Resin composition, cured article, prepreg, copper-clad laminate board, interlayer insulation film, and compound

Abstract

Provided are: a resin composition comprising a compound (A) that comprises at least one compound selected from the group consisting of a compound (A1) having two or more partial structures represented by formula (1) and a compound (A2) represented by formula (2) and a polymer (B) having a group crosslinkable with the compound (A) and an aromatic ring; a cured article; a prepreg; a copper-clad laminate board; an interlayer insulation film; and a compound. The explanation for each substituent in the formulae is as described in the description.

Description

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

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

[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 that can give a cured product having a low dielectric constant, a low dielectric dissipation factor, and a low elongation percentage, and that has a well-balanced excellent solubility, adhesion, and heat resistance. 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 having a low dielectric constant, a low dielectric dissipation factor, and a low elongation percentage, and that has a well-balanced excellent solubility, adhesion, and heat resistance. Another problem to be solved by one embodiment of the present invention is to provide a novel compound.

[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 compound (A) which is at least one of a compound (A1) having two or more partial structures represented by the following formula (1) and a compound (A2) represented by the following formula (2); and a polymer (B) having a group crosslinkable with the compound (A) and an aromatic ring.

[0009]

[0010] In formula (1), Ar represents an aromatic ring having 6 to 10 carbon atoms, L represents an oxygen atom, a methylene group, an alkylene group having 2 to 6 carbon atoms, or a group formed by combining two or more groups selected from these groups, and R １１ are each independently bonded to a carbon atom that is a ring member of Ar adjacent to the carbon atom that is a ring member of Ar to which L is bonded, and are a hydrogen atom or a monovalent organic group, provided that two R １１ At least one of R is a monovalent organic group; １２ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R １３ is an alkyl group having 1 to 10 carbon atoms, an allyl group, or a vinyl group, and m １１ is 4, and m １２ is 0 or 1, and * represents a binding site with another structure.

[0011]

[0012] In formula (2), R ２１ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms, or two R ２１ represents a ring structure having 5 to 10 ring members formed by combining together with the carbon atoms to which they are attached, and R ２２ and R ２３ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms, and at least one R ２２ is a group represented by formula (2-1), and at least one R２３ is a group represented by formula (2-1). ２２ At least one of the two substituents bonded to the two carbon atoms adjacent to the group represented by formula (2-1) is an alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms, and ２３ At least one of the two substituents bonded to the two carbon atoms adjacent to L and R is an alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms. １２ , and m １１ are L and R in formula (1). １２ , and m １１ and * is R ２２ or R ２３ represents the bonding site with the carbon atom of the benzene ring to which it is attached.

[0013] <2> The resin composition according to <1>, wherein the compound (A1) is a compound represented by the following formula (1-1) or the following formula (1-2):

[0014]

[0015] In formula (1-1), R １１ , R １２ , R １３ , L, m １１ , and m １２ is R in formula (1) １１ , R １２ , R １３ , L, m １１ , and m １２ It is synonymous with R １３ is an alkyl group having 1 to 5 carbon atoms, R １３ may be a linking group bonded to a carbon atom that is a ring member of another Ar in formula (1-1), and —CH ２ - may be replaced by -O- or -S-. A is a single bond or n １１A is an aryl group selected from the group consisting of an oxygen atom, a sulfur atom, an unsubstituted or substituted methylene group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by any one of the following formulae (10-1) to (10-3), or a group consisting of a combination of two or more of these groups; or A is R １３ and the carbon atoms to which they are attached are combined together to form a ring structure having 3 to 20 ring members, １１ represents an integer of 2 to 4. In formula (1-2), R １１ , R １２ , R １３ , L, m １１ , and m １２ is R in formula (1) １１ , R １２ , R １３ , L, m １１ , and m １２ However, A in formula (1-2) is bonded to a carbon atom that is a ring member of Ar and is adjacent to the carbon atom that is a ring member of Ar to which L is bonded. １３ is an alkyl group having 1 to 5 carbon atoms, R １３ may be a linking group bonded to a carbon atom that is a ring member of another Ar in formula (1-2), and —CH ２ - may be replaced by -O- or -S-. A is a single bond or n １２ a 2-valent group, which is an oxygen atom, a sulfur atom, an unsubstituted or substituted methylene group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by any one of the following formulas (10-1) to (10-3), or a group formed by combining two or more of these groups; １２ represents an integer of 2 to 4.

[0016]

[0017] In formulas (10-1) to (10-3), * represents a bonding site with Ar in formula (1-1) or formula (1-2).

[0018] <3> The resin composition according to <1> or <2>, wherein the polymer (B) is at least one resin selected from the group consisting of a polyphenylene ether resin, a polyfunctional vinyl aromatic copolymer, and a heteroaromatic-aromatic ether resin. <4> The resin composition according to any one of <1> to <3>, further comprising a polymerization initiator (C). <5> The resin composition according to any one of <1> to <4>, further comprising a hydrogenated styrene-based thermoplastic elastomer (E). <6> The resin composition according to any one of <1> to <5>, further comprising an organic solvent (D). <7> The resin composition according to any one of <1> to <6>, further comprising a filler (F). <8> A cured product comprising the resin composition according to any one of <1> to <7>. <9> A prepreg obtained by impregnating a fibrous substrate with the resin composition according to any one of <1> to <7>. <10> A copper-clad laminate obtained by laminating the prepreg according to <9> and a copper substrate. <11> An interlayer insulating film comprising the cured product according to <8>. <12> A compound having two or more partial structures represented by the following formula (1):

[0019]

[0020] In formula (1), Ar represents an aromatic ring having 6 to 10 carbon atoms, L represents an oxygen atom, a methylene group, an alkylene group having 2 to 6 carbon atoms, or a group formed by combining two or more groups selected from these groups, and R １１ is a group represented by the following formula (RN), and R １２ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R １３ is an alkyl group having 1 to 10 carbon atoms, an allyl group, or a vinyl group, and m １１ is 4, and m １２ is 0 or 1, and * represents a binding site with another structure.

[0021]

[0022] In formula (RN), CR represents an aromatic heterocycle having a nitrogen atom; １ is -N= or -CR ＣＲ２ =, and X ２ is =N- or =CR ＣＲ３ represents -, and Y１ is =N- or =CR ＣＲ４ represents -, and R ＣＲ１ ~R ＣＲ４ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R ＣＲ１ is R ＣＲ３ <13> The compound according to <12>, which is a compound represented by the following formula (1-2):

[0023]

[0024] In formula (1-2), R １１ , R １２ , R １３ , L, m １１ , and m １２ is R in the formula (1). １１ , R １２ , R １３ , L, m １１ , and m １２ However, A in formula (1-2) is bonded to a carbon atom that is a ring member of Ar and is adjacent to the carbon atom that is a ring member of Ar to which L is bonded. １３ is an alkyl group having 1 to 5 carbon atoms, R １３ may be a linking group bonded to a carbon atom that is a ring member of another Ar in formula (1-2), and CH ２ may be substituted with —O— or —S—. A is a single bond or n １２ a 2-valent group, which is an oxygen atom, a sulfur atom, an unsubstituted or substituted methylene group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by any one of the following formulas (10-1) to (10-3), or a group formed by combining two or more of these groups; １２ represents an integer of 2 to 4.

[0025]

[0026] In formulas (10-1) to (10-3), * represents the bonding site with Ar in formula (1-2).

[0027] According to one embodiment of the present invention, there is provided a resin composition that can yield a cured product having a low dielectric constant, a low dielectric dissipation factor, and a low elongation percentage, and that has a well-balanced excellent solubility, adhesion, and heat resistance. According to another embodiment of the present invention, there are provided a cured product, a prepreg, a copper-clad laminate, and an interlayer insulating film, that has a low dielectric constant, a low dielectric dissipation factor, and a low elongation percentage, and that has a well-balanced excellent solubility, adhesion, and heat resistance. According to another embodiment of the present invention, there is provided a novel compound.

[0028] 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.

[0029] Hereinafter, a resin composition, a cured product, a prepreg, a copper-clad laminate, and an interlayer insulating film according to one embodiment of the present invention will be described in detail.

