Thermosettable resin composition for forming wiring substrate, cured product, prepreg, and interlayer insulating film

Abstract

A thermosetting resin composition for forming a wiring board, a cured product, a prepreg, and an interlayer insulating film, the thermosetting resin composition for forming a wiring board containing: a polymer (A) having a structural unit represented by formula (1-1); and a copolymer (B) having a structural unit derived from ethylene or an alpha-olefin, a structural unit derived from an aromatic vinyl compound, and a structural unit derived from an aromatic polyfunctional vinyl compound. The details of formula (1-1) are shown in the description.

Description

TECHNICAL FIELD

[0001] The present application relates to a heat-curable resin composition for a wiring substrate, a hardened product, a prepreg, and an interlayer insulating film. BACKGROUND

[0002] In recent years, in the field of information communication, various electronic devices centered on communication devices such as mobile phones are advancing in high speed and large capacity transmission, and with the increase in information processing amount, mounting technologies such as high integration of semiconductor devices, high density and multilayer of wiring, and high frequency correspondence are rapidly developing. Therefore, not only is high heat resistance required for printed wiring boards and the like used in various electronic devices, but also close contact with wiring (for example, copper) that has been highly densified and fine, or reduction of loss during signal transmission in order to improve the transmission speed of electrical signals including high frequency bands, and the like. In order to meet the requirements, as a substrate material for an insulating layer used in a wiring board, a material having a lower dielectric constant and dielectric loss tangent is required.

[0003] As a material for coping with the high frequency, polyolefin resin, styrene resin, fluorine resin, polyphenylene ether resin (PPE), vinylbenzyl ether resin, or a composition using polyphenylene ether resin, and the like are known. Among them, PPE has excellent high frequency characteristics (dielectric characteristics) such as a low dielectric constant and less loss (dielectric loss) due to dielectric loss tangent, and is widely used as an insulating material for printed wiring boards of electronic devices such as mobile phones using high frequency bands.

[0004] On the other hand, not only is it required that the molding material such as the substrate material has excellent low dielectric characteristics, but also excellent heat resistance and the like. Accordingly, it is considered that the resin contained in the substrate material is modified (for example, vinyl group is introduced) in a manner that it can be polymerized together with a hardening agent or the like, thereby improving the heat resistance.

[0005] For example, in Patent Literature 1, a polyphenylene ether compound is described, which includes: a polyphenylene ether having a polyphenylene ether portion in the molecular structure and a vinylbenzyl group or the like at the molecular terminal and having a number average molecular weight of 1000 to 7000; and a crosslinking type hardening agent. In addition, for example, in Patent Literature 2, in order to further improve the heat resistance of the polyphenylene ether having a vinylbenzyl group at the molecular terminal, a resin composition with acenaphthene compound is described.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: International Publication No. 2004 / 067634

[0009] Patent Literature 2: International Publication No. 2020 / 017399 SUMMARY

[0010] PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] In electronic materials, it is required that, in addition to low dielectric constant or low dielectric loss tangent (hereinafter also referred to as "low dielectric loss tangent"), properties such as heat resistance, adhesion, and the like are also satisfied. In the compositions or laminates disclosed in the patent document 1 and the patent document 2, heat resistance, adhesion to copper wiring, and high frequency properties are not all excellent in good balance, and further improvement in low dielectric loss tangent of the composition or the laminate is required in order to cope with high frequency of information communication equipment aimed at high speed and large capacity information transmission.

[0012] An embodiment of the present application aims to provide a wiring substrate forming heat curable resin composition in which the balance of low dielectric loss tangent, adhesion, and heat resistance of the obtained hardened product is excellent. In addition, another embodiment of the present application aims to provide a hardened product, a prepreg, and an interlayer insulating film in which the balance of low dielectric loss tangent, heat resistance, and peelability is excellent.

[0013] MEANS OF SOLVING THE PROBLEM

[0014] The method for solving the problem includes the following modes.

[0015] <1> A wiring substrate forming heat curable resin composition, comprising:

[0016] a polymer (A) having a structural unit represented by the following formula (1-1); and

[0017] a copolymer (B) having a structural unit derived from ethylene or an α-olefin, a structural unit derived from an aromatic vinyl compound, and a structural unit derived from an aromatic multifunctional vinyl compound.

[0018] [Chemical Formula 1]

[0019]

[0020] In formula (1-1), R a1 is a divalent group represented by the following formula (2), R a2 is a divalent group selected from one of the following formulae (R a2 -1), (R a2 -2), and (R a2 -3).

[0021] [Chemical Formula 2]

[0022]

[0023] In formula (2), Ara1and Ara2are each independently an unsubstituted or substituted aromatic hydrocarbon group, L is a single bond, -O-, -S-, -N(R8)-, -C(O)-, -C(O)-O-, -C(O)-NH-, -S(O)-, -S(O)2-, -P(O)-, or a divalent organic group, R8is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbons, or a monovalent halogenated hydrocarbon group having 1 to 20 carbons, and y is an integer of 0 to 5. When y is 2 or more, the plurality of Ara1and L are each the same or different. Ra6and Ra7are each independently a single bond, a methylene group, or an alkylene group having 2 to 4 carbons.

[0024] [Chemical Formula 3]

[0025]

[0026] In formulae (Ra2-1) to (Ra2-3), R1is each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbons, a monovalent halogenated hydrocarbon group having 1 to 20 carbons, a nitro group, a cyano group, a primary to tertiary amino group, or a salt of a primary to tertiary amino group. n is each independently an integer of 0 to 2. When n is 2, the plurality of R1are the same or different and are part of a ring structure having 5 to 10 ring members which are bonded to each other.

[0027] <2> The thermosetting resin composition for forming a wiring substrate according to <1>, wherein the number average molecular weight of the copolymer (B) is 500 or more and 100,000 or less.

[0028] <3> The thermosetting resin composition for forming a wiring substrate according to <1> or <2>, wherein the aromatic vinyl compound in the copolymer (B) is an aromatic vinyl compound having 8 or more and 20 or less carbons, and the content of the structural unit derived from the aromatic vinyl compound is more than 0 mass% and 70 mass% or less, with respect to the mass of the total structural units of the copolymer (B).

[0029] <4> The thermosetting resin composition for forming a wiring substrate according to any one of <1> to <3>, wherein the α-olefin in the copolymer (B) is one or two or more selected from α-olefins having 3 or more and 20 or less carbons, and the total of the structural unit derived from ethylene or the α-olefin, the structural unit derived from the aromatic vinyl compound, and the structural unit derived from the aromatic multifunctional vinyl compound is 100 mass%, with respect to the mass of the total structural units of the copolymer (B).

[0030] <5> The thermosetting resin composition for forming a wiring substrate according to any one of <1> to <4>, further comprising a hardening compound (C) and an organic solvent (E).

[0031] The thermosetting resin composition for forming a wiring substrate according to any one of <1> to <6>, wherein the hardenable compound (C) is at least one compound selected from the group consisting of a vinyl compound, a maleimide compound, an allyl compound, an acrylic acid compound, a methacrylic acid compound, a mercaptan compound, an oxazine compound, a cyanate compound, an epoxy compound, an oxetane compound, a methylol compound, a benzocyclobutene compound, a propargyl compound, and a silane compound.

[0032] The thermosetting resin composition for forming a wiring substrate according to any one of <1> to <6>, further comprising a polymerization initiator (D).

[0033] The thermosetting resin composition for forming a wiring substrate according to any one of <1> to <7>, further comprising a filler (F).

[0034] The thermosetting resin composition for forming a wiring substrate according to any one of <1> to <8>, wherein the hardenable compound (C) is at least one compound selected from the group consisting of a vinyl compound, a maleimide compound, an allyl compound, an acrylic acid compound, a methacrylic acid compound, a mercaptan compound, an oxazine compound, a cyanate compound, an epoxy compound, an oxetane compound, a methylol compound, a benzocyclobutene compound, a propargyl compound, and a silane compound.

[0035] The thermosetting resin composition for forming a wiring substrate according to any one of <1> to <8>, wherein the hardenable compound (C) is at least one compound selected from the group consisting of a vinyl compound, a maleimide compound, an allyl compound, an acrylic acid compound, a methacrylic acid compound, a mercaptan compound, an oxazine compound, a cyanate compound, an epoxy compound, an oxetane compound, a methylol compound, a benzocyclobutene compound, a propargyl compound, and a silane compound.

[0036] The thermosetting resin composition for forming a wiring substrate according to any one of <1> to <8>, wherein the hardenable compound (C) is at least one compound selected from the group consisting of a vinyl compound, a maleimide compound, an allyl compound, an acrylic acid compound, a methacrylic acid compound, a mercaptan compound, an oxazine compound, a cyanate compound, an epoxy compound, an oxetane compound, a methylol compound, a benzocyclobutene compound, a propargyl compound, and a silane compound.

[0037] The thermosetting resin composition for forming a wiring substrate according to any one of <1> to <8>, wherein the hardenable compound (C) is at least one compound selected from the group consisting of a vinyl compound, a maleimide compound, an allyl compound, an acrylic acid compound, a methacrylic acid compound, a mercaptan compound, an oxazine compound, a cyanate compound, an epoxy compound, an oxetane compound, a methylol compound, a benzocyclobutene compound, a propargyl compound, and a silane compound.

[0038] Effects of the Invention

[0039] According to an embodiment of the present application, a thermosetting resin composition for forming a wiring substrate, which is excellent in low dielectric loss tangent, adhesiveness, and heat resistance of a resulting hardened product, can be provided. In addition, according to an embodiment of the present application, a hardened product, a prepreg, and an interlayer insulating film, which are excellent in balance of low dielectric loss tangent, adhesiveness, and heat resistance, can be provided. DETAILED DESCRIPTION

[0040] Hereinafter, a suitable embodiment of the present application will be described in detail. Furthermore, the present application is not limited only to the embodiment described below, and it should be understood to include various modifications implemented within the scope of the present application.

[0041] In the present specification, a numerical range described using "to" includes the numerical values described before and after "to" as lower limit values and upper limit values.

[0042] In the present specification, "polymer" is a concept including homopolymers and copolymers.

[0043] In the present specification, "~" indicating a numerical range means the same unit as recited at either of the front and the rear thereof, unless otherwise specified.

[0044] In the present specification, a combination of two or more preferred modes is a more preferred mode.

[0045] In the present specification, the term "α-olefin" does not include ethylene. Hereinafter, a polymer, a composition, a hardened product, a laminate, or an electronic part of an embodiment of the present application will be described in detail.

[0046] <Thermosetting resin composition for wiring substrate formation>

[0047] The thermosetting resin composition for wiring substrate formation (hereinafter, sometimes simply referred to as "thermosetting resin composition") of the present application contains: a polymer (A) having a structural unit represented by formula (1-1); and a copolymer (B) having a structural unit derived from ethylene or an α-olefin, a structural unit derived from an aromatic vinyl compound, and a structural unit derived from an aromatic multifunctional vinyl compound.

[0048] The thermosetting resin composition has the structure, and thus the balance of the low dielectric loss tangent, the adhesiveness, and the heat resistance of the hardened product obtained is excellent. Although the reason is not clear, it is presumed that the mechanism is as follows.

[0049] Since the thermosetting resin composition contains the polymer (A) having a specific structure and the copolymer (B) having a specific structural unit, the compatibility of the polymer (A) and the copolymer (B) becomes good, the hardened product obtained from the thermosetting resin composition has the heat resistance due to the structure of the polymer (A), and in addition, the low dielectric loss tangent is excellent by containing the polymer (A) and the copolymer (B), and thus it is inferred that the balance of the low dielectric loss tangent, the adhesiveness, and the heat resistance of the hardened product obtained from the thermosetting resin composition is excellent.

[0050] Hereinafter, each component of the thermosetting resin composition will be described in detail.

[0051] <<Polymer (A)>>

[0052] The polymer (A) has a structural unit represented by formula (1-1).

[0053] [Chemical Formula 4]

[0054]

[0055] In formula (1-1), Ra1is a divalent group represented by the following formula (2), and Ra2is a divalent group represented by one of the following formulas (Ra2-1), (Ra2-2), and (Ra2-3).

[0056] [Chemical Formula 5]

[0057]

[0058] In formula (2), Ara1and Ara2are each independently an unsubstituted or substituted aromatic hydrocarbon group, L is a single bond, -O-, -S-, -N(R8)-, -C(O)-, -C(O)-O-, -C(O)-NH-, -S(O)-, -S(O)2-, -P(O)-, or a divalent organic group, R8is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and y is an integer of 0 to 5. In the case where y is 2 or more, the plurality of Ara1and L are each the same or different. Ra6and Ra7are each independently a single bond, a methylene group, or an alkylene group having 2 to 4 carbon atoms.

[0059] [Ara1and Ara2]

[0060] As the unsubstituted or substituted aromatic hydrocarbon group represented by Ara1and Ara2, each is independently preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group, a naphthyl group, or an anthryl group, and particularly preferably a phenyl group or a naphthyl group.

[0061] The substituted aromatic hydrocarbon group preferably has 0 to 8, more preferably 0 to 4, and further preferably 0 to 2, number of substituents. If the number of substituents is within the above range, the polymerization reaction is stabilized, and a polymer having a certain molecular weight (narrow molecular weight distribution) is easily obtained, and a thermosetting resin composition using such a polymer is easily controlled in terms of the hardenability of a hardened product, or the flowability during pressing when a prepreg or a laminate is molded.

