoms.

[0063] Examples of the group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms include aromatic ring-containing groups such as a 3-isopropenylphenyl group, a 4-isopropenylphenyl group, a 2-allylphenyl group, a 2-methoxy-4-allylphenyl group, a 4-(1-propenyl)-2-methoxyphenyl group, a 4-vinylbenzyl group, a 3-vinylbenzyl group, and a 2-vinylbenzyl group, an allyl group, an acrylic group, and a methacrylic group.

[0064] The method for forming the polymer (A1) in which the terminals of the polymer (A1) are capped with the terminal group Y is not particularly limited, and any known method can be used.

[0065] Examples of the monomer for forming the terminal group Y include monohydric phenol compounds such as t-butylphenol, nonylphenol, 4-isopropenylphenol, 4-vinylphenol, 2-allylphenol, isoeugenol, tocotrienol, α-tocophenol, 4-hydroxyphenylmaleimide, and 2-phenylphenol; monovalent amine compounds such as 4-hexylaniline and diallylamine; monovalent thiol compounds such as 1-octanethiol; monovalent aliphatic halides such as allyl chloride, 4-(chloromethyl)styrene, and 3-(chloromethyl)styrene; monovalent acid halides such as acryl chloride, methacryl chloride, crotonoyl chloride, and cinnamoyl chloride; and monovalent acid anhydrides such as acrylic anhydride, crotonic anhydride, and methacrylic anhydride. The monomer for forming the terminal group Y may be used alone or in combination of two or more.

[0066] The polymer (A1) may contain a structural unit represented by the following formula (A1-2) by copolymerizing, in addition to a monomer that provides a structural unit of the above formula (A1-1), a monomer that provides a branched structure:

[0067]

[0068] In formula (A1-2), R ａ２ is the above formula (R ａ２ −1), (R ａ２ −2) and (R ａ２ -3), and R １２ each independently represents a substituted or unsubstituted divalent aromatic hydrocarbon group, R １３ represents a hydrocarbon group having 1 to 20 carbon atoms, m represents an integer of 1 to 6, and ** represents a bond to another structural unit in the polymer (A1).

[0069] The structural unit represented by formula (A1-2) is exemplified by structural units having the following partial structures, but is not limited thereto. ａ２ is the above formula (R ａ２ −1), (R ａ２ −2) and (R ａ２ -3) is a divalent group represented by one selected from the following:

[0070]

[0071] [Method for forming the structural unit represented by formula (A1-2)] The structural unit represented by formula (A1-2) can be formed by synthesizing the polymer represented by formula (A1-1) by removing the moiety (-R １２ -R １３ (R １２ -O-**)m-R １２ (-R １２ -R １３ (R １２ -O-**)m-R １２ Examples of the monomer that forms the bond (-) include compounds represented by the following formula (6):

[0072]

[0073] In the formula (6), R １３ is n having 1 to 20 carbon atoms ６１ represents a 2-valent hydrocarbon group, and R ６１ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms; n ６１ represents an integer of 2 to 4, and n ６２ represents an integer of 1 to 5, and n ６３ represents an integer of 0 to 4, provided that n ６２ and ６３ The total number is 1 to 5.

[0074] The lower limit of the weight average molecular weight (Mw) of polymer (A1) is preferably 1,500, more preferably 3,000, and particularly preferably 5,000, in terms of polystyrene, and the upper limit of the weight average molecular weight (Mw) of polymer (A) is preferably 500,000, more preferably 100,000, even more preferably 30,000, and particularly preferably 15,000, in terms of polystyrene. When the weight average molecular weight (Mw) of polymer (A1) is within the above range, it is excellent in balance with respect to adhesion, heat resistance, impregnation into glass cloth, moldability such as resin flow, etc. The weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) under the conditions described in the examples below.

[0075] [Modified Polyphenylene Ether Polymer (A2)] The modified polyphenylene ether polymer (A2) is, for example, a polymer having a structural unit represented by the following formula (A2-1).

[0076]

[0077] In formula (A2-1), R ｂ１１ and R ｂ１２ each independently represents an alkyl group; R ｂ１３ , R ｂ１４ , R ｂ２１ , R ｂ２２ , R ｂ２３ and R ｂ２４ each independently represents a hydrogen atom or an alkyl group; R ｂ３１ and R ｂ３２each independently represents a vinylphenyl group or a (meth)acryloyl group; L ｂ２１ is a single bond, -C(Ry) ２ -, -O-, -CO-, -S-, -SO-, or -SO ２ -; Ry's each independently represent a hydrogen atom or an alkyl group; Z's each independently represent a single bond or an alkanediyl group; n ｂ２１ and m ｂ２１ each independently represents an integer of 1 or more; ｂ２１ represents 0 or 1. ｂ２１ Units and meters ｂ２１ The units may be the same for each unit or may be different.

[0078] R ｂ１１ and R ｂ１２ R each independently represents an alkyl group, and is preferably a methyl group. ｂ１３ and R ｂ１４ R each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom. ｂ２１ and R ｂ２２ R each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a methyl group. ｂ２３ and R ｂ２４ are each independently a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably R ｂ２３ and R ｂ２４ One of the groups is a methyl group and the other is a hydrogen atom.

[0079] R ｂ３１ and R ｂ３２ are each independently a vinylphenyl group or a (meth)acryloyl group, and Z is a single bond, a methylene group, or an alkanediyl group. The alkanediyl group means a linear, branched, or cyclic divalent saturated hydrocarbon group. The alkanediyl group is preferably an alkanediyl group having 2 to 6 carbon atoms. Examples of the alkanediyl group include -CH ２ -CH ２ -, -CH(CH ３) -, -CH ２ -CH ２ -CH ２ -, -CH ２ -CH(CH ３ ) -, -CH(CH ３ )-CH ２ -, -C(CH ３ ) ２ Among these, R ｂ３１ and R ｂ３２ is a vinylphenyl group, and Z is a methylene group or an alkanediyl group having 2 to 6 carbon atoms (particularly preferably a methylene group (—CH ２ -)) or R ｂ３１ and R ｂ３２ is a (meth)acryloyl group, and Z is a single bond.

[0080] L ｂ２１ is a single bond, -C(Ry) ２ -, -O-, -CO-, -S-, -SO-, or -SO ２ -, preferably a single bond, -C(Ry) ２ Each Ry independently represents a hydrogen atom or an alkyl group, and preferably a hydrogen atom or a methyl group. ｂ２１ and m ｂ２１ are each independently an integer of 1 or more, preferably an integer of 1 to 200, and more preferably an integer of 1 to 100. ｂ２１ represents 0 or 1, preferably 1.

[0081] Commercially available modified polyphenylene ether polymers (A2) include, for example, "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether polymers) manufactured by Mitsubishi Gas Chemical Company, Inc.; and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether polymers) manufactured by SABIC Innovative Plastics.

[0082] The lower limit of the polystyrene-equivalent weight average molecular weight (Mw) of the polymer (A2) is preferably 2,000, more preferably 3,000, and the upper limit is preferably 500,000, more preferably 100,000, and even more preferably 30,000. The weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) under the conditions described in the Examples below.

[0083] [Polyfunctional vinyl aromatic copolymer (A3)] Examples of the polyfunctional vinyl aromatic copolymer (A3) (hereinafter also referred to as "polymer (A3)") include polyfunctional vinyl aromatic copolymers containing a structural unit (aa) derived from a divinyl aromatic compound and a structural unit (ab) derived from a monovinyl aromatic compound.

[0084] The divinylaromatic compound is not limited to, but may be, for example, a copolymer containing a structural unit (aa) derived from a divinylaromatic compound and a structural unit (ab) derived from a monovinyl aromatic compound, as shown in the following formula: These structural units may be arranged regularly or randomly.

[0085]

[0086] In the formula, R ａａ１ is an aromatic hydrocarbon group having 6 to 30 carbon atoms derived from a divinyl aromatic compound, and R ａａ２ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms derived from a monovinyl aromatic compound, h to k each independently represent an integer of 0 to 200, and i and j cannot both be 0.

[0087] The lower limit of the polystyrene-equivalent weight average molecular weight (Mw) of the polymer (A3) is preferably 2,000, more preferably 3,000, and the upper limit is preferably 500,000, more preferably 100,000, and even more preferably 30,000. The weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) under the conditions described in the Examples below.

[0088] The structural unit (aa) derived from the divinyl aromatic compound plays a role in forming a branched structure to impart polyfunctionality, and also plays a role as a crosslinking component to impart heat resistance when the resulting polyfunctional vinyl aromatic copolymer is thermally cured.

[0089] The monomer that provides the structural unit (aa) derived from the divinylaromatic compound is not particularly limited as long as it is an aromatic compound having two vinyl groups. Examples of the monomer that provides the structural unit (aa) derived from the divinylaromatic compound include divinylbenzene (including each positional isomer or a mixture thereof), divinylnaphthalene (including each positional isomer or a mixture thereof), and divinylbiphenyl (including each positional isomer or a mixture thereof). These may be used alone or in combination of two or more. From the viewpoint of excellent molding processability, divinylbenzene is more preferred as the monomer that provides the structural unit (aa) derived from the divinylaromatic compound.

[0090] The content of the structural unit (aa) derived from the divinyl aromatic compound is preferably 5 mol% or more and less than 98 mol%, based on 100 mol% of all structural units of the polyfunctional vinyl aromatic copolymer (A3). When the content of the structural unit (aa) derived from the divinyl aromatic compound is within the above range, the copolymer has a low dielectric loss tangent, high toughness, and excellent heat resistance, and when formed into a polymer composition, the copolymer has excellent moist heat resistance and thermal oxidative degradation resistance.

[0091] Examples of the monomer that provides the structural unit (ab) derived from the monovinyl aromatic compound include styrene and monovinyl aromatic compounds other than styrene. As the monovinyl aromatic compound, styrene is preferred because it can impart low dielectric properties and thermal oxidative degradation resistance.

[0092] The monovinyl aromatic compound (bab) other than styrene is not particularly limited as long as it is an aromatic compound having one vinyl group. Examples of the monovinyl aromatic compound (bab) other than styrene include vinyl aromatic compounds such as vinylnaphthalene and vinylbiphenyl; and alkyl-substituted vinyl aromatic compounds such as methylstyrene, dimethylstyrene, and ethylvinylbenzene. The monovinyl aromatic compound (bab) other than styrene can prevent gelation of the polyfunctional vinyl aromatic copolymer (A3) and facilitate adjustment of solvent solubility and processability. From the above perspective, the monovinyl aromatic compound (bab) other than styrene is preferably ethylvinylbenzene, ethylvinylbiphenyl, and ethylvinylnaphthalene, with ethylvinylbenzene being particularly preferred. The content of the structural unit (ab) derived from the monovinyl aromatic compound is preferably 2 mol% or more and less than 95 mol%, based on 100 mol% of the total structural units of the polyfunctional vinyl aromatic copolymer (A3). When the content of the structural unit (ab) derived from the monovinyl aromatic compound is within the above range, excellent moldability and excellent heat resistance of the cured product obtained when used as a resin composition are obtained.

[0093] The above-mentioned multifunctional vinyl aromatic copolymer (A3) is preferably soluble in any of toluene, xylene, tetrahydrofuran, dichloroethane and chloroform as solvent, and is preferably soluble in all of the above-mentioned solvents.In order to be a solvent-soluble and multifunctional copolymer, it is preferable that a part of the vinyl group of divinylbenzene remains uncrosslinked, and copolymer (A3) has an appropriate degree of crosslinking.Here, "solubility in solvent" means that the multifunctional vinyl aromatic copolymer (A3) dissolves in 100g of the above-mentioned solvent in an amount of 5g or more, more preferably dissolves in 30g or more, particularly preferably dissolves in 50g or more.

[0094] Furthermore, the polyfunctional vinyl aromatic copolymer (A3) may contain, as necessary, a structural unit (ac) other than (aa) and (ab) (hereinafter also referred to as "other structural unit (ac)") in addition to the structural unit (aa) derived from a divinyl aromatic compound and the structural unit (ab) derived from a monovinyl aromatic compound, provided that the effects of the present invention are not impaired. Examples of monomers that provide the other structural unit (ac) include trivinyl aromatic compounds, trivinyl aliphatic compounds, divinyl aliphatic compounds, and monovinyl aliphatic compounds.

[0095] Examples of monomers that provide the other structural unit (ac) include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diacrylate, butadiene, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, and triallyl isocyanurate. These may be used alone or in combination of two or more.