[0030] <Compound (A)> The compound (A) is at least one of a compound (A1) having two or more partial structures represented by the following formula (1) and a compound (A2) represented by the following formula (2). The compound (A) is a compound other than the polymer (B) described below, and is a compound that cures when irradiated with heat or light (e.g., visible light, ultraviolet light, near-infrared light, far-infrared light). The compound (A) may be used alone or in combination with two or more types. The compound (A) may require a polymerization initiator (D) described below for curing. Furthermore, the compound (A) may be used in combination with the compound (A1) and the compound (A2) described above, as well as other curable compounds described below.

[0031] [Compound (A1)] The compound (A1) is a compound having two or more partial structures represented by the following formula (1).

[0032]

[0033] In formula (1), Ar represents an aromatic ring having 6 to 10 carbon atoms, L represents an oxygen atom, a methylene group, an alkylene group having 2 to 6 carbon atoms, or a group formed by combining two or more groups selected from these groups, and R １１ are each independently bonded to a carbon atom adjacent to a carbon atom that is a member of the Ar ring to which L is bonded, and are a hydrogen atom or a monovalent organic group, provided that two R １１ At least one of R is a monovalent organic group; １２ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R １３ is an alkyl group having 1 to 10 carbon atoms, an allyl group, or a vinyl group, and m １１ is 4, and m １２ is 0 or 1, and * represents a binding site with another structure.

[0034] Examples of the aromatic ring represented by Ar include a benzene ring, a naphthyl ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, and a triazine ring.

[0035] [L] Examples of the group represented by L, which is a combination of two or more groups selected from an oxygen atom, a methylene group, and an alkylene group having 2 to 6 carbon atoms, include —O—C ｍ H ２ｍ -, -(O-C ｎ H ２ｎ )p-, where m is an integer of 1 to 6, n is 2 or 3, p is 2 or 3, and m is preferably 1 or 2, more preferably 1. From the viewpoints of good curability, an ability to increase the crosslink density of the resulting cured product, and ensuring heat resistance even when the molecular weight of the polymer (B) described below is kept low, L is preferably a methylene group or —O—C ｍ H ２ｍ A group represented by - (m is 1 or 2) is preferred, and -O-C ｍ H ２ｍ A group represented by - (m is 1 or 2) is more preferred, and -O-CH ２ A group represented by - is more preferred.

[0036] [R １１ ] The R １１Examples of the monovalent organic group represented by the formula (I) include an allyl group, a vinyl group, a (meth)acryloyl group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms, an unsubstituted or substituted aromatic heterocyclic group having 3 to 10 carbon atoms, and an unsubstituted or substituted aralkyl group having 7 to 15 carbon atoms.

[0037] Examples of the alkyl group include linear or branched alkyl groups having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a t-butyl group. Examples of the cycloalkyl group include monocyclic or polycyclic alicyclic hydrocarbon groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and a tricyclodecanyl group. Examples of the aromatic heterocyclic group include nitrogen-containing aromatic heterocyclic groups represented by the following formula (RN):

[0038]

[0039] In formula (RN), CR represents an aromatic heterocycle having a nitrogen atom; １ is -N= or -CR ＣＲ２ =, and X ２ is =N- or =CR ＣＲ３ represents -, and Y １ is =N- or =CR ＣＲ４ represents -, and R ＣＲ１ ~R ＣＲ４ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R ＣＲ１ is R ＣＲ３ may bond to form a ring structure, and * represents the bonding site with Ar in the above formula (1). ＣＲ１ and CR ＣＲ３ The ring structure formed by bonding is preferably an aromatic ring structure, more preferably a benzene ring.

[0040] Examples of the group represented by the formula (RN) include a pyrazolyl group, an imidazolyl group, a triazolyl group, a benzopyrazolyl group, a benzimidazolyl group, and a benzotriazolyl group. １１The compound (A2) in which is a group represented by the formula (RN) is a novel compound.

[0041] Examples of the aromatic group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a benzyl group and a naphthylmethyl group. Examples of the substituents of the monocyclic or polycyclic alicyclic hydrocarbon group, aromatic group, and aralkyl group include an alkyl group having 1 to 10 carbon atoms.

[0042] Compound (A1) is R １１ It is believed that the presence of R restricts the movement of the styrene bonded to L, thereby reducing the dielectric loss tangent of the resulting cured product. １１ As the alkyl group, a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, and an aralkyl group are preferred, a linear or branched alkyl group, an aryl group, and an aralkyl group are more preferred, and a linear or branched alkyl group having 1 to 5 carbon atoms, an aryl group, and a benzyl group are even more preferred.

[0043] The R １２ and R １３ The alkyl group having 1 to 10 carbon atoms represented by R １１ The alkyl group is the same as the alkyl group of the above, and the preferred embodiments are also the same.

[0044] The compound (A1) is preferably a compound represented by the following formula (1-1) or (1-2).

[0045]

[0046] In formula (1-1), R １１ , R １２ , R １３ , L, m １１ , and m １２ is R in formula (1) １１ , R １２ , R １３ , L, m １１ , and m １２ It is synonymous with R １３ is an alkyl group having 1 to 5 carbon atoms, R １３may be a linking group bonded to a carbon atom that is a ring member of another Ar in formula (1-1), and —CH ２ - may be replaced by -O- or -S-. A is a single bond or n １１ A is a valent group, which is an oxygen atom, a sulfur atom, an unsubstituted or substituted methylene group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by any one of the following formulas (10-1) to (10-3), or a group which is a combination of two or more of these groups; A is R １３ and the carbon atoms to which they are attached are combined together to form a ring structure having 3 to 20 ring members, １１ represents an integer of 2 to 4.

[0047] In formula (1-2), R １１ , R １２ , R １３ , L, m １１ , and m １２ is R in formula (1) １１ , R １２ , R １３ , L, m １１ , and m １２ However, A in formula (1-2) is bonded to a carbon atom that is a ring member of Ar and is adjacent to the carbon atom that is a ring member of Ar to which L is bonded. １３ is an alkyl group having 1 to 5 carbon atoms, R １３ may be a linking group bonded to a carbon atom that is a ring member of another Ar in formula (1-2), and —CH ２ - may be replaced by -O- or -S-. A is a single bond or n １２ a 2-valent group, which is an oxygen atom, a sulfur atom, an unsubstituted or substituted methylene group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by any one of the following formulas (10-1) to (10-3), or a group formed by combining two or more of these groups; １２ represents an integer of 2 to 4.

[0048] [A] Examples of the methylene substituent represented by A include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, and an aromatic group having 6 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 5 to 10 carbon atoms are each the same as R １１ The aromatic group having 6 to 10 carbon atoms has the same meaning as the alkyl group and cycloalkyl group represented by the following formula: Examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.

[0049] The alicyclic hydrocarbon group represented by A includes, for example, monocyclic hydrocarbon groups having 5 to 12 carbon atoms such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane. １１ pieces or n １２ a group in which n hydrogen atoms have been removed, a polycyclic hydrocarbon group such as norbornane, tricyclodecane, tetracyclododecane, adamantane, etc. １１ pieces or n １２ These alicyclic hydrocarbon groups may be substituted with an alkyl group having 1 to 10 carbon atoms.

[0050] The aromatic hydrocarbon group represented by A may be either a monocyclic or polycyclic ring. From the viewpoint of excellent heat resistance of the cured product obtained and further reducing the elongation percentage, the aromatic hydrocarbon group is selected from aromatic hydrocarbon groups having 6 to 14 carbon atoms. １１ pieces or n １２ A group in which n hydrogen atoms have been removed is preferred, and n is an aromatic hydrocarbon group having 10 to 14 carbon atoms. １１ pieces or n １２ More preferred are groups in which n hydrogen atoms have been removed. Examples of such groups include groups in which n hydrogen atoms have been removed from benzene, naphthalene, and fluorene. １１ pieces or n １２ These aromatic hydrocarbon groups may be substituted with an alkyl group having 1 to 10 carbon atoms.

