Resin composition, cured product, and electronic component

Abstract

One embodiment of the present invention relates to a resin composition containing a polymer (A) having a structural unit represented by formula (a1-1) and a hydrogenated styrene-based thermoplastic elastomer (B): in formula (a1-1), Ra1 is a divalent group represented by formula (a2), Ra2 is an unsubstituted or substituted divalent aromatic heterocyclic group, in formula (a2), Ra3 is a substituted or unsubstituted divalent aromatic heterocyclic group, and in formula (a1), Ra2 is a substituted or unsubstituted divalent aromatic heterocyclic group. In the formula, Ara1 and Ara2 are 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, y is an integer of 0-5, and Ra6 and Ra7 are each independently a single bond, a methylene group or a C2-4 alkylene group.

Description

Technical Field

[0001] One embodiment of the present invention relates to a resin composition, a cured material, or an electronic component. Background Technology

[0002] In recent years, the information and communication field has seen a continuous trend towards higher signal frequencies in information and communication equipment in order to achieve high-speed, high-capacity transmission. To address this trend towards higher frequencies, the requirements for low dielectric constant and low dielectric loss tangent are also constantly increasing for insulators used in printed circuit boards or semiconductor packages.

[0003] As materials to address the aforementioned high-frequency increase, polyolefin resins, styrene resins, fluoropolymers, polyphenylene ether resins, vinyl benzyl ether resins, or compositions using polyphenylene ether resins have been proposed (for example, see Patent Documents 1 to 6).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 7-188362

[0007] Patent Document 2: Japanese Patent Application Publication No. 2004-83680

[0008] Patent Document 3: Japanese Patent No. 3414556

[0009] Patent Document 4: Japanese Patent Application Publication No. 2003-306591

[0010] Patent Document 5: Japanese Patent No. 5649773

[0011] Patent Document 6: Japanese Patent Application Publication No. 2017-200997 Summary of the Invention

[0012] However, while existing materials such as the compositions described in Patent Documents 1 to 6 have low dielectric constant / low dielectric loss tangent to some extent, there is room for improvement in balancing low dielectric constant / low dielectric loss tangent with heat resistance.

[0013] One embodiment of the present invention provides a resin composition that yields a cured material with low dielectric constant / low dielectric loss tangent and excellent heat resistance, and an electronic component obtained from said cured material.

[0014] Technical means to solve the problem

[0015] The structure of the present invention is described below, for example. [1]

[0017] A resin composition comprising: a polymer (A) having a structural unit represented by the following formula (a1-1), and

[0018] Hydrogenated styrene-based thermoplastic elastomers (B).

[0019] [Chemistry 1]

[0020]

[0021] In formula (a1-1), R a1 R is the divalent base represented by the following equation (a2). a2 It is an unsubstituted or substituted divalent aromatic heterocyclic group; wherein, R a1 With R a2 different〕

[0022] [Chemistry 2]

[0023]

[0024] In formula (a2), Ar a1 and Ar a2 Each is an independent unsubstituted or substituted aromatic hydrocarbon group, where L is a single bond, -O-, -S-, or -N(R) 8 -, -C(O)-, -C(O)-O-, -C(O)-NH-, -S(O)-, -S(O)2-, -P(O)- or divalent organic groups, wherein R 8 It consists of a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halide hydrocarbon group having 1 to 20 carbon atoms, where y is an integer from 0 to 5. When y is 2 or higher, multiple Ar atoms are present. a1 And L are the same or different, R a6 and R a7 [Each is independently a single bond, a methylene group, or an alkylene group having 2 to 4 carbon atoms] [2]

[0026] According to the resin composition described in [1], wherein R of formula (a1-1) a2 It is a divalent base selected from one of the following formulas (1-1), (1-2) and (1-3).

[0027] [Chemistry 3]

[0028]

[0029] In equations (1-1) to (1-3), n is an independent integer from 0 to 2. When n is 1, R 1 Each of the two R's is an independent monovalent basis. When n = 2, the two R's... 1Each is independently a monovalent base, either the same or different, or two R... 1 Together with these bonded carbon atoms, they form a ring structure with 5 to 10 ring elements, wherein the monovalent group is a halogen atom, a monovalent hydrocarbon group with 1 to 20 carbon atoms, a monovalent halide hydrocarbon group with 1 to 20 carbon atoms, a nitro group, a cyano group, a primary amino to tertiary amino group, or a salt of a primary amino to tertiary amino group. [3]

[0031] According to the resin composition of [1] or [2], wherein the hydrogenated styrene-based thermoplastic elastomer (B) is at least one selected from the group consisting of hydrogenated styrene-butadiene copolymer, hydrogenated styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene block copolymer and hydrogenated styrene-ethylene-butene-styrene block copolymer. [4]

[0033] The resin composition according to any one of [1] to [3], wherein the styrene-derived structural units in the hydrogenated styrene thermoplastic elastomer (B) are present in an amount of 5% to 90% by mass. [5]

[0035] The resin composition according to any one of [1] to [4] further comprises a curing compound (C) other than the polymer (A) and the elastomer (B). [6]

[0037] A hardened material is a hardened material of a resin composition according to any one of [1] to [5]. [7]

[0039] An electronic component comprising a hardened material as described in [6].

[0040] The effects of the invention

[0041] According to one embodiment of the present invention, a resin composition is provided that yields a cured material with low dielectric constant / low dielectric loss tangent and excellent heat resistance (specifically, maintaining a low dielectric loss tangent even after heating). Furthermore, according to another embodiment of the present invention, a resin composition is provided that yields a cured material with a low dielectric loss tangent, excellent heat resistance, low coefficient of linear expansion, and good balance with adhesion to metal layers (especially copper layers). Moreover, according to another embodiment of the present invention, a resin composition is provided that yields a cured material with low dielectric loss tangent, low elongation, low coefficient of thermal expansion, and good balance with heat resistance and tensile properties. These cured materials are preferably used in electronic components such as circuit boards, semiconductor packages, or display substrates. Detailed Implementation

[0042] Hereinafter, preferred embodiments of the present invention will be described in detail. Furthermore, the present invention is not limited to the embodiments described below, but should be understood to include various modifications implemented without changing the spirit of the present invention.

[0043] In this specification, the numerical range indicated by “~” means that the values ​​before and after “~” are the lower and upper limits.

[0044] Resin Compositions

[0045] The resin composition of one embodiment of the present invention (hereinafter also referred to as "the composition") contains the following specific polymer (A) and hydrogenated styrene-based thermoplastic elastomer (B).

[0046] <Polymer (A)>

[0047] The polymer (A) has the structural unit represented by the following formula (a1-1).

[0048] Polymer (A) may be used alone or in combination with two or more.

[0049] The proportion of the structural unit represented by formula (a1-1) in polymer (A) is preferably 30 mol% or more, more preferably 50 mol% or more, more preferably 60 mol% or more, and preferably 99.5 mol% or less, more preferably 98 mol% or less, and more preferably 95 mol% or less.

[0050] [Chemistry 4]

[0051]

[0052] In equation (a1-1), R a1 R is the divalent base represented by the following equation (a2). a2 It is an unsubstituted or substituted divalent aromatic heterocyclic group. Wherein, R... a1 With R a2 different.

[0053] [R] a1 ]

[0054] R a1 It is the divalent base represented by the following formula (a2).

[0055] [Chemistry 5]

[0056]

[0057] In equation (a2), Ar a1 and Ar a2Each is an independent unsubstituted or substituted aromatic hydrocarbon group, where L is a single bond, -O-, -S-, or -N(R) 8 -, -C(O)-, -C(O)-O-, -C(O)-NH-, -S(O)-, -S(O)2-, -P(O)- or divalent organic groups, wherein R 8 It consists of a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halide hydrocarbon group having 1 to 20 carbon atoms, where y is an integer from 0 to 5. When y is 2 or higher, multiple Ar atoms are present. a1 And L are the same or different, R a6 and R a7 Each can be a single bond, a methylene group, or an alkylene group having 2 to 4 carbon atoms.

[0058] [Ar a1 and Ar a2 ]

[0059] As Ar a1 and Ar a2 The unsubstituted or substituted aromatic hydrocarbon group represented is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably phenyl, naphthyl or anthracene, and particularly preferably phenyl or naphthyl.

[0060] Ar a1 and Ar a2 The aromatic hydrocarbon groups represented can have 1 to 8 substituents. In terms of their good polymerizability and ability to synthesize polymers (A), Ar... a1 and Ar a2 The number of substituents in the aromatic hydrocarbon group is preferably 0 to 8, more preferably 0 to 4, and even more preferably 0 to 2.

[0061] As the Ar a1 and Ar a2 The substituents of the aromatic hydrocarbon group represented are not particularly limited. Examples include: allyl, (meth)acryloyloxy, halogen atom, monovalent hydrocarbon group with 1 to 20 carbon atoms, monovalent haloalkanes with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, alkylthio groups with 1 to 20 carbon atoms, nitro, cyano, carboxyl, sulfonic acid group, phosphonic acid group, phosphate group, hydroxyl, primary to tertiary amino groups, salts of carboxyl groups, salts of sulfonic acid groups, salts of phosphonic acid groups, salts of phosphate groups, salts of hydroxyl groups, or salts of primary to tertiary amino groups.

[0062] Among these, the substituents in the aromatic hydrocarbon group are preferably alkyl groups having 1 to 10 carbon atoms.

[0063] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0064] Examples of monovalent hydrocarbon groups with 1 to 20 carbon atoms include: monovalent chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups, and monovalent aromatic hydrocarbon groups.

[0065] Examples of the chain hydrocarbon groups include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl; alkenyl groups such as vinyl, propenyl, butenyl, and pentenyl; and alkynyl groups such as ethynyl, propynyl, butynyl, and pentynyl.

[0066] Examples of monovalent alicyclic hydrocarbon groups include: monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; polycyclic cycloalkyl groups such as norbornyl and adamantyl; monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl; and polycyclic cycloalkenyl groups such as norbornyl.

[0067] Examples of monovalent aromatic hydrocarbon groups include: aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthracene; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, and naphthylmethyl.

[0068] Examples of monovalent halogenated hydrocarbon groups with 1 to 20 carbon atoms include groups formed by substituting some or all of the hydrogen atoms of the monovalent hydrocarbon group with 1 to 20 carbon atoms with halogen atoms such as fluorine, chlorine, bromine, and iodine atoms.

[0069] Examples of alkoxy groups with 1 to 20 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentoxy, hexoxy, and octoxy.