[0096] The content of the other structural units (ac) is preferably less than 30 mol % relative to 100 mol % of all structural units constituting the polyfunctional vinyl aromatic copolymer (A3).

[0097] The polyfunctional vinyl aromatic copolymer (A3) can be obtained by a conventionally known polymerization method. Furthermore, a known chain transfer agent (CTR) may be added during polymerization to control the molecular weight.

[0098] The content of polymer (A), when the total mass of the solids in the composition is taken as 100 mass%, is preferably 0.05 mass% or more, more preferably 10 mass% or more, even more preferably 20 mass% or more, and is preferably 99.95 mass% or less, more preferably 90 mass% or less, even more preferably 80 mass% or less. When the content of polymer (A) is within the above range, it is preferable from the viewpoint of further improving the adhesiveness, heat resistance, curability, and electrical properties of the obtained cured product. The polymer (A) may be used alone or in combination of two or more types.

[0099] <Compound (B)> Compound (B) has two or more groups represented by the following formula (Y) and satisfies the following conditions (α1), (α2), and (α3): When compound (B) satisfies the above conditions, the obtained cured product has a low dielectric tangent.

[0100] The reasons why the resin composition of the present invention has excellent solubility in solvents and the resulting cured product has a low dielectric constant, a low dielectric dissipation factor, and a low elongation rate, as well as excellent heat resistance, are unclear, but the following mechanism is presumed. The inventors have discovered that, as one of the reasons, when the compound (B) has a group represented by formula (Y) and satisfies the following conditions (α1) to (α3), a resin composition containing the compound (B) and a polymer (A) having an ethylenically unsaturated double bond and a weight-average molecular weight (Mw) of 1,500 or more and 500,000 or less has excellent solubility in solvents, and the resulting cured product has a low dielectric constant, a low dielectric dissipation factor, and excellent heat resistance. Furthermore, because the compound (B) has two or more groups represented by formula (Y), and the groups represented by formula (Y) have good reactivity with the polymer (A), it is presumed that it becomes possible to adjust the crosslink density by, for example, adjusting the amount of compound (B) mixed or the reaction temperature. Furthermore, if sufficient reactivity and crosslinking density can be obtained even when the content of polymer (A), which has a higher molecular weight than compound (B), is reduced and the amount of compound (B) is increased, it is thought that it will be easy to adjust the viscosity to an appropriate level depending on the application of the composition, and it is presumed that it will be possible to ensure, for example, the ability to conform to substrates with uneven shapes, the ability to impregnate glass cloth, and moldability.

[0101] <<Condition (α1)>> Compound (B) has a molecular weight of 1,000 or less, preferably 200 to 1,000, more preferably 200 to 800, even more preferably 200 to 600, and particularly preferably 200 to 500. In the case of a non-polymerizable compound, the molecular weight is a calculated molecular weight, and in the case of a polymerizable compound, the molecular weight is determined by the GPC measurement method described in the Examples below.

[0102] <<Condition (α2)>> The compound (B) has a solubility in toluene at 25° C. and 1 atmospheric pressure of 20% by mass or more, preferably 30% by mass or more, and more preferably 50% by mass or more.

[0103] <<Condition (α3)>> Compound (B) has a 1% weight loss temperature measured by simultaneous differential thermal analysis and thermogravimetry (TG / DTA) that exceeds 130° C., preferably exceeds 130° C. and is equal to or lower than 500° C., and more preferably exceeds 130° C. and is equal to or lower than 450° C. The 1% weight loss temperature measured by simultaneous differential thermal analysis and thermogravimetry (TG / DTA) is determined by the measurement method described in the examples below.

[0104] Compound (B) has two or more groups represented by the following formula (Y): From the viewpoint of easily obtaining a cured product having a low dielectric constant, a low dielectric loss tangent, a low elongation percentage, and excellent heat resistance, compound (B) preferably has two or three groups represented by the following formula (Y) in one molecule.

[0105]

[0106] In formula (Y), R ３１ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * represents the bonding site with other moieties in compound (B). ３１ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0107] Compound (B) is preferably at least one compound selected from the group consisting of compounds represented by the following formula (1A), formula (1B) or formula (2), or compounds containing structural units represented by formula (4a), formula (4b) and formula (4c), and more preferably a compound represented by the following formula (1A), formula (1B) or formula (2).

[0108]

[0109] In formula (1A), R １１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; １２are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R １３ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. １３ n12 is an integer of 2 to 4, n13 is an integer of 0 to 6, n14 is an integer of 1 to 12, and n15 is 1 or 2; when n15 is 1, R １０ is a hydrogen atom, and when n15 is 2, R １０ is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms.

[0110]

[0111] In formula (1B), R １１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; １２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R １０ is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms; R ３１ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0112] <<R ３１ >> In formula (1B), R ３１ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. ３１ represents R of formula (Y) in the compound (B) described above. ３１ is synonymous with.

[0113] <R １１> The alkyl group having 1 to 5 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc. Examples of cycloalkyl groups having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc. Examples of aryl groups having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, and groups in which an alkyl group is bonded to the ring of these groups. Examples of alkyl groups having 1 to 5 carbon atoms substituted with an aryl group include alkyl groups having 1 to 5 carbon atoms substituted with a phenyl group, a naphthyl group, etc., and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc. substituted with a phenyl group, a naphthyl group, etc. R １１ are each independently preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, still more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0114] <R １２ > R １２ The alkyl group having 1 to 5 carbon atoms represented by the formula (I) includes the above-mentioned R １１ Examples of the alkyl group include alkyl groups having 1 to 5 carbon atoms represented by the formula: １２ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

[0115] <<n12, n13 and n14>> n12 is preferably 2 or 3. n13 is preferably an integer of 0 to 3. n14 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

[0116] <R １３The alkyl group having 1 to 5 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. The aryl group having 6 to 12 carbon atoms includes a phenyl group, a naphthyl group, and groups in which an alkyl group is bonded to the ring of these groups. One or more other R groups present on the same carbon atom or adjacent carbon atoms may be present. １３ Examples of the 5-10-membered ring structure formed by bonding with include an aromatic hydrocarbon ring structure having 6 to 10 ring members and an aromatic heterocyclic ring structure having 5 to 10 ring members. The ring structure may be monocyclic or polycyclic. In the case of a polycyclic ring, it may be a condensed ring of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The "number of ring members" refers to the number of carbon atoms or heteroatoms constituting the ring structure.

[0117] Examples of aromatic hydrocarbon ring structures include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an indene ring, etc. Examples of aromatic heterocyclic structures include oxygen atom-containing heterocyclic groups such as a furan ring, a pyran ring, a benzofuran ring, and a benzopyran ring, nitrogen atom-containing heterocyclic groups such as a pyrrole ring, a pyridine ring, a pyrimidine ring, an indole ring, a quinoline ring, and a diketopyrrolopyrrole ring, sulfur atom-containing heterocyclic groups such as a thiophene ring and a dibenzothiophene ring, silicon atom-containing heterocyclic groups such as a silafluorene ring, and heterocyclic groups containing two or more heteroatoms such as an oxazole ring and a thiazole group.

[0118] The 5- to 10-membered ring structure is preferably a benzene ring structure, a naphthalene ring structure, a thiophene ring structure, or a furan ring structure, more preferably a benzene ring structure or a naphthalene ring structure, and even more preferably a benzene ring structure. In the resin composition according to the present invention, it is believed that compound (B) preferably contains a low proportion of heteroatoms, such as oxygen atoms or sulfur atoms, which cause polarization in dielectrics. This is because a molecular design with a high hydrocarbon ratio is believed to be advantageous for electrical properties such as dielectric constant and dielectric dissipation factor. However, such a molecular design for compound (B) is expected to make synthesis difficult and to result in poor solubility in solvents. The inventors have speculated that even when compound (B) is designed with a reduced heteroatom content, as long as the above conditions (α1) to (α3) are satisfied, a resin composition containing compound (B) and a polymer (A) having an ethylenically unsaturated double bond will have excellent solubility in solvents, and the resulting cured product will have a low dielectric constant, low dielectric dissipation factor, and excellent heat resistance. Even when a structure having a heteroatom such as the heterocycle is introduced into compound (B), the above-mentioned effect is expected to be obtained by including in the resin composition compound (B) that has a molecular design that does not cause polarization (so that charges cancel each other out).

[0119] R １３ are each independently preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. １３ and a 5-8 membered ring structure formed by bonding with the above, more preferably an alkyl group having 1 to 3 carbon atoms or a benzene ring structure, and even more preferably an alkyl group having 1 to 3 carbon atoms.

[0120] <R １０> Examples of divalent hydrocarbon groups having 2 to 20 carbon atoms include divalent chain hydrocarbon groups having 2 to 18 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 18 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 18 carbon atoms. Examples of divalent chain hydrocarbon groups having 2 to 20 carbon atoms include groups obtained by removing two hydrogen atoms from ethane, propane, butane, hexane, octane, etc. Examples of divalent alicyclic hydrocarbon groups having 3 to 18 carbon atoms include groups obtained by removing two hydrogen atoms from alicyclic saturated hydrocarbons such as cyclopentane, cyclohexane, norbornane, and adamantane, and cyclic unsaturated hydrocarbons such as cyclopentene, cyclohexene, and norbornene. Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms include groups in which two hydrogen atoms have been removed from a benzene ring; an oxygen atom-containing heterocyclic group such as a naphthalene ring, an indene ring, an anthracene ring, a fluorene ring, a biphenylene ring, a phenanthrene ring, a furan ring, a pyran ring, a benzofuran ring, or a benzopyran ring; a nitrogen atom-containing heterocyclic group such as a pyrrole ring, a pyridine ring, a pyrimidine ring, an indole ring, a quinoline ring, or a diketopyrrolopyrrole ring; or a sulfur atom-containing heterocyclic group such as a thiophene ring or a dibenzothiophene ring.

[0121] In formula (1A), when n15 is 2, R １０ is preferably a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 10 carbon atoms, more preferably an unsubstituted methylene group or a divalent hydrocarbon group having 2 to 4 carbon atoms, particularly preferably a divalent chain hydrocarbon group having 2 to 4 carbon atoms, and most preferably a 2,2-propane-diyl group. １０ is preferably a substituted or unsubstituted methylene group.

[0122] The compound represented by formula (1A) or formula (1B) is preferably a compound represented by the following formula (1-1) or formula (1-2).

[0123]

[0124] In formula (1-1), R １１are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; R １２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R １３ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. １３ n12 is an integer of 2 to 4, n13 is an integer of 0 to 6, and n14 is an integer of 1 to 12. １１ , R １２ and R １３ and n12 to n14 are R in formula (1A). １１ , R １２ and R １３ and n12 to n14, and the preferred embodiments are also the same.

[0125]

[0126] In formula (1-2), R １１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; R １２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R １３ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. １３ n12 is an integer of 2 to 4, n13 is an integer of 0 to 6, and n14 is an integer of 1 to 12; R １０ is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms. １０ , R １１ , R １２ and R １３and n12 to n14 are R in formula (1A). １０ , R １１ , R １２ and R １３ and n12 to n14, and the preferred embodiments are also the same.

[0127] The method for producing the compound represented by the above formula (1A) or (1B) is not particularly limited, and known synthesis methods can be used.

[0128] <<Compound Represented by Formula (2)>> Compound (B) is preferably a compound represented by formula (2).

[0129]

[0130] In formula (2), A １ and A ２ represent groups represented by formula (A-1) and formula (A-2), respectively; n22 is an integer of 2 to 4; n25 is an integer of 1 to 4; R ２０ is a hydrogen atom when n25 is 1, and is a single bond, a substituted or unsubstituted methylene group, or an n25-valent hydrocarbon group having 2 to 10 carbon atoms when n25 is an integer of 2 to 4.

[0131] <<R ２０ >> R ２０ When n25 is an integer of 2 to 4, n22+n23+1 in formula (2) is preferably a single bond, a substituted or unsubstituted methylene group, or a divalent to tetravalent hydrocarbon group having 2 to 4 carbon atoms, more preferably a single bond or a substituted or unsubstituted methylene group, and even more preferably a single bond or an unsubstituted methylene group. However, when n25 in formula (2) is an integer of 2 to 4, n22+n23+1 in formula (2) is a number equal to or less than the maximum number of substituents on the aromatic ring included in formula (A-2).