[0051] A is preferably an unsubstituted or substituted methylene, oxygen atom, sulfur atom, alicyclic hydrocarbon group, aromatic hydrocarbon group, group represented by any one of the following formulae (10-1) to (10-3), or group combining two or more of these groups, and more preferably an oxygen atom, sulfur atom, alicyclic hydrocarbon group, aromatic hydrocarbon group, group represented by any one of the following formulae (10-1) to (10-3), or group combining any one of these groups with an unsubstituted or substituted methylene (with the proviso that Ar and the methine are not directly bonded). When A is any of these groups, compound (A1) is less susceptible to oxidation and has good curability, and the heat resistance of the resulting cured product can be excellent and the elongation can be reduced.

[0052]

[0053] In formulas (10-1) to (10-3), * represents a bonding site with Ar in formula (1-1) or formula (1-2).

[0054] Examples of the compound (A1) include, but are not limited to, the following compounds.

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064] As the compound (A1), A-1-4, A-1-18 to A-1-21, A-1-34, A-1-46, A-1-49, and A-1-53 are preferred.

[0065] [Compound (A2)] The compound (A2) is a compound represented by the following formula (2).

[0066]

[0067] In formula (2), R ２１ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms, or two R ２１ represents a ring structure having 5 to 10 ring members formed by combining together with the carbon atoms to which they are attached, and R ２２ and R ２３ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms, and at least one R ２２ is a group represented by formula (2-1), and at least one R ２３ is a group represented by formula (2-1). ２３ At least one of the two substituents bonded to the two carbon atoms adjacent to L and R is an alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms. １２ , and m １１ are L and R in formula (1). １２ , and m １１ and * is R ２２ or R ２３ represents the binding site with

[0068] R ２１ , R ２２ and R ２３ The alkyl group having 1 to 10 carbon atoms represented by the formula (1) is １１ The meaning and preferred embodiments are the same as those of the alkyl group having 1 to 10 carbon atoms. ２１ , R ２２ and R ２３ The unsubstituted or substituted aromatic group having 6 to 10 carbon atoms represented by the formula (1) is １１ It has the same meaning as the aromatic group represented by the following formula:

[0069] R ２１ , R ２２ and R ２３Examples of the substituent of the aromatic group having 6 to 10 carbon atoms represented by the formula (I) include an alkyl group having 1 to 10 carbon atoms.

[0070] Two R's ２１ Examples of ring structures having 5 to 10 ring members formed by combining these together with the carbon atoms to which they are bonded include alicyclic hydrocarbon structures such as cyclopentane, cyclohexane, and norbornane, and aromatic hydrocarbon structures such as benzene and naphthalene.

[0071] Examples of the compound (A2) include, but are not limited to, the following exemplary compounds.

[0072]

[0073]

[0074] The compound (A-2) is preferably A-2-6.

[0075] [Method for synthesizing compound (A)] The method for synthesizing compound (A) is not particularly limited, and known synthesis methods can be used. An example of the method for synthesizing compound (A) is described below. The method for synthesizing compound (A) is not particularly limited, and for example, compound (A) can be synthesized by etherifying a phenol compound serving as a mother nucleus in which R in the above exemplary compound is a hydrogen atom with a halogen compound represented by the following formula (1-1) using the Williamson method, which is a common method for synthesizing ethers.

[0076]

[0077] In formula (1-1), X represents a halogen atom, L and R １２ and m １１ are L and R in formula (1). １２ and m １１ X is preferably a chlorine atom or a bromine atom, more preferably a chlorine atom, because of its good reactivity and easy availability of raw materials.

[0078] The content of the compound (A), relative to 100 parts by mass of the polymer (B) described below, 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 250 parts by mass or less, more preferably 200 parts by mass or less, even more preferably 150 parts by mass or less.

[0079] It is preferable that the content of compound (A) is within the above range, since the electrical properties such as dielectric constant and dielectric loss tangent, heat resistance, adhesion and curability of the obtained cured product can be further improved, and the elongation can be further reduced, etc. Compound (A) may be used alone or in combination of two or more types.

[0080] [Other Curable Compounds] The compound (A) may be used in combination with a curable compound other than the compound (A) and the polymer (B) described below (hereinafter also referred to as "other curable compounds"). Examples of other curable compounds include vinyl compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, thiol compounds, oxazine compounds, cyanate compounds, epoxy compounds, oxetane compounds, methylol compounds, benzocyclobutene compounds, propargyl compounds, and silane compounds. In particular, from the viewpoint of compatibility and reactivity with the compound (A) and the polymer (B), the other curable compound is preferably at least one compound selected from the group consisting of vinyl compounds, maleimide compounds, and allyl compounds. When the compound (A) is used in combination with the other curable compounds, the content of the other curable compounds is 0 to 200 parts by mass, preferably 0 to 100 parts by mass, and more preferably 50 to 100 parts by mass, per 100 parts by mass of the compound (A).

[0081] <Polymer (B)> The polymer (B) is a polymer having a group capable of crosslinking with the compound (A) and an aromatic ring. The polymer (B) is preferably a polymer having a group capable of crosslinking with at least one compound (A), such as a vinyl group, an allyl group, or a (meth)acryloyl group. Examples of such polymers (B) include polyphenylene ether polymers, polyfunctional vinyl aromatic copolymers, and heteroaromatic-aromatic ether polymers, each of which has at least one vinyl group, allyl group, or (meth)acryloyl group at the main chain terminal or side chain of the polymer (B). Hereinafter, these may be abbreviated as "modified polyphenylene ether polymer," "modified polyfunctional vinyl aromatic copolymer," and "modified heteroaromatic-aromatic ether polymer," respectively. These polymers (B) are excellent in low dielectric constant and low dielectric dissipation factor. When used in combination with the compound (A) having the specific structure, crosslinking proceeds efficiently without increasing the molecular weight of the polymer (B), thereby ensuring heat resistance while maintaining a low dielectric constant and low dielectric dissipation factor. Furthermore, by not increasing the molecular weight of the polymer (B), a composition can be obtained that is excellent in balance of flowability and adhesiveness without impairing these properties.

[0082] [Modified Heteroaromatic-Aromatic Ether Polymer (B1)] The heteroaromatic-aromatic ether polymer (B1) (hereinafter also referred to as "polymer (B1)") may be, for example, a polymer (B1) having a structural unit represented by formula (B1-1).

[0083]

[0084] In formula (B1-1), R ａ１ is a divalent group represented by the following formula (B2), 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:

[0085]

[0086] In formula (B2), Ar ａ１ and Ar ａ２are 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 alkylene group having 2 to 4 carbon atoms.

[0087] [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 phenyl group, a naphthyl group or an anthryl group, and particularly preferably a phenyl group or a naphthyl group.

[0088] The substituent on the aromatic hydrocarbon group is not particularly limited and examples thereof include alkyl groups having 1 to 10 carbon atoms such as allyl groups, (meth)acryloyloxy groups, halogen atoms, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, and n-butyl groups; alkenyl groups such as ethenyl groups, propenyl groups, butenyl groups, and pentenyl groups; alkynyl groups having 2 to 10 carbon atoms such as ethynyl groups, propynyl groups, butynyl groups, and pentynyl groups; cycloalkyl groups having 5 to 10 carbon atoms such as cyclopentyl groups, cyclohexyl groups, and norbornyl groups; and aryl groups such as phenyl groups and naphthyl groups. Of these, alkyl groups are preferred as the substituent on the aromatic hydrocarbon group.

[0089] [L] Examples of the divalent organic group for L include an unsubstituted or substituted methylene group, an alkylene group having 2 to 20 carbon atoms, an arylene group having 6 to 10 carbon atoms, a group formed by combining two or more selected from the methylene group, alkylene group, and arylene group, or a group represented by the following formula (L1):

[0090]

[0091] 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):

[0092]

[0093] 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.

[0094] -N(R ８ )-R in ８ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and for example, ａ１ and Ar ａ２ Examples of the substituent of include the monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified above.