[0070] Examples of alkylthio groups with 1 to 20 carbon atoms include: methylthio, ethylthio, n-propylthio, isopropylthio, butylthio, pentylthio, hexylthio, and octylthio.

[0071] The substituents (R) in secondary amino groups (-NHR) and tertiary amino groups (-NR2) are not particularly limited; for example, monovalent hydrocarbon groups having 1 to 20 carbon atoms can be listed. As specific examples, groups that are exemplified as substituents in the following nitrogen-containing heteroaromatic rings can be listed.

[0072] The cation at the cation site in salts constituting carboxyl groups, sulfonic acid groups, phosphonic acid groups, phosphate groups, and hydroxyl groups is not particularly limited; examples include Na. + Known cations, etc.

[0073] The anion in the anionic site of the salt constituting an amino group is not particularly limited; examples include Cl. - Known anions, etc.

[0074] [L]

[0075] The divalent organic group in L is preferably an organic group having 1 to 20 carbon atoms, for example: unsubstituted or substituted methylene, alkylene having 2 to 20 carbon atoms, arylene having 6 to 10 carbon atoms, a group composed of two or more selected from the methylene, alkylene and arylene, or a group represented by the following formula (L1).

[0076] [Chemistry 6]

[0077]

[0078] In equation (L1), R c Examples include unsubstituted or substituted divalent alicyclic hydrocarbon groups with 5 to 30 ring elements, groups represented by the following formula (L2), or divalent groups introduced by compounds represented by the following formula (L3) or formula (L4).

[0079] [Chemistry 7]

[0080]

[0081] In formula (L2), Ar in equation (a2) a1 and Ar a2 [Key-chain bond]

[0082] [Chemistry 8]

[0083]

[0084] Examples of alkylene groups with 2 to 20 carbon atoms in L include: ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, neopentylene, 4-methylpentane-2,2-diyl, nonane-1,9-diyl, and decane-1,1-diyl.

[0085] Examples of arylene groups with 6 to 10 carbon atoms in L include: phenylene, methylphenylene, and naphthylene.

[0086] In equation (L2), R 9 and R 10 Each of the following is an independent monovalent chain hydrocarbon group consisting of a hydrogen atom, a fluorine atom, or 1 to 20 carbon atoms, and k is an independent integer from 0 to 4.

[0087] R in the above equation (L1) cThe divalent alicyclic hydrocarbon group with 5 to 30 unsubstituted or substituted ring members can be exemplified by: unsubstituted or substituted monocyclic alicyclic hydrocarbon group with 5 to 15 ring members, unsubstituted or substituted monocyclic fluorinated alicyclic hydrocarbon group with 5 to 15 ring members, unsubstituted or substituted polycyclic alicyclic hydrocarbon group with 7 to 30 ring members, and unsubstituted or substituted polycyclic fluorinated alicyclic hydrocarbon group with 7 to 30 ring members.

[0088] Examples of unsubstituted or substituted monocyclic alicyclic hydrocarbon groups with 5 to 15 ring elements include: cyclopentane-1,1-diyl, cyclohexane-1,1-diyl, 3,3,5-trimethylcyclohexane-1,1-diyl, cyclopentene-3,3-diyl, cyclohexene-3,3-diyl, cyclooctane-1,1-diyl, cyclodecane-1,1-diyl, cyclododecane-1,1-diyl, and groups in which some or all of the hydrogen atoms are substituted by a monovalent chain hydrocarbon group having 1 to 20 carbon atoms.

[0089] As the fluorinated alicyclic hydrocarbon group of a monocyclic ring with 5 to 15 ring elements, which is either unsubstituted or substituted, for example, a group in which part or all of the hydrogen atoms of the group is substituted with fluorine atoms.

[0090] Examples of polycyclic alicyclic hydrocarbon groups with 7 to 30 ring members, whether unsubstituted or substituted, include norbornene, norbornene, adamantane, and tricyclic [5.2.1.0]. 2,6 Decane, pinane, camphane, decahydronaphthalene, tricyclic [2.2.1.0] 2,6 A group consisting of two hydrogen atoms bonded to a carbon atom of polycyclic alicyclic hydrocarbons such as heptane, perhydroanthracene, perhydroazine, cyclopentano-hydrophenanthrene, and bicyclic [2.2.2]-2-octene; or a group consisting of one or all of the hydrogen atoms of these groups being replaced by a monovalent chain hydrocarbon group having 1 to 20 carbon atoms.

[0091] As the fluorinated alicyclic hydrocarbon group of polycyclic rings with 7 to 30 ring elements, which is either unsubstituted or substituted, for example, a group in which part or all of the hydrogen atoms of the group is substituted with fluorine atoms.

[0092] -N(N) in L 8 R in )- 8 It consists of 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.

[0093] As monovalent hydrocarbon groups having 1 to 20 carbon atoms and monovalent halide hydrocarbon groups having 1 to 20 carbon atoms, examples include Ar, etc. a1 Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms and monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms are shown in the figure.

[0094] From the viewpoint of the structural stability of polymer (A), L is preferably a single bond, -O-, -S-, -C(O)-, a substituted or unsubstituted methylene group, an alkylene group having 2 to 5 carbon atoms, or a group represented by the formula (L1).

[0095] [y]

[0096] In formula (a2), y is an integer from 0 to 5. From the viewpoint of the structural stability of polymer (A), y is preferably an integer from 0 to 3, and more preferably 0 or 1.

[0097] [R a6 and R a7 ]

[0098] As R a6 and R a7 Alkylenes having 2 to 4 carbon atoms, for example: ethylene, n-propylene, isopropylene, n-butylene, sec-butylene. As R a6 and R a7 From the viewpoint that the polymer (A) can be synthesized with good polymerizability, single bonds, methylene or ethylene are preferred independently.

[0099] As R becomes part of the inclusion formula (a1-1) a1 The monomeric form of the raw material (i.e., the divalent group represented by formula (a2)) may include, for example, diol compounds such as PRIPLAST 1901, 1838, 3186, 3192, 3197, and 3199 (manufactured by Croda Japan Co., Ltd.), in addition to the compounds represented by the formulas below. Furthermore, these monomeric forms may be used alone or in two or more forms.

[0100] [Chemistry 9]

[0101]

[0102] [Chemistry 10]

[0103]

[0104] [Chemistry 11]

[0105]

[0106] [R] a2 ]

[0107] R a2 It is an unsubstituted or substituted divalent aromatic heterocyclic group. Wherein, R... a1 With R a2 different.

[0108] As R a2 The unsubstituted or substituted divalent aromatic heterocyclic groups represented may include nitrogen-containing aromatic heterocyclic groups, oxygen-containing aromatic heterocyclic groups, sulfur-containing aromatic heterocyclic groups, etc., among which nitrogen-containing aromatic heterocyclic groups are preferred.

[0109] Examples of nitrogen-containing aromatic heterocyclic groups include: pyrrole rings, pyridine rings, pyrimidine rings, pyrazine rings, pyridazine rings, triazine rings, quinoline rings, isoquinoline rings, quinoxaline rings, phthalazine rings, quinazoline rings, naphthidine rings, carbazole rings, acridine rings, and phenazine rings. Among these, pyrimidine rings are preferred from the viewpoint that polymers (A) can be synthesized with good polymerizability and that polymers (A) with excellent solubility in various organic solvents can be readily obtained.

[0110] The positions of the two bonds (bonded to O) on the nitrogen-containing heteroaromatic ring are not particularly limited, but from the viewpoint that the polymer (A) can be synthesized with good polymerizability, the meta position is preferred.

[0111] As R a2 The substituents of the divalent aromatic heterocyclic group can be, for example, halogen atoms, monovalent hydrocarbon groups having 1 to 20 carbon atoms, monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms, groups formed by substitution of these hydrocarbon groups or a portion thereof by at least one selected from oxygen and sulfur atoms, nitro, cyano, maleimide, salts of primary amino to tertiary amino or primary amino to tertiary amino groups.

[0112] Specific examples of these substituents can be listed as Ar. a1 The aromatic hydrocarbon group represented has the same substituents as the group exemplified.

[0113] In terms of polymerizability and reactivity, R can synthesize polymers (A) with good reactivity. a2 The divalent aromatic heterocyclic group represented preferably has 0 to 2 substituents.

[0114] R a2 Preferably, it is a divalent base represented by one of the following formulas (1-1), (1-2) and (1-3).

[0115] [Chemistry 12]

[0116]

[0117] In equations (1-1) to (1-3), n is an independent integer from 0 to 2. When n is 1, R 1 Each of the two R's is an independent monovalent basis. When n = 2, the two R's... 1 Each is independently a monovalent base, either the same or different, or two R... 1 Together with these bonded carbon atoms, they form a ring structure with 5 to 10 ring elements. The monovalent group is a halogen atom, a monovalent hydrocarbon group with 1 to 20 carbon atoms, a monovalent halide hydrocarbon group with 1 to 20 carbon atoms, a nitro group, a cyano group, or a salt of a primary amino to a tertiary amino group or a primary amino to a tertiary amino group.

[0118] As R 1 Specific examples of the bases in the Ar can be listed as examples of the Ar. a1 The aromatic hydrocarbon group represented has the same substituents as the group exemplified.

[0119] As R 1 From the viewpoint of improving polymerization reactivity and the solubility of the obtained polymer (A), halogen atoms, alkyl groups having 1 to 3 carbon atoms, or aromatic hydrocarbon groups having 6 to 10 carbon atoms are preferred, and fluorine atoms, chlorine atoms, methyl, ethyl, or phenyl groups are more preferred. From the same viewpoint, n is preferably 0 or 1, and more preferably 0.

[0120] From the viewpoint of improving polymerization reactivity, the position of the divalent group represented by one of formulas (1-1), (1-2) and (1-3) as the other bond relative to one of the bonds is preferably meta or para, and more preferably meta, as the divalent group represents one of the bonds.

[0121] Furthermore, from the perspective of improving polymerization reactivity and increasing solubility in various organic solvents, as R a2 Preferably, it is a base represented by the formula (1-2) having a pyrimidine skeleton.