[0132]

[0133] In formula (A-1), R ２１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 1 to 5 carbon atoms substituted with an aryl group; R ２２are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ２４ is a single bond, a substituted or unsubstituted methylene group, or an alkanediyl group having 2 to 10 carbon atoms, and # in formula (A-1) represents the bonding site with ## in formula (A-2). ２Ｘ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; R ２３ are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom, n23 is an integer of 0 to 4, and n24 is 0 or 1, ## in formula (A-2) represents a bonding site with # in formula (A-1), and * represents R in formula (2). ２０ represents a bonding site with. However, when n25 in formula (2) is 1, n23 + n22 is a number equal to or less than the maximum number of substituents on the aromatic ring contained in formula (A-2), and when n25 in formula (2) is 2 to 4, n22 + n23 + 1 is a number equal to or less than the maximum number of substituents on the aromatic ring contained in formula (A-2). The maximum number of substituents is, for example, 4 when n24 is 0, or 6 when n24 is 1.

[0134] <<R ２１ >> R ２１ The alkyl group having 1 to 5 carbon atoms, the aryl group having 6 to 12 carbon atoms, and the alkyl group having 1 to 5 carbon atoms substituted with an aryl group, which are represented by the formula (1A) or (1B), １１ These groups have the same meanings as the alkyl group having 1 to 5 carbon atoms, the aryl group having 6 to 12 carbon atoms, and the alkyl group having 1 to 5 carbon atoms substituted with an aryl group, represented by the following formula:

[0135] R ２１ are each independently preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms, even more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0136] <<R２２ >> R ２２ The alkyl group having 1 to 5 carbon atoms represented by the formula (1A) or (1B) is R １１ R has the same meaning as the alkyl group having 1 to 5 carbon atoms represented by the following formula: ２２ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

[0137] <<R ２３ >> R ２３ The alkyl group having 1 to 5 carbon atoms represented by the formula (1A) or (1B) is R １１ R has the same meaning as the alkyl group having 1 to 5 carbon atoms represented by the following formula: ２３ Examples of the halogen atom in R include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom. ２３ are each independently preferably an alkyl group having 1 to 3 carbon atoms or a halogen atom, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom, and even more preferably a fluorine atom.

[0138] <<n22, n23 and n24>> n22 is preferably 2 or 3. n23 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 1. n24 is preferably 1.

[0139] <<n25>> n25 is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1. However, when n25 in formula (2) is 1, n23+n22 is a number equal to or less than the maximum number of substituents on the aromatic ring included in formula (A-2), and when n25 in formula (2) is 2 or 3, n22+n23+1 is a number equal to or less than the maximum number of substituents on the aromatic ring included in formula (A-2).

[0140] <<R ２Ｘ >> R ２Ｘ The halogen atom represented by R ２３ The meanings and preferred embodiments are the same as those of the halogen atom in R ２Ｘ The alkyl group having 1 to 5 carbon atoms represented by the formula (1) is R１１ The alkoxy group having 1 to 5 carbon atoms may be a chain or cyclic alkoxy group. Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, and a pentyloxy group. R ２Ｘ is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, and more preferably a halogen atom or an alkyl group having 1 to 3 carbon atoms.

[0141] <<R ２４ >> R ２４ is preferably a single bond, a substituted or unsubstituted methylene group, or an alkanediyl group having 2 to 4 carbon atoms, more preferably a single bond or a substituted or unsubstituted methylene group, and even more preferably a single bond or an unsubstituted methylene group.

[0142] The compound represented by formula (2) is preferably a compound represented by the following formula (2-1):

[0143]

[0144] In formula (2-1), A １ and A ２ represent groups represented by formula (A-1) and formula (A-3), respectively, and n22 is an integer of 2 to 4.

[0145]

[0146] In formula (A-1), R ２１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; R ２２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ２４ is a single bond, a substituted or unsubstituted methylene group, or an alkanediyl group having 2 to 10 carbon atoms, and # in formula (A-1) represents the bonding site with ## in formula (A-3). ２Ｘare each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms; R ２３ are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom, n22 is an integer of 2 to 4, n23 is an integer of 0 to 4, n24 is 0 or 1, and ## in formula (A-3) represents a bonding site with # in formula (A-1), provided that n23 + n22 is a number equal to or less than the maximum number of substituents on the aromatic ring contained in formula (A-3).

[0147] R in formula (A-1) and formula (A-3) in formula (2-1) ２１ , R ２２ , R ２３ , R ２４ and R ２Ｘ and n22 to n24 are R in formula (A-1) and formula (A-2) in formula (2). ２１ , R ２２ , R ２３ , R ２４ and R ２Ｘ and n22 to n24, and the preferred embodiments are also the same.

[0148] The above formula (2-1) can also be expressed as the following formula (2-1-1):

[0149]

[0150] R in formula (2-1-1) ２１ , R ２２ , R ２３ , R ２４ and R ２Ｘ and n22 to n24 are R in formula (A-1) and formula (A-2) in formula (2). ２１ , R ２２ , R ２３ , R ２４ and R ２Ｘ and n22 to n24, and the preferred embodiments are also the same.

[0151] Compound (B) is preferably a compound represented by formula (2), in which n25 is 1 or 2 (however, when n25 is 1, n23+n22 is a number equal to or less than the maximum number of substituents on the aromatic ring contained in formula (A-2), and when n is 2, n22+n23+1 is a number equal to or less than the maximum number of substituents on the aromatic ring contained in formula (A-2)). Such compound (B) can also be represented by the following formula (2-2-2).

[0152]

[0153] In formula (2-2-2), R ２１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; ２２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n22 is an integer of 2 to 4, n23 is an integer of 0 to 4, n24 is 0 or 1, and n25 is 1 or 2, R ２Ｘ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; R ２３ are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom, ２４ is a single bond, a substituted or unsubstituted methylene group, or an alkanediyl group having 2 to 10 carbon atoms; R ２０ is a single bond, a substituted or unsubstituted methylene group, or an alkanediyl group having 2 to 10 carbon atoms. ２０ , R ２１ , R ２２ , R ２３ , R ２４ and R ２Ｘ represents R in formula (A-1) and formula (A-2) in formula (2). ２０ , R ２１ , R ２２ , R ２３ , R ２４ and R ２ＸHowever, when n25 is 1, n23 + n22 is a number equal to or less than the maximum number of substituents on the aromatic ring contained in the above formula (A-2), and when n25 is 2, n22 + n23 + 1 is a number equal to or less than the maximum number of substituents on the aromatic ring contained in the above formula (A-2) in formula (2-2-2).

[0154] Among the compounds represented by the above formula (2-1) or formula (2-1-1), R ２４ is a single bond, and R ２Ｘ As a method for producing a compound in which is a fluorine atom, for example, the synthesis method shown in the following scheme can be mentioned, but the present invention is not limited to this synthesis method.

[0155]

[0156] In the above formula, R ２Ｘ is a fluorine atom, R ２１ , R ２２ , R ２３ , n22, n23, and n24 are R in formula (A-1) and formula (A-2) in formula (2) ２１ , R ２２ , and R ２３ and n22 to n24 have the same meanings and preferred embodiments, provided that n23+n22 is a number equal to or less than the maximum number of substituents on the aromatic ring contained in the above formula (A-2).

[0157] Among the compounds represented by the above formula (2-1), R ２４ A compound in which R is a substituted or unsubstituted methylene group or an alkanediyl group having 2 to 10 carbon atoms can be synthesized, for example, according to the following scheme, but the present invention is not limited to this synthesis method. ２Ｘ is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

[0158]

[0159] In the above scheme, R ２Ｘ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; R ２２ , R ２３, n22, n23, n24 and n25 are R in formula (A-1) and formula (A-2) in formula (2), respectively. ２２ , R ２３ , n22, n23, n24, and n25, and preferred embodiments are also the same. However, when n25 is 1, n23+n22 is a number equal to or less than the maximum number of substituents on the aromatic ring included in the above formula (A-2), and when n25 is 2, n22+n23+1 is a number equal to or less than the maximum number of substituents on the aromatic ring included in the above formula (A-2).

[0160] More specifically, the reaction represented by the above scheme involves adding aluminum chloride and dichloromethane to a reaction vessel under a nitrogen atmosphere, stirring the mixture, and cooling the resulting suspension to 0°C. Benzyl chloride is added to the mixture and stirred, followed by dropwise addition of mesitylene. After the addition is complete, the reaction solution is warmed to room temperature and stirred, and then added dropwise to 1N hydrochloric acid cooled to 0°C. The mixture is then warmed to room temperature and stirred for 30 minutes, after which separation is performed. The resulting organic layer is washed multiple times with water, and the solvent is distilled off to obtain intermediate (b). Aluminum chloride is dispersed in dichloromethane in a reaction vessel and cooled to 0°C. Acetyl chloride is added dropwise to the mixture and stirred, and a mixture of dichloromethane and diphenylmethane is added dropwise. After the addition is complete, the reaction solution is warmed to room temperature and stirred, and then added dropwise to 1N hydrochloric acid cooled to 0°C. After the addition is complete, the mixture is warmed to room temperature and stirred. The resulting reaction solution is then separated, and the organic layer is washed multiple times with ultrapure water, and the solvent is distilled off. The resulting solution was stirred at room temperature, and hexane was added to crystallize intermediate (b').

[0161] Compound (b') and methanol are added to a reaction vessel and cooled to 0°C. Sodium borohydride is added and the mixture is allowed to react at room temperature, then cooled to 0°C. Ethyl acetate and 1N hydrochloric acid are added, the mixture is heated to room temperature, stirred, and separated. The resulting organic layer is washed multiple times with ultrapure water, and the solvent is distilled off to obtain intermediate (b'') (however, the intermediate is not shown in the scheme).

[0162] Next, compound (b''), p-toluenesulfonic acid monohydrate, BHT (dibutylhydroxytoluene), and toluene are added to a reaction vessel and reacted by heating. After cooling to room temperature, 5% aqueous sodium bicarbonate is added and the layers are separated. The resulting organic layer is washed twice with ultrapure water and concentrated. Hexane and silica gel are added to the resulting crude product and stirred, the silica gel is removed by filtration, and the filtrate is concentrated to obtain the target compound (2-1).

[0163] The compound (B) may be a compound represented by the following formula (3).

[0164]

[0165] In formula (3), R ３１ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; R ３２ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0166] <<R ３１ >> R ３１ Each of R independently represents preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. ３１ is R in formula (Y) ３１ is synonymous with.

[0167] <<R ３２ >> R ３２ each independently preferably represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

[0168] The compound represented by formula (3) may be synthesized by a known method, or a commercially available product may be used.

[0169] The compound (B) may be a compound containing structural units represented by formula (4a), formula (4b) and formula (4c).

[0170]

[0171] In formula (4a), formula (4b) and formula (4c), Ar ４１ and Ar ４２ each independently represents a divalent aromatic hydrocarbon group;４１ represents a hydrogen atom or a chain hydrocarbon group having 1 to 5 carbon atoms; R ４２ represents a vinyl group or a monovalent organic group having a vinyl group, R ４３ represents a group derived from a chain diene hydrocarbon compound, * represents a bonding site with another structural unit, n41 represents 1 or 2, and where the total number of structural units a, b, and c is 1, a is 0.1 to 0.8, b is 0.1 to 0.8, and c is 0 to 0.8.

[0172] [Structural unit represented by formula (4a)] In formula (4a), R ４１ is preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. ４１ Examples of groups containing a divalent aromatic hydrocarbon group represented by the formula (I) include divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms. The aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of aromatic hydrocarbon groups include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, and a biphenylene group. Among these, the phenylene group or the naphthalenediyl group is preferred as the aromatic hydrocarbon group.

[0173] [Structural unit represented by formula (4b)] In formula (4b), Ar ４２ Examples of the divalent aromatic hydrocarbon group represented by the formula (I) include aromatic hydrocarbon groups having 6 to 20 carbon atoms. The aromatic hydrocarbon group may be monocyclic or polycyclic. The aromatic hydrocarbon group having 6 to 20 carbon atoms is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrenediyl group, and a biphenylene group. Of these, the divalent aromatic hydrocarbon group is preferably a phenylene group or a biphenylene group.

[0174] In formula (4b), R ４２ As the monovalent organic group having a vinyl group represented by the formula (Y-1), for example, a group represented by the following formula (Y-1) is preferred.