[0095] From the viewpoint of the structural stability of the polymer (B1), L is preferably a single bond, —O—, —S—, —C(O)—, a substituted or unsubstituted methylene group, an alkylene group having 2 to 5 carbon atoms, or the formula (L1).

[0096] [y] In formula (B2), y is an integer of 0 to 5. From the viewpoint of the structural stability of the polymer (B1), y is preferably an integer of 0 to 3, and more preferably 0 or 1.

[0097] R in formula (B1-1) ａ１ Examples of monomers that serve as raw materials for the moiety containing (i.e., the divalent group represented by formula (B2)) 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.

[0098]

[0099]

[0100]

[0101] <R ａ２ > 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:

[0102]

[0103] 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.

[0104] 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.

[0105] 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 ...

[0106] 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 formula (Rａ２ -2) is preferred.

[0107] <<Group Crosslinking with Compound (A)>> The heteroaromatic-aromatic polymer (B1) has a terminal group Y represented by the following formula (a) at the end of the structural unit represented by formula (B1-1) as a group crosslinking with the compound (A), or has a terminal group Y represented by the following formula (a) at the end of the structural unit represented by formula (B1-1) as a group crosslinking with the compound (A), ａ１ and Ar ａ２ The unsubstituted or substituted aromatic hydrocarbon group represented by the formula (I) has an allyl group, a (meth)acryloyloxy group, or an alkenyl group as a substituent.

[0108]

[0109] In formula (a), Y is a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, an unsubstituted or substituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic ring.

[0110] Such an end group Y is preferably a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, and examples thereof 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.

[0111] The method for forming the polymer (B1) in which the terminals of the polymer (B1) are capped with the terminal group Y is not particularly limited, and any known method can be used.

[0112] 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.

[0113] The polymer (B1) may contain a structural unit represented by the following formula (B1-2) by copolymerizing, in addition to a monomer that provides a structural unit of the above formula (B1-1), a monomer that provides a branched structure:

[0114]

[0115] In formula (B1-2), 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 (B1).

[0116] Examples of the structural unit represented by formula (B1-2) include, but are not limited to, structural units having the following partial structures:

[0117]

[0118] [Method for forming the structural unit represented by formula (B1-2)] The structural unit represented by formula (B1-2) can be formed by synthesizing the polymer represented by formula (B1-1) 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):

[0119]

[0120] 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.

[0121] The lower limit of the weight average molecular weight (0) of polymer (B1) is preferably 1,000, 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 (B) 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 (B) 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.

[0122] [Modified Polyphenylene Ether Polymer (B2)] The modified polyphenylene ether polymer (B2) can be, for example, a polymer (B2) having a structural unit represented by the following formula (B2-1).

[0123]

[0124] In formula (B2-1), 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 ｂ３２ each 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 alkylene 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.

[0125] 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 ｂ２４are 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.

[0126] R ｂ３１ and R ｂ３２ are each independently a vinylphenyl group or a (meth)acryloyl group, and Z is a single bond or an alkylene group. The alkylene group means a linear, branched, or cyclic divalent saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group include -CH ２ -, -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 -, etc. Preferably, R ｂ３１ and R ｂ３２ is a vinylphenyl group, and Z is an alkylene group (particularly preferably -CH ２ -) or R ｂ３１ and R ｂ３２ is a (meth)acryloyl group, and Z is a single bond.

[0127] 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 ｂ２１are 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.

[0128] Commercially available modified polyphenylene ether polymers (B1) 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.

[0129] [Polyfunctional vinyl aromatic copolymer (B3)] Examples of the polyfunctional vinyl aromatic copolymer (B3) (hereinafter also referred to as "polymer (B3)") include polyfunctional vinyl aromatic copolymers containing a repeating unit (ba) derived from a divinyl aromatic compound, a repeating unit (bb) derived from a monovinyl aromatic compound, and other repeating units (bc).

[0130] The repeating unit (ba) derived from the divinylaromatic compound or the like is not limited, but examples thereof include repeating units (ba) derived from the divinylaromatic compound or the like represented by the following formulae (ba2) to (ba4): These structural units may be arranged regularly or randomly.

[0131]

[0132] In the formula, R ｂａ１ is an aromatic hydrocarbon group having 6 to 30 carbon atoms derived from a divinyl aromatic compound, and R ｂａ２ is an aromatic hydrocarbon group having 6 to 30 carbon atoms derived from a monovinyl aromatic compound, and h to k are each independently an integer of 0 to 200, provided that the sum of their numbers is 2 to 20,000.

[0133] The repeating unit (ba) derived from the divinyl aromatic compound plays a role in forming a branched structure to impart polyfunctionality, and also plays a role as a cross-linking component to impart heat resistance when the resulting polyfunctional vinyl aromatic copolymer is thermally cured.

[0134] The monomer that gives the repeating unit (ba) derived from the divinyl aromatic compound is not particularly limited as long as it is an aromatic compound having two vinyl groups. Examples of the monomer that gives (ba) 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 can be used alone or in combination of two or more. From the viewpoint of molding processability, divinylbenzene is more preferred as the monomer that gives (ba).

[0135] The structural unit (ba) derived from the divinyl aromatic compound accounts for 5 mol % or more and less than 98 mol %, relative to 100 mol % of all structural units of the polyfunctional vinyl aromatic copolymer (B3), so that the copolymer has a low dielectric tangent, high toughness, and excellent heat resistance, and when formed into a polymer composition, the copolymer has excellent moist heat resistance and resistance to thermal oxidative degradation.

[0136] Examples of the monomer that provides the repeating unit (bb) 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.

[0137] The monovinyl aromatic compound (bb) 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 (bb) 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 (bb) other than styrene prevents gelation of the polyfunctional vinyl aromatic copolymer (B3) and facilitates adjustment of solvent solubility and processability. From the above viewpoints, the monovinyl aromatic compound (bb) is preferably ethylvinylbenzene, ethylvinylbiphenyl, or ethylvinylnaphthalene, with ethylvinylbenzene being particularly preferred. The polyfunctional vinyl aromatic copolymer (B3) contains structural units (bb) derived from the monovinyl aromatic compound in an amount of 5 mol% or more but less than 98 mol% based on the total, resulting in excellent moldability and excellent heat resistance of the cured product obtained when made into a resin composition.

[0138] The polyfunctional vinyl aromatic copolymer (B3) is preferably soluble in any of toluene, xylene, tetrahydrofuran, dichloroethane and chloroform as a solvent, and is preferably soluble in all of the above solvents. In order to be a solvent-soluble polyfunctional copolymer, the copolymer (B3) preferably has an appropriate degree of crosslinking, with some of the vinyl groups of divinylbenzene remaining uncrosslinked.

[0139] Examples of the monomer that provides the other structural unit (bc) include trivinyl aromatic compounds, trivinyl aliphatic compounds, divinyl aliphatic compounds, and monovinyl aliphatic compounds.

[0140] Examples of the other monomer components 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.

[0141] The amount of the other monomer component is preferably less than 30 mol % relative to 100 mol % of all structural units constituting the polyfunctional vinyl aromatic copolymer (B3).

[0142] The polyfunctional vinyl aromatic copolymer (B3) 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.

[0143] The content of polymer (B) is preferably 0.05% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, and is preferably 99.95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less, based on the total solid content of the composition being 100% by mass. A content of polymer (B) within the above range is preferable because it can further improve the adhesiveness, heat resistance, curability, and electrical properties of the resulting cured product. The polymer (B) may be used alone or in combination of two or more types.

[0144] <Other Components> The resin composition according to the present invention (hereinafter, may also be simply referred to as "the composition") contains compound (A), which is at least one of compound (A1) having two or more partial structures represented by formula (1) above and compound (A2) represented by formula (2) above, and polymer (B) described above having a group crosslinkable with compound (A) and an aromatic ring. In addition to compound (A) and polymer (B), the resin composition may further contain other components within a range that does not impair the effects of the present invention.

[0145] Examples of the other components include a polymerization initiator (C), an organic solvent (D), additives for imparting various functions, and a filler (F). The composition may also contain a thermoplastic resin as a polymer other than the compound (A) and the polymer (B) 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 two or more may be used.