[0122] As to become the inclusion of said R a2Monomeric forms of some of the raw materials can be listed, for example: 4,6-dichloropyrimidine, 4,6-dibromopyrimidine, 2,4-dichloropyrimidine, 2,5-dichloropyrimidine, 2,5-dibromopyrimidine, 5-bromo-2-chloropyrimidine, 5-bromo-2-fluoropyrimidine, 5-bromo-2-iodopyrimidine, 2-chloro-5-fluoropyrimidine, 2-chloro-5-iodopyrimidine, 2-phenyl-4,6-dichloropyrimidine, 2-methylthio-4,6-dichloropyrimidine, 2-methylsulfonyl-4,6-dichloropyrimidine, 5-methyl-4,6-dichloropyrimidine, 2-amino-4,6-dichloropyrimidine, 5-amino-4,6-dichloropyrimidine, 2,5-diamino-4,6-dichloropyrimidine, 4-amino-2,6-dichloropyrimidine, 5-methoxy-4,6-dichloropyrimidine Pyrimidine compounds such as chloropyrimidine, 5-methoxy-2,4-dichloropyrimidine, 2-methyl-4,6-dichloropyrimidine, 6-methyl-2,4-dichloropyrimidine, 5-methyl-2,4-dichloropyrimidine, 5-nitro-2,4-dichloropyrimidine, 4-amino-2-chloro-5-fluoropyrimidine, 2-methyl-5-amino-4,6-dichloropyrimidine, and 5-bromo-4-chloro-2-methylthiopyrimidine; pyridazine compounds such as 3,6-dichloropyridazine, 3,5-dichloropyridazine, and 4-methyl-3,6-dichloropyridazine; and pyrazine compounds such as 2,3-dichloropyrazine, 2,6-dichloropyrazine, 2,5-dibromopyrazine, 2,6-dibromopyrazine, 2-amino-3,5-dibromopyrazine, and 5,6-dicyano-2,3-dichloropyrazine. Furthermore, these monoisotropy compounds can be used alone or in combination with more than one type.

[0123] [Other structural units]

[0124] Polymer (A) may have other structural units besides those represented by formula (a1-1), as needed. In this case, the structural units represented by formula (a1-1) are bonded to each other or to the other structural units.

[0125] When polymer (A) has multiple structural units represented by formula (a1-1), multiple R a1 They can be the same or different. The situation described applies to R. a2 The same applies to other structural units.

[0126] There are no particular limitations on the other structural units mentioned above. For example, branch structural units represented by the following equation (a1-2), terminal base Y represented by the following equation (I), and any other structural units may be listed.

[0127] [Branch Structure Unit]

[0128] The polymer (A) may also contain the branched structural unit represented by the following formula (a1-2) by copolymerizing the monomer that provides the structural unit of the formula (a1-1) with the monomer that provides the branched structure.

[0129] [Chemistry 13]

[0130]

[0131] In equation (a1-2), R a2 With R in the above formula (a1-1) a2 For the same meaning, R 12 Each is independently an unsubstituted or substituted divalent aromatic hydrocarbon group, R 13 It is a hydrocarbon group with 1 to 20 carbon atoms, where m is an integer from 1 to 6. For bonding with other structural units in polymer (A).

[0132] The structural unit represented by equation (a1-2) can be used to illustrate structural units with the following partial structures, but is not limited to these.

[0133] [Chemistry 14]

[0134]

[0135] As a method for synthesizing the polymer (A) having the branched structural unit, one example is that, when synthesizing the structural unit represented by formula (a1-1), the portion (-R) sandwiched between two oxygen atoms in formula (a1-2) is provided. 12 -R 13 (R 12 -O- ) m -R 12 -) is a method for reacting monotonically. As a means of providing (-R) 12 -R 13 (R 12 -O- ) m -R 12 -) monotonous forms, for example, compounds represented by the following formula (6).

[0136] [Chemistry 15]

[0137]

[0138] In the above equation (6), R 13 n is a carbon number from 1 to 20 61 valence hydrocarbon group, R 61 Each is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, n 61n is an integer from 2 to 4. 62 n is an integer from 1 to 5. 63 It is an integer between 0 and 4. Where n 62 With n 63 The total number is 1 to 5.

[0139] Furthermore, in the compounds represented by formula (6), the total number of hydroxyl groups is 3 or more.

[0140] [Terminal group]

[0141] Polymer (A) may also have a terminal group Y represented by the following formula (I) at the end of the structural unit represented by formula (a1-1).

[0142] [Chemistry 16]

[0143]

[0144] Furthermore, the terminal group Y is bonded to the end of the main chain of polymer (A), specifically forming the terminal portion of polymer (A) as represented by formula (a1-1-1) or formula (a1-1-2). That is, the terminal group Y is associated with the main chain of polymer (A). a1 and R a2 The end (e.g., R) a1 and R a2 The substituents in the group are different from the substituents in the group.

[0145] [Chemistry 17]

[0146]

[0147] In equations (a1-1-1) and (a1-1-2), Y independently has the same meaning as Y in equation (I), and Z is O, S, or N(R). Z ), R Z For hydrogen atoms or Y, R a1 and R a2 Independently related to R in the aforementioned equation (a1-1) a1 and R a2 [For the same meaning]

[0148] In formula (I), Y is a group containing an ethylene unsaturated double bond with 3 to 50 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group with 6 to 50 carbon atoms, an unsubstituted or substituted aliphatic hydrocarbon group with 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing aromatic heterocyclic group. Among these, a group containing an ethylene unsaturated double bond with 3 to 50 carbon atoms is preferred.

[0149] To improve dielectric properties, the terminal group Y is preferably an aromatic hydrocarbon group or an aliphatic hydrocarbon group or a nitrogen-containing heteroaromatic group with low polarization. In the case of also containing ethylene unsaturated double bonds, the crosslinking density can be increased, and thus heat resistance or hardening properties can be expected.

[0150] Examples of groups containing an ethylene-unsaturated double bond with 3 to 50 carbon atoms include: 3-isopropenylphenyl, 4-isopropenylphenyl, 2-allylphenyl, 2-methoxy-4-allylphenyl, 4-(1-propenyl)-2-methoxyphenyl, 4-vinylbenzyl, 3-vinylbenzyl, 2-vinylbenzyl, etc., containing aromatic rings, allyl, acrylic, methacrylic acid, etc.

[0151] Examples of aromatic hydrocarbon groups having 6 to 50 carbon atoms include: aryl groups such as phenyl, biphenyl, tolyl, xylyl, naphthyl, and anthracene; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, and naphthylmethyl.

[0152] Examples of aliphatic hydrocarbon groups having 6 to 50 carbon atoms include: monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; polycyclic cycloalkyl groups such as norbornyl and adamantyl; monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl; and polycyclic cycloalkenyl groups such as norbornyl.

[0153] As an unsubstituted nitrogen-containing aromatic heterocyclic group, examples include R. a2 Examples of nitrogen-containing aromatic heterocyclic groups are shown in the text.

[0154] Regarding the unsubstituted or substituted aromatic hydrocarbon groups with 6 to 50 carbon atoms and the substituents in the unsubstituted or substituted aliphatic hydrocarbon groups with 6 to 50 carbon atoms, specific examples can be listed as the R... a2 The substituents in the divalent aromatic heterocyclic group are exemplified by the group.

[0155] There are no particular limitations on the method for forming a polymer (A) that seals the ends of a polymer (A) with end groups Y. Known methods can be used, but when synthesizing polymer (A), it is preferable to use a monolith for forming end groups Y.

[0156] Examples of monovalent phenolic compounds used for forming the terminal group Y include: tert-butylphenol, nonylphenol, 4-isopropenylphenol, 4-vinylphenol, 2-allylphenol, isoeugenol, tocotrienol, α-tocopherol, 4-hydroxyphenylmaleimide, 2-phenylphenol, etc.; monovalent amine compounds such as 4-hexylaniline and diallylamine; monovalent thiols such as 1-octanethiol; monovalent aliphatic halides such as allyl chloride, 4-(chloromethyl)styrene, 3-(chloromethyl)styrene; monovalent acid halides such as acryloyl chloride, methacryloyl chloride, crotonyl chloride, cinnamicyl chloride, etc.; and monovalent acid anhydrides such as acrylic anhydride, crotonic anhydride, methacrylic anhydride, etc.

[0157] Furthermore, the monomer used for forming the terminal Y group can be a single type or two or more types.

[0158] [Arbitrary structural unit]

[0159] Examples of monomers derived from the aforementioned structural units include: diphenyl carbonate, diphenyl thiocarbonate, diphenyl selenocarbonate, phosgene, thiophosgene, selenophosgene, and other compounds containing structural units comprising carbonate, thiocarbonate, or selenocarbonate bonds; phosphine oxide compounds such as bis(fluorophenyl)phenylphosphine oxide, bis(fluorophenyl)naphthylphosphine oxide, and bis(fluorophenyl)anthraylphosphine oxide; and dihalides of dicarboxylic acids such as dichloride of phthalate, dichloride of isophthalate, and dichloride of terephthalate. Furthermore, one or more of these monomers may be used.

[0160] [Method for synthesizing polymer (A)]

[0161] The method for synthesizing polymer (A) is not particularly limited, and known methods can be used. For example, it can be synthesized by reacting it in an organic solvent to form a polymer containing R. a1 A portion of the raw material in a single volume, becoming a component containing said R a2 The raw materials, in their monomeric form and, if necessary, other monomeric forms providing the aforementioned structural units, are heated together with an alkali metal or alkali metal compound to synthesize the mixture. The monomeric form providing the other structural units may also be used to form a mixture containing the aforementioned R... a1 A portion of the raw material in single volume and becoming containing said R a2 The reaction is carried out by heating and mixing the monomers of some of the raw materials after polymerization.

[0162] Alkali metals and alkali metal compounds

[0163] In the synthesis of polymer (A), when hydroxyl-containing compounds such as phenolic compounds are used as raw materials, the alkali metal and alkali metal compounds react with the hydroxyl-containing compounds to form alkali metal salts.

[0164] Examples of such alkali metals and alkali metal compounds include:

[0165] Alkali metals such as lithium, sodium, and potassium;

[0166] Lithium hydride, sodium hydride, potassium hydride, and other alkali metal hydrides;

[0167] Lithium hydroxide, sodium hydroxide, potassium hydroxide, and other alkali metal hydroxides;

[0168] Alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate;

[0169] Alkali metal bicarbonates such as lithium bicarbonate, sodium bicarbonate, and potassium bicarbonate.

[0170] Among these, alkali metal carbonates are preferred, and potassium carbonate is more preferred.

[0171] When synthesizing polymer (A), when using compounds containing hydroxyl groups, the amount of alkali metal and alkali metal compound used is preferably 1, more preferably 1.1, and even more preferably 1.2, as 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 compounds used in the synthesis of polymer (A), and preferably 3, more preferably 2, and even more preferably 1.8.