[0175]

[0176] In formula (Y-1), L ４２ represents a single bond, a methylene group, or an alkanediyl group having 2 or 3 carbon atoms, n41 represents 1 or 2, * represents Ar in formula (4), ４２ represents the binding site with L ４２ is preferably a single bond or a methylene group. Examples of the group represented by formula (Y-1) include a vinylphenylmethyl group.

[0177] [Structural unit represented by formula (4c)] In formula (4c), R ４３ The chain diene hydrocarbon compound forming the group derived from the chain diene hydrocarbon compound represented by the formula (I) is preferably a linear diene hydrocarbon compound, more preferably a linear diene hydrocarbon compound having 10 or less carbon atoms. Examples of the linear diene hydrocarbon compound having 10 or less carbon atoms include 1,2-butadiene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,4-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, and 1,9-decadiene. Of these, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene are preferred. ４３ Examples of the group derived from a chain diene hydrocarbon compound represented by the formula (I) include groups in which two hydrogen atoms have been removed from the chain diene hydrocarbon compound.

[0178] <<Numbers of Structural Units a, b and c>> Preferably, a is 0.2 to 0.8, b is 0.2 to 0.8, and c is 0 to 0.6, relative to the total number of the structural units a, b and c being 1.

[0179] Compounds containing structural units represented by formula (4a), formula (4b), and formula (4c) may further contain structural units other than those represented by formula (4a), formula (4b), and formula (4c) (hereinafter simply referred to as "other structural units"). Examples of other structural units include cyclic dienes such as cyclopentadiene and 1,3-cyclohexadiene, N-substituted maleimides such as cyclohexylmaleimide and phenylmaleimide, and (meth)acrylates such as methyl methacrylate, butyl methacrylate, and octyl methacrylate. The content of the other structural units is preferably 0.1 or less, more preferably 0.05 or less, relative to the total number of structural units a, b, and c (1).

[0180] The content of compound (B) is preferably 15 parts by mass or more, more preferably 25 parts by mass or more, even more preferably 35 parts by mass or more, and is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 55 parts by mass or less, when the total content of the polymer (A) and compound (B) is 100 parts by mass.

[0181] When the content of the compound (B) is within the above range, it is preferable from the viewpoints that the electrical properties such as low dielectric constant and low dielectric loss tangent, heat resistance, adhesion and curability of the obtained cured product can be further improved, and the elongation percentage can be further reduced, etc. The compound (B) may be used alone or in combination of two or more types.

[0182] Examples of the compound (B) include the following exemplary compounds, however, the present invention is not limited to these compounds.

[0183]

[0184] It is believed that by selecting a highly symmetric structure as the compound (B), a cured product having a lower coefficient of linear expansion (CTE) is more likely to be obtained.

[0185] <Other Components> In addition to the compound (B) and the polymer (A), the resin composition according to the present invention may further contain components other than the compound (B) and the polymer (A) (hereinafter, these may also be referred to as "other components"), as long as the effects of the present invention are not impaired.

[0186] Examples of the other components include a polymerization initiator (C), an organic solvent (D), additives for imparting various functions, and a filler (F). The resin composition may also contain a thermoplastic resin (E) as a polymer other than the compound (B) and the polymer (A) in order to adjust the physical properties of the composition, such as fluidity, heat resistance, and electrical properties. Each of these other components may be used alone or in combination of two or more.

[0187] [Polymerization initiator (C)] The resin composition preferably further contains a polymerization initiator (C). Examples of the polymerization initiator (C) include thermal or photoradical polymerization initiators, cationic curing agents, and anionic curing agents. Among these, thermal radical polymerization initiators are preferred as the polymerization initiator (C).

[0188] Examples of the thermal radical polymerization initiator include organic peroxides such as dicumyl peroxide, 1,1-di(t-butylperoxy)cyclohexane, di(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, and benzoyl peroxide; and azo compounds such as azobisbutyronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis(isobutyrate), and 2,2'-azobis(2-methylbutyronitrile).

[0189] When the resin composition contains a polymerization initiator (C), the content of the polymerization initiator (C) is not particularly limited as long as the resin composition is well cured and a cured product is obtained. Specifically, the content of the polymerization initiator (C) is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the total solid content of the polymer (A) and the compound (B). The polymerization initiator (C) may be used alone or in combination of two or more types.

[0190] [Organic Solvent (D)] The resin composition preferably further contains an organic solvent (D). Examples of the organic solvent (D) include amide solvents, ester solvents, ketone solvents, ether solvents, sulfone solvents, hydrocarbon solvents such as benzene, toluene, and xylene, polyfunctional solvents such as 1-methoxy-2-propanol and propylene glycol methyl ether acetate, trialkoxybenzenes (alkoxy group carbon number: 1 to 4), and methylene chloride.

[0191] When the resin composition contains an organic solvent (D), the content of the solvent in the resin composition is not particularly limited, and is, for example, preferably 0 parts by mass or more and 2000 parts by mass or less, more preferably 0 parts by mass or more and 1000 parts by mass or less, relative to 100 parts by mass of the total solid content of the polymer (A) and the compound (B). Furthermore, when the solubility of the polymer (A) or the compound (B) in the organic solvent (D) is high, the content of the organic solvent (D) in the resin composition may be 50 parts by mass or more and 200 parts by mass or less. The organic solvent (D) may be one type alone, or two or more types may be used in combination.

[0192] [Additives] Examples of additives used for the purpose of imparting the various functions include antioxidants, flame retardants, and adhesion aids. Specific examples of compounds include hindered phenol compounds, phosphorus compounds, sulfur compounds, metal compounds, and hindered amine compounds. Among these, hindered phenol compounds are preferred.

[0193] [Thermoplastic Resin (E)] Suitable examples of the thermoplastic resin (E) include hydrogenated styrene-based thermoplastic elastomers. The hydrogenated styrene-based thermoplastic elastomer may have some or all of the double bonds of the styrene-based thermoplastic elastomer hydrogenated. When the resin composition contains a hydrogenated styrene-based thermoplastic elastomer, a cured product with a lower dielectric constant and a lower dielectric loss tangent is more likely to be obtained.

[0194] The hydrogenated styrene-based thermoplastic elastomer may be synthesized or may be a commercially available product. Examples of commercially available hydrogenated styrene-based thermoplastic elastomers include Tuftec (registered trademark) H1517, H1062, H1041, H1043, S.O.E. (registered trademark) S1605 (all manufactured by Asahi Kasei Corporation, hydrogenated styrene-butadiene copolymer resins), Tuftec (registered trademark) M1913 (manufactured by Asahi Kasei Corporation, carboxylic acid-modified hydrogenated styrene-butadiene copolymer resin), Dynaron (registered trademark) 8903P (manufactured by ENEOS Materials Corporation, hydrogenated styrene-butadiene copolymer resin), Kraton (registered trademark) A1535 (KRATON Co., hydrogenated styrene-butadiene copolymer resin), Septon (registered trademark) V9461 (Kuraray Co., Ltd., hydrogenated styrene-4-methylstyrene-isoprene-butadiene copolymer resin having a styryl group), Tuftec (registered trademark) P1500 (Asahi Kasei Corporation, selectively hydrogenated styrene-butadiene copolymer resin), Tuftec (registered trademark) MP10 (Asahi Kasei Corporation, amine-modified selectively hydrogenated styrene-butadiene copolymer resin), Dynaron (registered trademark) 2324P (ENEOS Materials Corporation, hydrogenated styrene-butadiene (random) copolymer resin), and Tufprene (registered trademark) 912 (Asahi Kasei Corporation, styrene-butadiene copolymer resin).

[0195] The content of the thermoplastic resin (E) is preferably 3 to 90 mass%, more preferably 5 to 70 mass%, and even more preferably 5 to 50 mass%, relative to 100 mass% of the total solid content of the polymer (A) and the compound (B), from the viewpoints of obtaining a cured product that is excellent in compatibility and dispersibility of the thermoplastic resin (E) with other components and excellent in heat resistance and low dielectric loss tangent. The thermoplastic resin (E) may be used alone or in combination of two or more kinds.

[0196] [Filler (F)] The resin composition preferably further contains a filler (F). Examples of the filler (F) include organic fillers and inorganic fillers. Examples of inorganic fillers include silicas such as natural silica, fused silica, and amorphous silica, white carbon, titanium white, aerosil, alumina, talc, natural mica, synthetic mica, clay, barium sulfate, E-glass, A-glass, C-glass, L-glass, D-glass, S-glass, S-glass, and M-glass G20. Suitable examples of organic fillers include organic particles. Examples of organic particles are not particularly limited, and include (meth)acrylate resin particles, styrene resin particles, silicone resin particles, nylon resin particles, polyethylene resin particles, fluororesin particles, urethane resin particles, and liquid crystal polymer (hereinafter, sometimes referred to as "LCP") particles. The organic particles may be synthesized or commercially available. Examples of commercially available organic particles include polytetrafluoroethylene (PTFE) particles such as MPT-D116 and MPT-D115 (manufactured by Mitsubishi Pencil Co., Ltd.), LCP particles such as XYDAR (registered trademark) LF-31P (manufactured by ENEOS Corporation), and cross-linked polystyrene (PS) particles such as the SBX series (manufactured by Sekisui Plastics Co., Ltd.).

[0197] When the resin composition contains a filler (F), the content of the filler (F) is, for example, preferably 0.1 parts by mass or more and 300 parts by mass or less relative to 100 parts by mass of the total solid content of the polymer (A) and the compound (B). The filler (F) may be dispersed in a solvent by the polymer (A). The filler (F) may be used alone or in combination of two or more types.

[0198] [Method for preparing resin composition] The method for preparing the resin composition is not particularly limited and may be a known method, for example, by uniformly mixing the polymer (A), the compound (B), and the other components. In this case, the order of mixing the components, the mixing conditions, etc. are not particularly limited, and a conventionally known mixer may be used for mixing.

[0199] <<Cured Product>> A cured product according to one embodiment of the present invention (hereinafter also referred to as the "main cured product") comprises the resin composition described above. The cured product is a cured product of the aforementioned resin composition and is obtained by curing the aforementioned resin composition. The main cured product may be, for example, a partially cured product of the resin composition obtained by drying the solvent from the resin composition.

[0200] [Glass Transition Temperature (Tg)] The lower limit of the glass transition temperature (Tg) of the cured product is preferably 170° C., more preferably 200° C., and the upper limit is, for example, 400° C. When the Tg is within the above range, melt molding can be more easily performed, and a cured product with excellent heat resistance can be easily obtained.

[0201] Tg is determined by preparing a test piece (width: 3 mm x length: 1 cm) and measuring it under nitrogen using a dynamic viscoelasticity measuring device (Seiko Instruments Inc., model number "EXSTAR4000") from 50°C to 300°C at a heating rate of 10°C / min and 1 Hz, and then measuring it again at a heating rate of 10°C / min and 1 Hz up to 300°C, and measuring tan δ at this time as the glass transition temperature (Tg). When two or more tan δ are present, the lowest value is taken as Tg.

[0202] The dielectric loss tangent (tan δ) of the cured product is preferably 0.0025 or less, more preferably 0.0018 or less, and even more preferably 0.0015 or less, from the viewpoint of reducing transmission loss, etc. The lower limit is not particularly limited, but is preferably 0.0005 or more. Specifically, the dielectric loss tangent can be measured by the method described in the examples below.

[0203] The elongation of the present cured product, as determined by the same method as in the Examples, is 10% or less, more preferably 5% or less, and even more preferably 3% or less, with no particular lower limit. When the elongation is within this range, the difference in elongation between the present cured product and metal species such as copper wiring can be reduced. The elongation is determined by the method described in the Examples below.

[0204] The shape of the cured product is not particularly limited, and a suitable shape can be selected depending on the application, purpose, etc. Examples of the shape of the cured product include a film, a plate, a rod, etc. For example, a film-shaped cured product can be obtained by melt molding or cast molding the resin composition.

[0205] The thickness of the cured product is not particularly limited and may be appropriately selected depending on the desired application. The thickness of the cured product is, for example, 10 μm or more, preferably 30 μm or more, and for example, 2 mm or less, preferably 1 mm or less.

[0206] The laminate may include a layer of the cured product (cured product layer) and a substrate. The laminate may include two or more substrate layers, two or more cured product layers, or a conventionally known layer other than the substrate and the cured product layer. When the laminate includes two or more substrate layers, cured product layers, or other layers, these may be the same layer (plate) or different layers (plates).