[0146] [Polymerization initiator (C)] The present composition preferably further contains a polymerization initiator (C). Examples of the polymerization initiator (C) include thermal or photoradical initiators, cationic curing agents, and anionic curing agents. Among these, thermal radical initiators are preferred as the polymerization initiator (C).

[0147] Examples of the thermal radical 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).

[0148] When the present composition contains a polymerization initiator (C), the content ratio of the polymerization initiator (C) is preferably within a range in which the present composition is cured well and a cured product is obtained. Specifically, the content ratio 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 compound (A) and the polymer (B). The polymerization initiator (C) may be used alone or in combination of two or more kinds.

[0149] [Organic Solvent (D)] The present 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 having 1 to 4 carbon atoms), and methylene chloride.

[0150] When the composition contains an organic solvent (D), the content of the solvent in the composition is not particularly limited, and is, for example, preferably 0 to 2000 parts by mass, more preferably 0 to 1000 parts by mass, per 100 parts by mass of the total solid content of the compound (A) and the polymer (B). Furthermore, when the solubility of the compound (A) or the polymer (B) in the organic solvent (D) is high, the content of the organic solvent (D) in the composition may be 50 to 200 parts by mass. The organic solvent (D) may be a single type, or two or more types may be used in combination.

[0151] [Hydrogenated styrene-based thermoplastic elastomer (E)] The present composition may further contain a hydrogenated styrene-based thermoplastic elastomer (E) (hereinafter, may also be simply referred to as "elastomer (E)." The elastomer (E) refers to an elastomer in which some or all of the double bonds of a styrene-based thermoplastic elastomer have been hydrogenated. By containing the hydrogenated styrene-based thermoplastic elastomer (E), the present composition can easily produce a cured product with a lower dielectric constant and a lower dielectric dissipation factor. The elastomer (E) may be used alone or in combination of two or more types.

[0152] Examples of the elastomer (E) include hydrogenated styrene-based thermoplastic elastomers obtained by hydrogenating some or all of the carbon-carbon double bonds in copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, etc. As the elastomer (E), at least one copolymer selected from the group consisting of hydrogenated styrene-butadiene copolymer, hydrogenated styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene block copolymer, and hydrogenated ethylene-ethylene-butylene-styrene block copolymer is preferred, since a cured product having a lower dielectric constant and a lower dielectric loss tangent can be easily obtained.

[0153] The hydrogenation rate of the elastomer (E) is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, still more preferably 80% or more, and particularly preferably 90% or more. The hydrogenation rate is determined by measuring the iodine value of the elastomer (E).

[0154] The content of styrene-derived structural units in the elastomer (E) (hereinafter also referred to as "styrene amount") is preferably 5 to 90 mass %, more preferably 10 to 80 mass %, and even more preferably 15 to 75 mass %, based on the total structural units of the elastomer (E). By using an elastomer (E) having a styrene amount within the above range, it is possible to easily obtain a cured product that has a well-balanced low dielectric constant, low dielectric loss tangent, heat resistance, low coefficient of linear expansion, and excellent adhesion to a metal layer (particularly a copper layer). The styrene amount can be calculated from the proportion of styrene used in synthesizing the elastomer (E), and can also be calculated from the ratio of styrene used in synthesizing the elastomer (E) at 400 MHz. １ It can be determined by measuring H-NMR.

[0155] The elastomer (E) may be synthesized or may be a commercially available product. Commercially available hydrogenated styrene-based thermoplastic elastomers include, for example, 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).

[0156] The content of the elastomer (E) is preferably 3 to 100 mass%, more preferably 10 to 80 mass%, and even more preferably 15 to 70 mass%, relative to 100 mass% of the total solid content of the polymer (A) and the compound (B), from the viewpoints of achieving excellent compatibility and dispersibility of the elastomer (E) with other components, excellent heat resistance and low dielectric tangent, and imparting toughness to the cured product.

[0157] [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.

[0158] [Filler (F)] The present 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, and M-glass G20.

[0159] When the 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 compound (A) and the polymer (B). The filler (F) may be dispersed in a solvent by the polymer (B). The filler (F) may be used alone or in combination of two or more types.

[0160] [Method for preparing the present composition] The method for preparing the present composition is not particularly limited and may be a known method, for example, by uniformly mixing the compound (A), the polymer (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.

[0161] <<Cured Product>> A cured product according to one embodiment of the present invention (hereinafter also referred to as "present cured product") comprises the present composition. The cured product is a cured product of the present composition described above, and is obtained by curing the present composition described above. The present cured product may be, for example, a partially cured product of the present composition obtained by drying the solvent from the present composition.

[0162] [Glass Transition Temperature (Tg)] The lower limit of the 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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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-like cured product can be obtained by melt molding or cast molding the composition.

[0167] 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.

[0168] 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).

[0169] 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.

[0170] <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.

[0171] 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.

[0172] 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.

[0173] <<Prepreg>> The prepreg according to the present invention is obtained by impregnating a fibrous substrate plate with the present 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.

[0174] <<Applications>> The composition and cured product can be suitably used as structural materials in the transportation industry, such as the aircraft and automobile industries, and as electrical and electronic materials in the electrical and electronics industry. Specifically, the composition and cured product can be suitably used in, for example, 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 wave 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 product have a low dielectric tangent, excellent adhesion, and heat resistance.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] Synthesis Example 1 Synthesis of Compound A-1-1 Compound (26.49 g) represented by the following formula (PA1-1) (BisOC-FL, manufactured by Honshu Chemical Industry Co., Ltd.), chloromethylstyrene (23.37 g), and potassium carbonate (19.35 g) were weighed into a glass reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a condenser, and N-methyl-2-pyrrolidone (79.48 g) was added, followed by a reaction at 80°C for 4 hours under a nitrogen atmosphere. After allowing the vessel to cool to room temperature, the salt was removed by filtration, and the resulting solution was poured into methanol (2250 g). The precipitated solid was filtered off, washed with a small amount of methanol, and then dried under reduced pressure at 40°C for 12 hours using a vacuum dryer to obtain Compound A-1-1 as a pale yellow solid. Compound A-1-1 was confirmed to be a compound having the structure shown in Table 1. １ This was confirmed by H-NMR.

[0179]

[0180] <<Synthesis of Compound A-1-54>> A compound (47.77 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula (PA1-54), m,p-chloromethylstyrene (24.21 g), and potassium carbonate (13.53 g) were weighed into a glass reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a condenser, and N-methyl-2-pyrrolidone (71.65 g) was added, followed by a reaction at 80°C for 4 hours under a nitrogen atmosphere. After the vessel was allowed to cool to room temperature, the salt was removed by filtration, and the resulting solution was poured into methanol (2250 g). The precipitated solid was filtered off, washed with a small amount of methanol, and then dried for 12 hours at 40°C under reduced pressure using a vacuum dryer, yielding a pale yellow solid compound. The resulting compound １ When the H-NMR (400 MHz) spectrum was measured, the chemical shifts shown below were confirmed, and the target compound A-1-54 having the following structure was obtained.

[0181]

[0182]

[0183] The chemical shifts of the protons of the above A-1-54 were as follows: No. 9 hydrogen: 0.76 ppm (18H) No. 7 hydrogen: 1.34 ppm (12H) No. 8 hydrogen: 1.72 ppm (4H) No. 4 hydrogen: 4.17-4.26 ppm (2H) No. 3 hydrogen: 4.35-4.46 ppm (4H) No. 15 hydrogen: 5.08-5.20 ppm (2H) No. 16 hydrogen: 5.51-5.67 ppm (2H) No. 14 hydrogen: 6.45-6.64 ppm (2H) No. 10-13 hydrogen: 6.87-7.22 ppm (8H) No. Hydrogen of No. 6: 7.23-7.29 ppm (2H) Hydrogen of No. 1: 7.41-7.48 ppm (4H) Hydrogen of No. 5: 7.63-7.70 ppm (2H) Hydrogen of No. 2: 7.93-8.01 ppm (4H)

[0184] Compounds A-1-2 to A-1-9, A-2-1, A-1-25, and A-1-30 shown in Table 1 were synthesized in the same manner as compound A-1-1, except that the corresponding bisphenol compounds were used instead. The resulting compounds were confirmed to be the compounds shown in Table 1 by the same confirmation method as used in the synthesis of compound A-1-1.