[0172] organic solvents

[0173] Examples of organic solvents include:

[0174] Ether-based solvents include tetrahydrofuran (THF), dioxane, cyclopentylmethyl ether, anisole, phenethyl ether, diphenyl ether, dialkoxybenzene, and trialkoxybenzene.

[0175] Nitrogen-containing solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolium ketone;

[0176] Ester solvents such as γ-butyrolactone;

[0177] Sulfur-containing solvents such as sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, and diphenyl sulfone;

[0178] Ketone solvents such as benzophenone, 2-heptanone, cyclohexanone, and methyl ethyl ketone;

[0179] Halogen-based solvents such as dichloromethane, chloroform, and chlorobenzene;

[0180] Aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

[0181] Among these organic solvents, 2-heptanone, cyclohexanone, N-methyl-2-pyrrolidone, toluene, and xylene are preferred, and N-methyl-2-pyrrolidone, 2-heptanone, and cyclohexanone are more preferred.

[0182] The lower limit of the reaction temperature during the synthesis is preferably 50°C, more preferably 80°C, and the upper limit is preferably 300°C, more preferably 200°C.

[0183] The lower limit of the reaction time during the synthesis is preferably 1 hour, more preferably 2 hours, and even more preferably 3 hours. The upper limit is preferably 100 hours, more preferably 50 hours, and even more preferably 24 hours.

[0184] When a monomer for forming terminal Y groups is added after polymerization to suppress gelation of the polymer solution, the reaction temperature is preferably 0°C, more preferably 10°C, as the lower limit of the reaction temperature, and preferably 130°C, more preferably 110°C, as the upper limit of the reaction temperature.

[0185] When the reaction is carried out by adding the monolith for forming the terminal group Y after polymerization, the lower limit of the reaction time is preferably 1 hour, more preferably 2 hours, and even more preferably 3 hours, and the upper limit is preferably 48 hours, more preferably 24 hours, and even more preferably 10 hours.

[0186] [Physical properties of polymer (A)]

[0187] The lower limit of the polystyrene-converted weight average molecular weight (Mw) of polymer (A) is preferably 1,000, more preferably 2,000, particularly preferably 3,000, and the upper limit is preferably 500,000, more preferably 100,000, and even more preferably 30,000.

[0188] If the Mw of polymer (A) is within the range described, it is easy to obtain a cured product with excellent adhesion to metal layers (especially copper layers) and heat resistance, and it is easy to obtain a composition with a good and excellent balance of impregnation properties of glass cloth, resin flow and other formability.

[0189] The weight-average molecular weight (Mw) can be determined by gel permeation chromatography (GPC) under the conditions described in the examples described later.

[0190] [Content of polymer (A)]

[0191] When the total mass of the solid components in this composition is set to 100% by mass, the content of polymer (A) is preferably 0.05% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, and preferably 97% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.

[0192] If the content of polymer (A) is within the range described, the obtained cured material can be further improved in terms of adhesion to metal layers (especially copper layers), heat resistance, curing properties and electrical properties.

[0193] <Hydrogenated Styrene-based Thermoplastic Elastomers (B)>

[0194] This composition contains a hydrogenated styrene-based thermoplastic elastomer (B). The elastomer (B) refers to an elastomer in which some or all of the double bonds of a styrene-based thermoplastic elastomer are hydrogenated.

[0195] By including hydrogenated styrene-based thermoplastic elastomer (B) in this composition, it is easier to obtain cured products with low dielectric constant and low dielectric loss tangent.

[0196] Elastomer (B) can be used alone or in combination with two or more.

[0197] As an elastomer (B), examples include hydrogenated styrene-based thermoplastic elastomers, which are formed by hydrogenating some or all of the carbon-carbon double bonds in copolymers such as styrene-butadiene copolymers and styrene-isoprene copolymers.

[0198] As an elastomer (B), it is preferable to select at least one from the group consisting of hydrogenated styrene-butadiene copolymer, hydrogenated styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene block copolymer and hydrogenated styrene-ethylene-butene-styrene block copolymer, in order to more easily obtain a hardened material with low dielectric constant / low dielectric loss tangent.

[0199] The hydrogenation rate of the elastomer (B) is preferably 50% or more, more preferably 60% or more, more preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

[0200] In addition, the hydrogenation rate is determined by measuring the iodine value of the elastomer (B).

[0201] The content of styrene-derived structural units in the elastomer (B) (hereinafter also referred to as "styrene content") is preferably 5% to 90% by mass, more preferably 10% to 80% by mass, and even more preferably 15% to 75% by mass.

[0202] If an elastomer (B) with a styrene content within the aforementioned range is used, a cured product with a good and excellent balance of low dielectric constant / low dielectric loss tangent, heat resistance, low coefficient of linear expansion, and adhesion to metal layers (especially copper layers) can be easily obtained. Furthermore, if the styrene content in the elastomer (B) is within the aforementioned range, there is a tendency to obtain a cured product with a low dielectric loss tangent, low elongation, low coefficient of thermal expansion, and a good and excellent balance of heat resistance and tensile properties.

[0203] The amount of styrene can be calculated based on the proportion of styrene used in the synthesis of elastomer (B). Additionally, it can be determined by analyzing a 400 MHz... 1 H-NMR ( 1 H-Nuclear magnetic resonance, 1 The result is determined by H-NMR.

[0204] The content of elastomer (B) in this composition is preferably 3% to 90% by mass relative to the total solid components of polymer (A) and elastomer (B), more preferably 5% to 70% by mass, even more preferably 5% to 60% by mass, even more preferably 5% to 50% by mass, and particularly preferably 5% to 40% by mass.

[0205] If the content of elastomer (B) is 3% by mass or more, it is easier to obtain a cured product with a low dielectric constant and a low dielectric loss tangent. If it is 90% by mass or less, the compatibility of elastomer (B) with other components in the composition is improved, thereby achieving sufficient dispersion and making it easier to obtain a cured product with excellent heat resistance and a low dielectric loss tangent. In addition, if the content of elastomer (B) is within the aforementioned range, there is a tendency to obtain a cured product with a good and excellent balance of low dielectric loss tangent, heat resistance, low coefficient of linear expansion, and adhesion to metal layers (especially copper layers) and / or a low dielectric loss tangent, low elongation, low coefficient of thermal expansion, and a good and excellent balance of heat resistance and tensile properties.

[0206] <Other Ingredients>

[0207] This composition contains a polymer (A) and an elastomer (B), but may also contain other components without compromising the effects of the invention.

[0208] Other components may include, for example, a curing compound (C), a polymerization initiator (D), additives for imparting various functions (e.g., fillers (E), antioxidants), an organic solvent (F), polymerization inhibitors for increasing stability, lubricants, and foaming agents. Additionally, the composition may also contain a thermoplastic resin, other than polymer (A) and elastomer (B), used to adjust the composition's flowability, heat resistance, electrical properties, etc.

[0209] These other ingredients can be used individually or in combination with two or more.

[0210] [Cure compound (C)]

[0211] The composition preferably also contains a hardening compound (C).

[0212] The curing compound (C) is a curing compound other than polymer (A) and elastomer (B), and is a compound that is cured by heat or light irradiation.

[0213] Examples of curing compounds (C) include: vinyl compounds, maleimide compounds, allyl compounds, acrylic acid compounds, methacrylic acid compounds, thiols, oxazine compounds, cyanate compounds, epoxy compounds, oxetane compounds, hydroxymethyl compounds, benzocyclobutene compounds, propargyl compounds, and silane compounds.

[0214] In particular, from the viewpoint of compatibility and reactivity with polymer (A), the curing compound (C) is preferably at least one compound selected from the group consisting of vinyl compounds, maleimide compounds and allyl compounds.

[0215] When the composition contains a curing compound (C), the content of the curing compound (C) is preferably 2 to 100 parts by mass relative to 100 parts by mass of the total solid components of the polymer (A) and elastomer (B), more preferably 5 to 75 parts by mass, and even more preferably 8 to 50 parts by mass.

[0216] If the content of the hardening compound (C) is within the range described, the toughness and heat resistance of the hardened product obtained from this composition can be further improved.

[0217] [Polymerization initiator (D)]

[0218] The composition preferably also contains a polymerization initiator (D).

[0219] Examples of polymerization initiators (D) include thermal free radical initiators, photofree radical initiators, cationic curing agents, anionic curing agents, and other polymerization initiators. Among these, thermal free radical initiators are preferred as polymerization initiators (D).

[0220] Examples of thermal free radical initiators include: dicumyl peroxide, 1,1-di(tert-butylperoxy)cyclohexane, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyn-3, benzoyl peroxide, and other organic peroxides; azo compounds such as azobisbutyronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobis(2,4-dimethylpentanonitrile), 1,1'-azobis(cyclohexane-1-carbamate), dimethyl-2,2'-azobis(isobutyrate), and 2,2'-azobis(2-methylbutyronitrile).

[0221] When the composition contains a polymerization initiator (D), the content of the polymerization initiator (D) is preferably within the range where the composition can be well cured to obtain a cured product. Specifically, it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and more preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the total solid components of the polymer (A) and elastomer (B).

[0222] 〔additive〕

[0223] Additives used to impart the aforementioned functions include, for example: fillers (E), antioxidants, flame retardants, adhesion promoters, antibacterial agents, colorants, and release agents.

[0224] [Packaging (E)]

[0225] This composition may also contain filler (E).

[0226] As the filler (E), organic fillers or inorganic fillers can be listed, among which inorganic fillers are preferred.

[0227] Examples of inorganic fillers include: natural silica, fused silica, amorphous silica, and other silica-based materials; precipitated silica, titanium dioxide, silica aerogel, 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.

[0228] When the composition contains filler (E), the content of filler (E) is preferably 0.1 parts by mass or more and 300 parts by mass or less, relative to 100 parts by mass of the total solid components of polymer (A) and elastomer (B).

[0229] [Organic solvent (F)]

[0230] This composition preferably also contains an organic solvent (F).

[0231] Examples of organic solvents (F) include: amide solvents; ester solvents; ketone solvents; ether solvents; sulfone solvents; hydrocarbon solvents such as benzene, toluene, and xylene; multifunctional solvents such as 1-methoxy-2-propanol and propylene glycol methyl ether acetate; trialkoxybenzene (alkoxy group has 1 to 4 carbon atoms) and dichloromethane.

[0232] When this composition contains an organic solvent (F), the content of said solvent (F) in the composition is not particularly limited. For example, it is preferably 0 parts by mass or more and 2000 parts by mass or less, more preferably 0 parts by mass or more and 1000 parts by mass or less, relative to 100 parts by mass of the total solid components of polymer (A) and elastomer (B). In addition, if the polymer (A) has high solubility for the organic solvent (F), the content of said organic solvent (F) in the composition can be set to 50 parts by mass or more and 200 parts by mass or less.