[0062] There is no particular limitation on the substituents in the aromatic hydrocarbon group, and examples include an allyl group, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxyl group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a hydroxyl group, a primary to tertiary amino group, a salt of a carboxyl group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxyl group, and a salt of a primary to tertiary amino group.

[0063] Among these, as the substituents in the aromatic hydrocarbon group, a monovalent hydrocarbon group having 1 to 20 carbon atoms and an allyl group are preferred.

[0064] There is no particular limitation on the halogen atom, and examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0065] The carbon number 1 to 20 monovalent hydrocarbon group is not particularly limited, and can be, for example, a chain or cyclic hydrocarbon group.

[0066] As the cyclic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group can be exemplified.

[0067] The cyclic hydrocarbon group can be a monocyclic ring, or a fused ring (polycyclic ring).

[0068] As the chain hydrocarbon group, a straight-chain or branched-chain saturated or unsaturated hydrocarbon group can be exemplified. As the chain hydrocarbon group, for example, an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and the like; an alkenyl group such as ethenyl, propenyl, butenyl, pentenyl, and the like; an alkynyl group such as ethynyl, propynyl, butynyl, pentynyl, and the like can be exemplified.

[0069] As the alicyclic hydrocarbon group, for example, a monocyclic ring cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like; a polycyclic ring cycloalkyl group such as norbornyl, adamantyl, and the like; a monocyclic ring cycloalkenyl group such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like; a polycyclic ring cycloalkenyl group such as norbornenyl, and the like can be exemplified.

[0070] The aromatic hydrocarbon group is not particularly limited, and can be exemplified by, for example, an aryl group such as phenyl, tolyl, xylyl, naphthyl, anthryl, and the like; an aralkyl group such as benzyl, phenylethyl, phenylpropyl, naphthylmethyl, and the like.

[0071] As the carbon number 1 to 20 monovalent halogenated hydrocarbon group, for example, a group in which a part or all of the hydrogen atoms of the carbon number 1 to 20 monovalent hydrocarbon group are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be exemplified.

[0072] As the carbon number 1 to 20 alkoxy group, for example, methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentoxy, hexyloxy, octyloxy, and the like can be exemplified.

[0073] As the carbon number 1 to 20 alkylthio group, for example, methylthio, ethylthio, n-propylthio, isopropylthio, butylthio, pentoxy, hexylthio, octylthio, and the like can be exemplified.

[0074] In the case where the amino group is a secondary amino group and a tertiary amino group, the substituents (R) in the secondary amino group (-NHR) and the tertiary amino group (-NR2) are not particularly limited, and as the substituents (R), for example, a carbon number 1 to 20 monovalent hydrocarbon group can be exemplified.

[0075] As specific examples, the groups exemplified as substituents in the unsubstituted nitrogen-containing heteroaromatic ring described later can be exemplified.

[0076] The cationic site of the cation constituting the salt of a carboxyl group, the salt of a sulfonic acid group, the salt of a phosphonic acid group, the salt of a phosphoric acid group, and the salt of a hydroxyl group is not particularly limited, and known cations such as Na+ can be mentioned.

[0077] The anionic site of the anion constituting the salt of an amino group is not particularly limited, and known anions such as Cl" can be mentioned.

[0078] The Ara1 and the Ara2 can each independently be an aromatic hydrocarbon group having an allyl group in terms of easiness in obtaining a hardened product having a high crosslinking density and the like.

[0079] 〔L〕

[0080] As the divalent organic group in L, a divalent organic group having a carbon number of 1 to 20 is preferred, and for example, methylene, an alkylene group having a carbon number of 2 to 20, a halogenated methylene group, a halogenated alkylene group having a carbon number of 2 to 20, a divalent Cardo structure, or a group represented by the following formula (L1) can be mentioned.

[0081] [Chemical Formula 6]

[0082]

[0083] In formula (L1), Rc is a divalent alicyclic hydrocarbon group having a ring member number of 5 to 30, which is unsubstituted or substituted.

[0084] As the alkylene group having a carbon number of 2 to 20 in L, for example, ethylene, n-propylene, i-propylene, n-butylene, sec-butylene, neopentylene, 4-methyl-pentane-2,2-diyl, nonane-1,9-diyl, decane-1,1-diyl, and the like can be mentioned.

[0085] As the halogenated methylene group in L, for example, a group in which a part or all of the hydrogen atoms of methylene are substituted with halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be mentioned.

[0086] As the halogenated alkylene group having a carbon number of 2 to 20 in L, for example, a group in which a part or all of the hydrogen atoms of the alkylene group having a carbon number of 2 to 20 are substituted with halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like can be mentioned.

[0087] As the divalent Cardo structure in L, for example, a divalent group derived from fluorene represented by the following formula (L2) (i.e., a group in which two hydrogen atoms in a compound having a fluorene skeleton are removed) can be mentioned.

[0088] [Chemical Formula 7]

[0089]

[0090] In formula (L2), R8and R9are each independently a hydrogen atom, a fluorine atom, or a monovalent chain hydrocarbon group having a carbon number of 1 to 20, and k is each independently an integer of 0 to 4.

[0091] As the divalent cardo structure, for example, a structure derived from a compound represented by the following formula can be exemplified.

[0092] [Chemical Formula 8]

[0093]

[0094] As the unsubstituted or substituted divalent alicyclic hydrocarbon group having a ring member number of 5 to 30 represented by Rc in formula (L1), for example, an unsubstituted or substituted monocyclic alicyclic hydrocarbon group having a ring member number of 5 to 15, an unsubstituted or substituted monocyclic fluorinated alicyclic hydrocarbon group having a ring member number of 5 to 15, a polycyclic alicyclic hydrocarbon group having a ring member number of 7 to 30, a polycyclic fluorinated alicyclic hydrocarbon group having a ring member number of 7 to 30, and the like can be exemplified.

[0095] As the unsubstituted or substituted monocyclic alicyclic hydrocarbon group having a ring member number of 5 to 15, for example, a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, a 3,3,5-trimethylcyclohexane-1,1-diyl group, a cyclopentene-3,3-diyl group, a cyclohexene-3,3-diyl group, a cyclooctane-1,1-diyl group, a cyclodecane-1,1-diyl group, a cyclododecane-1,1-diyl group, a group in which a part or all of the hydrogen atoms of these groups are substituted with a monovalent chain hydrocarbon group having a carbon number of 1 to 20, and the like can be exemplified.

[0096] As the unsubstituted or substituted monocyclic fluorinated alicyclic hydrocarbon group having a ring member number of 5 to 15, for example, a group in which a part or all of the hydrogen atoms of the group exemplified as the monocyclic alicyclic hydrocarbon group having a ring member number of 5 to 15 are substituted with fluorine atoms can be exemplified.

[0097] As the unsubstituted or substituted polycyclic alicyclic hydrocarbon group having a ring member number of 7 to 30, for example, a group in which two hydrogen atoms bonded to one carbon atom of a polycyclic alicyclic hydrocarbon such as norbornane, norbornene, adamantane, tricyclo[5.2.1.02,6]decane, pinane, camphane, decalin, tricyclo[2.2.1.02,6]heptane (nortricyclane), perhydroanthracene, perhydroazulene, cyclopentano-hydrophenanthrene, bicyclo[2.2.2]-2-octene, and the like are bonded; a group in which a part or all of the hydrogen atoms of these groups are substituted with a monovalent chain hydrocarbon group having a carbon number of 1 to 20, and the like can be exemplified.

[0098] As the unsubstituted or substituted polycyclic fluoroaliphatic hydrocarbon group having 7 to 30 ring members, for example, a group in which a part or all of the hydrogen atoms of the polycyclic aliphatic hydrocarbon group having 7 to 30 ring members exemplified as the ring member number is replaced with a fluorine atom can be exemplified.

[0099] R8in -N(R8)- in L is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbons, or a monovalent halogenated hydrocarbon group having 1 to 20 carbons. As the monovalent hydrocarbon group having 1 to 20 carbons and the monovalent halogenated hydrocarbon group having 1 to 20 carbons, for example, the monovalent hydrocarbon group having 1 to 20 carbons and the monovalent halogenated hydrocarbon group having 1 to 20 carbons exemplified in Ara1 and Ara2, respectively, can be exemplified.

[0100] As L, from the viewpoint of the structural stability of the polymer (A), a single bond, -0-, -S-, -C(O)-, -S(O)-, -S(O)2-, -C(O)-NH-, -C(O)-O-, methylene, an alkylene group having 2 to 5 carbons, the formula (L1), a halogenated methylene group, a halogenated alkylene group having 2 to 10 carbons, or a divalent cardo structure is preferable.

[0101] 〔y〕

[0102] In the formula (2), y is an integer of 0 to 5. From the viewpoint of the structural stability of the polymer (A), y is preferably 0 to 4, and more preferably 0 to 3.

[0103] 〔Ra6and Ra7〕

[0104] In the formula (2), Ra6and Ra7are each independently a single bond, a methylene group, or an alkylene group having 2 to 4 carbons.

[0105] As the alkylene group having 2 to 4 carbons, for example, ethylene, n-propylene, i-propylene, n-butylene, sec-butylene, and the like can be exemplified. As Ra6and Ra7, from the viewpoint that the polymer (A) can be synthesized with good polymerizability, a single bond, a methylene group, or an ethylene group is preferable.

[0106] As a monomer that is a raw material of a moiety containing Ra1in formula (1-1) (i.e., a divalent group represented by formula (2)), for example, the following can be cited: dihydroxyphenyl compounds such as p-benzenediol, m-benzenediol, o-benzenediol, phenyl-p-benzenediol, and the like; bisphenol compounds such as 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-allylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 4,4'-(1,3-dimethylidenebutylidene)bisphenol, 1,1-bis(4-hydroxyphenyl)nonane, bis(4-hydroxyphenyl)sulfone, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 4,4'-cyclo-dodecylidenebisphenol, 4,4'-decylidenebisphenol, and the like; diol compounds such as PRIPLAST 1901, 1838, 3186, 3192, 3197, 3199 (manufactured by Croda Japan (K.K.)), and the like. In addition, one of these monomers can be used alone, or two or more of them can be used.

[0107] <Ra2>

[0108] Ra2is a divalent group represented by one of the following formulae (Ra2-1), (Ra2-2), and (Ra2-3).

[0109] [Chemical Formula 9]

[0110]

[0111] In formulae (Ra2-1) to (Ra2-3), R1is each independently a halogen atom, a monovalent hydrocarbon group having a carbon number of 1 to 20, a monovalent halogenated hydrocarbon group having a carbon number of 1 to 20, a nitro group, a cyano group, a primary to tertiary amino group, or a salt of a primary to tertiary amino group, and n is each independently an integer of 0 to 2. In the case where n is 2, the plurality of R1are the same or different, and are part of a ring structure of a ring member number of 5 to 10 that are combined with each other and with the carbon atom to which they are bonded.

[0112] The halogen atom represented by R1in the formula (Ra2-1) to the formula (Ra2-3) can be exemplified by a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0113] The monovalent hydrocarbon group having a carbon number of 1 to 20 represented by R1in the formula (Ra2-1) to the formula (Ra2-3) can be exemplified by a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like.

[0114] The chain hydrocarbon group can be exemplified by an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and the like; an alkenyl group such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and the like; an alkynyl group such as an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, and the like.

[0115] The alicyclic hydrocarbon group can be exemplified by a monocyclic ring alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like; a polycyclic ring alkyl group such as a norbornyl group, an adamantyl group, and the like; a monocyclic ring alkenyl group such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and the like; a polycyclic ring alkenyl group such as a norbornenyl group, and the like.

[0116] The aromatic hydrocarbon group can be exemplified by an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, and the like; an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and the like.

[0117] The monovalent halogenated hydrocarbon group having a carbon number of 1 to 20 represented by R1may be exemplified by a group in which a part or all of the hydrogen atoms of the monovalent hydrocarbon group having a carbon number of 1 to 20 exemplified as the group represented by R1are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0118] From the viewpoint of improving the polymerizability, R1is preferably a halogen atom, a monovalent hydrocarbon group having a carbon number of 1 to 3, a monovalent halogenated hydrocarbon group having a carbon number of 1 to 3, a nitro group, and a cyano group, and more preferably a fluorine atom, a chlorine atom, a methyl group, a nitro group, and a cyano group. From the same viewpoint, n is preferably 0 or 1, and more preferably 0.

[0119] In the divalent group represented by one of the formula (Ra2-1), the formula (Ra2-2), and the formula (Ra2-3), from the viewpoint of improving the polymerizability, the position of the other bonding bond with respect to one of the bonding bonds is preferably meta and para, and more preferably meta.

[0120] In addition, from the viewpoints of improving the polymerizability and improving the solubility in various organic solvents, Ra2is preferably the group represented by the formula (Ra2-2) having a pyrimidine skeleton.

[0121] <<Terminal Group>>

[0122] The polymer (A) can have a terminal group Y represented by the following formula (a) at the terminal of the structural unit represented by formula (1-1).

[0123] [Chemical Formula 10]

[0124]

[0125] In formula (a), Y is a group having an ethylenically unsaturated double bond having a carbon number of 3 to 50, an unsubstituted or substituted aromatic hydrocarbon group having a carbon number of 6 to 50, an unsubstituted or substituted aliphatic hydrocarbon group having a carbon number of 6 to 50, or an unsubstituted nitrogen-containing heteroaromatic ring, and in the case where the aromatic hydrocarbon group or the aliphatic hydrocarbon group has a substituent, the substituent is a group other than a hydroxyl group.