[0185] In Tables 1 and 2, a-1, a-2, and a-3 are the following compounds: a-1: TAIC (triallyl isocyanurate), manufactured by Shinryo Corporation (formerly MGC); a-2: DVB960 (divinylbenzene), manufactured by Nippon Steel Chemical & Material Co., Ltd.; a-3: BVPE (bis(4-vinylphenyl)ethane), manufactured by Shanghai Shengyi Co., Ltd.

[0186]

[0187]

[0188] In Tables 1 and 2, R represents a group represented by the following formula: In the formula, the wavy line represents a link to another binding site.

[0189]

[0190] Synthesis Example 2 Synthesis of Polymer (B1-1) 2,2-bis(4-hydroxy-3-methylphenyl)propane (64.09 g), 4,6-dichloro-2-phenylpyrimidine (31.08 g), 4,6-dichloropyrimidine (6.86 g), and potassium carbonate (46.65 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, chloromethylstyrene (22.01 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 from the diluted solution 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. The solid was then dried under reduced pressure at 80°C for 12 hours using a vacuum dryer, thereby obtaining a polymer (B1-1) represented by the following formula, having a number average molecular weight (Mn) of 1,400 and a weight average molecular weight (Mw) of 3,100.

[0191]

[0192] Synthesis Example 3 Synthesis of Polymer (B1-2) 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (33.85 g), 4,6-dichloro-2-phenylpyrimidine (16.66 g), and potassium carbonate (18.66 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (42.50 g) was added. The mixture was reacted at 100°C for 6 hours under a nitrogen atmosphere. After the reaction, m,p-(chloromethyl)styrene (8.68 g) was added dropwise with the vessel cooled to 10°C, and the mixture was reacted at 100°C for 4 hours. The resulting reaction solution was diluted with N-methyl-2-pyrrolidone (55.0 g), and the salt was removed from the diluted solution by filtration. The resulting solution was then poured into methanol (6900 g). 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 60°C for 12 hours using a vacuum dryer to obtain a polymer (B1-2) represented by the following formula, having a number average molecular weight (Mn) of 1,600 and a weight average molecular weight (Mw) of 3,400.

[0193]

[0194] Synthesis Example 4 <<Synthesis of Polymer (b1-1)>> A polymer (b1-1) represented by the following formula and having a number average molecular weight (Mn) of 1500 and a weight average molecular weight (Mw) of 3900 was obtained by synthesis 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-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 N-methyl-2-pyrrolidone (135.36 g).

[0195]

[0196] Synthesis Example 5 Synthesis of Polymer (B3-1) According to the method described in Example 1 of JP-A No. 2016-190899, a polymer (B3-1) having a Mw of 2500 and represented by the following formula was obtained.

[0197]

[0198] Other polymers used in the examples are listed below. Polymer (B2-1): Vinylbenzyl-modified polyphenylene ether resin (manufactured by Mitsubishi Gas Chemical Company, Inc., product name: "OPE-2St (Mw 1200)"

[0199]

[0200] Polymer (b2-1): Polyphenylene ether resin (manufactured by SABIC Corporation, product name: SA90 (Mw 1700))

[0201]

[0202] Polymer (B4-1): butadiene-styrene random copolymer (manufactured by CRAY VALLEY, product name: Ricon 100, Mn 45000)

[0203] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn)] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymers synthesized in Synthesis Examples 2 to 4 above were measured using a GPC device (manufactured by Tosoh Corporation, model number: "HLC-8320") under the following conditions: 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 Concentration of measurement sample: 0.1% by mass

[0204] [Examples 1 to 28 and Comparative Examples 1 to 6] Compositions were prepared by mixing the components shown in the column for composition type in Table 3 below in a mix rotor to the ratio (parts by mass) shown in the column for composition blending ratio, and adjusting the concentration with toluene to the solids concentration shown in Table 3 for each example. Note that "-" in Table 3 means that the corresponding component was not included.

[0205]

[0206] Details of each component in Table 3 are as follows: <Polymerization initiator (C)> C1: dicumyl peroxide (manufactured by NOF Corporation) <Organic solvent (D)> D1: toluene <Filler (F)> F1: fused spherical silica "GT grade" (average particle size: 3 μm) (manufactured by Denka Company Limited)

[0207] <Preparation of Cured Film> Each of the compositions obtained in the above Examples and Comparative Examples was applied to copper foil (model number: CF-T49A-DS-HD2, manufactured by Fukuda Metals Co., Ltd.) using a Baker-type applicator (gap: 125 μm), followed by heating at 100°C for 5 minutes and drying at 140°C for 5 minutes to form a coating film. Copper foil (model number: CF-T49A-DS-HD2, manufactured by Fukuda Metals 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: 18 μm, cured film: 50 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 50 μm-thick cured film.

[0208] <Heat Resistance (Tg)> Test pieces (width: 3 mm x length: 1 cm) were cut from the cured film prepared above, and measured using a dynamic viscoelasticity measuring device (Seiko Instruments Inc., model number: "EXSTAR4000") at a heating rate of 10°C / min from 50°C to 300°C at 1 Hz. The tan δ measured here was taken as the glass transition temperature (Tg) and evaluated according to the following criteria. The results are shown in Table 4. When two or more tan δ values ​​were present, the lowest value was taken as the Tg. Evaluation criteria of "3", "4", and "5" indicate excellent heat resistance. (Evaluation Criteria) 2: Tg<170°C 3: 170°C≦Tg<180°C 4: 180°C≦Tg<200°C 5: 200°C≦Tg

[0209] <Adhesion (Peel Strength)> The compositions obtained in the above Examples and Comparative Examples were applied as varnishes for evaluation onto copper foil (model number: CF-V9S-SV, manufactured by Fukuda Metal Co., Ltd.), heated at 100°C for 5 minutes, and then dried at 130°C for 5 minutes to form a coating film. Copper foil (model number: CF-V9S-SV, manufactured by Fukuda Metal Co., Ltd.) was placed on the resulting coating film, vacuum pressed at 150°C for 5 minutes, and then baked at 200°C for 2 hours under nitrogen to produce a cured film with copper foil (copper foil: 18 μm, cured film: 10 μm), which was used as a sample for peel strength testing.

[0210] Test pieces (width: 5 mm x length: 10 cm) were cut out from the peel strength samples prepared above, and the cured film-coated copper foil (one copper foil and cured film laminated portion in the peel strength sample) was pulled in a 90-degree direction at 500 mm / min using an Instron 5567 manufactured by Instron Corporation. The peel strength was measured in accordance with IPC-TM-650 2.4.9 and evaluated according to the following evaluation criteria. The results are shown in Table 4. (Evaluation criteria) 3: Peel strength < 0.50 N / mm 4: 0.50 N / mm ≦ peel strength < 0.070 N / mm 5: 0.70 N / mm ≦ peel strength

[0211] <Dielectric Loss Tangent> Test specimens (width: 6 cm x length: 6 cm) were cut out from the prepared cured films, and the dielectric loss tangent (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 results are shown in Table 4. A rating of "3" or higher on the evaluation criteria can be said to be within the practically acceptable range. (Evaluation Criteria) 1: 0.0030<Df 2: 0.0025<Df≦0.0030 3: 0.0020<Df≦0.0025 4: 0.0015<Df≦0.0020 5: Df≦0.0015

[0212] <Elongation> Each of the compositions obtained in the above Examples and Comparative Examples was applied to copper foil (model number: CF-T49A-DS-HD2, manufactured by Fukuda Metals 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: CF-T49A-DS-HD2, manufactured by Fukuda Metals 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: 18 μm, cured film: 50-100 μm). The prepared copper foil-attached cured film was immersed in a 40% by mass iron chloride solution, the copper foil was removed from the copper foil-attached cured film, washed with water, and dried at 80°C for 30 minutes to prepare a film for elongation measurement. The elongation of the prepared evaluation film was measured using a TMA measuring device (Seiko Instruments, SSC-5200 model). At this time, 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 results are shown in Table 4. Note that a rating of 3 or more according to the following evaluation criteria can be said to be a low elongation. Elongation (%) = (length of test piece at 260°C - initial length of test piece) / initial length of test piece × 100 (Evaluation criteria) 2: 10% < elongation 3: 5% < elongation ≦ 10% 4: 3% < elongation ≦ 5% 5: elongation ≦ 3%

[0213] <Solubility> For each of the Examples and Comparative Examples, all components of the resin composition used were dissolved in toluene (TL) at the following concentrations. The evaluation was performed with a score of 5 when all components of the resin composition were dissolved in TL at 50% by mass or more, 4 when they were dissolved in TL at 30% by mass or more but less than 50% by mass, 3 when they were dissolved in TL at 20% by mass or more but less than 30% by mass, and 2 when they were dissolved in TL at less than 20% by mass. The results are shown in Table 4.