[0207] The substrate may be an inorganic substrate, a metal substrate, a resin substrate, or the like, from the viewpoints of adhesiveness and practicality. The substrate may also be a prepreg. Examples of the inorganic substrate include inorganic substrates containing silicon, silicon carbide, silicon nitride, alumina, glass, gallium nitride, or the like as components. Examples of the metal substrate include metal substrates containing copper, aluminum, gold, silver, nickel, palladium, or the like as components. The shape of the metal substrate is not particularly limited, and may be a plate, metal foil, or the like.

[0208] Examples of the resin substrate include resin substrates containing liquid crystal polymer, polyimide, polyphenylene sulfide, polyether ether ketone, polyamide (nylon), polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, polyolefin, and the like.

[0209] The cured product layer can be formed by curing the composition by the method described in the section on cured products. The thickness of the cured product layer is not particularly limited, but is, for example, 1 μm to 3 mm.

[0210] <<Prepreg>> The prepreg according to the present invention is obtained by impregnating a fibrous substrate plate with the resin composition. The substrate is not particularly limited, and suitable examples include fibrous substrate plates such as glass cloth, aramid nonwoven fabric, and polyester nonwoven fabric. The prepreg may be a cured prepreg.

[0211] <Copper-Clad Laminate> The copper-clad laminate according to the present invention is a laminate of a prepreg described below and a copper substrate, and is preferably a laminate of a prepreg described below and a copper foil.

[0212] <<Applications>> The resin composition and cured product can be suitably used as structural materials in the transportation industry, such as the aircraft industry and the automobile industry, and as electrical and electronic materials in the electrical and electronics industry. Specific examples include sealing materials for electrical and electronic components, interlayer insulating films, and stress relaxation primers; laminate applications (e.g., prepregs, copper-clad laminates, (multilayer) printed wiring boards, interlayer adhesives, solder resists, and solder pastes); adhesive applications (e.g., adhesive sheets for forming insulating layers, thermally conductive adhesives, and adhesive sheets); structural adhesives and prepregs used in various structural materials; various coatings; optical component applications (e.g., optical films such as wavelength plates and retardation plates, various special lenses such as conical lenses, spherical lenses, and cylindrical lenses, and lens arrays); and insulating films for printed wiring boards. In particular, interlayer insulating films made from the cured products have low dielectric tangents, excellent adhesion, and heat resistance.

[0213] Examples of the electronic components include circuit boards, semiconductor packages, and display substrates. The cured product (cured film) can be used for these electronic components as prepregs, copper-clad laminates, printed wiring boards, adhesive sheets for forming insulating layers, surface protective films, rewiring layers, or planarizing films. Because the cured product can maintain its insulating properties even under high temperature and high humidity, electronic components equipped with the cured product can protect circuit patterns from external environments such as dust, heat, and humidity, and have excellent insulation reliability between circuit patterns, enabling stable operation over many years.

[0214] For example, the cured product can be used to fill metal between patterns formed on the cured product (cured film) by plating or the like, and if necessary, further cured products (cured films) can be stacked and metal filling can be repeated to form a rewiring layer, thereby producing an electronic component having a substrate and a rewiring layer including metal wiring and an insulating film.

[0215] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples in any way.

[0216] [Polymer A] [Synthesis Example 1] 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (25.4 g), 4,6-dichloropyrimidine (11.2 g), and potassium carbonate (14.0 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (85 g) was added. The mixture was reacted at 130°C for 6 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was diluted with N-methyl-2-pyrrolidone (300 g). The salt was removed by filtration, and the resulting solution was then poured into methanol (6 kg). The precipitated solid was filtered off, washed with a small amount of methanol, and recovered by filtration again. The solid was then dried under reduced pressure at 120°C for 12 hours using a vacuum dryer to obtain polymer (A-1) having a structural unit represented by the following formula:

[0217]

[0218] Synthesis Example 2 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (86.92 g), 4,6-dichloropyrimidine (47.58 g), and potassium carbonate (59.66 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (64.00 g) was added. The mixture was reacted at 130°C for 6 hours under a nitrogen atmosphere. After the reaction, allyl bromide (10.67 g) was added dropwise to the vessel cooled to 10°C, and the mixture was reacted at 70°C for 6 hours. The resulting reaction solution was diluted with N-methyl-2-pyrrolidone (368.0 g), and the salt was removed from the diluted solution by filtration. The resulting solution was then poured into methanol (19.40 kg). The precipitated solid was filtered off, washed with a small amount of methanol, and recovered by filtration again. The solid was then dried under reduced pressure at 120°C for 12 hours using a vacuum dryer to obtain a polymer (A-2) represented by the following formula:

[0219]

[0220] Synthesis Example 3 Polymer (A-3) represented by the following formula was obtained in the same manner as in Synthesis Example 2, except that the raw materials and alkali metal compound used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (51.27 g), isopropenylphenol (7.83 g), 4,6-dichloro-2-phenylpyrimidine (51.51 g), and potassium carbonate (35.93 g).

[0221]

[0222] Synthesis Example 4 Polymer (A-4) represented by the following formula was obtained in the same manner as in Synthesis Example 2, except that the raw materials and alkali metal compound used were changed to 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (33.85 g), 4,6-dichloro-2-phenylpyrimidine (16.66 g), m,p-chloromethylstyrene (8.680 g), potassium carbonate (18.66 g), and N-methyl-2-pyrrolidone (42.50 g).

[0223]

[0224] Synthesis Example 5 Polymer (A-5) represented by the following formula was obtained in the same manner as in Synthesis Example 2, except that the raw materials and alkali metal compound used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (25.63 g), 4,6-dichloro-2-phenylpyrimidine (29.25 g), 2-allylphenol (8.131 g), and potassium carbonate (24.31 g).

[0225]

[0226] Synthesis Example 6 Polymer (A-6) represented by the following formula was obtained in the same manner as in Synthesis Example 2, except that the raw materials used were changed to 2,2-bis(3-methyl-4-hydroxyphenyl)propane (64.09 g), 4,6-dichloro-2-phenylpyrimidine (31.08 g), 4,6-dichloropyrimidine (6.86 g), potassium carbonate (46.65 g), and m,p-chloromethylstyrene (22.01 g).

[0227]

[0228] Synthesis Example 7: 2,2-bis(3-methyl-4-hydroxyphenyl)propane (51.27 g), α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (21.23 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), and potassium carbonate (51.31 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (113.92 g) was added. The mixture was reacted at 130°C for 6 hours under a nitrogen atmosphere. After the reaction, m,p-chloromethylstyrene (38.55 g) was added dropwise with the vessel cooled to 10°C, and the mixture was reacted at 65°C for 6 hours. The resulting reaction solution was diluted with N-methyl-2-pyrrolidone (258.1 g), and the salt was removed by filtration. The resulting solution was then poured into methanol (4960 g). The precipitated solid was filtered off, washed with a small amount of methanol, and recovered by filtration again, and then dried under reduced pressure at 80°C for 12 hours using a vacuum dryer to obtain polymer (A-7) represented by the following formula: In the following formula, * represents a bond to any **.

[0229]

[0230] Polymer (A-8): Terminally modified polyphenylene ether (product name: Noryl ＴＭ SA9000 resin, manufactured by Sabic

[0231]

[0232] Polymer (A-9): Vinylbenzyl-modified polyphenylene ether resin (manufactured by Mitsubishi Gas Chemical Co., Inc., product name: "OPE-2St (Mw 1200)"

[0233]

[0234] [Synthesis Example 8] Copolymer A described in Example 1 of WO 2018 / 181842 was synthesized. It was confirmed that an equivalent copolymer was obtained by the method described in this example. The obtained copolymer was designated comparative polymer (A-10).

[0235] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn)] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polymers (A1) to (A7) and (A-10) synthesized in Synthesis Examples 1 to 8 and polymer (a1) used in Comparative Example 1 below were measured using a GPC apparatus (manufactured by Tosoh Corporation, model number: "HLC-8320") under the following conditions. The results are shown in Table 1. Column: "TSKgel α-M" manufactured by Tosoh Corporation and "TSKgelguard column α" manufactured by Tosoh Corporation connected together Developing solvent: N-methyl-2-pyrrolidone Column temperature: 40°C Flow rate: 1.0 mL / min Sample concentration: 0.75% by mass Sample injection amount: 50 μL Detector: refractometer Standard substance: monodisperse polystyrene Measurement sample concentration: 0.1% by mass

[0236]

[0237] [Compound B] (B-1) [Synthesis Example 9: Synthesis of compound (B-1)] Compound (B-1) was synthesized according to the following reaction scheme.

[0238] Aluminum chloride (99.1 g) was dispersed in dichloromethane (150 g) in a reaction vessel and cooled to 0°C. Acetyl chloride (63.0 g) was added dropwise thereto over 30 minutes. After the dropwise addition, the mixture was stirred for an additional 10 minutes, and a mixture of dichloromethane (50 g) and diphenylmethane (50.0 g) was added dropwise thereto over 45 minutes. After the dropwise addition, the reaction solution was warmed to room temperature and stirred for an additional 60 minutes. The reaction solution was added dropwise to 1N hydrochloric acid (250 g) cooled to 0°C over 90 minutes. After the dropwise addition was completed, the mixture was warmed to room temperature and stirred for an additional 60 minutes. The layers were separated, and the organic layer was washed four times with ultrapure water (100 g). The solvent was distilled off to a weight of 62.5 g. The resulting solution was stirred at room temperature, and hexane (391 g) was added to cause crystallization. The crystals were filtered to obtain compound (b-1) (55.5 g). １ H NMR (CDCl ３ ): δ7.90 (d, 4H), 7.27 (d, 4H), 4.09 (s, 2H), 2.58 (s, 6H)

[0239] Compound (b-1) (55.5 g) and methanol (160 g) were added to a reaction vessel and cooled to 0°C. Sodium borohydride (16.9 g) was added and the mixture was stirred at room temperature for 60 minutes. After the reaction, the mixture was cooled to 0°C, and ethyl acetate (267 g) and 1N hydrochloric acid (321 g) were added. After warming to room temperature, the mixture was stirred for 10 minutes and then separated. The resulting organic layer was washed three times with ultrapure water (213 g). The solvent was distilled off to obtain compound (b'-1) (51.7 g). １ H NMR (CDCl ３ ): δ7.32 (d, 4H), 7.20 (d, 4H), 4.90 (dt, 2H), 3.99 (s, 2H), 1.77 (d, 2H), 1.51 (d, 6H)

[0240] Compound (b'-1) (51.7 g, 0.202 mol), p-toluenesulfonic acid monohydrate (0.383 g), BHT (0.0446 g), and toluene (5000 g) were added to a reaction vessel and reacted at 110°C for 8 hours. After cooling to room temperature, 5% aqueous sodium bicarbonate (500 g) was added and the mixture was separated. The resulting organic layer was washed twice with ultrapure water (500 g) and concentrated. Hexane (200 g) and silica gel (30.0 g) were added to the resulting crude product and stirred for 10 minutes. The silica gel was removed by filtration, and the filtrate was concentrated to obtain compound (B-1) (33.3 g). １ H NMR (CDCl ３ ): δ7.33 (d, 4H), 7.14 (d, 4H), 6.70 (dd, 2H), 5.76 (d, 2H), 5.19 (d, 2H), 3.95 (s, 2H)

[0241]

[0242] (B-2) [Synthesis Example 10: Synthesis of compound (B-2)] Compound (B-2) was synthesized according to the following reaction scheme.

[0243] Under a nitrogen atmosphere, magnesium (13.5 g) and diethyl ether (378 g) were added to a reaction vessel equipped with a condenser, and the mixture was stirred at room temperature. Methyl iodide (75.3 g) was added dropwise over 1 hour. After the addition was completed, the mixture was stirred at room temperature for an additional 30 minutes. The mixture was cooled to 0°C, and a solution of (b-1) (60.9 g) dissolved in diethyl ether (378 g) was added dropwise over 1 hour. After the addition was completed, the mixture was warmed to room temperature and then stirred for an additional 2 hours. The reaction solution was poured into saturated aqueous ammonium chloride solution (328 g) cooled to 0°C to terminate the reaction. After the reaction was terminated, the layers were separated, and the organic layer was washed with ultrapure water (328 g). The solvent was evaporated to obtain compound (b-2) (65.9 g).