[0126] Further, in the case where the terminal group Y is bonded at the terminal of the main chain of the polymer (A), a partial structure represented by the following formula (a1) or formula (a2) is formed at the terminal portion of the polymer (A).

[0127] In the case, the terminal group Y is a group different from the group constituting the terminal portion (for example, the substituent in Ara1, Ara2, and Ra2) in Ra1 and Ra2 in formula (1-1).

[0128] [Chemical Formula 11]

[0129]

[0130] In formula (a1) and formula (a2), Y has the same meaning as Y in formula (a), and Ra1 and Ra2 have the same meaning as Ra1 and Ra2 in formula (1-1).

[0131] As a specific example of the polymer (A) having a terminal group Y represented by formula (a), the polymer represented by the following formula (3) or formula (4) can be cited. Here, the "main chain" means the longest bonding chain in the polymer.

[0132] [Chemical Formula 12]

[0133]

[0134] In formula (3) and formula (4), Ra1 and Ra2 each independently have the same meaning as Ra1 and Ra2 in formula (1-1), and the preferable modes are also the same. Y has the same meaning as Y in formula (a), and the preferable modes are also the same. n is an integer of 0 to 100, and more preferably 2 to 30.

[0135] From the viewpoint of improving the dielectric properties, the terminal group Y is preferably a polarizable aromatic hydrocarbon group or an aliphatic hydrocarbon group, or a nitrogen-containing heteroaromatic ring group. In the case where the terminal group Y is a group having an ethylenically unsaturated double bond, the crosslinking density is increased, so that the resin composition has excellent hardenability, and the obtained hardened product has excellent heat resistance.

[0136] As the group having an ethylenically unsaturated double bond having a carbon number of 3 to 50 represented by Y, for example, there can be mentioned: 3-isopropenylphenyl, 4-isopropenylphenyl, 2-allylphenyl, 2-methoxy-4-allylphenyl, 4-(l-propenyl)-2-methoxyphenyl, 4-vinylbenzyl, 3-vinylbenzyl, 2-vinylbenzyl, and the like aromatic ring-containing groups; allyl group; acrylic acid group; methacrylic acid group; and the like.

[0137] As the aromatic hydrocarbon group having a carbon number of 6 to 50 represented by Y, for example, there can be mentioned: phenyl group; biphenyl group; tolyl group; xylyl group; naphthyl group; anthryl group; and the like aryl groups; benzyl group; phenylethyl group; phenylpropyl group; naphthylmethyl group; and the like aralkyl groups; and the like.

[0138] As the aliphatic hydrocarbon group having a carbon number of 6 to 50 represented by Y, for example, there can be mentioned: cyclopropyl group; cyclobutyl group; cyclopentyl group; cyclohexyl group; and the like monocyclic cycloalkyl groups; norbornyl group; adamantyl group; and the like polycyclic cycloalkyl groups; cyclopropenyl group; cyclobutenyl group; cyclopentenyl group; cyclohexenyl group; and the like monocyclic cycloalkenyl groups; norbornenyl group; and the like polycyclic cycloalkenyl groups; and the like.

[0139] As the unsubstituted nitrogen-containing heteroaromatic ring represented by Y, for example, there can be mentioned: pyrrole ring; pyridine ring; pyrimidine ring; pyrazine ring; pyridazine ring; triazine ring; quinoline ring; isoquinoline ring; quinoxaline ring; oxazine ring; quinazoline ring; naphthylidine ring; carbazole ring; acridine ring; phenoxazine ring; and the like, among which, the pyrimidine ring is preferred.

[0140] As the substituent in the unsubstituted or substituted aromatic hydrocarbon group having a carbon number of 6 to 50, the unsubstituted or substituted aliphatic hydrocarbon group having a carbon number of 6 to 50, and the unsubstituted nitrogen-containing heteroaromatic ring represented by Y, there can be mentioned a group other than a hydroxyl group.

[0141] As the substituent, there is no particular limitation, and for example, there can be mentioned: allyl group; halogen atom; monovalent hydrocarbon group having a carbon number of 1 to 20; monovalent halogenated hydrocarbon group having a carbon number of 1 to 20; alkoxy group having a carbon number of 1 to 20; alkylthio group having a carbon number of 1 to 20; nitro group; cyano group; carboxyl group; sulfonic acid group; phosphonic acid group; phosphoric acid group; primary to tertiary amino group; salt of carboxyl group; salt of sulfonic acid group; salt of phosphonic acid group; salt of phosphoric acid group; salt of primary to tertiary amino group. Among these, the allyl group is preferred.

[0142] As a method for forming the polymer having the terminal group Y sealing the terminal of the polymer (A), a method in which, in addition to using a monomer forming Ra1 or Ra2 in the formula (1-1) as a raw material, a monomer for forming the terminal group Y selected from the group consisting of a monovalent phenol compound, a monovalent amine compound, a monovalent thiol compound, a monovalent aliphatic halide, a monovalent acid halide, and a monovalent acid anhydride is used as a raw material can be exemplified.

[0143] As a method for synthesizing the polymer (A) containing the terminal group Y having an ethylenically unsaturated double bond having a carbon number of 3 to 50, for example, in order to avoid a case where the ethylenically unsaturated double bonds react with each other and gelation occurs when a monomer that is a raw material of a portion containing Ra1 and a monomer that is a raw material of a portion containing Ra2 are polymerized, the monomer for forming the terminal group Y can be reacted after the monomer that is a raw material of a portion containing Ra1 and the monomer that is a raw material of a portion containing Ra2 are polymerized.

[0144] As the monomer for forming the terminal group Y, for example, a monovalent phenol compound such as t-butylphenol, nonylphenol, 4-isopropenylphenol, 4-vinylphenol, 2-allylphenol, iso-eugenol, tocotrienol, a-tocopherol, 4-hydroxyphenylmaleimide, 2-phenylphenol, a monovalent amine compound such as 4-hexylaniline, diallylamine, a monovalent thiol compound such as 1-octanethiol, a monovalent aliphatic halide such as allyl chloride, 4-(chloromethyl)styrene, 3-(chloromethyl)styrene, a monovalent acid halide such as acryloyl chloride, methacryloyl chloride, crotonyl chloride, cinnamyl chloride, and a monovalent acid anhydride such as acrylic anhydride, crotonic anhydride, methacrylic anhydride can be exemplified.

[0145] In addition, the monomer for forming the terminal group Y can be used alone or two or more kinds can be used.

[0146] The polymer (A) can also contain a structural unit represented by the following formula (1-2).

[0147] [Chem. 13]

[0148]

[0149] In the formula (1-2), Ra2 is a divalent group selected from one of the formula (Ra2-1), the formula (Ra2-2), and the formula (Ra2-3), R12 independently represents a substituted or unsubstituted divalent aromatic hydrocarbon group, R13 represents a hydrocarbon group having a carbon number of 1 to 20, and m represents an integer of 1 to 6, represents a bonding bond to other structural units in the polymer (A).

[0150] The formula (1-2) can be represented by the following formula (1-2a).

[0151] [Chemical Formula 14]

[0152]

[0153] In the formula (1-2a), Ra2and R12have the same meanings as in the formula (1-2). R13xrepresents a hydrocarbon group having a carbon number of 1 to 20, which has at least one group represented by the following formula (1-2b) bonded thereto in addition to two R12.

[0154] [Chemical Formula 15]

[0155]

[0156] In the formula (1-2b), represents a bonding bond to R13x, represents a bonding bond to other structural units in the polymer (A), and R12has the same meaning as R12in the formula (1-2).

[0157] [R12]

[0158] The unsubstituted aromatic hydrocarbon group (arylene group) in R12may be a monocyclic ring or a fused ring. The carbon atom number of the unsubstituted aromatic hydrocarbon group is preferably 6 to 20, and more preferably 6 to 18. As the aromatic hydrocarbon group, for example, phenylene, naphthylene, anthrylene, and the like can be exemplified.

[0159] There is no particular limitation on the substituent in the substituted aromatic hydrocarbon group in R12, and for example, an allyl group, a halogen atom, a monovalent hydrocarbon group having a carbon number of 1 to 20, a monovalent halogenated hydrocarbon group having a carbon number of 1 to 20, an alkoxy group having a carbon number of 1 to 20, an alkylthio group having a carbon number of 1 to 20, a nitro group, a cyano group, and a carboxyl group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a hydroxyl group, a primary to tertiary amino group, and a salt of these, and the like can be exemplified.

[0160] From the viewpoint of increasing the glass transition temperature (Tg) of the polymer (A), R12in the formula (1-2) or formula (1-2a) is preferably each independently a group represented by the following formula (5).

[0161] Further, the bond represented by a straight line across the side of the ring structure represents substitution of any hydrogen atom of the ring structure. In addition, the bond represented by a straight line across a plurality of ring structures represents substitution of any hydrogen atom in any of the ring structures.

[0162] [Chemical Formula 16]

[0163]

[0164] In the formula (5), R51independently represents an alkyl group having 1 to 10 carbons, an alkoxy group having 1 to 10 carbons, or a cyclic alkyl group having 3 to 10 carbons, n52represents an integer of 0 to 4, and n53represents an integer of 0 to 2, represents a bond to R13in the formula (1-2) or R13xin the formula (1-2a), represents a bond to O in the formula (1-2) or the formula (1-2a).

[0165] n52preferably represents an integer of 1 to 3, and more preferably represents 1 or 2. n53preferably represents 0 or 1, and more preferably represents 1.

[0166] In addition, from the viewpoint of maintaining a low dielectric constant, a low dielectric loss tangent, and improving heat resistance (for example, Tg of the polymer (A)), the group represented by the formula (5) is preferably a group represented by the following formula (5-1) or the following formula (5-2).

[0167] [Chemical Formula 17]

[0168]

[0169] In the formula (5-1) and the formula (5-2), R51independently represents an alkyl group having 1 to 10 carbons, an alkoxy group having 1 to 10 carbons, or a cyclic alkyl group having 3 to 10 carbons, R52represents an alkyl group having 1 to 10 carbons, an alkoxy group having 1 to 10 carbons, or a cyclic alkyl group having 3 to 10 carbons, n53represents an integer of 0 to 2, n54represents an integer of 0 to 3, and n55represents an integer of 0 to 2, represents a bond to R13in the formula (1-2) or R13xin the formula (1-2a), represents a bond to an oxygen atom in the formula (1-2) or the formula (1-2a).

[0170] The alkyl group having 1 to 10 carbons in the R51and the R52may be linear or branched. The alkyl group having 1 to 10 carbons is preferably an alkyl group having 1 to 8 carbons, and more preferably an alkyl group having 1 to 6 carbons. As the alkyl group having 1 to 10 carbons, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, and the like can be exemplified.

[0171] As the alkoxy group having 1 to 10 carbons in the R51and the R52, an alkoxy group having 1 to 8 carbons is preferable, and for example, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a butoxy group, a pentoxy group, a hexyloxy group, an octyloxy group, and the like can be exemplified.

[0172] As the cycloalkyl group having 3 to 10 carbons in the R51and R52, a cycloalkyl group having 3 to 8 carbons is preferable, and examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

[0173] n53and n53in the formula (5) have the same meaning, and the preferable modes are also the same. The n54represents an integer of 0 to 3, preferably an integer of 0 to 2, and the n55represents an integer of 0 to 2, preferably 0 or 1.

[0174] [R13and R13x]

[0175] The R13represents a group that introduces a branched structure in the structural unit represented by the formula (1-2).

[0176] The hydrocarbon group having 1 to 20 carbons in the R13and R13xmay be a linear or branched hydrocarbon group having 1 to 20 carbons, a cyclic hydrocarbon group having 3 to 20 carbons, or a combination thereof. In addition, the branched structure is preferably a structure formed by a tertiary carbon or a quaternary carbon in the R13and R13x.

[0177] In the case where the hydrocarbon group is linear or branched, a linear or branched hydrocarbon group having 1 to 10 carbons is preferable, a linear or branched hydrocarbon group having 1 to 6 carbons is more preferable, and a linear or branched hydrocarbon group having 1 to 4 carbons is further preferable.

[0178] As the cyclic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group can be used.

[0179] As the alicyclic hydrocarbon group, an alicyclic hydrocarbon group having 3 to 10 carbons is preferable, an alicyclic hydrocarbon group having 3 to 8 carbons is more preferable, and an alicyclic hydrocarbon group having 3 to 6 carbons is further preferable.

[0180] As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 18 carbons is preferable, and an aromatic hydrocarbon group having 6 to 12 carbons is more preferable.

[0181] The R13is preferably a group represented by -(L-Z)nZ-.

[0182] The L represents a single bond or an alicyclic hydrocarbon group having 3 to 10 carbons, the Z represents a linear or branched hydrocarbon group having 1 to 10 carbons, and the nZ represents 1 or 2.

[0183] The alicyclic hydrocarbon group having 3 to 10 carbons in the L is preferably an alicyclic hydrocarbon group having 3 to 6 carbons. The linear or branched hydrocarbon group having 1 to 10 carbons in the Z is preferably a linear or branched hydrocarbon group having 1 to 6 carbons, and more preferably a linear or branched hydrocarbon group having 1 to 4 carbons.

[0184] The R13in the formula (1-2) is preferably a group represented by -(L-Z)nZ-. represents a bonding bond with other constitutional units in the polymer (A).

[0185] The other constitutional unit in the polymer (A) can be a constitutional unit represented by other formula (1-2), can be a constitutional unit represented by the formula (1-1), can be the terminal group Y, or can be other constitutional units described later.