[0233] <Preparation method of this composition>

[0234] There are no particular limitations on the preparation method of this composition, and known preparation methods can be listed, such as preparing it by uniformly mixing the polymer (A), elastomer (B) and the other components. In this case, there are no particular limitations on the mixing order and mixing conditions of the components, and existing known mixers can also be used during mixing.

[0235] Hardened materials

[0236] The cured product of one embodiment of the present invention (hereinafter also referred to as "this cured product") is a cured body of the present composition, which can be obtained by curing the present composition. This cured product may also be, for example, a partially cured product of the present composition obtained by drying the solvent from the present composition.

[0237] There are no particular limitations on the method for hardening the composition; for example, methods involving heating the composition to harden it can be listed. Regarding the heating conditions, for example, a temperature within the range of 100°C to 250°C and a time within the range of 10 minutes to 120 minutes, the heating conditions can be set according to the desired degree of hardening. The heating process for hardening can be performed in one step, or it can be divided into multiple steps by changing the temperature or time.

[0238] This cured material exhibits excellent heat resistance, maintaining a low dielectric constant and low dielectric loss tangent even after heating. While the reason for this is uncertain, it is believed that the cured material of the resin composition containing polymer (A) and elastomer (B) not only has high bond energy in the main chain or side chain of polymer (A) and elastomer (B), but also has fewer residual unsaturated bonds in elastomer (B), thus resulting in excellent heat aging resistance.

[0239] The lower limit of the heat resistance (Tg) of this cured material is preferably 150°C, more preferably 180°C, and the upper limit is, for example, 400°C. With the Tg within this range, melt forming is easier, and a cured material with excellent heat resistance can be easily obtained. Specifically, the Tg can be determined using the method described in the following examples.

[0240] In terms of reducing transmission loss, the dielectric loss tangent (tanδ) of this cured material is preferably less than 0.0025, more preferably less than 0.0018, and even more preferably less than 0.0015, particularly preferably less than 0.0015, with no particular limitation on the lower limit, but preferably 0.0005 or higher. Specifically, the dielectric loss tangent can be measured using the method described in the following embodiments.

[0241] In terms of readily obtainable hardened materials that are less prone to deformation due to heat, the coefficient of linear expansion of this hardened material is preferably 50 ppm / K or less, more preferably 25 ppm / K or less, and even more preferably less than 25 ppm / K. Specifically, the coefficient of linear expansion can be measured using the method described in the following examples.

[0242] Regarding the elongation of this hardened material, in the event that electronic components containing this hardened material undergo expansion or other deformation due to the generated heat, or when stress is applied to the substrate during the formation of through holes or pores, the absorbed energy (mJ) is preferably 10 mJ or more, more preferably 15 mJ or more, and even more preferably 20 mJ or more, when the electronic components containing this hardened material undergo expansion or other deformation due to the generated heat, or when stress is applied to the substrate during the formation of through holes or pores, by absorbing these strain energies.

[0243] Regarding the coefficient of thermal expansion of this cured material, it is preferable that, when the electronic component containing this cured material undergoes expansion or other deformation caused by the generated heat, the coefficient of thermal expansion is not significantly different from that of the surrounding components (such as copper). Using a thermomechanical analysis (TMA) measuring device (manufactured by Seiko Instruments, SSC-5200 type), the coefficient of thermal expansion at 80°C to 120°C during cooling is preferably 150 ppm or less, more preferably 130 ppm or less, when the temperature is increased from room temperature to 200°C to 250°C at a rate of 5°C / min and then cooled to 0°C at a rate of 5°C / min.

[0244] Regarding the concentration of chloride ions in this hardener, it is preferably 5 ppm or less for the sake of insulation reliability, and more preferably 3 ppm or less for the sake of suppressing discoloration of copper wiring.

[0245] When this cured material is used to form an interlayer insulation layer for wiring in contact with copper wiring, the cured material will be located between adjacent copper wiring. By setting the concentration of chloride ions within the aforementioned range, the diffusion of copper and other materials from copper wiring into this cured material can be suppressed, and short circuits between wirings via the diffused copper and other materials can be suppressed. As a result, the insulation reliability of the laminate containing the wiring can be significantly improved.

[0246] The concentration of chloride ions can be determined, for example, using the following procedure.

[0247] The hardened material and ultrapure water, used as the extraction solution, were placed in a heat-resistant container made of Teflon (registered trademark) and heated. The extraction solution was then filtered and analyzed using ion chromatography.

[0248] The shape of this cured material is not particularly limited, and a suitable shape can be selected according to the application or purpose. Examples of shapes for cured materials include: film, plate, and rod. For example, a film-shaped cured material can be obtained by melt-forming or casting this composition.

[0249] There is no particular limitation on the thickness of this cured material; it can be selected appropriately according to the desired application. When the cured material is in the form of a film, its thickness is, for example, 10 μm or more, preferably 30 μm or more, and for example, 2 mm or less, preferably 1 mm or less.

[0250] This hardener can also be made into a laminate comprising the hardener (hardener layer) and a substrate.

[0251] The laminate may also be a prepreg made by impregnating the composition in a substrate such as glass cloth, polyaramid nonwoven fabric, or polyester nonwoven fabric and then curing it.

[0252] Alternatively, the laminate may be, for example, a laminate of the prepreg and the copper substrate, i.e., a copper-clad laminate.

[0253] The laminate may have two or more substrate layers, two or more hardened layers, or other known layers besides the substrate and hardened layers. When the laminate has two or more substrate layers, hardened layers, or other layers, these may be the same layer (plate) or different layers (plates).

[0254] From the viewpoint of adhesion to the cured material or practical application, examples of substrates include inorganic substrates, metal substrates, and resin substrates. Alternatively, a prepreg may also be used as the substrate.

[0255] Examples of inorganic substrates include those composed of silicon, silicon carbide, silicon nitride, aluminum oxide, glass, gallium nitride, etc.

[0256] Examples of metal substrates include those composed of copper, aluminum, gold, silver, nickel, palladium, etc. The shape of the metal substrate is not particularly limited and can be a plate, metal foil, etc.

[0257] Examples of resin substrates that include liquid crystal polymers, polyimide, polyphenylene sulfide, polyetheretherketone, polyamide (nylon), polyethylene terephthalate, polyethylene naphthalate, cyclic olefin polymers, and polyolefins are included.

[0258] The hardened layer can be formed, for example, by hardening the composition.

[0259] The thickness of the hardened layer is not particularly limited, for example, it is 1 μm to 3 mm.

[0260] <Uses>

[0261] This composition and the cured product are preferably used in structural materials for transport aircraft industries such as the aircraft industry or the automobile industry, and in electrical and electronic materials for the electrical and electronic industry. Specifically, for example, they are suitable for: sealing materials, interlayer insulating films, and stress-relieving primers for electrical and electronic components; laminate applications (e.g., prepregs, copper-clad laminates, (multilayer) printed wiring boards, interlayer adhesives, solder resists, solder pastes); adhesive applications (e.g., adhesive sheets for insulating layer formation, thermally conductive adhesives, adhesive sheets); structural adhesives and prepregs used in various structural materials; various coatings; optical component applications (e.g., optical films such as wavelength plates and phase refraction plates; various special lenses such as conical lenses, spherical lenses, and cylindrical lenses; lens arrays); and insulating films for printed wiring boards.

[0262] In particular, the interlayer insulating film containing the hardened material has a low dielectric loss tangent and excellent adhesion to metal layers (especially copper layers) and heat resistance.

[0263] Electronic Components

[0264] An electronic component according to one embodiment of the present invention includes the aforementioned cured material. The electronic component may include two or more of the aforementioned cured materials. In the case of including two or more of the aforementioned cured materials, these may be identical or different.

[0265] Examples of such electronic components include: circuit boards, semiconductor packages, or display substrates.

[0266] The aforementioned hardened material (hardened film) can be used as a prepreg, copper-clad laminate, printed wiring board, bonding sheet for insulating layer formation, surface protective film, rewiring layer, or planarization film for these electronic components.

[0267] The cured material can maintain its insulation properties even under high temperature and high humidity conditions. Therefore, electronic components containing the cured material can protect circuit patterns from the influence of external environments such as dust, heat, and moisture. Furthermore, the insulation between circuit patterns is highly reliable and can operate stably for many years.

[0268] Regarding the aforementioned hardened material, for example, metal is filled between patterns formed on the hardened material (hardened film) by plating or other methods. The hardened material (hardened film) is then laminated and filled with metal as needed, and this operation is repeated to form a rewiring layer. Thus, electronic components having a substrate and a rewiring layer comprising metal wiring and an insulating film can be manufactured.

[0269] Example

[0270] The following describes one embodiment of the present invention in more detail based on examples, but the present invention is not limited to these examples.

[0271] [Synthesis example 1]

[0272] In a four-necked separable flask equipped with a stirrer, 20.3 g (60.0 mmol) of bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 8.9 g (40.0 mmol) of 2,5-di-tert-butylhydroquinone, 14.9 g (100.0 mmol) of 4,6-dichloropyrimidine, and 18.7 g (135.0 mmol) of potassium carbonate were added, along with 102.9 g of N-methyl-2-pyrrolidone. The reaction was carried out under nitrogen atmosphere at 130 °C for 6 hours. After the reaction was completed, 206 g of N-methyl-2-pyrrolidone was added for dilution. After removing the salt by filtration, the resulting solution was added to methanol (7 kg). The precipitated solid was filtered and separated, washed with a small amount of methanol, filtered and separated again and recovered, and then dried in a vacuum dryer at 120°C for 12 hours under reduced pressure to obtain a polymer (A1) having the structural unit represented by the following formula (1).

[0273] [Chemistry 18]

[0274]

[0275] [Synthesis example 2]

[0276] 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (25.4 g, 75.0 mmol), 4,6-dichloropyrimidine (11.2 g, 75.0 mmol), and potassium carbonate (14.0 g, 101.3 mmol) were measured into a four-necked separable flask including a stirrer, and N-methyl-2-pyrrolidone (85 g) was added. The reaction was carried out under nitrogen atmosphere at 130°C for 6 hours. After the reaction was completed, N-methyl-2-pyrrolidone (300 g) was added for dilution. After removing the salt by filtration, the obtained solution was added to methanol (6 kg). The precipitated solid was filtered and separated, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120°C for 12 hours using a vacuum dryer to obtain a polymer (A2) having the structural unit represented by the following formula (2).