[0214]

[0215] <Heat Resistance (ΔDf)> For the compositions of Examples 1, 15, and 21, the obtained cured films were heat-treated in an oven at 150°C (in air) for 500 hours, and the dielectric dissipation factor of each film was measured before and after the heat treatment. The dielectric dissipation factor before the heat treatment was Df(t0), and the dielectric dissipation factor after the heat treatment was Df(t1). Evaluation was performed using the following evaluation criteria: ΔDf = Df(t1) - Df(t0). The results are shown in Table 5. (Evaluation Criteria) A: ΔDf<0.0010 B: 0.0010≦ΔDf<0.0100 C: 0.0100≦ΔDf<0.0200

[0216]

[0217] It can be seen that the cured products obtained from the compositions of Examples 1 to 24 have a lower dielectric constant, lower dielectric dissipation factor, and lower elongation than the cured products obtained from the compositions of Comparative Examples 1 to 6, and also have a well-balanced and excellent property in solubility, adhesion, and heat resistance.

[0218] [Examples 101 to 108] The components shown in the column for composition type in Table 6 below were mixed in a mix rotor to achieve the ratio (parts by mass) shown in the column for composition blending ratio, and the concentration was adjusted with toluene to achieve the solids concentration shown in Table 6 for each example, to prepare a composition. Note that "-" in Table 6 means that the corresponding component was not included. Details of component (E) in Table 6 are as follows. The other components used were the same as those in Table 3 above.

[0219] <Hydrogenated styrene-based thermoplastic elastomer (E)> E1: S.O.E. S1605 (hydrogenated styrene-butadiene copolymer resin), manufactured by Asahi Kasei Corporation, styrene content: 67% by mass E2: Tuftec H1062 (hydrogenated styrene-butadiene copolymer resin), manufactured by Asahi Kasei Corporation, styrene content: 18% by mass

[0220]

[0221] <Preparation of Cured Film> Each of the compositions obtained in Examples 101 to 108 was applied to copper foil (model number: CF-T49A-DS-HD2, manufactured by Fukuda Metals Co., Ltd.) using a Baker-type applicator (gap: 125 μm), followed by heating at 100°C for 5 minutes and drying at 140°C for 5 minutes to form a coating film. Copper foil (model number: CF-T49A-DS-HD2, manufactured by Fukuda Metals 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: 18 μm, cured film thickness: 80±20 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 80±20 μm.

[0222] <Heat Resistance (Tg)> Test pieces (width: 3 mm x length: 1 cm) were cut from the cured films prepared above, and measured using a dynamic viscoelasticity measuring device (Seiko Instruments Inc., model number: EXSTAR4000) at a heating rate of 10°C / min and 1 Hz from 50°C to 300°C. The tan δ measured here was taken as the glass transition temperature (Tg) and evaluated according to the following evaluation criteria. The results are shown in Table 7. When two or more tan δ values ​​were present, the lowest value was taken as Tg. Evaluation criteria of "3", "4", and "5" indicate excellent heat resistance. (Evaluation Criteria) 2: Tg<170°C 3: 170°C≦Tg<180°C 4: 180°C≦Tg<200°C 5: 200°C≦Tg

[0223] <Adhesion (Peel Strength)> The compositions obtained in Examples 101 to 108 were each prepared as varnishes for evaluation, which were then applied to copper foil (model number: CF-V9S-SV, manufactured by Fukuda Metal Co., Ltd.), heated at 100°C for 5 minutes, and then dried at 130°C for 5 minutes to form a coating film. Copper foil (model number: CF-V9S-SV, manufactured by Fukuda Metal Co., Ltd.) was placed on the resulting coating film, vacuum pressed at 150°C for 5 minutes, and then baked at 200°C for 2 hours under nitrogen to produce a cured film with copper foil (copper foil: 18 μm, cured film 10±3 μm), which was used as a sample for peel strength testing.

[0224] Test pieces (width: 5 mm x length: 10 cm) were cut out from the peel strength samples prepared above, and the cured film-coated copper foil (one copper foil and cured film laminated portion in the peel strength sample) was pulled in a 90-degree direction at 500 mm / min using an Instron 5567 manufactured by Instron Corporation. The peel strength was measured in accordance with IPC-TM-650 2.4.9 and evaluated according to the following evaluation criteria. The results are shown in Table 7. (Evaluation criteria) 3: Peel strength < 0.50 N / mm 4: 0.50 N / mm ≦ peel strength < 0.070 N / mm 5: 0.70 N / mm ≦ peel strength

[0225] <Dielectric Loss Tangent> Test specimens (width: 6 cm x length: 6 cm) were cut out from the prepared cured films, and the dielectric loss tangent (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 evaluation criteria. The results are shown in Table 7. A rating of "3" or higher on the evaluation criteria can be said to be within the practically acceptable range. (Evaluation Criteria) 1: 0.0030<Df 2: 0.0025<Df≦0.0030 3: 0.0020<Df≦0.0025 4: 0.0015<Df≦0.0020 5: Df≦0.0015

[0226] <Elongation> Each of the compositions obtained in Examples 101 to 108 was applied to a copper foil (model number: CF-T49A-DS-HD2, manufactured by Fukuda Metals 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. A copper foil (model number: CF-T49A-DS-HD2, manufactured by Fukuda Metals Co., Ltd.) was placed on the resulting coating film, vacuum pressed at 160°C for 10 minutes, and then baked at 200°C for 2 hours under nitrogen to produce a copper foil-attached cured film (copper foil: 18 μm, cured film: 80±20 μmμm). The prepared copper foil-attached cured film was immersed in a 40% by mass iron chloride solution, and the copper foil was removed from the copper foil-attached cured film. The film was then washed with water and dried at 80°C for 30 minutes to prepare a film for elongation measurement. The elongation of the prepared evaluation film was measured using a TMA measuring device (Seiko Instruments, SSC-5200 model). At this time, 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 evaluation criteria. The results are shown in Table 7. Note that a rating of 3 or more according to the following evaluation criteria can be said to be a low elongation. Elongation (%) = (length of test piece at 260°C - initial length of test piece) / initial length of test piece × 100 (Evaluation criteria) 2: 10% < elongation 3: 5% < elongation ≦ 10% 4: 3% < elongation ≦ 5% 5: elongation ≦ 3%

[0227] <Coefficient of Thermal Expansion (α1)> Test specimens (width: 0.3 cm x length: 2 cm) were cut from the prepared cured films to prepare films for evaluation. The elongation of the evaluation films was measured using a TMA measuring device (Seiko Instruments, SSC-5200). The evaluation films were heated from room temperature to 200-250°C at a rate of 5°C / min, and then cooled to 0°C at a rate of 5°C / min. The coefficient of thermal expansion [α1 (ppm)] from 80-120°C upon cooling was determined and evaluated according to the following evaluation criteria. The results are shown in Table 7. A score of 4 or higher according to the following evaluation criteria can be considered to be a low coefficient of thermal expansion. (Evaluation Criteria) 2: 160 ppm > α1 3: 131 < α1 ≦ 160 ppm 4: 71 < α1 ≦ 130 ppm 5: α1 ≦ 70 ppm

[0228] <Solubility> For each of Examples 101 to 108, all components of the resin composition used were dissolved in toluene (TL) at the following concentrations. The evaluation was performed with a score of 5 when all components of the resin composition were soluble in TL at 50% by mass or more, 4 when they were soluble in TL at 30% by mass or more but less than 50% by mass, 3 when they were soluble in TL at 20% by mass or more but less than 30% by mass, and 2 when they were soluble in TL at less than 20% by mass. The results are shown in Table 7.