[0186] Further, in the constitutional unit (1-2) represented by the formula (1-2) in the polymer (A), In the case where R2a in the constitutional unit represented by other formula (1-2) or the constitutional unit represented by the formula (1-1) represents a bonding bond, the R2a in the constitutional unit represented by other formula (1-2) or the constitutional unit represented by the formula (1-1) is bonded to R2a, and is not bonded to O (oxygen atom).

[0187] The constitutional unit represented by the formula (1-2) or the formula (1-2a) exemplifies a constitutional unit having the following partial structure, but is not limited thereto.

[0188] [Chemical Formula 18]

[0189]

[0190] (Method for forming constitutional unit represented by formula (1-2) or formula (1-2a))

[0191] As a method for forming the constitutional unit represented by the formula (1-2) or the formula (1-2a), a method in which a monomer forming a portion (-R12-R13(R12-O- )m-R12-) in the formula (1-2) or a monomer forming a portion (-R12-R13x-R12-) in the formula (1-2a) which is sandwiched by two oxygen atoms is reacted with a monomer forming Ra2.

[0192] As a monomer forming (-R12-R13(R12-O- )m-R12-) or (-R12-R13x-R12-), for example, a compound represented by the following formula (6) can be exemplified.

[0193] [Chemical Formula 19]

[0194]

[0195] In the formula (6), R13represents a divalent hydrocarbon group having a carbon number of 1 to 20, R61independently represents an alkyl group having a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 10, or a cycloalkyl group having a carbon number of 3 to 10, n61represents an integer of 2 to 4, n62represents an integer of 1 to 5, and n63represents an integer of 0 to 4, where the total number of n62and n63is an integer of 1 to 5.

[0196] The compound represented by the formula (6) is preferably a compound represented by the following formula (6-1) or the following formula (6-2).

[0197] [Chemical Formula 20]

[0198]

[0199] In the formula (6-1) and the formula (6-2), R13, R61, and n61have the same meanings as R13, R61, and n61in the formula (6).

[0200] As the monomer forming (-R12-R13(R12-O- (m-R12-), exemplified compounds shown below can be exemplified, but the present application is not limited to these compounds.

[0201] [Chemical Formula 21]

[0202]

[0203] With respect to 100 mol% of the total structural units contained in the polymer (A), the content of the structural unit represented by the formula (1-2) or the formula (1-2a) is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 90 mol% or less, and further preferably 20 mol% or more and 80 mol% or less.

[0204] <<Other Structural Unit>>

[0205] The polymer (A) can have, as necessary, a structural unit other than the structural units represented by the formula (1-1) and the formula (1-2) or the formula (1-2a) (hereinafter also referred to as "other structural unit").

[0206] Therefore, the repeating unit represented by the formula (1-1) can exemplify a structural unit in which the repeating units are bonded to each other or a structural unit in which the repeating unit is bonded to the other structural unit or the terminal group Y represented by the formula (a).

[0207] In the case where the polymer (A) has a plurality of the repeating unit represented by formula (1-1), the plurality of Ra1may be the same or different. The same applies to Ra2or other repeating units.

[0208] As other structural units, for example, there can be mentioned structural units derived from a compound containing a carbonate bond, a thiocarbonate bond or a selenocarbonate bond, such as diphenyl carbonate, diphenyl thiocarbonate, diphenyl selenocarbonate, phosgene, thiophosgene, selenophosgene and the like; a dihydroxy compound such as benzene glycol, cyclohexane dimethanol and the like; a phosphine oxide compound such as bis(fluorophenyl)phenylphosphine oxide, bis(fluorophenyl)naphthylphosphine oxide, bis(fluorophenyl)anthrylphosphine oxide and the like; a dihalide of a dicarboxylic acid such as phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride and the like; and the like.

[0209] The monomer(s) that derive other structural units can be used singly or in combination of two or more.

[0210] [Synthesis method of polymer (A)]

[0211] The synthesis method of the polymer (A) is not particularly limited, and a known synthesis method can be used. As the synthesis method of the polymer (A), for example, there can be mentioned a method in which a monomer that is a raw material of a moiety containing the Ra1, a monomer that is a raw material of a moiety containing the Ra2, a monomer for forming the terminal group Y as necessary and / or the compound represented by formula (6), a monomer that derives other structural units, and a polymerization inhibitor, an alkali metal or an alkali metal compound and the like are heated together in an organic solvent.

[0212] The monomer(s) that derive other structural units and / or the monomer(s) for forming the terminal group Y can also be reacted by heating a mixture after polymerizing the monomer that is a raw material of a moiety containing the Ra1, the monomer that is a raw material of a moiety containing the Ra2, and the compound represented by formula (6) as necessary.

[0213] The monomer(s) that derive the Ra1and other structural units or the monomer(s) for forming the terminal group Y can also be reacted by heating a mixture after polymerizing the monomer that is a raw material of a moiety containing the Ra2, and the monomer that is a raw material of a moiety containing the R13or R13x.

[0214] - Alkali metal and alkali metal compound -

[0215] In the synthesis of the polymer (A), in the case where a compound having a hydroxyl group such as a phenol compound is used as a raw material, the alkali metal and the alkali metal compound react with the compound having a hydroxyl group to form an alkali metal salt.

[0216] As such alkali metals and alkali metal compounds, for example, the following can be mentioned:

[0217] Lithium, sodium, potassium, and the like alkali metals;

[0218] Lithium hydride, sodium hydride, potassium hydride, and the like alkali metal hydrides;

[0219] Lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like alkali metal hydroxides;

[0220] Lithium carbonate, sodium carbonate, potassium carbonate, and the like alkali metal carbonates;

[0221] Lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and the like alkali metal bicarbonates.

[0222] Of these, alkali metal carbonates are preferred, and potassium carbonate is more preferred.

[0223] In the synthesis of the polymer (A), in the case where a compound having a hydroxyl group is used, the lower limit of the ratio of the number of moles of alkali metal atoms to the number of moles of hydroxyl groups in all the compounds used in the synthesis of the polymer (A) is preferably 1, more preferably 1.1, and still more preferably 1.2, and the upper limit of the ratio is preferably 3, more preferably 2, and still more preferably 1.8.

[0224] - Organic Solvents -

[0225] As the organic solvents, for example, the following can be mentioned:

[0226] Tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether, anisole, phenetol, diphenyl ether, dialkoxybenzene, trialkoxybenzene, and the like ether-based solvents;

[0227] N,N-dimethylacetamide (DMAc), N,N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and the like nitrogen-containing solvents;

[0228] Gamma-butyrolactone and the like ester-based solvents;

[0229] Sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, and the like sulfur-containing solvents;

[0230] Benzophenone, 2-heptanone, cyclohexanone, methyl ethyl ketone, and the like ketone-based solvents;

[0231] Dichloromethane, chloroform, chlorobenzene, and the like halogen-based solvents;

[0232] Benzene, toluene, xylene, and the like aromatic hydrocarbon-based solvents.

[0233] Among these organic solvents, 2-heptanone, cyclohexanone, N-methyl-2-pyrrolidone, toluene, xylene are preferred, and N-methyl-2-pyrrolidone, 2-heptanone, cyclohexanone are more preferred.

[0234] As a lower limit of the reaction temperature at the time of the synthesis, 50°C is preferred, and 80°C is more preferred. As an upper limit of the reaction temperature, 300°C is preferred, and 200°C is more preferred.

[0235] As a lower limit of the reaction time at the time of the synthesis, 1 hour is preferred, 2 hours is more preferred, and 3 hours is further preferred. As an upper limit of the reaction time, 100 hours is preferred, 50 hours is more preferred, and 24 hours is further preferred.

[0236] In order to suppress gelation of the polymerization solution, as a lower limit of the reaction temperature at the time of adding the monomer for forming the terminal group Y after the polymerization, 0°C is preferred, and 10°C is more preferred. As an upper limit of the reaction temperature, 130°C is preferred, and 110°C is more preferred.

[0237] As a lower limit of the reaction time at the time of adding the monomer for forming the terminal group Y after the polymerization, 1 hour is preferred, 2 hours is more preferred, and 3 hours is further preferred. As an upper limit of the reaction time, 48 hours is preferred, 24 hours is more preferred, and 10 hours is further preferred.

[0238] [Physical properties of the polymer (A)]

[0239] As a lower limit of the weight average molecular weight (Mw) of the polymer (A), 1,000 in terms of polystyrene is preferred, 2,000 is more preferred, 3,000 is further preferred, and 5,000 is particularly preferred. As an upper limit of the weight average molecular weight (Mw) of the polymer (A), 500,000 in terms of polystyrene is preferred, 100,000 is more preferred, 50,000 is further preferred, 30,000 is more preferred, and 15,000 is particularly preferred.

[0240] If the weight average molecular weight (Mw) of the polymer (A) is within the range, the balance of the adhesiveness, the heat resistance, the impregnation property for glass cloth, the resin flowability, and the like is good and excellent.

[0241] The weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) under the conditions described in the Examples below.

[0242] The dielectric loss tangent (tan δ) of the polymer (A) is preferably not more than 0.0030, more preferably not more than 0.0020, and further preferably not more than 0.0012, in terms of reducing the transmission loss and the like when a composition containing the polymer (A) is produced. The lower limit of the dielectric loss tangent (tan δ) is not particularly limited, and is preferably not less than 0.0005.

[0243] Specifically, the dielectric loss tangent can be obtained by the measurement method described in the Examples below.

[0244] The content ratio of the polymer (A) is preferably not less than 0.05% by mass, more preferably not less than 10% by mass, and further preferably not less than 20% by mass, and is preferably not more than 99.95% by mass, more preferably not more than 90% by mass, and further preferably not more than 80% by mass, in terms of the total mass of the solid components in the composition being 100% by mass.

[0245] If the content ratio of the polymer (A) is within the range described above, it is preferable in terms of further improving the adhesion, heat resistance, curability, and electrical properties of the obtained hardened product, and the like.

[0246] The polymer (A) can be one alone or two or more in combination.

[0247] In the case where the thermosetting resin composition contains two or more kinds of the polymer (A), for example, the polymers (A) having different weight average molecular weights (Mw) can be mixed and adjusted to the desired properties and the like within the range of the weight average molecular weight (Mw).

[0248] <CO-POLYMER (B)>

[0249] The thermosetting resin composition contains a copolymer (B) having a structural unit derived from ethylene or an α-olefin, a structural unit derived from an aromatic vinyl compound, and a structural unit derived from an aromatic multifunctional vinyl compound (hereinafter sometimes simply referred to as "copolymer (B)").

[0250] Hereinafter, the details of each structural unit possessed by the copolymer (B) will be described.

[0251] <α-OLEFIN>

[0252] The α-olefin is an olefin having a double bond at the terminal and having a carbon number of 3 or more.

[0253] The α-olefin is preferably a compound consisting essentially of carbon atoms and hydrogen atoms, and containing substantially no oxygen atom or nitrogen atom, halogen atom, and the like, and examples thereof include one or more selected from the group consisting of linear or branched α-olefins, and cyclic olefins having a carbon number of 5 or more and 20 or less.

[0254] As the α-olefin, an α-olefin having 3 or more and 20 or less carbon atoms is preferable, and a linear or branched α-olefin having 3 or more and 20 or less carbon atoms is more preferable. As the α-olefin, there is no particular limitation, and examples thereof include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, and the like.

[0255] The structural unit derived from ethylene or an α-olefin can be contained singly or two or more kinds can be contained in the copolymer (B).

[0256] In the copolymer (B), the content of the structural unit derived from ethylene or an α-olefin (the total of the contents thereof in the case where two or more kinds of structural units derived from ethylene or an α-olefin are contained) is preferably 35% by mass or more, and particularly preferably 45% by mass or more.

[0257] wherein the total of the structural unit derived from ethylene or an α-olefin, the structural unit derived from an aromatic vinyl compound, and the structural unit derived from an aromatic multifunctional vinyl compound is 100% by mass.

[0258] If the content of the structural unit derived from ethylene or an α-olefin is 35% by mass or more, the toughness (elongation) of the finally obtained hardened product is improved, and the occurrence of cracks in the middle of hardening, or the reduction in the impact resistance of the hardened product, and the occurrence of cracks in the hardened product in a heat cycle test can be suppressed.

[0259] The content of the structural unit derived from ethylene or an α-olefin in the copolymer (B) is preferably 90% by mass or less.

[0260] In the case where the structural unit derived from ethylene and the structural unit derived from an α-olefin are contained in the copolymer (B), and in the case where the mass ratio of the structural unit derived from an α-olefin to the structural unit derived from ethylene is 1 / 7 or less, and more preferably 1 / 10 or less, the breaking strength (breaking point strength) and the breaking elongation (breaking point elongation) of the obtained hardened product are improved, and the peeling strength from a copper foil or a copper wiring is improved, and thus it is preferable.

[0261] The content of the structural unit derived from an α-olefin contained in the copolymer (B) is more preferably 6% by mass or less, and most preferably 4% by mass or less. In the case where it is such a content, it is more preferable because the peeling strength from a copper foil or a copper wiring is further improved.

[0262] In the combination of ethylene and an α-olefin, the glass transition temperature of the ethylene-α-olefin-aromatic vinyl compound-aromatic multifunctional vinyl compound chain of the finally obtained hardened product can be appropriately adjusted in the range of approximately -60°C to -5°C depending on the kind and content of the α-olefin.