[0277] [Chemistry 19]

[0278]

[0279] [Synthesis example 3]

[0280] 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (62.08 g), 4,6-dichloropyrimidine (30.99 g), 4-isopropenylphenol (2.170 g), and potassium carbonate (38.83 g) were weighed into a four-necked separable flask including a stirrer, and N-methyl-2-pyrrolidone (64.00 g) was added. The reaction was carried out under nitrogen atmosphere at 130°C for 6 hours. After the reaction was completed, N-methyl-2-pyrrolidone (368.0 g) was added for dilution, and the solution after salt removal by filtration was added to methanol (19.4 kg). The precipitated solid was filtered and separated, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 120°C for 12 hours using a vacuum dryer to obtain a polymer (A3) having the structural unit represented by the following formula (3).

[0281] [Chemistry 20]

[0282]

[0283] [Synthesis Example 4]

[0284] 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 measured into a four-necked separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (64.00 g) was added. The reaction was carried out under nitrogen atmosphere at 130°C for 6 hours. After the reaction, bromopropylene (10.67 g) was added dropwise while the flask was cooled to 10°C, and the reaction was carried out at 70°C for 6 hours. The resulting reaction solution was diluted with N-methyl-2-pyrrolidone (368.0 g), and the salt was removed from the diluted solution by filtration. The resulting solution was then added to methanol (19.40 kg). The precipitated solid was filtered and separated, and the solid was washed with a small amount of methanol. After being filtered and separated again and recovered, it was dried in a vacuum dryer at 120°C for 12 hours under reduced pressure to obtain the polymer (A4) represented by the following formula (4).

[0285] [Chemistry 21]

[0286]

[0287] [Synthesis example 5]

[0288] Except for changing the raw materials and alkali metal compounds used to 2,2-bis(4-hydroxy-3-methylphenyl)propane (51.27 g), 4-isopropenylphenol (7.83 g), 4,6-dichloro-2-phenylpyrimidine (51.51 g), and potassium carbonate (35.93 g), the polymer (A5) represented by the following formula (5) was synthesized using the same process as in Synthesis Example 3.

[0289] [Chemistry 22]

[0290]

[0291] [Synthesis example 6]

[0292] 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 weighed into a four-necked separable flask including a stirrer, and N-methyl-2-pyrrolidone (42.50 g) was added. The mixture was reacted for 6 hours under nitrogen atmosphere and at 100°C.

[0293] After the reaction, 11.53 g of chloromethylstyrene was added dropwise to the flask while it was cooled to 10°C, and 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 for dilution. After removing the salt from the diluted solution by filtration, the obtained solution was added to methanol (6900 g). The precipitated solid was filtered and separated, washed with a small amount of methanol, filtered again and recovered, and then dried under reduced pressure at 60°C for 12 hours using a vacuum dryer to obtain the polymer (A6) represented by formula (6).

[0294] [Chemistry 23]

[0295]

[0296] [Synthesis Example 7]

[0297] Except for changing the raw materials, alkali metal compounds and organic solvents used to 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (33.85 g), 4,6-dichloro-2-phenylpyrimidine (16.66 g), m, p-(chloromethyl)styrene (8.680 g), potassium carbonate (18.66 g), and N-methyl-2-pyrrolidone (42.50 g), the polymer (A7) represented by the following formula (7) was synthesized using the same process as in Synthesis Example 6.

[0298] [Chemistry 24]

[0299]

[0300] [Synthesis example 8]

[0301] Except for changing the raw materials and alkali metal compounds used 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 polymer (A8) represented by the following formula (8) was synthesized using the same process as in Synthesis Example 3.

[0302] [Chemistry 25]

[0303]

[0304] [Synthesis Example 9]

[0305] In a four-necked separable flask equipped with a stirrer, 51.27 g of bis(3-methyl-4-hydroxyphenyl)propane, 21.23 g of α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 41.43 g of 4,6-dichloro-2-phenylpyrimidine, and 51.31 g of potassium carbonate were added, along with 113.92 g of N-methyl-2-pyrrolidone. The reaction was carried out under nitrogen atmosphere at 130°C for 6 hours. After the reaction, 38.55 g of m,p-(chloromethyl)styrene was added dropwise while the flask was cooled to 10°C, and the reaction was carried out at 65°C for 6 hours. The resulting reaction solution was diluted with 258.1 g of N-methyl-2-pyrrolidone, and the salt was removed from the diluted solution by filtration. The resulting solution was then added to methanol (4960 g). The precipitated solid was filtered and separated, washed with a small amount of methanol, filtered and separated again and recovered, and then dried in a vacuum dryer at 80°C for 12 hours under reduced pressure to obtain the polymer (A9) represented by the following formula (9).

[0306] [Chemistry 26]

[0307]

[0308] The formula indicates that polymer (A9) is a polymer having the structural unit described above. In the formula... Indicates any The polymer (A9) is bonded, with the group represented by formula (Y) at the polymer end. The same applies in the following synthetic examples.

[0309] [Synthesis Example 10]

[0310] Except for changing the raw materials and alkali metal compounds used 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 m,p-(chloromethyl)styrene (49.15 g), the polymer (A10) represented by the following formula (10) was synthesized using the same procedure as in Synthesis Example 9.

[0311] [Chemistry 27]

[0312]

[0313] [Synthesis Example 11]

[0314] Except for changing the raw materials and alkali metal compounds used 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 m,p-(chloromethyl)styrene (28.91 g), the polymer (A11) represented by the following formula (11) was synthesized using the same procedure as in Synthesis Example 9.

[0315] [Chemistry 28]

[0316]

[0317] [Synthesis Example 12]

[0318] Except for changing the raw materials and alkali metal compounds used to 2,2-bis(3-methyl-4-hydroxyphenyl)propane (64.09 g), 4,6-dichloro-2-phenylpyrimidine (31.08 g), 4,6-dichloropyrimidine (6.86 g), potassium carbonate (46.65 g), and m, p-(chloromethyl)styrene (22.01 g), the polymer (A12) represented by the following formula (12) was synthesized using the same process as in Synthesis Example 9.

[0319] [Chemistry 29]

[0320]

[0321] [Comparison using polymer (ca1)]

[0322] • End-modified polyphenylene ether (product name: Noryl SA9000 resin, manufactured by Saudi Basic Industries Corporation (Sabic), polymer represented by the following formula (ca1))

[0323] [Chemistry 30]

[0324]

[0325] [The Y does not contain an aromatic heterocyclic structure]

[0326] [Comparison using polymer (ca2)]

[0327] • Maleimide compound (product name: MBI-3000, manufactured by Designer Molecules)

[0328] [Comparison using polymer (ca3)]

[0329] The copolymer A described in Example 1 of International Publication No. 2018 / 181842, having structural units derived from monomers (i) to (iii) as shown in the following formulas, was confirmed to be obtained by the method described in the example, equivalent to that of Example 1. The obtained copolymer was designated as the comparative polymer (ca3).

[0330] [Chemistry 31]

[0331]

[0332] [Weight-average molecular weight (Mw) and number-average molecular weight (Mn)]

[0333] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymers (A1) to (A12) synthesized in Synthetic Examples 1 to 12, and the comparative polymers (ca1) to (ca3) were determined using a GPC apparatus (manufactured by Tosoh Corporation, model: "HLC-8320") under the following conditions. The results are shown in Table 1.

[0334] Column: A column consisting of "TSK gel α-M" manufactured by Tosoh Corporation and "TSK gelguard column α" manufactured by Tosoh Corporation.

[0335] Developing solvent: N-methyl-2-pyrrolidone

[0336] Column temperature: 40℃

[0337] Flow rate: 1.0 mL / min

[0338] Sample concentration: 0.75% by mass

[0339] Sample injection volume: 50 μL

[0340] Detector: Refractometer

[0341] Standard material: Monodisperse polystyrene

[0342] Concentration of the sample used for determination: 0.1% by mass

[0343] [Table 1]

[0344]

[0345] [Examples 1-28 and Comparative Examples 1-4]

[0346] The components listed in Table 2 were mixed using a mix rotor at the ratios (parts by mass) shown in the "Composition Ratio" column. For each test example, the concentration was adjusted using toluene to achieve the concentration of the solid components shown in Table 2, thereby preparing the resin composition. Furthermore, "-" in Table 2 indicates that the corresponding component is not included.

[0347] [Table 2]

[0348]

[0349] Furthermore, details of each component in Table 2 are as follows.

[0350] <Hydrogenated Styrene-based Thermoplastic Elastomers (B)>

[0351] Hereinafter, "styrene content" refers to the content of styrene-derived structural units in hydrogenated styrene-based thermoplastic elastomers (B).

[0352] (B1): Tuftec H1517 (hydrogenated styrene-butadiene copolymer resin, manufactured by Asahi Kasei Corporation, styrene content: 43% by mass)

[0353] (B2): Tuftec H1062 (hydrogenated styrene-butadiene copolymer resin, manufactured by Asahi Kasei Corporation, styrene content: 18% by mass)

[0354] (B3): Tuftec H1041 (hydrogenated styrene-butadiene copolymer resin, manufactured by Asahi Kasei Corporation, styrene content: 30% by mass)

[0355] (B4): Tuftec H1043 (hydrogenated styrene-butadiene copolymer resin, manufactured by Asahi Kasei Corporation, styrene content: 67% by mass)

[0356] (B5): Tuftec M1913 (Carboxylic acid modified hydrogenated styrene-butadiene copolymer resin, manufactured by Asahi Kasei Corporation, styrene content: 30% by mass)

[0357] (B6): SOE S1605 (hydrogenated styrene-butadiene copolymer resin, manufactured by Asahi Kasei Corporation, styrene content: 67% by mass)

[0358] (B7): Dynaron 8903P (hydrogenated styrene-butadiene copolymer resin, manufactured by ENEOS Materials Co., Ltd., styrene content: 35% by mass)

[0359] (B8): Kraton A1535 (hydrogenated styrene-butadiene copolymer resin, manufactured by Kraton Corporation, styrene content: 57% by mass)

[0360] (B9): Septon V9461 (hydrogenated styrene / 4-methylstyrene / isoprene / butadiene copolymer resin with styrene group, manufactured by Kuraray (stock), styrene content: 30% by mass)

[0361] (B10): Tuftec P1500 (selected hydrogenated styrene-butadiene copolymer resin, manufactured by Asahi Kasei Corporation, styrene content: 30% by mass)

[0362] (B11): Tuftec MP10 (amine-modified selective hydrogenated styrene-butadiene copolymer resin, manufactured by Asahi Kasei Corporation, styrene content: 30% by mass)

[0363] (B12): Dynaron 2324P (hydrogenated styrene-butadiene copolymer resin, manufactured by ENEOS Materials Co., Ltd., styrene content: 16% by mass)

[0364] (b1): Tufprene 912 (styrene-butadiene copolymer resin, manufactured by Asahi Kasei Corporation)

[0365] <Curing compound (C)>

[0366] (C1): DVB960 (manufactured by Nippon Steel Chemical & Materials Co., Ltd., divinylbenzene)

[0367] (C2): Bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane (Product name: BMI-70, manufactured by KI Chemical Co., Ltd.)