[0244] (b-2) (65.9 g), p-toluenesulfonic acid monohydrate (8.81 g), dibutylhydroxytoluene (0.0510 g), and toluene (1005 g) were added to a reaction vessel equipped with a Dean-Stark tube, and the mixture was refluxed and reacted for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and a 5% aqueous solution of sodium bicarbonate (500 g) was added and stirred for 10 minutes, followed by separation. The organic layer was washed with ultrapure water (500 g), and the solvent was distilled off. To the crude compound (B-2) obtained, hexane (250 g) and silica gel (50.0 g) were added, and the mixture was stirred for 10 minutes, and the silica gel was removed by filtration. The solvent was distilled off from the filtrate, yielding compound (B-2) (48.9 g).

[0245]

[0246] (B-3) [Synthesis Example 11: Synthesis of compound (B-3)] Compound (B-3) was synthesized according to the following reaction scheme.

[0247] Under a nitrogen atmosphere, bisphenol A (60.5 g) and dichloromethane (528 g) were added to a reaction vessel and cooled to 0°C. Trifluoromethanesulfonic anhydride (187 g) was added dropwise over 10 minutes, and then pyridine (52.4 g) was added dropwise over 30 minutes. After the dropwise addition was completed, the reaction solution was warmed to room temperature and stirred for an additional 23 hours. Ultrapure water (528 g) was added to terminate the reaction, and the organic layer was recovered by separation. The obtained organic layer was washed three times with ultrapure water (258 g), and the solvent was removed by distillation to obtain compound (b-3) (125 g). １ H NMR (CDCl ３ ): δ7.30-7.23 (m, 4H), 7.22-7.14 (m, 4H), 1.69 (s, 6H)

[0248] (b-3) (125 g), lithium chloride (53.9 g), dibutylhydroxytoluene (0.0560 g), bis(triphenylphosphine)palladium(II) dichloride (1.78 g), N,N-dimethylformamide (1126 g), and tributylvinyltin (169 g) were placed in a reaction vessel, and the atmosphere inside the vessel was replaced with nitrogen. The mixture was heated to 80°C and reacted for 15 hours. The reaction solution was cooled to room temperature, and water (1126 g), ethyl acetate (513 g), and hexane (513 g) were added and stirred, followed by separation. The resulting organic layer was washed four more times with water (1126 g). Silica gel (50.0 g) was added and stirred for 10 minutes, and the silica gel was removed by filtration. The resulting solution was concentrated to obtain compound (B-3) (52.4 g).

[0249]

[0250] (B-4) [Synthesis Example 12: Synthesis of Compound (B-4)] A pressure-resistant reaction vessel containing a magnetic rotor was heated and dried, and then the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 300 μmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 1.2 mmol of tris(2-methoxyphenyl)phosphine, 1.2 mmol of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (hereinafter also referred to as "XPhos"), 300 μmol of ADK STAB (hereinafter also referred to as "LA-7RD"), 60 mmol of cesium carbonate, and 30 mmol of pivalic acid were added. The inside of the reaction vessel was evacuated using a vacuum pump, and then the atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 30 mL of tetrahydrofuran, 30 mmol of 4-chlorostyrene, and 90 mmol of 1,2,3,5-tetrafluorobenzene were then added. The reaction vessel was sealed with a stopper, and the reaction solution was heated to 100°C using an oil bath and reacted for 8 hours while stirring. After the reaction was completed, the oil bath was removed and the solution was allowed to cool to room temperature. Toluene was then added to dilute the solution, and the solution was washed three times with water. The washed organic layer was concentrated using an evaporator to obtain compound (B-4).

[0251] The synthesis scheme of compound (B-4) is shown below.

[0252]

[0253] The NMR measurement results of the compound (B-4) are shown below. １ H-NMR (400MHz, CDCl ３ ): δ=5.33 (d, J=10.9Hz, 2H), 5.83 (d, J=18Hz, 2H), 6.76 (dd, J=18Hz and 11Hz, 2H), 7.43 (d, J=8Hz, 4H), 7.52 (d, J=8Hz, 4H).

[0254] (B-5) [Synthesis Example 13: Synthesis of Compound (B-5)] 59.1 mmol of 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene was added to a 500 mL four-neck flask containing a magnetic rotor, and the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 114 mL of dichloromethane and 590 mmol of pyridine were added, followed by cooling to 0°C in an ice bath, and 177 mol of trifluoromethanesulfonic anhydride was added dropwise. The four-neck flask was then returned to room temperature and reacted for 4 hours with stirring. The four-neck flask was again cooled to 0°C, and a 10% by mass aqueous hydrochloric acid solution was added to acidify the aqueous layer, after which the aqueous layer was separated. The organic layer was further washed twice with a 10% by mass aqueous hydrochloric acid solution and three times with pure water, and then concentrated using an evaporator. The resulting pale yellow oily liquid was purified by column chromatography (silica gel, toluene) to obtain BOC-FL-OTf (B-5(a)) as a highly viscous oily liquid.

[0255] The synthesis scheme of the compound (B-5(a)) is shown below.

[0256]

[0257] A pressure-resistant polymerization vessel containing a magnetic rotor was heated and dried, and then the internal atmosphere was replaced with nitrogen to form a nitrogen atmosphere. 7.41 mmol of BOC-FL-OTf (B-5(a)) obtained in Synthesis Example 13, 0.741 mmol of bis(triphenylphosphine)palladium(II) dichloride, 75.5 mmol of lithium chloride, and 0.371 mmol of LA-7RD were added. The inside of the reaction vessel was evacuated using a vacuum pump, and the atmosphere was replaced with nitrogen to form a nitrogen atmosphere. 40 mL of N,N-dimethylformamide and 17.8 mmol of tributyl(vinyl)tin were then added. The reaction vessel was then sealed with a stopper, and the reaction solution was heated to 125°C using an oil bath and reacted for 3 hours with stirring. After completion of the reaction, the oil bath was removed, and the mixture was allowed to cool to room temperature. Toluene was then added, and the mixture was washed three times with water. The washed organic layer was concentrated using an evaporator, and the resulting pale yellow oily liquid was purified by column chromatography (silica gel, toluene) and then concentrated to obtain compound (B-5) as a white powder.

[0258] The synthesis scheme of compound (B-5) is shown below.

[0259]

[0260] The NMR measurement results of the compound (B-5) are shown below. １ H-NMR (400MHz, CDCl ３ ): δ=2.11 (s, 3H), 5.20 (td, J=10 and 2Hz, 2H), 5.53 (dd, J=17 and 2Hz, 1H), 5.59 (dd, J=17 and 2Hz, 1H), 7.00-7.55 (m, 12H), 7.90 (d, J=2Hz, 2H).

[0261] (B-6) [Synthesis Example 14: Synthesis of Compound (B-6(a))] 57.9 mmol of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was added to a 500 mL four-neck flask containing a magnetic rotor, and the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 100 mL of dichloromethane and 579 mmol of pyridine were added, and the mixture was cooled to 0°C in an ice bath, and 177 mol of trifluoromethanesulfonic anhydride was added dropwise. The four-neck flask was then returned to room temperature, and the mixture was allowed to react for 4 hours with stirring. The four-neck flask was again cooled to 0°C, and a 10% aqueous hydrochloric acid solution was added to acidify the aqueous layer, which was then separated. The organic layer was further washed twice with a 10% aqueous hydrochloric acid solution and three times with pure water, and then concentrated using an evaporator. The resulting pale yellow oily liquid was purified by column chromatography (silica gel, toluene) to obtain BOC-TMC-OTf (B-6(a)) as a highly viscous oily liquid.

[0262] The synthesis scheme of the compound (B-6(a)) is shown below.

[0263]

[0264] Synthesis Example 15: Synthesis of Compound (B-6) A pressure-resistant polymerization vessel containing a magnetic rotor was heated and dried, and then the internal atmosphere was replaced with nitrogen to form a nitrogen atmosphere. 7.41 mmol of BOC-TMC-OTf (B-6(a)) obtained in Synthesis Example 14, 0.741 mmol of bis(triphenylphosphine)palladium(II) dichloride, 75.5 mmol of lithium chloride, and 0.371 mmol of LA-7RD were added. The inside of the reaction vessel was evacuated using a vacuum pump, and the atmosphere was replaced with nitrogen to form a nitrogen atmosphere. 40 mL of N,N-dimethylformamide and 17.8 mmol of tributyl(vinyl)tin were then added. The reaction vessel was then sealed with a stopper, and the reaction solution was heated to 125°C using an oil bath and reacted for 3 hours with stirring. After completion of the reaction, the oil bath was removed, and the mixture was allowed to cool to room temperature. Thereafter, toluene was added, and the mixture was washed three times with water. The washed organic layer was concentrated using an evaporator, and the resulting pale yellow oily liquid was purified by column chromatography (silica gel, toluene) and then concentrated to obtain compound (B-6) as a white powder.

[0265] The synthesis scheme of compound (B-6) is shown below.

[0266]

[0267] The NMR measurement results of the compound (B-6) are shown below. １ H-NMR (400MHz, CDCl ３ ): δ=0.38 (s, 3H), 0.87 (d, J=13Hz, 1H), 0.96-1.01 (bs, 6H), 1.12 (dd, J=14Hz and 12Hz, 1H), 1.37 (d, J = 13Hz, 1H), 1.90 (d, J = 14Hz, 1H), 2.01 (m, 1H), 2.28 (s, 3H), 2.30 (s, 3H), 2.48 (d, J = 11Hz, 1H), 2.71 (d, J = 14Hz, 1H), 5.20 (td, J = 10 and 2Hz, 2H), 5.53 (dd, J=17 and 2Hz, 1H), 5.59 (dd, J=17 and 2Hz, 1H), 6.86 (td, J=18 and 11Hz, 2H), 6.99-7.38 (m, 6H).

[0268] (B-7) [Synthesis Example 16: Synthesis of compound (B-7)] Compound (B-7) was synthesized according to the following reaction scheme.

[0269] Under a nitrogen atmosphere, 98.8 g of aluminum chloride and 250 g of dichloromethane were added to a reaction vessel and stirred, and the suspension was cooled to 0°C. 93.8 g of benzyl chloride was added over 10 minutes and stirred for an additional 10 minutes. Next, 25.5 g of mesitylene was added dropwise over 30 minutes. After the dropwise addition was completed, the reaction solution was warmed to room temperature and stirred for 3 hours. The reaction solution was added dropwise to 500 g of 1N hydrochloric acid cooled to 0°C over 1 hour, warmed to room temperature, and stirred for 30 minutes. The layers were separated, and the resulting organic layer was washed three times with 500 g of water. The solvent was distilled off, yielding 69.4 g of (b-7). (B-7) was obtained in the same manner as in Synthesis Example 9, except that (b-7), (b'-7), and (b"-7) were used as raw materials and intermediates. However, the number of moles of compounds excluding (b-7), (b'-7), (b"-7) and the solvent was 1.5 times that of Synthesis Example 9.

[0270]

[0271] (B-8) [Synthesis Example 17: Synthesis of Compound (B-8)] A pressure-resistant reaction vessel containing a magnetic rotor was heated and dried, and then the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 150 μmol of tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, 600 μmol of tris(2-methoxyphenyl)phosphine, 600 μmol of XPhos, 500 μmol of LA-7RD, 60 mmol of cesium carbonate, and 15 mmol of pivalic acid were added. The inside of the reaction vessel was evacuated using a vacuum pump, and the atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 30 mL of tetrahydrofuran, 49.5 mmol of 4-chlorostyrene, and 15 mmol of 1,2,3,5-tetrafluorobenzene were then added. The reaction vessel was sealed with a stopper, and the reaction solution was heated to 100°C using an oil bath and reacted for 8 hours with stirring. After completion of the reaction, the oil bath was removed and the mixture was allowed to cool to room temperature. The mixture was then diluted with toluene and washed three times with water. The washed organic layer was concentrated using an evaporator to obtain compound (B-8).

[0272] The synthesis scheme of compound (B-8) is shown below.

[0273]

[0274] The NMR measurement results of the compound (B-8) are shown below. １ H-NMR (400MHz, CDCl ３ ): δ=5.31 (d, J=11Hz, 3H), 5.82 (d, J=18Hz, 3H), 6.76 (dd, J=18Hz and 11Hz, 3H), 7.39-7.62 (m, 12H).