[0263] << Aromatic vinyl compound >>

[0264] The aromatic vinyl compound is an aromatic hydrocarbon compound having one vinyl group in one molecule, and is preferably an aromatic vinyl compound having a carbon number of 8 or more and 20 or less. As the aromatic vinyl compound, for example, styrene, p-methylstyrene, p-isobutylstyrene, various kinds of vinyl naphthalenes, various kinds of vinyl anthracenes, and the like can be exemplified.

[0265] The content of the structural unit derived from the aromatic vinyl compound is preferably more than 0 mass% and 70 mass% or less, more preferably 10 mass% or more and less than 60 mass%, when the mass of the entire structural unit constituting the copolymer (B) is taken as 100 mass%.

[0266] The structural unit derived from the aromatic vinyl compound can be contained singly in the copolymer (B), or two or more kinds can be contained.

[0267] << Aromatic multifunctional vinyl compound >>

[0268] The aromatic multifunctional vinyl compound is a compound having a plurality of vinyl groups and a single or a plurality of aromatic groups in one molecule. That is, the aromatic multifunctional vinyl compound is a compound in which the other vinyl groups remaining even in a state in which one of the plurality of vinyl groups is used for polymerization can react.

[0269] The carbon number of the aromatic multifunctional vinyl compound is preferably 5 or more and 20 or less, more preferably 8 or more and 20 or less.

[0270] The aromatic multifunctional vinyl compound is preferably an aromatic hydrocarbon compound having two vinyl groups in one molecule, and for example, various kinds of divinylbenzenes of ortho, meta, and para positions, or a mixture of these, divinyl naphthalene, divinyl anthracene, p-(2-propenyl)styrene, p-(3-butenyl)styrene, 1,2-bis(vinylphenyl)ethane, and the like can be exemplified.

[0271] Among these, as the aromatic multifunctional vinyl compound, various kinds of divinylbenzenes of ortho, meta, and para positions, or a mixture of these are preferable, and a mixture of divinylbenzenes of meta and para positions is most preferable.

[0272] In the present specification, these divinylbenzenes are sometimes described as divinylbenzene-based compounds. In the case where a divinylbenzene-based compound is used as the aromatic multifunctional vinyl compound, the hardening efficiency is excellent when the resin composition is subjected to a hardening treatment, and the hardening of the resin composition is easy, and thus is preferable.

[0273] Each of the above monomers of ethylene, α-olefin, aromatic vinyl compound, and aromatic multifunctional vinyl compound can also include a polar group, an olefin including, for example, an oxygen atom, a nitrogen atom, or the like, an aromatic vinyl compound including an oxygen atom or a nitrogen atom, or the like, or an aromatic multifunctional vinyl compound including an oxygen atom, a nitrogen atom, or the like. The content of structural units derived from monomers including a polar group is preferably 10% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less, relative to the mass of the total structural units of the copolymer (B), and most preferably substantially no structural units derived from monomers including a polar group are included.

[0274] By setting the content of structural units derived from monomers including a polar group to 10% by mass or less, the low dielectric properties (low dielectric constant / low dielectric loss) of the hardened product obtained by hardening the thermosetting resin composition are further improved.

[0275] When the mass of the total structural units constituting the copolymer (B) is set to 100% by mass, the content of structural units derived from the aromatic multifunctional vinyl compound is preferably more than 0% by mass and 70% by mass or less, and more preferably 10% by mass or more and less than 60% by mass.

[0276] The structural units derived from the aromatic multifunctional vinyl compound can be included alone or two or more kinds can be included in the copolymer (B).

[0277] The number average molecular weight (Mn) of the copolymer (B) is preferably 500 or more and 100,000 or less, more preferably 20,000 or more and 100,000 or less, and further preferably 30,000 or more and 100,000 or less.

[0278] If the number average molecular weight (Mn) is 500 or more, it is possible to easily impart good properties such as high breaking point strength, high breaking point elongation, and the like to the finally obtained hardened product, and toughness is easily imparted, which is preferable. Specifically, the tensile breaking point elongation (tensile breaking elongation) is preferably 30% or more. In the case where the number average molecular weight (Mn) is 20,000 or more, the thermosetting resin composition in an unhardened state is less likely to become tacky, and an effect of improving thermoplasticity can be obtained.

[0279] If the number average molecular weight (Mn) is 100,000 or less, molding processing of the thermosetting resin composition before hardening is easily performed.

[0280] The number average molecular weight (Mn) is determined by gel permeation chromatography (GPC) under the conditions described in the Examples below.

[0281] The content of the structural unit derived from the aromatic vinyl compound in the copolymer (B) is preferably 10% by mass or greater and less than 60% by mass, when the total mass of the structural units constituting the copolymer (B) is taken as 100% by mass.

[0282] In the case where the content of the structural unit derived from the aromatic vinyl compound is less than 60% by mass, the glass transition temperature of the hardened product of the finally obtained composition is not easily brought to the vicinity of room temperature, and the decrease in toughness at low temperatures can be suppressed, and in addition, the decrease in elongation can also be suppressed.

[0283] In addition, in the case where the content of the structural unit derived from the aromatic vinyl compound is less than 60% by mass, the peel strength with respect to a metal foil, particularly a copper foil, can be improved as compared to the case where it is 60% by mass or greater.

[0284] The content of the structural unit derived from the aromatic vinyl compound in the copolymer (B) is particularly preferably 10% by mass or greater and 55% by mass or less, when the total mass of the structural units constituting the copolymer (B) is taken as 100% by mass. If the content of the structural unit derived from the aromatic vinyl compound is 10% by mass or greater, the decrease in aromaticity of the copolymer (B) can be suppressed, and the tightness with respect to the flame retardant or the filler becomes good, and in the case where the composition contains a flame retardant, the exudation can also be suppressed, and the ease of filling of the filler can be improved. In addition, if the content of the structural unit derived from the aromatic vinyl compound is 10% by mass or greater, a hardened product having high peel strength with respect to a metal foil, particularly a copper foil, or a copper wiring can be easily obtained.

[0285] In the copolymer (B), the content of the vinyl group derived from the structural unit derived from the aromatic multifunctional vinyl compound (hereinafter also referred to as "aromatic multifunctional vinyl unit") is preferably 1.5 or greater and less than 20, and more preferably 3 or greater and less than 20, with respect to the number average molecular weight of the copolymer (B).

[0286] If it is 1.5 or greater, the crosslinking efficiency is excellent, and the storage elastic modulus at high temperatures can be further improved. By setting the content of the vinyl group within the range described above, the mechanical properties such as the breaking strength, the breaking elongation, and the like at room temperature can be easily maintained or improved, and the crosslinking efficiency or the crosslinking density is further improved, and the storage elastic modulus at high temperatures is improved, and this is preferable. In particular, in the case where the amount of use of the aromatic multifunctional vinyl compound is relatively low, the effect becomes significant.

[0287] The vinyl content derived from the aromatic polyfunctional vinyl unit (e.g., divinylbenzene unit) relative to the number average molecular weight (Mn) in the copolymer (B) is calculated by comparing the number average molecular weight (Mn) converted to standard polystyrene by GPC (gel permeation chromatography) method known to those skilled in the art with the vinyl content derived from the aromatic polyfunctional vinyl compound determined by1H-NMR (1H-Nuclear magnetic resonance).

[0288] As an example, in the case where the vinyl content derived from the aromatic polyfunctional vinyl unit in the copolymer (B) is 0.095 mass% based on the intensity comparison of the area of each peak determined by1H-NMR and the number average molecular weight (Mn) converted to standard polystyrene based on GPC determination is 68,000, the molecular weight of the vinyl derived from the aromatic polyfunctional vinyl unit in the number average molecular weight (Mn) is the product of them, i.e., 64.8, which becomes 2.4 by dividing it by the formula weight of the vinyl, 27.

[0289] That is, the vinyl content derived from the aromatic polyfunctional vinyl unit relative to the number average molecular weight (Mn) in the copolymer (B) is calculated to be 2.4.

[0290] The assignment of the peak determined by1H-NMR of the copolymer (B) is calculated by known literature. In addition, the method of calculating the composition of the copolymer (B) based on the comparison of the area of the peak determined by1H-NMR can also be calculated by known methods.

[0291] In addition, in the present specification, in the case where the aromatic polyfunctional vinyl unit in the copolymer (B) is, for example, a divinylbenzene unit, the content of the divinylbenzene unit is calculated based on the peak intensity of the vinyl derived from the divinylbenzene unit (determined based on1H-NMR).

[0292] That is, based on the vinyl content derived from the divinylbenzene unit, the content of the divinylbenzene unit is calculated assuming that one of the vinyls is derived from one divinylbenzene unit in the copolymer (B).

[0293] The copolymer (B) exemplified is an ethylene-styrene-divinylbenzene copolymer, an ethylene-propylene-styrene-divinylbenzene copolymer, an ethylene-1-hexene-styrene-divinylbenzene copolymer, and an ethylene-1-octene-styrene-divinylbenzene copolymer, and the like.

[0294] The copolymer (B) is preferably any one of (1) to (3) below, more preferably all of (1) to (3).

[0295] (1) The number average molecular weight (Mn) of the copolymer (B) is preferably 500 or greater and 100,000 or less, more preferably 20,000 or greater and 100,000 or less, and further preferably 30,000 or greater and 100,000 or less.

[0296] (2) The aromatic vinyl compound is preferably an aromatic vinyl compound having a carbon number of 8 or greater and 20 or less, and the content of the structural unit derived from the aromatic vinyl compound is preferably more than 0 mass% and 70 mass% or less, more preferably 10 mass% or greater and less than 60 mass%, when the entirety of the structural units constituting the copolymer (B) is taken as 100 mass%.

[0297] (3) The α-olefin in the copolymer (B) is preferably one or two or more selected from α-olefins having a carbon number of 3 or greater and 20 or less, and the total of the structural unit derived from ethylene or the α-olefin, the structural unit derived from the aromatic vinyl compound, and the structural unit derived from the aromatic multifunctional vinyl compound is 100 mass%.

[0298] The copolymer (B) can further satisfy the following (4). (4) The aromatic multifunctional vinyl compound is an aromatic multifunctional vinyl compound having a carbon number of 5 or greater and 20 or less and having a plurality of vinyl groups in one molecule, and the content of the vinyl groups derived from the aromatic multifunctional vinyl unit is preferably 1.5 or greater and less than 20, with respect to the number average molecular weight (Mn) of the copolymer (B).

[0299] [Method for producing copolymer (B)]

[0300] There is no particular limitation on the method for producing the copolymer (B) in general, and a known production method can be used. As the production method, for example, the production method described in Japanese Patent Application Publication No. 2009-161743, Japanese Patent Application Publication No. 2010-280771, or International Publication No. 2000 / 37517 can be cited.

[0301] There is no particular limitation on the method for synthesizing the copolymer (B), and a known synthesis method can be used. The copolymer (B) can be obtained, for example, by copolymerizing each of the monomers of the α-olefin, the aromatic vinyl compound, and the aromatic multifunctional vinyl compound, respectively.

[0302] <<Curable compound (C)>>

[0303] The thermally curable resin composition can contain a curable compound (C).

[0304] The curable compound (C) is a compound other than the polymer (A) and the copolymer (B), and is a compound that is cured by irradiation of heat or light (e.g., visible light, ultraviolet light, near-infrared light, far-infrared light). In addition, the curable compound (C) can be used in combination with a curing aid described later.

[0305] There is no particular limitation on the curable compound (C), and examples 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, silane compounds, and the like.

[0306] Among these, in terms of compatibility with the polymer (A), reactivity, and the like, as the curable compound (C), at least one compound selected from the group consisting of 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 is preferable, and at least one compound selected from the group consisting of vinyl compounds, maleimide compounds, and allyl compounds is particularly more preferable.

[0307] The curable compound (C) can be used alone or two or more kinds can be used in combination.

[0308] As the vinyl compound, for example, compounds represented by the following formulae (b-1-1) to (b-1-5) can be exemplified. Among these, in the present application, the vinyl compound is not limited to these exemplified compounds.

[0309] [Chemical Formula 22]

[0310]

[0311] In formulae (b-1-2) and (b-1-4), n is independently an integer of 1 to 5000. In formula (b-1-5), l, m, and n are independently integers of 1 to 5000.

[0312] As the maleimide compound, for example, compounds represented by the following formulae (b-2-1) to (b-2-8) can be exemplified. Among these, in the present application, the maleimide compound is not limited to these exemplified compounds.

[0313] [Chemical Formula 23]

[0314]

[0315] In formula (b-2-4), formula (b-2-5), formula (b-2-7), and formula (b-2-8), n is independently an integer of 1 to 50.

[0316] As the allyl compound, for example, compounds represented by the following formulae (b-3-1) to (b-3-6) can be exemplified. Among them, in the present application, the allyl compound is not limited to these exemplified compounds.

[0317] [Chemical 24]

[0318]

[0319] As the acrylic compound, for example, compounds represented by the following formulae (b-4-1) to (b-4-7) can be exemplified. Among them, in the present application, the acrylic compound is not limited to these exemplified compounds.

[0320] [Chemical 25]

[0321]

[0322] In formula (b-4-1), formula (b-4-2), formula (b-4-3), and formula (b-4-6), n is independently an integer of 1 to 50. In formula (b-4-3), m is an integer of 1 to 50. In formula (b-4-6), R is a hydrocarbon group having a carbon number of 1 to 20.

[0323] As the methacrylic compound, there is no particular limitation, and for example, bisphenol A type epoxy methacrylate, phenol novolak type epoxy methacrylate, trimethylolpropane methacrylate, dipentaerythritol hexamethacrylate, SA-9000 (manufactured by Sabic), and the like can be exemplified.