[0368] (C3): Triallyl isocyanurate (Product name: TAIC, manufactured by Mitsubishi Chemical Group, Inc.)

[0369] <Free Radical Polymerization Initiator (D)>

[0370] (D1): Dicumyl peroxide (manufactured by Nippon Oil Co., Ltd.)

[0371] <Preparation of the Hardened Film (P)>

[0372] The polymers synthesized in Synthesis Examples 1 to 12 or comparative polymers ca1 to ca3 were mixed with dicumyl peroxide at a mass ratio of 99.5:0.5 using a stirring rotor. The concentration was adjusted by using toluene to a solid content of 50% by mass, thereby preparing varnishes (resin compositions) (varnishes A1 to A12, varnishes a1 to a3).

[0373] The obtained varnish was applied to copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) using a Becker applicator (gap: 125 μm). The varnish was then dried at 100°C for 5 minutes, followed by drying at 140°C for 5 minutes, and finally calcined at 200°C for 2 hours under nitrogen. The resulting hardened film with the copper foil was then immersed in a 40% (w / w) ferric chloride solution. After removing the copper foil, the film was washed with water and dried in an oven at 80°C for 30 minutes, thus producing a hardened film (P) with a thickness of 50 μm.

[0374] <Preparation of Hardened Film (C)>

[0375] The compositions obtained in the examples and comparative examples were applied to copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) using a Becker applicator (gap: 125 μm). The foil was dried at 100°C for 5 minutes, then dried at 140°C for 5 minutes, and finally calcined at 200°C for 2 hours under nitrogen. The resulting hardened film with copper foil was immersed in a 40% (w / w) ferric chloride solution. After removing the copper foil, the film was washed with water and dried in an oven at 80°C for 30 minutes, thereby producing a hardened film (C) with a thickness of 50 μm.

[0376] <Dielectric loss tangent (Df)>

[0377] Test pieces (width: 6 cm × length: 6 cm) were cut from the prepared hardened films (P) and (C), and the dielectric loss tangent (Df) of the test pieces at 10 GHz was determined using the cavity resonator method (AET (strand) manufacturing, dielectric constant measurement system TE mode resonator).

[0378] <Electrical characteristics (ΔDf)>

[0379] The following criteria were used to evaluate ΔDf, expressed by the following formula, when the Df of the hardened film (C) is set as Df(C) and the Df of the hardened film (P) is set as Df(P). The results are shown in Table 3. Furthermore, Df(P) in the following formula refers to the Df of the hardened film (P) obtained using the same polymer as the polymer in the compositions obtained in each test example that is used to determine Df(C) as the raw material for the hardened film (C). For example, in the case where Df(C) in the following formula refers to the Df of the hardened film (C) obtained using the composition obtained in Example 1, Df(P) in the following formula refers to the Df of the hardened film (P) obtained using the polymer (A1) obtained in Synthesis Example 1.

[0380] ΔDf = Df(P) - Df(C)

[0381] -Evaluation Criteria-

[0382] A: ΔDf > 0.0003

[0383] B: 0 ≦ ΔDf ≦ 0.0003

[0384] C: ΔDf < 0

[0385] <Heat resistance (ΔDf150)>

[0386] For the film obtained by heating the hardened film (C) in an oven at 150°C (in air) for 500 hours, the dielectric loss tangent was measured before and after the heat treatment, using the same method as for measuring the dielectric loss tangent (Df). The dielectric loss tangent before heat treatment was defined as Df(t0), and the dielectric loss tangent after heat treatment was defined as Df(t1). The heat resistance (ΔDf150) was calculated based on the change in dielectric loss tangent before and after heat treatment, using the following formula, and evaluated according to the following criteria. The results are shown in Table 3.

[0387] ΔDf150 = Df(t1) - Df(t0)

[0388] -Evaluation Criteria-

[0389] A: ΔDf150 < 0.0010

[0390] B: 0.0010 ≦ ΔDf150 < 0.0100

[0391] C: 0.0100 ≦ ΔDf150 < 0.0200

[0392] [Table 3]

[0393]

[0394] As shown in Table 3, it can be seen that the hardened films of Examples 1 to 28 have lower dielectric loss tangent and better heat resistance compared with the hardened films of Comparative Examples 1 to 4.

[0395] [Examples 29-32]

[0396] A resin composition was prepared by mixing polymer (A), hydrogenated styrene-based thermoplastic elastomer (B), free radical polymerization initiator (D), and filler (E) in the proportions (parts by mass) listed in Table 4 using a stirring rotor, and adjusting the concentration of toluene to 60% by mass of the solid components.

[0397] [Table 4]

[0398]

[0399] In addition, details of the packing material (E) in Table 4 are as follows.

[0400] <Packaging (E)>

[0401] (E1): Molten spherical silica, GT grade (manufactured by Denka (Denka) Co., Ltd., average particle size: 3 μm)

[0402] <Preparation of Hardened Film>

[0403] Except for using the compositions obtained in Examples 29-32, a hardened film with a thickness of 50 μm was prepared in the same manner as in Example 1.

[0404] <Dielectric loss tangent>

[0405] Test pieces (width: 6 cm × length: 6 cm) were cut from the fabricated hardened film. The dielectric loss tangent at 10 GHz was measured using the cavity resonator method (AET (strand) fabrication, dielectric constant measurement system TE mode resonator), and evaluated according to the following evaluation criteria. The results are shown in Table 5. A low dielectric loss tangent can be considered when the following evaluation criteria are "A" or "B".

[0406] -Evaluation Criteria-

[0407] The case where the dielectric loss tangent is less than 0.0015 is designated as "A", the case where the dielectric loss tangent is greater than or equal to 0.0015 but less than 0.0025 is designated as "B", and the case where the dielectric loss tangent is greater than or equal to 0.0025 is designated as "C".

[0408] <Glass transition temperature (Tg)>

[0409] Test pieces (width: 3 mm × length: 1 cm) were cut from the prepared hardened film. Using a dynamic viscoelasticity measuring device (Seiko Instruments, Inc., Model: EXSTAR 4000), the dynamic viscoelasticity was measured at a frequency of 1 Hz when the temperature was increased from 50°C to 300°C at a heating rate of 10°C / min. The tanδ value at this point was set as the glass transition temperature (Tg). Furthermore, when more than two tanδ values ​​were present, the lowest value was used as Tg. The obtained Tg was evaluated according to the following evaluation criteria. The results are shown in Table 5. When the following evaluation criteria are "A" or "B", the heat resistance can be considered excellent.

[0410] -Evaluation Criteria-

[0411] The case where Tg exceeds 180℃ is designated as "A", the case where Tg is above 150℃ but below 180℃ is designated as "B", and the case where Tg is below 150℃ is designated as "C".

[0412] <Coefficient of Thermal Expansion (CTE)>

[0413] Test pieces (width: 3 mm × length: 2 cm) were cut from the prepared hardened film, and the coefficient of linear expansion (CTE) of the test pieces was determined using an SSC-5200 TMA measuring apparatus (manufactured by Seiko Instruments). The test pieces were heated from room temperature to 260°C at a rate of 5°C / min, and then heated at 260°C for 10 minutes to remove residual solvent and shaping strain. Afterwards, the pieces were cooled to 40°C, stabilized at this temperature for 30 minutes, and then heated from 40°C to 260°C at a rate of 5°C / min, and the temperature was scanned. The CTE was calculated based on the dimensional changes from 80°C to 120°C. The obtained CTE was evaluated according to the following evaluation criteria. The results are shown in Table 5. A low CTE can be considered when the following evaluation criteria are "A" or "B".

[0414] -Evaluation Criteria-

[0415] The case with CTE less than 25 ppm / K is designated as "A", the case with CTE more than 25 ppm / K but less than 50 ppm / K is designated as "B", and the case with CTE more than 50 ppm / K is designated as "C".

[0416] <Peel strength>

[0417] The compositions obtained in Examples 29-32 were applied to copper foil (model: CF-V9S-SV, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.), heated at 100°C for 5 minutes, and dried at 130°C for 5 minutes to form a coating film. Copper foil (model: CF-V9S-SV, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) was overlapped on the obtained coating film, vacuum pressed at 150°C for 5 minutes, and then calcined at 200°C for 2 hours under nitrogen to produce a hardened film with copper foil (copper foil thickness: 18 μm, hardened film thickness: 10 μm), which was used as a peel strength sample.

[0418] A test piece (width: 5 mm × length: 10 cm) was cut from the prepared peel strength sample. Using a universal testing machine (Instron 5567), the test piece (a portion of the copper foil and hardened film stacked in the peel strength sample) was stretched at 90 degrees at 500 mm / min. The peel strength was determined according to IPC-TM-650 (Test Method Manual) 2.4.9, and evaluated according to the following evaluation criteria. The results are shown in Table 5. When the following evaluation criteria are "A" or "B", the adhesion to the copper foil can be considered excellent.

[0419] -Evaluation Criteria-

[0420] Cases with a peel strength of 0.7 N / mm or higher are designated as "A", cases with a peel strength of 0.5 N / mm or higher but less than 0.7 N / mm are designated as "B", and cases with a peel strength of less than 0.5 N / mm are designated as "C".

[0421] [Table 5]

[0422]

[0423] As shown in Table 5, it can be seen that the hardened films obtained in Examples 29 to 32 have a good and excellent balance of low dielectric loss tangent, heat resistance, low coefficient of linear expansion, and adhesion to metal layers (especially copper layers).

[0424] [Examples 33-41 and Comparative Examples 5 and 6]

[0425] The components listed in Table 6 were mixed using a stirring rotor at the ratios (parts by mass) shown in the "Composition Ratio" column. For each test example, the concentration was adjusted using toluene to achieve the concentration of the solid components shown in Table 6, thereby preparing the resin composition. Furthermore, "-" in Table 6 indicates that the corresponding component is not included.