[0275] (B-9) [Synthesis Example 18: Synthesis of Compound (B-9(a))] 18.69 g of 4,4',4'',4'''-[isopropylidenebis(cyclohexane-4-yl-1-ylidene)]tetrakis(2-methylphenol) was added to a 500 mL four-neck flask containing a magnetic rotor, and the internal atmosphere was replaced with nitrogen to create a nitrogen atmosphere. 100 mL of dichloromethane and 47.6 mL of pyridine were added, and the mixture was cooled to 0°C in an ice bath, and 29.8 mL of trifluoromethanesulfonic anhydride was added dropwise. The four-neck flask was then returned to room temperature, and the mixture was reacted for 3 hours with stirring. The four-neck flask was again cooled to 0°C, and a 10% aqueous hydrochloric acid solution was added to acidify the aqueous layer, which was then separated. The organic layer was further washed twice with a 10% aqueous hydrochloric acid solution and three times with pure water, and then concentrated using an evaporator. The resulting pale yellow oily liquid was purified by column chromatography (silica gel, toluene) to obtain TOC-4HBPA-OTf (B-9(a)) as a powder.

[0276] The synthesis scheme of the compound (B-9(a)) is shown below.

[0277]

[0278] Synthesis Example 19: Synthesis of Compound (B-9) A pressure-resistant polymerization vessel containing a magnetic rotor was heated and dried, and then the internal atmosphere was replaced with nitrogen to form a nitrogen atmosphere. 3.00 mmol of TOC-4HBPA-OTf (B-9(a)) obtained in Synthesis Example 18, 0.600 mmol of bis(triphenylphosphine)palladium(II) dichloride, 61.1 mmol of lithium chloride, and 0.300 mmol of LA-7RD were added. The inside of the reaction vessel was evacuated using a vacuum pump, and the atmosphere was replaced with nitrogen to form a nitrogen atmosphere. 63 mL of N,N-dimethylformamide and 14.4 mmol of tributyl(vinyl)tin were then added. The reaction vessel was then sealed with a stopper, and the reaction solution was heated to 125°C using an oil bath and reacted for 3 hours with stirring. After completion of the reaction, the oil bath was removed, and the mixture was allowed to cool to room temperature. Toluene was then added, and the mixture was washed three times with water. The washed organic layer was concentrated using an evaporator, and the resulting pale yellow oily liquid was purified by column chromatography (silica gel, toluene) and then concentrated to obtain compound (B-9) as a white powder.

[0279] The synthesis scheme of compound (B-9) is shown below.

[0280]

[0281] The NMR measurement results of the compound (B-9) are shown below. １ H-NMR (400MHz, CDCl ３ ): δ = 0.52 (s, 6H), 1.19 (q, J = 13Hz, 4H), 1.61 (d, J = 12Hz, 4H), 1.83 (t, J = 11 Hz, 4H), 2.27 (s, 6H), 2.32 (s, 6H), 2.71 (d, J = 13Hz, 4H), 5.21 (ddd, J = 18, 11 and 1Hz, 4H), 5.21 (ddd, J=18, 11 and 1Hz, 4H), 5.54 (dd, J=18 and 2Hz, 2H), 5.62 (dd, J=18 and 2Hz, 2H), 6.81-6.91 (m, 4H), 6.94-6.99 (m, 4H), 7.09 (s, 2H), 7.17 (d, J = 8Hz, 2H), 7.31 (d, J = 8Hz, 2H), 7.42 (d, J = 8Hz, 2H).

[0282] (B-10) [Synthesis Example 20: Synthesis of compound (B-10)] Compound (B-10) was synthesized according to the following reaction scheme.

[0283] Under a nitrogen atmosphere, polystyrene (70.0 g, Mn = 810), acetyl chloride (18.4 g), and dichloromethane (700 g) were added to a reaction vessel and stirred at 0°C. Aluminum chloride (31.4 g) was added over 15 minutes, and the reaction solution was warmed to room temperature. After warming, the mixture was stirred at room temperature for an additional 3 hours. The reaction solution was added dropwise to 1N hydrochloric acid (350 g) cooled to 0°C over 1 hour, warmed to room temperature, and stirred for an additional 30 minutes. The layers were separated, and the resulting organic layer was washed four times with ultrapure water (350 g). The solvent was removed, and the resin was redissolved in tetrahydrofuran (140 g). This resin solution was added dropwise to stirred methanol (1000 g). The precipitated solid was filtered to obtain (b-10) (69.8 g, acetylation rate 32%). １３ C NMR (CDCl ３): δ197.7, 152.0-149.0, 146.0-143.1, 135.1, 129.5-125.5, 46.0-39.6, 26.5

[0284] (b-10) (69.8 g, acetylation rate 32%) and methanol (700 g) were added to a reaction vessel, stirred, and cooled to 0°C. Sodium borohydride (14.4 g) was added over 15 minutes, the temperature was raised to room temperature, and stirring was continued for an additional 3 hours. The reaction solution was cooled again to 0°C, and ethyl acetate (400 g) was added, followed by the addition of 2N hydrochloric acid (800 g) over 1 hour. The layers were separated, and the resulting organic layer was washed three times with ultrapure water (800 g). The solvent was distilled off to obtain (b'-10) (70.3 g). １３ C NMR (DMSO-d ６ ): δ148.1-142.3, 131.6-123.1, 68.6, 26.4

[0285] In a reaction vessel equipped with a Dean-Stark tube, (b'-10) (70.3 g), p-toluenesulfonic acid monohydrate (3.59 g), dibutylhydroxytoluene (0.416 g), and toluene (7000 g) were added and heated under reflux for 8 hours. After cooling to room temperature, a 5% aqueous solution of sodium bicarbonate (700 g) was added and the mixture was separated. The resulting organic layer was washed twice with ultrapure water (700 g) and the solvent was distilled off. The crude product was redissolved in tetrahydrofuran (140 g), and this resin solution was added dropwise to stirred methanol (1000 g). The precipitated solid was filtered off to obtain compound (B-10) (47.6 g). １３ The results of the C NMR measurement are shown below. １３ C NMR (DMSO-d ６ ): δ146.4-139.8, 134.0, 130.1-121.6, 112.4, 29.1-24.6

[0286]

[0287] (B-11) [Synthesis Example 21: Synthesis of compound (B-11)] Compound (B-11) was synthesized according to the following reaction scheme.

[0288] Styrene (40.0 g), p-chlorostyrene (22.8 g), and dehydrated toluene (70.0 g) were mixed to prepare a monomer solution. Under a nitrogen atmosphere, dehydrated toluene (420 g) and n-butyllithium (1.6 mol / L, 49.1 ml) were added to a reaction vessel and cooled to 0°C. The prepared monomer solution was added dropwise over 10 minutes, and the reaction was continued for another 3 hours. Methanol (5.03 g) was added to terminate the polymerization. The obtained resin solution was added dropwise to stirred methanol (2800 g). The precipitated solid was filtered and dried to obtain (b-11) (59.2 g).

[0289] Under a nitrogen atmosphere, magnesium (3.85 g), tetrahydrofuran (230 g), and iodine (0.788 g) were added to a reaction vessel equipped with a condenser and stirred at 60°C for 15 minutes. Next, a solution of (b-11) (59.2 g) in tetrahydrofuran (180 g) was added dropwise over 30 minutes, and after the completion of the dropwise addition, the mixture was heated at 60°C for an additional 30 minutes. [1,3-bis(diphenylphosphino)propane]dichloronickel(II) (5.04 g) and 1-chloromethyl-4-vinylbenzene (24.9 g) were added to the reaction solution, and the mixture was reacted at 60°C for 4 hours. After the reaction solution was cooled to room temperature, ethyl acetate (450 g) and 1N hydrochloric acid (450 g) were added and the mixture was separated. The resulting organic layer was washed four times with ultrapure water (450 g). The resulting resin solution was filtered using a Kiriyama funnel with 1 cm of silica on filter paper, and the solvent from the filtrate was distilled off. The crude product was redissolved in tetrahydrofuran (120 g), and the resin solution was added dropwise to stirred methanol (900 g). The precipitated solid was filtered and dried to obtain compound (B-11) (53.2 g).

[0290]

[0291] (B-12) [Synthesis Example 22: Synthesis of compound (B-12)] Compound (B-12) was synthesized according to the following reaction scheme.

[0292] Styrene (27.1 g), p-chlorostyrene (36.1 g), butadiene (15% by mass hexane solution, 46.9 g), and dehydrated toluene (70.0 g) were mixed to prepare a monomer solution. Under a nitrogen atmosphere, dehydrated toluene (420 g) and n-butyllithium (1.6 mol / L, 54.8 ml) were added to a reaction vessel and cooled to 0°C. The prepared monomer solution was added dropwise over 10 minutes, and the reaction was continued for another 3 hours. Methanol (5.63 g) was added to terminate the polymerization. The obtained resin solution was added dropwise to stirred methanol (2800 g). The precipitated solid was filtered and dried to obtain (b-12) (68.5 g).

[0293] Under a nitrogen atmosphere, magnesium (6.30 g), tetrahydrofuran (260 g), and iodine (1.29 g) were added to a reaction vessel equipped with a condenser and stirred at 60°C for 15 minutes. Next, a solution of (a-15) (68.5 g) in tetrahydrofuran (210 g) was added dropwise over 30 minutes, and after the completion of the dropwise addition, the mixture was heated at 60°C for an additional 30 minutes. To the reaction solution, [1,3-bis(diphenylphosphino)propane]dichloronickel(II) (8.26 g) and 1-chloromethyl-4-vinylbenzene (40.7 g) were added, and the mixture was reacted at 60°C for 4 hours. After the reaction solution was cooled to room temperature, ethyl acetate (500 g) and 1N hydrochloric acid (500 g) were added and the mixture was separated. The resulting organic layer was washed four times with ultrapure water (500 g). The resulting resin solution was filtered using a Kiriyama funnel with 1 cm of silica on filter paper, and the solvent from the filtrate was distilled off. The crude product was redissolved in tetrahydrofuran (140 g), and the resin solution was added dropwise to stirred methanol (1000 g). The precipitated solid was filtered and dried to obtain compound (B-12) (57.8 g).

[0294]

[0295] (B-13) [Synthesis Example 23: Synthesis of compound (B-13)] Compound (B-13) was synthesized in the same manner as in Synthesis Example 9, except that diphenylmethane was changed to 93.5 g of the following compound (ba13). The NMR measurement results of compound (B-13) are shown below. １ H NMR (CDCl ３): δ7.15-7.08 (m, 12H), 6.72 (dd, 2H), 5.76 (d, 2H), 5.20 (d, 2H), 1.67 (s, 12H)

[0296]

[0297] (B-14) [Synthesis Example 24: Synthesis of compound (B-14)] Compound (B-14) was synthesized in the same manner as in Synthesis Example 13, except that 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene was changed to 59.1 mmol of the following compound (ba14). The NMR measurement results of compound (B-14) are shown below. １ H-NMR (400MHz, CDCl ３ ): δ = 0.87 (s, 6H), 1.32-2.02 (br, 28H), 2.72 (quin, 2H), 5.20 (td, J = 10 and 2Hz, 2H), 5.53 (dd, J = 17 and 2Hz, 1H), 5.59 (dd, J = 17 and 2Hz, 1H), 6.86 (td, J=18 and 11Hz, 2H), 6.99-7.38 (m, 6H).

[0298]

[0299] In Table 5, b-1 to b-5 are the following compounds: b-1: TAIC (manufactured by Shinryo Corporation (formerly MGC), triallyl isocyanurate) b-2: DVB960 (manufactured by Nippon Steel Chemical & Material Co., Ltd., divinylbenzene) b-3: BVPE (1,2-bis(vinylphenyl)ethane) b-4: TVPB (4,4''-divinyl-5'-(4-vinylphenyl)-1,1':3',1''-terphenyl) b-5: -70 (manufactured by K.I. Chemical Co., Ltd.), bismaleimide

[0300]

[0301]

[0302]

[0303]

[0304] [Examples 1 to 61 and Comparative Examples 1 to 9] The components listed in the "Composition Type" column in Table 6 or Table 7 below were mixed in a mixer rotor to the ratio (parts by mass) listed in the "Composition Blend Ratio" column, and the concentrations of Examples 1 to 41, 43 to 61, and Comparative Examples 1 to 9 were adjusted with toluene, and Example 42 was adjusted with a 50 / 50 (mass ratio) toluene / methyl ethyl ketone mixture to achieve the solids concentration shown in Table 6 or Table 7. A "-" in Table 6 or Table 7 indicates that the corresponding component was not included.