[0324] As the thiol compound, there is no particular limitation, and for example, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(2-(3-hydrothio butyryloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, 2-(dibutylamino)-1,3,5-triazine-4,6-dithiol, 6-diallylamino-1,3,5-triazine-2,4-dithiol, and the like can be exemplified.

[0325] As the silane compound, there is no particular limitation, and for example, KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like can be exemplified.

[0326] As the oxazine compound, for example, compounds represented by the following formulae (b-5-1) to (b-5-5) can be exemplified. Among them, in the present application, the oxazine compound is not limited to these exemplified compounds.

[0327] [Chem. 26]

[0328]

[0329] As the cyanate compound, for example, compounds represented by the following Formulas (b-6-1) to (b-6-7) can be exemplified. In the present application, the cyanate compound is not limited to these exemplified compounds.

[0330] [Chem. 27]

[0331]

[0332] In Formulas (b-6-6) and (b-6-7), n is independently an integer of 0 to 30.

[0333] As the epoxy compound, there is no particular limitation, and for example, compounds represented by the following Formulas (b-7-1) to (b-7-5) can be exemplified.

[0334] As the epoxy compound, for example, the following can also be exemplified: polyglycidyl ether of dicyclopentadiene-phenol polymer, phenol novolak-type liquid epoxy compound, cresol novolak-type epoxy compound, epoxy of styrene-butadiene block copolymer, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, XER-81 (manufactured by JSR (Co., Ltd.), epoxy group-containing nitrile butadiene rubber (NBR) particles), JP-100 (manufactured by Nippon Zeon (Co., Ltd.)), and the like.

[0335] [Chem. 28]

[0336]

[0337] In Formula (b-7-5), n is an integer of 0 to 5000.

[0338] As the oxetane compound, for example, compounds represented by the following Formulas (b-8-1) to (b-8-3) can be exemplified. In the present application, the oxetane compound is not limited to these exemplified compounds.

[0339] [Chem. 29]

[0340]

[0341] In Formulas (b-8-1) and (b-8-2), n is independently an integer of 0 to 30.

[0342] As the hydroxymethyl compound, there is no particular limitation, and for example, the hydroxymethyl compounds described in Japanese Patent Application Publication No. 2006-178059 and Japanese Patent Application Publication No. 2012-226297 can be exemplified. Specifically, for example, melamine-based hydroxymethyl compounds such as polyhydroxymethylated melamine, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, and the like; glycoluril-based hydroxymethyl compounds such as polyhydroxymethylated glycoluril, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, and the like; compounds obtained by hydroxymethylation of guanamine such as 3,9-bis[2-(3,5-diamino-2,4,6-triazinyl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis[2-(3,5-diamino-2,4,6-triazinyl)propyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, and the like, and compounds obtained by alkyl etherification of all or a part of the active hydroxymethyl groups in the compounds, and the like can be exemplified.

[0343] As the benzocyclobutene compound, there is no particular limitation, and for example, the compounds described in Japanese Patent Application Publication No. 2005-60507 can be exemplified.

[0344] As the propargyl compound, for example, the compounds represented by the following formulae (b-9-1) to (b-9-2) can be exemplified. In the present application, the propargyl compound is not limited to these exemplified compounds.

[0345] [Chemical 30]

[0346]

[0347] [Content ratio of the curable compound (C)]

[0348] In a case where the entire solid content in the curable resin composition is taken as 100% by mass, the content ratio of the compound (C) in the thermally curable resin composition is preferably 0.05% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 50% by mass or less.

[0349] If the content ratio of the curable compound (C) is in the range, it is preferable in terms of further improving the strength, heat resistance, and the like of the cured product obtained from the thermally curable resin composition.

[0350] In addition, in the case where the total of the solid components of the polymer (A) and the copolymer (B) in the thermally curable resin composition is set to 100% by mass, the lower limit value of the content ratio of the curable compound (C) is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more, and the upper limit value of the content ratio of the curable compound (C) is preferably 99% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less.

[0351] If the content ratio of the curable compound (C) is within the range, it is preferable in terms of further improving the toughness, heat resistance, and the like of the obtained cured product.

[0352] <<Polymerization Initiator (D)>>

[0353] The thermally curable resin composition can also contain a polymerization initiator (D).

[0354] There is no particular limitation on the polymerization initiator (D), and known polymerization initiators used in thermally curable resin compositions can be exemplified. As the polymerization initiator (D), for example, a thermal or photo radical polymerization initiator, a cationic hardener, an anionic hardener, and the like can be exemplified.

[0355] As the thermal or photo radical polymerization initiator, for example, organic peroxides such as dicumyl peroxide, 1,1-di(tert-butylperoxy)cyclohexane, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, benzoyl peroxide, and the like; 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), 2,2'-azobis(2-methylbutyronitrile), and the like can be exemplified.

[0356] As the cationic hardener, for example, SP70, SP172, CP66 manufactured by ADEKA Co., Ltd., "CI2855", "CI2823" manufactured by Japan Cabot Co., Ltd.; "SI100", "SI150" manufactured by San Nopco Ltd.; and the like can be exemplified, in which BF4, PF6, SbF6, and the like are set as counter anions, diallyl sulfonium salts, trialkyl sulfonium salts, butyltriphenylphosphonium thiocyanate, and the like phosphonium salts, boron trifluoride, and the like.

[0357] As the anion hardening agent, for example, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-methyl-4-methylimidazole, 2-methylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazolin-(1)]-ethyl-S-triazine, 2,4-diamino-6-[2-ethyl-4-methylimidazolin-(1)]-ethyl-S-triazine, and the like; phosphorus compounds such as triphenylphosphine; amine compounds such as 4,4'-diaminodiphenylmethane; and the like can be exemplified.

[0358] Further, as the hardening aid when the silane compound is used as the hardening compound (C), for example, platinum black, platinum tetrachloride, chloroplatinic acid, a reaction product of chloroplatinic acid with monohydric alcohol, a complex of chloroplatinic acid with olefins, platinum bisacetylacetate, and the like can be exemplified as platinum catalysts; palladium catalysts; rhodium catalysts; and the like can be exemplified as platinum group metal catalysts; zinc benzoate, zinc octoate.

[0359] As the hardening aid when the oxazine compound is used as the hardening compound (C), for example, phenol and derivatives thereof, cyanate, a Bronsted acid such as p-toluenesulfonic acid, adipic acid, p-toluenesulfonate, 4,4'-diaminodiphenyl sulfone, an aromatic amine compound such as melamine, a base such as 2-ethyl-4-methylimidazole, boron trifluoride, a Lewis acid, and the like can be exemplified as hardening agents.

[0360] In the case where the thermally hardening resin composition contains a hardening aid, the content ratio of the hardening aid is preferably in a range in which the composition can be well hardened to obtain a hardened product. Specifically, relative to 100 parts by mass of the total of the solid components of the polymer (A) and the copolymer (B), it is preferably 0.000001 parts by mass or more, more preferably 0.001 parts by mass or more, and it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

[0361] < Organic solvent (E) >

[0362] The thermally hardening resin composition preferably further contains an organic solvent (E), and more preferably further contains the hardening compound (C) and the organic solvent (E).

[0363] As the organic solvent (E), for example, amide-based solvents such as N,N-dimethylformamide; ester-based solvents such as γ-butyrolactone, butyl acetate; ketone-based solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, 2-heptanone; ether-based solvents such as 1,2-methoxyethane, anisole, tetrahydrofuran; multifunctional solvents such as 1-methoxy-2-propanol, propylene glycol methyl ether acetate; sulfone-based solvents such as dimethyl sulfoxide; dichloromethane, benzene, toluene, xylene, trialkoxybenzene (carbon number of alkoxy group: 1 to 4) can be exemplified.

[0364] The content ratio of the organic solvent (E) is not particularly limited and can be appropriately changed according to the purpose. For example, it is preferably 0 mass% or more and 2000 mass% or less, more preferably 0 mass% or more and 1000 mass% or less, with respect to 100 mass% of the total of the solid components of the polymer (A), the copolymer (B), and the curable compound (C).

[0365] In addition, in the case where the solubility of the polymer (A) or the copolymer (B) and the curable compound (C) in the organic solvent (E) is high, the content ratio of the organic solvent (E) can be set to 50 mass% or more and 200 mass% or less.

[0366] <<Filler (F)>>

[0367] The thermosetting resin composition can contain a filler (F). The filler (F) is not particularly limited and can be an inorganic filler or an organic filler.

[0368] As the inorganic filler, there is no particular limitation and, for example, silicas such as natural silica, fused silica, and amorphous silica; white carbon, titanium white, fumed silica, alumina, talc, natural mica, synthetic mica, clay, barium sulfate, E-glass, A-glass, C-glass, L-glass, D-glass, S-glass, S-glass, M-glass G20, and the like can be exemplified.

[0369] The inorganic filler can also be surface-treated. As the surface treatment agent, there is no particular limitation and a known surface treatment agent can be used. As the surface treatment agent, for example, silane coupling agents and the like can be exemplified.

[0370] In the case where the thermosetting resin composition contains an inorganic filler, the content ratio of the inorganic filler is, for example, preferably 0.1 mass% or more and 300 mass% or less, with respect to 100 mass% of the total of the solid components of the polymer (A) and the copolymer (B). In addition, the inorganic filler can also be in a state of being dispersed in a solvent by the polymer (A).

[0371] As the organic filler, fluorine-based resins or particles such as polytetrafluoroethylene (PTFE), polyperfluoroalkoxy resin, polyfluorinated ethylene propylene resin, polytetrafluoroethylene-polyethylene copolymer, polystyrene resin or particles, rubber-like resins or particles such as polybutadiene and styrene butadiene resin, and hollow particles having divinylbenzene or divinylbiphenyl as a shell can be exemplified.

[0372] In the case where the thermohardening resin composition contains an organic filler, the content ratio of the organic filler 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 of the solid components of the polymer (A) and the copolymer (B). The organic filler can also be in a state of being dispersed in a solvent by the polymer (A).

[0373] < additives >

[0374] The thermohardening resin composition can also contain components other than the polymer (A), the copolymer (B), the hardening compound (C), the polymerization initiator (D), the organic solvent (E), and the filler (F) (hereinafter also referred to as "other components") for the purpose of imparting various functions. As the other components, additives such as antioxidants, flame retardants, and adhesion aids can be cited.

[0375] As the antioxidant, for example, a hindered phenol-based compound, a phosphorus-based compound, a sulfur-based compound, a metal-based compound, a hindered amine-based compound can be cited. Among these, as the antioxidant, a hindered phenol-based compound is also preferable.

[0376] As the hindered phenol compound, a compound having a molecular weight of 500 or more is preferred. As the hindered phenol compound having a molecular weight of 500 or more, for example, the following compounds can be listed: triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylphenylazo)-3,5-triazine, pentaerythritol tetrakis[3-(3,5-tert-butyl-4-hydroxyphenyl)propionate], 1,1,3-tris[2-methyl-4-〔3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy〕-5-tert-butylphenyl]butane, 2,2-thio-bis-ethylene glycol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 3,9-bis[2-〔3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy〕-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 2,6-di-tert-butyl-p-cresol (BHT), 1,3,5-tris(3,5-di-tert-butyl-4- hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione [ADEKA Manufacturing, AO-020], 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol) [ADEKA Manufacturing, AO-030], 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol [ADEKA Manufacturing, AO-040], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene [ADEKA Manufacturing, AO-330].

[0377] As the hindered amine-based compound, for example, 2, 2, 6, 6-tetramethyl-4- hydroxypiperidine-1-oxyl [ADEKA (K.K.) manufactured, Adekastab LA-7RD] ; IRGASTAB UV 10 (4, 4'- [(1, 10-di-oxyl-1, 10-decanediyl) bis (oxyl)] bis [2, 2, 6, 6-tetramethyl] -1- piperidinyloxy] (CAS. 2516-92-9), TINUVIN 123 (4-hydroxy-2, 2, 6, 6-tetramethylpiperidine-N- oxyl) (all of which are manufactured by BASF Corporation) ; FA-711HM, FA-712HM (2, 2, 6, 6-tetramethylpiperidylmethyl methacrylate, manufactured by Showa Denko Materials, K.K.) ; TINUVIN 111FDL, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 765, TINUVIN 770DF, TINUVIN 5100, SANOL LS-2626, CHIMASSORB 119FL, CHIMASSORB 2020FDL, CHIMASSORB 944 FDL, TINUVIN 622 LD (all of which are manufactured by BASF Corporation) ; LA-52, LA-57, LA-62, LA-63P, LA-68LD, LA-77Y, LA-77G, LA-81, LA-82 (1, 2, 2, 6, 6-pentamethyl-4-piperidylmethyl methacrylate), LA-87 (all of which are manufactured by ADEKA (K.K.).

[0378] In the case where the thermosetting resin composition contains the additive, the content ratio of the additive is preferably 0.001 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total of the solid components of the polymer (A) and the copolymer (B).

[0379] [Method for producing the thermosetting resin composition]

[0380] The thermosetting resin composition can be produced, for example, by uniformly mixing the polymer (A), the copolymer (B), the hardening compound (C), the polymerization initiator (D), the organic solvent (E), and the filler (F), and the other components. In this case, the order of mixing, the mixing conditions, and the like are not particularly limited, and a conventionally known mixing machine can be used at the time of mixing.