[0426] [Table 6]

[0427]

[0428] <Preparation of Hardened Film>

[0429] Using a Becker applicator (gap: 125 μm), the compositions obtained in Examples 33-41 and Comparative Examples 5 and 6 were applied onto copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metals, Inc.). The coating was heated at 100°C for 5 minutes and then dried at 140°C for 5 minutes to form a film. Copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metals, Inc.) was then overlapped on the obtained coating. The film was vacuum pressed at 160°C for 10 minutes and then calcined at 200°C under nitrogen for 2 hours, thereby producing a hardened film with copper foil (copper foil: 18 μm, hardened film: 100 ± 25 μm). The prepared hardened film with copper foil was immersed in a 40% ferric chloride solution to remove the copper foil. After washing with water, the film was dried in an oven at 80°C for 30 minutes, thereby producing a hardened film with a thickness of 100 ± 25 μm.

[0430] <Dielectric loss tangent (Df)>

[0431] Test pieces (width: 6 cm × length: 6 cm) were cut from the prepared hardened film. The dielectric loss tangent (Df) of the test pieces at 10 GHz was measured using the cavity resonator method (AET (strand) fabrication, dielectric constant measurement system TE mode resonator), and evaluated according to the following criteria. The results are shown in Table 7. Under the evaluation criteria of “3” to “5”, the dielectric loss tangent can be considered low, which is within the practically permissible range.

[0432] -Evaluation Criteria-

[0433] 3: 0.0020 ≦ Df < 0.0025

[0434] 4: 0.0015 ≦ Df < 0.0020

[0435] 5: Df < 0.0015

[0436] <Heat resistance (ΔDf150)>

[0437] The obtained hardened film underwent the same heat treatment and dielectric loss tangent measurement as in Example 1 for evaluating heat resistance (ΔDf150). The dielectric loss tangent before heat treatment was set as Df(t0), and the dielectric loss tangent after heat treatment was set as Df(t1). The heat resistance (ΔDf150) was calculated based on the change in dielectric loss tangent before and after heat treatment, using the following formula, and evaluated according to the following criteria. The results are shown in Table 7.

[0438] ΔDf150 = Df(t1) - Df(t0)

[0439] -Evaluation Criteria-

[0440] 3: 0.0100 ≦ ΔDf150 < 0.0200

[0441] 4: 0.0010 ≦ ΔDf150 < 0.0100

[0442] 5: ΔDf150 < 0.0010

[0443] <Glass transition temperature (Tg)>

[0444] Test pieces (width: 3 mm × length: 1 cm) were cut from the prepared hardened film. Dynamic viscoelasticity was measured using a dynamic viscoelasticity measuring device (Seiko Instruments, Inc., Model: EXSTAR 4000) at a frequency of 1 Hz when the temperature was increased from 50°C to 300°C at a heating rate of 10°C / min. The tanδ value at this point was set as the glass transition temperature (Tg), and the results were evaluated using the following criteria. The results are shown in Table 7. Furthermore, when more than two tanδ values ​​were present, the lowest value was set as Tg.

[0445] Furthermore, under the evaluation criteria of "4" and "5" below, it can be said that the heat resistance is excellent.

[0446] -Evaluation Criteria-

[0447] 3: Tg≦150℃

[0448] 4: 150℃<Tg≦180℃

[0449] 5: 180℃ < Tg

[0450] <Elongation>

[0451] Using a Becker applicator (gap: 125 μm), the compositions obtained in Examples 33-41 and Comparative Examples 5 and 6 were applied onto copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metals, Inc.). The coating was heated at 100°C for 5 minutes and then dried at 140°C for 5 minutes to form a coating film. Copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metals, Inc.) was overlapped on the obtained coating film, and the film was vacuum pressed at 160°C for 10 minutes, followed by calcination at 200°C under nitrogen for 2 hours, thereby producing a hardened film with copper foil (copper foil: 18 μm, hardened film: 100 ± 25 μm). The prepared hardened film with copper foil was immersed in a 40% ferric chloride solution to remove the copper foil, washed with water, and dried at 80°C for 30 minutes to produce a film for elongation measurement.

[0452] The elongation of the prepared elongation measurement film was measured using a TMA measuring apparatus (manufactured by Seiko Instruments, SSC-5200). The film was heated from room temperature to 300°C at a rate of 5°C / min, and the elongation at the initial time point (room temperature) to 260°C was calculated. The results were evaluated according to the following criteria. The results are shown in Table 7. Furthermore, evaluation criteria “3” to “5” indicate a practically acceptable range, while evaluation criteria “4” and “5” indicate a low elongation.

[0453] Elongation (%) = (Length of test piece at 260℃ - Length of test piece at initial (room temperature)) / Length of test piece at initial (room temperature) × 100

[0454] -Evaluation Criteria-

[0455] 2: 30% < elongation

[0456] 3: 15% < elongation ≤ 30%

[0457] 4: 7% < elongation ≤ 15%

[0458] 5: Elongation ≤ 7%

[0459] <Coefficient of thermal expansion (α1)>

[0460] Test pieces (width: 0.3 cm × length: 2 cm) were cut from the prepared hardened film to serve as evaluation films. The elongation of the evaluation films was measured using a TMA measuring apparatus (manufactured by Seiko Instruments, SSC-5200). The evaluation films were heated from room temperature to 200°C–250°C at a rate of 5°C / min, and then cooled to 0°C at a rate of 5°C / min. The coefficient of thermal expansion [α1 (ppm)] at 80°C–120°C during cooling was calculated, and the films were evaluated according to the following evaluation criteria. The results are shown in Table 7. Furthermore, under evaluation criteria “4” and “5”, the coefficient of thermal expansion is considered low.

[0461] -Evaluation Criteria-

[0462] 2:170 ppm<α1

[0463] 3: 150 ppm < α1 ≤ 170 ppm

[0464] 4: 130 ppm < α1 ≤ 150 ppm

[0465] 5: α1≦130 ppm

[0466] <Elongation at break: energy absorbed>

[0467] The compositions obtained in Examples 33-41 and Comparative Examples 5 and 6 were applied to copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metals, Inc.) using a Becker applicator (gap: 125 μm). The coating was heated at 100°C for 5 minutes and then dried at 140°C for 5 minutes to form a coating film. Copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metals, Inc.) was then overlapped on the obtained coating film. The film was vacuum pressed at 160°C for 10 minutes and then calcined at 200°C under nitrogen for 2 hours, thereby producing a hardened film with copper foil (copper foil: 18 μm, hardened film: 100 ± 25 μm). The prepared hardened film with copper foil was immersed in a 40% ferric chloride solution to remove the copper foil. After washing with water, the film was dried at 80°C for 30 minutes to produce a membrane with a thickness of 100 ± 25 μm for energy absorption measurement.

[0468] The stress-strain curves of the fabricated absorbance measurement membrane were determined using an EZ-LX type tensile testing apparatus (manufactured by Shimadzu Corporation). The absorbed energy (mJ) was calculated from the area of ​​the obtained stress-strain curves and evaluated according to the following criteria. The results are shown in Table 7. Furthermore, evaluation criteria “3” to “5” below indicate a practically acceptable range, while evaluation criteria “4” and “5” below indicate sufficiently high tensile elongation. Membranes with high tensile elongation have high absorbance and excellent tensile properties.

[0469] -Evaluation Criteria-

[0470] 2:5 mJ ≤ absorbed energy < 10 mJ

[0471] 3: 10 mJ ≤ absorbed energy < 15 mJ

[0472] 4:15 mJ ≤ absorbed energy < 20 mJ

[0473] 5:20 mJ≦Absorbed Energy

[0474] [Table 7]

[0475]

[0476] As shown in Table 7, it can be seen that the hardened films of Examples 33 to 41 have lower dielectric loss tangent, lower elongation and lower coefficient of thermal expansion, and better and more balanced heat resistance and tensile properties compared with the hardened films of Comparative Examples 5 to 6.

Claims

1. A resin composition comprising: a polymer (A) having a structural unit represented by the following formula (a1-1), and... Hydrogenated styrene-based thermoplastic elastomers (B); [Chemistry 1] In equation (a1-1), R a1 R is the divalent base represented by the following equation (a2). a2 It is an unsubstituted or substituted divalent aromatic heterocyclic group, wherein, R a1 With R a2 different; [Chemistry 2] In equation (a2), Ar a1 and Ar a2 Each is an independent unsubstituted or substituted aromatic hydrocarbon group, where L is a single bond, -O-, -S-, or -N(R) 8 -, -C(O)-, -C(O)-O-, -C(O)-NH-, -S(O)-, -S(O)2-, -P(O)- or divalent organic groups, wherein R 8 It consists of a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halide hydrocarbon group having 1 to 20 carbon atoms, where y is an integer from 0 to 5. When y is 2 or higher, multiple Ar atoms are present. a1 And L are the same or different, R a6 and R a7 Each can be a single bond, a methylene group, or an alkylene group having 2 to 4 carbon atoms.

2. The resin composition according to claim 1, wherein, R in the above formula (a1-1) a2 It is a divalent base selected from one of the following formulas (1-1), (1-2), and (1-3); [Chemistry 3] In equations (1-1) to (1-3), n is an independent integer from 0 to 2. When n is 1, R 1 Each of the two R's is an independent monovalent basis. When n = 2, the two R's... 1 Each is independently a monovalent base, either the same or different, or two R... 1 Together with these bonded carbon atoms, they form a ring structure with 5 to 10 ring elements. The monovalent group is a halogen atom, a monovalent hydrocarbon group with 1 to 20 carbon atoms, a monovalent halide hydrocarbon group with 1 to 20 carbon atoms, a nitro group, a cyano group, or a salt of a primary amino to a tertiary amino group or a primary amino to a tertiary amino group.

3. The resin composition according to claim 1, wherein, The hydrogenated styrene-based thermoplastic elastomer (B) is selected from at least one group consisting of hydrogenated styrene-butadiene copolymer, hydrogenated styrene-butadiene-styrene block copolymer, hydrogenated styrene-isoprene block copolymer, and hydrogenated styrene-ethylene-butene-styrene block copolymer.

4. The resin composition according to claim 1, wherein, The hydrogenated styrene-based thermoplastic elastomer (B) contains styrene-derived structural units in a proportion of 5% to 90% by mass.

5. The resin composition according to claim 1, further comprising a curing compound (C) other than the polymer (A) and the elastomer (B).

6. A cured product, which is a cured product of the resin composition as claimed in claim 1.

7. An electronic component comprising the hardened material as described in claim 6.

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