[0305]

[0306]

[0307] Details of each component in Table 6 or Table 7 are as follows: <Polymerization initiator (C)> C1: dicumyl peroxide (manufactured by NOF Corporation) C2: Perbutyl P (α,α'-di(t-butylperoxy)diisopropylbenzene, manufactured by NOF Corporation) C3: Perbutyl C (t-butylcumyl peroxide, manufactured by NOF Corporation)

[0308] <Filler (F)> F1: Fused spherical silica "GT grade" (average particle size: 3 μm) (manufactured by Denka Co., Ltd.)

[0309] <Solubility> Compound (B) used in the examples and comparative examples was dissolved in toluene (TL) under conditions of 25°C and 1 atmosphere, and the solubility of compound (B) was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 8 or Table 9. Evaluation criteria of "4" and "5" indicate excellent solubility. -Evaluation criteria- 5: Compound (B) was dissolved in toluene (TL) at 50% by mass or more. 4: Compound (B) was dissolved in toluene (TL) at 30% by mass or more and less than 50% by mass. 3: Compound (B) was dissolved in toluene (TL) at 20% by mass or more and less than 30% by mass. 2: Compound (B) was dissolved in toluene (TL) at 10% by mass or more and less than 20% by mass. 1: Compound (B) was dissolved in toluene (TL) at less than 10% by mass.

[0310] <Compatibility> The compositions prepared in the Examples and Comparative Examples were dissolved and mixed in toluene (TL) at a solids concentration of 30% or more under conditions of 25°C and 1 atmosphere, and the compositions were then visually inspected and evaluated according to the following evaluation criteria. The evaluation results are shown in Table 8 or Table 9. A rating of "5" on the evaluation criteria indicates excellent compatibility. - Evaluation criteria - 5: The composition was compatible with toluene (TL). 4: The composition was cloudy. 3: Phase separation occurred between toluene (TL) and the composition, or the solid content of the composition was undissolved.

[0311] <Heat resistance (Td1)> Compound (B) used in the examples and comparative examples was weighed into a pan, and measured using a TG-DTA (manufactured by NETZSCH Corporation, model number: "TG 209 F1 Libra (registered trademark)") from 30°C to 600°C at a heating rate of 20°C / min. The 1% weight loss temperature at this time was defined as Td1, and evaluated according to the following criteria. The evaluation results are shown in Table 8 or Table 9. Note that compounds with evaluation criteria of "4" and "5" can be said to have excellent heat resistance. - Evaluation criteria - 5: Td1 is 250°C or higher. 4: Td1 is 200°C or higher but lower than 250°C. 3: Td1 is 130°C or higher but lower than 200°C. 2: Td1 is 100°C or higher but lower than 130°C. 1: Td1 is lower than 100°C.

[0312] <Preparation of Cured Film> The compositions obtained in the above Examples and Comparative Examples were applied to copper foil (model number: SI-VSP-AM2R; Taiwan Copper Foil Co., Ltd.) using a Baker-type applicator (gap: 125 μm), heated at 100°C for 5 minutes, and then dried at 140°C for 5 minutes to form a coating film. Copper foil (model number: SI-VSP-AM2R; Taiwan Copper Foil Co., Ltd.) was placed on the resulting coating film, vacuum pressed at 160°C for 10 minutes, and then baked at 200°C under nitrogen for 2 hours to produce a copper foil-attached cured film (copper foil thickness: 18 μm, cured film thickness: 50 to 100 μm). The resulting copper foil-attached cured film was immersed in a 40% by mass iron chloride solution, the copper foil was removed, washed with water, and dried in an oven at 80°C for 30 minutes to produce a cured film with a thickness of 50 to 100 μm.

[0313] <Dielectric Dissipation Factor> Test specimens (width: 6 cm x length: 6 cm) were cut out from the prepared cured films, and the dielectric dissipation factor (Df) of the test specimens at 10 GHz was measured using a cavity resonator method (TE mode resonator, dielectric constant measurement system, manufactured by AET Corporation), and evaluated according to the following criteria. The evaluation results are shown in Table 8 or Table 9. In the evaluation criteria, a value of "4" or higher can be said to have a low dielectric dissipation factor. -Evaluation criteria- 1: 0.0020<Df (i.e., the dielectric dissipation factor exceeds 0.0020). 2: 0.0016<Df≦0.0020 (i.e., the dielectric dissipation factor is greater than 0.0016 and equal to or less than 0.0020). 3: 0.0013<Df≦0.0016 (i.e., the dielectric dissipation factor is greater than 0.0013 and equal to or less than 0.0016). 4: 0.0010<Df≦0.0013 (i.e., the dielectric dissipation factor is greater than 0.0013 and equal to or less than 0.0016). 5: Df≦0.0010 (i.e., the dielectric dissipation factor is equal to or less than 0.0010).

[0314] <Elongation> Test specimens (width: 3-4 mm x length: 2 cm) were cut from the prepared cured films and measured using a Seiko Instruments SSC-5200 TMA measuring device. The evaluation film was heated from room temperature to 300°C at a rate of 5°C / min, and the elongation of the film from the initial temperature to 260°C was calculated and evaluated according to the following criteria. The evaluation results are shown in Table 8 or Table 9. Note that, according to the following evaluation criteria, a score of 3 indicates a low elongation, and a score of 4 or higher indicates an even lower elongation. Elongation (%) = (length of test piece at 260°C - initial length of test piece) / initial length of test piece × 100 Evaluation criteria 1: 5% < elongation (i.e., elongation exceeds 5%) 2: 4% < elongation ≦ 5% (i.e., elongation exceeds 4% and is 5% or less) 3: 3% < elongation ≦ 4% (i.e., elongation exceeds 3% and is 4% or less) 4: 2% < elongation ≦ 3% (i.e., elongation exceeds 2% and is 3% or less) 5: elongation ≦ 2% (i.e., elongation is 2% or less)

[0315] <Dielectric Constant> Each of the compositions obtained in Examples 1 to 61 was spin-coated onto a 3-inch quartz substrate, dried at 100°C for 5 minutes, and baked at 200°C for 2 hours under nitrogen to prepare a substrate for dielectric constant measurement in which a cured film was formed on the quartz substrate. The dielectric constant of the quartz substrate before coating and the prepared substrate for dielectric constant measurement were each measured at 10 GHz using a cavity resonator method (dielectric constant measurement system TE mode resonator, manufactured by AET Corporation).

[0316] When the dielectric constant when a quartz substrate was used was Dk1, the thickness of the quartz substrate was t1, the dielectric constant of the cured film was Dk2, the thickness of the cured film was t2, and when the dielectric constant when a substrate for dielectric constant measurement was used was Dk3, the thickness of the substrate for dielectric constant measurement was t3, the dielectric constant (Dk2) of the cured film was calculated using the following formula: Dielectric constant (Dk2) of cured film = {(Dk3 × t3) - (Dk1 × t1)} / t2 The dielectric constants (Dk2) of the cured films made from the compositions of Examples 1 to 61 were all 2.5 to 2.6, which were low dielectric constants.

[0317]

[0318]

[0319] It can be seen that the cured products obtained from the compositions of Examples 1 to 61 have a lower dielectric constant, a lower dielectric dissipation factor, and a lower elongation percentage, as well as excellent heat resistance, compared to the cured products obtained from the compositions of Comparative Examples 1 to 9.

Claims

1. A resin composition comprising: a polymer (A) having an ethylenically unsaturated double bond and having a weight average molecular weight (Mw) of 1,500 or more and 500,000 or less; and a compound (B) having two or more groups represented by the following formula (Y) and satisfying the following conditions (α1), (α2), and (α3): In formula (Y), R ３１ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and * represents a bonding site with other parts in compound (B). <Conditions> (α1) The molecular weight is 1,000 or less. (α2) The solubility in toluene at 25°C and 1 atmosphere is 20% by mass or more. (α3) The 1% weight loss temperature measured by simultaneous differential thermal analysis - thermogravimetry (TG / DTA) is greater than 130°C.

2. The resin composition according to claim 1, wherein the polymer (A) is at least one resin selected from the group consisting of polyphenylene ether resins, polyfunctional vinyl aromatic copolymers, and heteroaromatic-aromatic ether resins.

3. The resin composition according to claim 1, wherein the compound (B) is at least one compound selected from the group consisting of compounds represented by the following formula (1A), formula (1B) or formula (2), or compounds containing structural units represented by formula (4a), formula (4b) and formula (4c). In formula (1A), R １１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; １２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R １３ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. １３ n12 is an integer of 2 to 4, n13 is an integer of 0 to 6, n14 is an integer of 1 to 12, and n15 is 1 or 2; when n15 is 1, R １０ is a hydrogen atom, and when n15 is 2, R １０ is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms. In formula (1B), R １１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; R １２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R １０ is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms; R ３１ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In formula (2), A １ and A ２ represent groups represented by the following formula (A-1) and formula (A-2), respectively, n22 is an integer of 2 to 4, n25 is an integer of 1 to 4, R ２０ is a hydrogen atom when n25 is 1, and is a single bond, a substituted or unsubstituted methylene group, or an n25-valent hydrocarbon group having 2 to 10 carbon atoms when n25 is an integer of 2 to 4. In formula (A-1), R ２１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; R ２２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ２４ is a single bond, a substituted or unsubstituted methylene group, or an alkanediyl group having 2 to 10 carbon atoms, and # in formula (A-1) represents the bonding site with ## in formula (A-2). ２Ｘ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; R ２３ are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom, n23 is an integer of 0 to 4, n24 is 0 or 1, ## in formula (A-2) represents a bonding site with # in formula (A-1), * represents R in formula (2), ２０ where n25 in formula (2) is 1, n23+n22 is a number equal to or less than the maximum number of substituents on the aromatic ring included in formula (A-2), and where n25 in formula (2) is 2 to 4, n22+n23+1 is a number equal to or less than the maximum number of substituents on the aromatic ring included in formula (A-2). In formula (4a), formula (4b) and formula (4c), Ar ４１ and Ar ４２ each independently represents a divalent aromatic hydrocarbon group; ４１ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms; R ４２ each independently represents a vinyl group or a monovalent organic group having a vinyl group; R ４３ represents a group derived from a chain diene hydrocarbon compound, * represents a bonding site with another structural unit, n41 is 1 or 2, and the total number of structural units a, b, and c is 1, where a is 0.1 to 0.8, b is 0.1 to 0.8, and c is 0 to 0.

8.

4. The resin composition according to claim 3, wherein compound (B) is a compound represented by formula (1A) or formula (1B), and the compound represented by formula (1A) or formula (1B) is a compound represented by the following formula (1-1) or formula (1-2): In formula (1-1), R １１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; １２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R １３ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. １３ n12 is an integer of 2 to 4, n13 is an integer of 0 to 6, and n14 is an integer of 1 to 12. In formula (1-2), R １１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; １２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R １３ are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or one or more other R groups present on the same carbon atom or adjacent carbon atoms. １３ n12 is an integer of 2 to 4, n13 is an integer of 0 to 6, and n14 is an integer of 1 to 12; R １０ is a single bond, a substituted or unsubstituted methylene group, or a divalent hydrocarbon group having 2 to 20 carbon atoms.

5. The resin composition according to claim 3, wherein compound (B) is a compound represented by formula (2), and the compound represented by formula (2) is a compound represented by formula (2-1) below: In formula (2-1), A １ and A ２ represent groups represented by the following formula (A-1) and formula (A-3), respectively, and n22 is an integer of 2 to 4. In formula (A-1), R ２１ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms substituted with an aryl group; R ２２ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ２４ is a single bond, a substituted or unsubstituted methylene group, or an alkanediyl group having 2 to 10 carbon atoms, and # in formula (A-1) represents the bonding site with ## in formula (A-3). ２Ｘ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; R ２３ are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom, n22 is an integer of 2 to 4, n23 is an integer of 0 to 4, n24 is 0 or 1, and ## in formula (A-3) represents a bonding site with # in formula (A-1), provided that n23 + n22 is a number equal to or less than the maximum number of substituents on the aromatic ring contained in formula (A-3).

6. The resin composition according to claim 1, further comprising a polymerization initiator (C).

7. The resin composition according to claim 1, further comprising an organic solvent (D).

8. The resin composition according to claim 1, further comprising a thermoplastic resin (E) different from the polymer (A) and the compound (B).

9. The resin composition according to claim 1, further comprising a filler (F).

10. A cured product made from the resin composition of claim 1.

11. A prepreg obtained by impregnating a fibrous substrate with the resin composition described in claim 1.

12. A copper clad laminate obtained by laminating the prepreg according to claim 11 and a copper substrate.

13. An interlayer insulating film comprising the cured product according to claim 10.

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