[0381] <Hardened product>

[0382] The hardened product of the present application contains the thermosetting resin composition. The hardened product is a hardened body obtained by hardening the thermosetting resin composition.

[0383] The hardened product may, for example, also be a partially hardened product of the thermosetting resin composition obtained by drying the solvent from the thermosetting resin composition.

[0384] The hardening method of the thermosetting resin composition is not particularly limited, and known hardening methods can be used, and a method of thermally hardening by heating or a method of photohardening by irradiation of light, etc. can be generally exemplified. In addition, the hardening method can also be a combination of a plurality of hardening methods.

[0385] In the case of thermal hardening, the heating temperature is preferably 50°C or higher, more preferably 100°C or higher, further preferably 120°C or higher, and is preferably 250°C or lower, more preferably 220°C or lower. The heating time is preferably 0.1 hours or more, more preferably 0.5 hours or more, and is preferably 36 hours or less, more preferably 5 hours or less.

[0386] In the case of photohardening, as the light for irradiation, visible light, ultraviolet rays, near infrared rays, far infrared rays, etc. can be exemplified.

[0387] << Glass transition temperature (Tg) >>

[0388] The lower limit of the glass transition temperature (Tg) of the hardened product is preferably 100°C, more preferably 110°C, and the upper limit is, for example, 300°C. By having the Tg within the range, melt molding can be more easily performed, and in addition, a hardened product having excellent heat resistance can be easily obtained.

[0389] The glass transition temperature (Tg) can be obtained by the measurement method described in the Examples described later.

[0390] The dielectric loss tangent (tan δ) of the hardened product is preferably 0.0025 or less, more preferably 0.0018 or less, further preferably 0.0015 or less, and the lower limit is not particularly limited, and is preferably 0.0005 or more, in terms of reduction of transmission loss, etc.

[0391] Specifically, the dielectric loss tangent can be obtained by the method described in the Examples described later.

[0392] The shape of the hardened product is not particularly limited, and an appropriate shape can be appropriately selected depending on the use or purpose, etc. As the shape of the hardened product, a film shape, a plate shape, a rod shape, etc. can be exemplified. For example, by melt molding or cast molding the thermosetting resin composition, a hardened product in a film shape can be obtained.

[0393] The thickness of the hardened product is not particularly limited and can be appropriately selected depending on the intended use. As the thickness, for example, 10 μm or more, preferably 30 μm or more, and, for example, 2 mm or less, preferably 1 mm or less.

[0394] In addition, a laminate including the hardened product layer and a substrate can also be produced.

[0395] The laminate can include two or more substrates, two or more hardened product layers, or other layers in addition to the substrate and the hardened product layer. With respect to the laminate, the substrate and the hardened product layer can be in contact, or other layers can be included between the substrate and the hardened product layer. In the case where the laminate has two or more substrates, hardened product layers, or other layers, these can each be the same layer (board), or can be different layers (boards).

[0396] As the substrate, from the viewpoints of adhesion or practicality, for example, an inorganic substrate, a metal substrate, a resin substrate, or the like can be cited. In addition, the prepreg described later can also be used as the substrate.

[0397] As the inorganic substrate, for example, an inorganic substrate having silicon, silicon carbide, silicon nitride, alumina, glass, gallium nitride, or the like as a component can be cited.

[0398] As the metal substrate, for example, a metal substrate having copper, aluminum, gold, silver, nickel, palladium, or the like as a component can be cited. The shape of the metal substrate is not particularly limited and can be a plate, a metal foil, or the like.

[0399] The copper-clad laminate of the present application is a laminate of the prepreg described later and a copper substrate, and is preferably a laminate of the prepreg described later and a copper foil.

[0400] As the resin substrate, for example, a resin substrate having liquid crystal polymer, polyimide, polyphenylene sulfide, polyether ether ketone, polyamide (nylon), polyethylene terephthalate, polyethylene naphthalate, cyclic olefin polymer, polyolefin, or the like as a component can be cited.

[0401] The method for forming the hardened product layer is not particularly limited and, for example, the hardening methods described in the column of the hardened product can be cited.

[0402] The thickness of the hardened product layer is not particularly limited and, for example, 1 μm to 3 mm.

[0403] <<Prepreg>>

[0404] The prepreg of the present application is one in which the thermosetting resin composition is impregnated in a fibrous base material board.

[0405] There is no particular limitation on the base material, and for example, a fibrous base material such as a glass cloth, a polyaramid nonwoven fabric, a polyester nonwoven fabric, or the like can be suitably cited. The prepreg can be a hardened prepreg.

[0406] [USES]

[0407] The thermosetting resin composition and the hardened product can be suitably used for structural materials used in the aircraft industry or the transportation machine industry such as the automobile industry, electrical and electronic materials used in the electrical and electronic industry, and the like. Specifically, for example, it can be suitably used for: a sealing material for electrical and electronic parts, an interlayer insulating film (film), a stress relaxation primer; a laminate board use (for example, a prepreg, a copper-clad laminate, a (multilayer) printed wiring board, an interlayer adhesive, a solder resist, a solder paste); an adhesive use (for example, an insulating layer-forming adhesive sheet, a thermally conductive adhesive, an adhesive sheet); a structural adhesive used in various structural materials, a prepreg; various coating, optical part uses (for example, an optical film such as a wavelength plate, a phase difference plate; various special lenses such as a conical lens, a spherical lens, a cylindrical lens; a lens array), an insulating film for a printed wiring board. In particular, an interlayer insulating film including the thermosetting resin composition is excellent in low dielectric loss tangent, adhesiveness, and heat resistance.

[0408] As the electronic part, a circuit board, a semiconductor package, a display board, or the like can be cited. The hardened product (hardened film) can be used as a prepreg, a copper-clad laminate, a printed wiring board, an insulating layer-forming adhesive sheet, a surface protective film, a rewiring layer, or a planarization film for these electronic parts.

[0409] The hardened product can maintain insulating properties even under high temperature and high humidity, and thus an electronic part including the hardened product can protect a circuit pattern from external environments such as dust, heat, humidity, and the like, and is excellent in insulating reliability between circuit patterns, and can stably operate for a long period of time.

[0410] The hardened product is filled with a metal between patterns formed on the hardened product (hardened film) by plating or the like, and further, the hardened product (hardened film) is optionally laminated and filled with a metal, and the operation is repeated to form a rewiring layer. Thus, an electronic part having a substrate and a rewiring layer including a metal wiring and an insulating film can be manufactured.

[0411] EMBODIMENT

[0412] Hereinafter, the present application will be more specifically described based on examples, but the present application is not limited by any of these examples.

[0413] [SYNTHESIS EXAMPLE 1]

[0414] In a four-necked separable flask including a stirring device, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (20.3 g), 2,5-di-tert-butylhydroquinone (8.9 g), 4,6-dichloropyrimidine (14.9 g), and potassium carbonate (18.7 g) were charged, and N-methyl-2-pyrrolidone (102.9 g) was added, and the reaction was performed under nitrogen atmosphere at 130°C for 6 hours. After the completion of the reaction, dilution was performed by adding N-methyl-2-pyrrolidone (206 g), and after the removal of the salt by filtration, the solution was poured into methanol (7 kg). The precipitated solid was separated by filtration, washed with a small amount of methanol, separated by filtration again, recovered, and then dried in a vacuum drying machine under reduced pressure at 120°C for 12 hours to obtain a polymer (Al) having a structural unit represented by the following formula (1).

[0415] [Chemical Formula 31]

[0416]

[0417] [Synthesis Example 2]

[0418] In a four-necked separable flask including a stirring device, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (20.3 g), 2,5-di-tert-butylhydroquinone (8.9 g), 4,6-dichloropyrimidine (14.9 g), and potassium carbonate (18.7 g) were charged, and N-methyl-2-pyrrolidone (102.9 g) was added, and the reaction was performed under nitrogen atmosphere at 130°C for 6 hours. After the completion of the reaction, dilution was performed by adding N-methyl-2-pyrrolidone (206 g), and after the removal of the salt by filtration, the solution was poured into methanol (7 kg). The precipitated solid was separated by filtration, washed with a small amount of methanol, separated by filtration again, recovered, and then dried in a vacuum drying machine under reduced pressure at 120°C for 12 hours to obtain a polymer (Al) having a structural unit represented by the following formula (1).

[0419] [Chemical Formula 32]

[0420]

[0421] [Synthesis Example 3]

[0422] In a four-neck separable flask including a stirring device, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (62.08 g), 4,6-dichloropyrimidine (30.99 g), isopropenylphenol (2.170 g), and potassium carbonate (38.83 g) were charged, and N-methyl-2-pyrrolidone (64.00 g) was added, and the reaction was performed under nitrogen atmosphere at 130°C for 6 hours. After the reaction, the solution was diluted by adding N-methyl-2-pyrrolidone (368.0 g), and the salt was removed by filtration, and the obtained solution was poured into methanol (19.4 kg). The precipitated solid was separated by filtration, and the solid was washed with a small amount of methanol, and separated by filtration again and recovered, and then dried in a vacuum drier under reduced pressure at 120°C for 12 hours, to obtain a polymer (A3) having a structural unit represented by the following formula (3).

[0423] [Chemical Formula 33]

[0424]

[0425] [Synthesis Example 4]

[0426] In a four-neck separable flask including a stirring device, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (86.92 g), 4,6-dichloropyrimidine (47.58 g), and potassium carbonate (59.66 g) were charged, and N-methyl-2-pyrrolidone (64.00 g) was added, and the reaction was performed under nitrogen atmosphere at 130°C for 6 hours. After the reaction, allyl bromide (10.67 g) was added dropwise while the vessel was cooled to 10°C, and the reaction was performed at 70°C for 6 hours. The obtained reaction solution was diluted by adding N-methyl-2-pyrrolidone (368.0 g), and the salt was removed by filtration, and the obtained solution was poured into methanol (19.40 kg). The precipitated solid was separated by filtration, and the solid was washed with a small amount of methanol, and separated by filtration again and recovered, and then dried in a vacuum drier under reduced pressure at 120°C for 12 hours, to obtain a polymer (A4) represented by the following formula (4).

[0427] [Chemical Formula 34]

[0428]

[0429] [Synthesis Example 5]

[0430] A polymer (A5) represented by the following formula (5) was synthesized by the same procedure as in Synthesis Example 3, except that 2,2-bis(4-hydroxy-3-methylphenyl)propane (51.27 g), isopropenylphenol (7.83 g), 4,6-dichloro-2-phenylpyrimidine (51.51 g), and potassium carbonate (35.93 g) were used as the starting material and the alkali metal compound.

[0431] [Chemical Formula 35]

[0432]

[0433] [Synthesis Example 6]

[0434] In a four-neck separable flask including a stirring device, 2,2-bis(4-hydroxy-3-methylphenyl)propane (26.43 g), 4,6-dichloro-2-phenylpyrimidine (17.08 g), and potassium carbonate (19.23 g) were charged, and N-methyl-2-pyrrolidone (42.50 g) was added, and the reaction was carried out under a nitrogen atmosphere at 100°C for 6 hours. After the reaction, meta, para-(chloromethyl)styrene (11.53 g) was added dropwise while the vessel was cooled to 10°C, and then the reaction was carried out at 100°C for 4 hours. N-methyl-2-pyrrolidone (55.0 g) was added to the obtained reaction solution to dilute it, and the salt was removed by filtration from the resulting solution, and then the obtained solution was put into methanol (6900 g). The precipitated solid was separated by filtration, and the solid was washed with a small amount of methanol, and then separated by filtration again and recovered, and then dried using a vacuum drier under reduced pressure at 60°C for 12 hours, to obtain a polymer (A6) represented by the following formula (6).

[0435] [Chemical Formula 36]

[0436]

[0437] [Synthesis Example 7]

[0438] A polymer (A7) represented by the following formula (7) was synthesized by the same procedure as in Synthesis Example 6, except that 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (33.85 g), 4,6-dichloro-2-phenylpyrimidine (16.66 g), meta, para-chloromethylstyrene (8.680 g), potassium carbonate (18.66 g), and N-methyl-2-pyrrolidone (42.50 g) were used as the starting material and the alkali metal compound.

[0439] [Chemical Formula 37]

[0440]

[0441] [Synthesis Example 8]

[0442] Except that the raw material and alkali metal compound used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (25.63 g), 4,6-dichloro-2-phenylpyrimidine (29.25 g), 2-allylphenol (8.131 g), and potassium carbonate (24.31 g), the same procedure as in Synthesis Example 3 was used for the synthesis, and a polymer represented by the following formula (8) (A8) was obtained.

[0443] [Chemical Formula 38]

[0444]

[0445] [Synthesis Example 9]

[0446] In a four-neck separable flask including a stirring device, 2,2-bis(3-methyl-4-hydroxyphenyl)propane (51.27 g), α,α,α'-tris(4-hydroxyphenyl)-l-ethyl-4-isopropylbenzene (21.23 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), and potassium carbonate (51.31 g) were charged, and N-methyl-2-pyrrolidone (113.92 g) was added, and the reaction was performed under nitrogen atmosphere at 130°C for 6 hours. After the reaction, chloromethylstyrene (38.55 g) was added dropwise while the vessel was cooled to 10°C, and then the reaction was performed at 65°C for 6 hours. N-methyl-2-pyrrolidone (258.1 g) was added to the obtained reaction solution to dilute it, and the salt was removed from the diluted solution by filtration, and then the obtained solution was put into methanol (4960 g). The precipitated solid was separated by filtration, and the solid was washed with a small amount of methanol, and then separated by filtration again and recovered, and then dried using a vacuum drier under reduced pressure at 80°C for 12 hours, whereby a polymer represented by the following formula (9) (A9) was obtained.