[0229] <Tensile Properties: Absorbed Energy> Each of the compositions obtained in Examples 101 to 108 was applied to copper foil (model number: CF-T49A-DS-HD2, manufactured by Fukuda Metal 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: CF-T49A-DS-HD2, manufactured by Fukuda Metal Co., Ltd.) was placed on the resulting coating film, vacuum pressed at 160° C. for 10 minutes, and then baked at 200° C. for 2 hours under nitrogen to produce a cured film with copper foil (copper foil: 18 μm, cured film: 100 μm). The prepared cured film with copper foil was immersed in a 40% by mass iron chloride solution, and the copper foil was removed from the cured film with copper foil. The film was then washed with water and dried at 80°C for 30 minutes to prepare a 100 μm thick film for elongation measurement. The elongation of the prepared evaluation film was measured using an EZ-LX tensile testing machine (manufactured by Shimadzu Corporation). The absorbed energy (mJ) was calculated from the area of ​​the obtained stress-strain curve and evaluated according to the following criteria. The results are shown in Table 7. Note that a rating of 4 or higher on the following criteria indicates that a film with high tensile strength and large tensile elongation has high absorbed energy and excellent tensile properties. (Evaluation Criteria) 2: 5≦Absorbed energy<10 3: 10≦Absorbed energy<15 4: 15≦Absorbed energy<20 5: Absorbed energy≧20mJ

[0230]

[0231] It can be seen that the cured products obtained from the compositions of Examples 101 to 108 have a high dielectric constant, a low dielectric dissipation factor, and a low elongation percentage, and also have a well-balanced and excellent property in terms of solubility, adhesion, and heat resistance, as well as excellent tensile properties.

Claims

1. A resin composition comprising: a compound (A) which is at least one of a compound (A1) having two or more partial structures represented by the following formula (1) and a compound (A2) represented by the following formula (2); and a polymer (B) having an aromatic ring and a group crosslinkable with the compound (A). In formula (1), Ar represents an aromatic ring having 6 to 10 carbon atoms, L represents an oxygen atom, a methylene group, an alkylene group having 2 to 6 carbon atoms, or a group formed by combining two or more groups selected from these groups, and R １１ each independently represents a hydrogen atom or a monovalent organic group, and is bonded to a carbon atom that is a member of the ring of Ar adjacent to the carbon atom that is a member of the ring of Ar to which L is bonded; １１ At least one of R is a monovalent organic group. １２ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R １３ is an alkyl group having 1 to 10 carbon atoms, an allyl group, or a vinyl group, m １１ is 4, m １２ is 0 or 1, and * represents a binding site with another structure. In formula (2), R ２１ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms, or two R ２１ represents a ring structure having 5 to 10 ring members formed by combining with each other together with the carbon atom to which they are attached, R ２２ and R ２３ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms, and at least one R ２２ is a group represented by formula (2-1), and at least one R ２３ is a group represented by formula (2-1). ２２ At least one of the two substituents bonded to the two carbon atoms adjacent to each other is an alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms, and R ２３ At least one of the two substituents bonded to the two carbon atoms adjacent to L and R is an alkyl group having 1 to 10 carbon atoms or an unsubstituted or substituted aromatic group having 6 to 10 carbon atoms. １２ , and m １１ are L and R in formula (1). １２ , and m １１ and * is R ２２ Or R ２３ represents the bonding site with the carbon atom of the benzene ring to which it is bonded.

2. The resin composition according to claim 1, wherein the compound (A1) is a compound represented by the following formula (1-1) or (1-2): In formula (1-1), R １１ , R １２ , R １３ , L, m １１ , and m １２ is R in formula (1) １１ , R １２ , R １３ , L, m １１ , and m １２ It is the same as R. １３ When R is an alkyl group having 1 to 5 carbon atoms, １３ may be a linking group bonded to a carbon atom that is a ring member of another Ar in formula (1-1), and —CH ２ - may be replaced by -O- or -S-. A is a single bond or n １１ A is an aryl group selected from the group consisting of an oxygen atom, a sulfur atom, an unsubstituted or substituted methylene group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by any one of the following formulae (10-1) to (10-3), or a group consisting of a combination of two or more of these groups; １３ and the carbon atom to which they are attached are combined together to form a ring structure having 3 to 20 ring members, １１ represents an integer of 2 to 4. In formula (1-2), R １１ , R １２ , R １３ , L, m １１ , and m １２ is R in formula (1) １１ , R １２ , R １３ , L, m １１ , and m １２ However, A in formula (1-2) is bonded to a carbon atom that is a member of another ring adjacent to the carbon atom that is a member of the ring of Ar to which L is bonded. １３ When R is an alkyl group having 1 to 5 carbon atoms, １３ may be a linking group bonded to a carbon atom which is a ring member of another Ar in formula (1-2), and CH ２ may be substituted with -O- or -S-. A is a single bond or n １２ represents an oxygen atom, a sulfur atom, an unsubstituted or substituted methylene group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by any one of the following formulas (10-1) to (10-3), or a group formed by combining two or more of these groups; １２ represents an integer of 2 to 4. In formulas (10-1) to (10-3), * represents a bonding site with Ar in formula (1-1) or formula (1-2).

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

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

5. The resin composition according to claim 1, further comprising a hydrogenated styrene-based thermoplastic elastomer (E).

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

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

8. A cured product made from the resin composition according to claim 1.

9. A prepreg obtained by impregnating a fibrous substrate with the resin composition according to claim 1.

10. A copper-clad laminate obtained by laminating the prepreg according to claim 9 and a copper substrate.

11. An interlayer insulating film comprising the cured product according to claim 8.

12. A compound having two or more partial structures represented by the following formula (1): In formula (1), Ar represents an aromatic ring having 6 to 10 carbon atoms, L represents an oxygen atom, a methylene group, an alkylene group having 2 to 6 carbon atoms, or a group formed by combining two or more groups selected from these groups, and R １１ is a group represented by the following formula (RN), １２ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R １３ is an alkyl group having 1 to 10 carbon atoms, an allyl group, or a vinyl group, m １１ is 4, m １２ is 0 or 1, and * represents a binding site with another structure. In formula (RN), CR represents an aromatic heterocycle having a nitrogen atom; １ is -N= or -CR ＣＲ２ =, and X ２ =N- or =CR ＣＲ３ - represents Y １ =N- or =CR ＣＲ４ - represents R ＣＲ１ ~R ＣＲ４ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R ＣＲ１ is R ＣＲ３ may bond to form a ring structure, and * represents the bonding site with Ar in the above formula (1).

13. The compound according to claim 12, which is a compound represented by the following formula (1-2): In formula (1-2), R １１ , R １２ , R １３ , L, m １１ , and m １２ is R in the formula (1). １１ , R １２ , R １３ , L, m １１ , and m １２ However, A in formula (1-2) is bonded to a carbon atom that is a member of another ring adjacent to the carbon atom that is a member of the ring of Ar to which L is bonded. １３ When R is an alkyl group having 1 to 5 carbon atoms, １３ may be a linking group bonded to a carbon atom which is a ring member of another Ar in formula (1-2), and CH ２ may be substituted with -O- or -S-. A is a single bond or n １２ represents an oxygen atom, a sulfur atom, an unsubstituted or substituted methylene group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by any one of the following formulas (10-1) to (10-3), or a group formed by combining two or more of these groups; １２ represents an integer of 2 to 4. In formulas (10-1) to (10-3), * represents a bonding site with Ar in formula (1-2).

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