[0447] [Chemical Formula 39]

[0448]

[0449] The formula represents a polymer (A9) having the structural unit. In the formula, represents a bond to any one of and the polymer (A9) has a group represented by the formula (Y) at the terminal of the polymer. The same applies in the following synthesis examples.

[0450] [Synthesis Example 10]

[0451] The same procedure as Synthesis Example 9 was used except that the raw materials used were changed to 2,2-bis(3-methyl-4-hydroxyphenyl)propane (51.27 g), 4,4',4",4"'-(propane-2,2-diylbis(cyclohexane-4,1,1-triyl))tetraphenol (28.84 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), potassium carbonate (55.98 g), and chloromethylstyrene (49.15 g), to synthesize the following polymer (A10) represented by Formula (10) (yield 121.50 g, 88%).

[0452] [Chemical Formula 40]

[0453]

[0454] [Synthesis Example 11]

[0455] The same procedure as Synthesis Example 9 was used except that the raw materials used were changed to 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (56.77 g), α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (15.92 g), 4,6-dichloro-2-phenylpyrimidine (31.07 g), potassium carbonate (38.48 g), and chloromethylstyrene (28.91 g), to synthesize the following polymer (A11) represented by Formula (11).

[0456] [Chemical Formula 41]

[0457]

[0458] [Synthesis Example 12]

[0459] The same procedure as Synthesis Example 9 was used except that the raw materials used were changed to 2,2-bis(3-methyl-4-hydroxyphenyl)propane (64.09 g), 4,6-dichloro-2-phenylpyrimidine (31.08 g), 4,6-dichloropyrimidine (6.86 g), potassium carbonate (46.65 g), and chloromethylstyrene (22.01 g), to synthesize the following polymer (A12) represented by Formula (12).

[0460] [Chemical Formula 42]

[0461]

[0462] [Comparative Polymer (a1)]

[0463] • End-modified polyphenylene ether (product name: Noryl TMSA9000 resin, manufactured by Sabic)

[0464] [Chemical Formula 43]

[0465]

[0466] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn)]

[0467] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymers (A1) to (A12) synthesized in Synthesis Examples 1 to 12 and the polymer (a1) used in Comparative Example 1 below were determined using a GPC apparatus (manufactured by Tosoh Corporation, model: "HLC-8320") under the following conditions. The results are shown in Table 1.

[0468] • Column: A column consisting of "TSK gel α-M" manufactured by Tosoh Corporation and "TSK gel guardcolumn α" manufactured by Tosoh Corporation.

[0469] • Developing solvent: N-methyl-2-pyrrolidone

[0470] • Column temperature: 40℃

[0471] • Flow rate: 1.0 mL / min

[0472] • Sample concentration: 0.75% by mass

[0473] • Sample injection volume: 50 μL

[0474] • Detector: Refractometer

[0475] • Standard reference material: Monodisperse polystyrene

[0476] • Concentration of the sample used for determination: 0.1% by mass

[0477] [Table 1]

[0478]

[0479] [Examples 1-21 and Comparative Examples 1 and 2]

[0480] The components listed in Table 2 were mixed using a mix rotor at the ratios (parts by mass) specified in the composition mixing ratio column, and the concentration was adjusted using toluene (E1) to a solids concentration of 50% by mass, thereby preparing a thermosetting resin composition. Details of each component in Table 2 are shown below.

[0481] <Copolymer (B)>

[0482] • (Bl): Ethylene-styrene-l-octene-divinylbenzene copolymer (number average molecular weight: 22,000, content of structural units derived from aromatic vinyl compound: 40 mass%)

[0483] • (B2): Ethylene-styrene-divinylbenzene copolymer (number average molecular weight: 8,000, content of structural units derived from aromatic vinyl compound: 48 mass%)

[0484] • (B3): Ethylene-styrene-l-octene-divinylbenzene copolymer (number average molecular weight: 22,000, content of structural units derived from aromatic vinyl compound: 60 mass%)

[0485] • (B4): Ethylene-styrene-divinylbenzene copolymer (number average molecular weight: 8,000, content of structural units derived from aromatic vinyl compound: 63 mass%)

[0486] • (bl): Styrene butadiene thermoplastic elastomer (product name: Tufprene (registered trademark) 912, manufactured by Asahi Kasei Corporation)

[0487] <Curable compound (C)>

[0488] • (Cl): DVB960 (manufactured by Nippon Shokubai & Materials, divinylbenzene)

[0489] • (C2): Bis-(3-ethyl-5-methyl-4-maleimido phenyl)methane (product name: BMI-70, manufactured by KI Chemical Industry Co., Ltd.)

[0490] • (C3): Triallyl isocyanurate (product name: TAIC (Shin-Ning (former MGC)) manufactured)

[0491] <Free radical polymerization initiator (D)>

[0492] • (Dl): Dicumyl peroxide (manufactured by NOF Corporation)

[0493] • (D2): 2,2'-Azobis(N-butyl-2-methylpropanamide) (product name: Vam-110, manufactured by FUJIFILM Wako Pure Chemical Corporation and Wako Pure Chemical Industries, Ltd.)

[0494] <Organic solvent (E)>

[0495] • (El): Toluene

[0496] <Filler (F)>

[0497] • (Fl): Spherical silica (product name: FB-3SDC, manufactured by DENKA (Electric Chemical) Corporation)

[0498] • (F2): Spherical alumina (product name: DAW-05, manufactured by DENKA (K.K.)

[0499] [Table 2]

[0500]

[0501] <Production of hardened film>

[0502] The composition obtained in the Examples and Comparative Examples was applied to a copper foil (type: CF-T49A-DS-HD2, manufactured by Fukuda Metal Foil & Powder Co., Ltd.) using a bar coater (gap: 125 μm), and then dried at 100°C for 5 minutes, then at 140°C for 5 minutes, and then calcined at 200°C for 2 hours under nitrogen. The hardened film with the copper foil obtained was immersed in a 40 mass% iron chloride solution, the copper foil was removed, and then washed with water, dried in an oven at 80°C for 30 minutes, thereby producing a hardened film having a thickness of 50 μm.

[0503] <Glass transition temperature (Tg)>

[0504] A test piece (width: 3 mm x length: 1 cm) was cut from the hardened film produced, and using a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments (K.K.), type: "EXSTAR 4000"), measurement was performed at a temperature increase rate of 10°C / minute from 50°C to 300°C at 1 Hz, and the tan δ at this time was set as the glass transition temperature (Tg). Further, in the case where there were two or more tan δ, the one showing the lowest value was adopted as the Tg. The Tg value obtained was evaluated according to the following evaluation criteria. In the case where the following evaluation criteria was "A" or "B", it can be said that the heat resistance was excellent.

[0505] -Evaluation criteria-

[0506] The case where the Tg exceeded 180°C was set as A, the case where the Tg exceeded 150°C and was 180°C or less was set as B, and the case where the Tg was 150°C or less was set as C.

[0507] The results are shown in Table 3.

[0508] <Peeling strength>

[0509] The composition obtained in the examples and comparative examples was applied to a copper foil (model: CF-V9S-SV, Fukuda Metal Foil & Powder Co., Ltd.), heated at 100°C for 5 minutes, and then dried at 130°C for 5 minutes, to form a coating film. A copper foil (model: CF-V9S-SV, Fukuda Metal Foil & Powder Co., Ltd.) was overlaid on the obtained coating film, vacuum-pressed at 150°C for 5 minutes, and then calcined under nitrogen at 200°C for 2 hours, to produce a hardened film with a copper foil (copper foil: 18 μm, hardened film: 10 μm), which was used as a sample for peeling strength.

[0510] A test piece (width: 5 mm x length: 10 cm) was cut from the produced sample for peeling strength, and a universal testing machine (manufactured by Instron Corporation, model: "Instron 5567") was used to stretch the test piece (the laminated portion of one copper foil and the hardened film in the sample for peeling strength) in the 90-degree direction at 500 mm / minute, and the peeling strength was measured in accordance with "IPC-TM-650 (Test Method Manual) 2.4.9" and evaluated according to the following evaluation criteria. In the case where the evaluation criteria described below were "A" or "B", it can be said that the adhesiveness was excellent.

[0511] Evaluation Criteria

[0512] The case where the peeling strength was 0.7 N / mm or more was evaluated as "A", the case where the peeling strength was 0.5 N / mm or more and less than 0.7 N / mm was evaluated as "B", and the case where the peeling strength was less than 0.5 N / mm was evaluated as "C".

[0513] The results are shown in Table 3.

[0514] Dielectric Loss Tangent

[0515] A test piece (width: 6 cm x length: 6 cm) was cut from the produced hardened film, and a cavity resonator method (manufactured by AET Co., Ltd., dielectric constant measuring system TE mode resonator) was used to measure the dielectric loss tangent of the test piece at 10 GHz, and the dielectric loss tangent was evaluated according to the following evaluation criteria. In the case where the evaluation criteria described below were "A" or "B", it can be said that the dielectric loss tangent was excellent.

[0516] Evaluation Criteria

[0517] The case where the dielectric loss tangent was less than 0.0015 was evaluated as "A", the case where the dielectric loss tangent was 0.0015 or more and less than 0.0025 was evaluated as "B", and the case where the dielectric loss tangent was 0.0025 or more was evaluated as "C".

[0518] The results are shown in Table 3.

[0519] [Table 3]

[0520]

[0521] As shown in Table 3, it is known that the hardened films of Examples 1 to 21 are excellent in the balance of heat resistance, adhesion, and low dielectric loss tangent, as compared with the hardened films of Comparative Examples 1 and 2.

Claims

1. A thermosetting resin composition for forming a wiring substrate, comprising: Polymer (A) having the structural unit represented by the following formula (1-1); and A copolymer (B) having structural units derived from ethylene or α-olefins, structural units derived from aromatic vinyl compounds, and structural units derived from aromatic polyfunctional vinyl compounds. [Chemistry 1] [In equation (1-1), Ra1 is the divalent base represented by equation (2) below, and Ra2 is the divalent base represented by one of the following equations (Ra2-1), (Ra2-2), and (Ra2-3).] [Chemistry 2] [In formula (2), Ara1 and Ara2 are independently unsubstituted or substituted aromatic hydrocarbon groups, L is a single bond, -O-, -S-, -N(R8)-, -C(O)-, -C(O)-O-, -C(O)-NH-, -S(O)-, -S(O)2-, -P(O)- or a divalent organic group, R8 is a hydrogen atom, a monovalent hydrocarbon group with 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group with 1 to 20 carbon atoms, y is an integer from 0 to 5, and when y is 2 or more, multiple Ara1 and L are the same or different, and Ra6 and Ra7 are independently single bonds, methylene or alkylene groups with 2 to 4 carbon atoms.] [Chemistry 3] [Formula (R)] a2 -1) ~ Formula (R) a2 In -3), R 1 Each of the following is an independent salt of a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent haloalkyl group having 1 to 20 carbon atoms, a nitro group, a cyano group, a primary to tertiary amino group, or a primary to tertiary amino group, where n is an independent integer from 0 to 2. When n is 2, multiple R... 1 [A ring structure with 5 to 10 ring elements that are the same or different and are formed by combining with each other and together with the carbon atoms they are bonded to.] 2. The thermosetting resin composition for forming a wiring substrate according to claim 1, wherein, The copolymer (B) has an average molecular weight of 500 or more and less than 100,000.

3. The thermosetting resin composition for forming a wiring substrate according to claim 1, wherein, The aromatic vinyl compound in the copolymer (B) is an aromatic vinyl compound with 8 or more carbon atoms and 20 or fewer carbon atoms. When the total mass of all structural units constituting the copolymer (B) is set to 100% by mass, the content of structural units derived from aromatic vinyl compounds is more than 0% by mass and less than 70% by mass.

4. The thermosetting resin composition for forming a wiring substrate according to claim 1, wherein, The α-olefin in the copolymer (B) is one or more α-olefins selected from α-olefins having 3 or more carbon atoms and less than 20 carbon atoms. The total mass of the structural units derived from ethylene or α-olefins, the structural units derived from aromatic vinyl compounds, and the structural units derived from aromatic polyfunctional vinyl compounds is 100 by mass relative to the total mass of all constituent units of the copolymer (B).

5. The thermosetting resin composition for forming a wiring substrate according to claim 1 further comprises a curing compound (C) and an organic solvent (E).

6. The thermosetting resin composition for forming a wiring substrate according to claim 5, wherein, The curing compound (C) is at least one compound selected from the group consisting of vinyl compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic acid compounds, thiols, oxazine compounds, cyanate compounds, epoxy compounds, oxetane compounds, hydroxymethyl compounds, benzocyclobutene compounds, propargyl compounds, and silane compounds.

7. The thermosetting resin composition for forming a wiring substrate according to claim 1 or 5 further comprises a polymerization initiator (D).

8. The thermosetting resin composition for forming a wiring substrate according to claim 1 or 5, further comprising filler (F).

9. A cured material comprising the thermosetting resin composition for forming a wiring substrate as described in claim 1 or 5.

10. A prepreg is formed by impregnating a thermosetting resin composition for forming a wiring substrate as described in claim 1 or 5 in a fibrous substrate.

11. A copper-clad laminate, which is a laminate of a prepreg and a copper substrate as described in claim 10.

12. An interlayer insulating film comprising the thermosetting resin composition for forming a wiring substrate as described in claim 1 or 5.

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