Polymer, composition, cured product, laminate, and electronic component

Abstract

One embodiment of the present invention relates to a polymer, a composition, a cured product, a laminate, and an electronic component. The polymer has a repeating structural unit represented by formula (1). [R11 represents a divalent substituted or unsubstituted nitrogen-containing heteroaromatic ring, R12 independently represents a divalent substituted or unsubstituted aromatic hydrocarbon group, R13 represents a C1-20 hydrocarbon group to which at least one group represented by formula (a1) is bonded in addition to two R12 groups, X1 independently represents-O-,-S-or-N (R14)-, * represents a bond to R13, and X represents a hydrogen atom or a hydrogen atom, and X represents a hydrogen atom or a hydrogen atom. And * * represents a bond to another structural unit in the polymer (A). ] # imgabs0 #

Description

Technical Field

[0001] One embodiment of the present invention relates to a polymer, a composition, a cured product, a laminate, or an electronic component. Background Art

[0002] In the field of information communication in recent years, in order to achieve high-speed and high-capacity transmission, the high-frequency of the signal band of information communication equipment is constantly developed. In order to cope with the high frequency, the requirements for low dielectric constant / low dielectric loss tangent materials are constantly improved for the insulators used in printed wiring boards or semiconductor packages. In addition, since the insulator is connected to metal wiring such as copper, it is expected that the expansion (linear expansion coefficient) of the insulator material caused by the heat during conduction is close to the metal species of the wiring, etc.

[0003] As materials for coping with such high frequency, polyolefin resins, styrene resins, fluororesins, polyphenylene ether resins, vinyl benzyl ether resins, or compositions using polyphenylene ether resins have been proposed (Patent Documents 1 to 6).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Laid-Open 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] Problems to be solved by the invention

[0013] However, although the conventional materials such as the compositions described in Patent Documents 1 to 6 are excellent to a certain extent in terms of low dielectric constant and low dielectric loss tangent, they do not necessarily satisfy all the requirements for the properties required of electronic materials such as heat resistance and adhesion.

[0014] For example, although the composition or fluororesin using polyphenylene ether resin has low dielectric constant / low dielectric loss tangent or excellent heat resistance, it is not sufficient for the adhesion of low roughening copper foil, and the difference with the linear expansion coefficient of copper is large. In addition, sometimes when forming copper wiring, it is caused by the difference with the linear expansion coefficient of copper, causing disconnection or poor connection etc. Therefore, in order to reduce the difference of the linear expansion coefficient, usually there is a method for using inorganic filler, but if the addition is too much, there is a problem of reducing the adhesion with copper wiring. In this way, the composition or fluororesin using polyphenylene ether resin is difficult to obtain the balance of various physical properties. In addition, the composition recorded in patent documentation 6 has room for improvement in terms of low dielectric properties.

[0015] One of the objects of the present invention is to provide a polymer having a low dielectric constant and a low dielectric loss tangent, and to provide a composition and a laminate having a low dielectric constant and a low dielectric loss tangent and having a good balance and excellent curability, adhesion, heat resistance and linear expansion coefficient.

[0016] Technical means of solving problems

[0017] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by the following structural examples. The structural examples of the present invention are as follows. [1]

[0019] A polymer (A) having a repeating structural unit represented by the following formula (1).

[0020] [Chemistry 1]

[0021]

[0022] [In the formula (1),

[0023] R 11 represents a divalent substituted or unsubstituted nitrogen-containing heteroaromatic ring,

[0024] R 12 independently represent a divalent substituted or unsubstituted aromatic hydrocarbon group,

[0025] R 13 Indicates that the two R 12 In addition, at least one hydrocarbon group having 1 to 20 carbon atoms is bonded to a group represented by the following formula (a1),

[0026] X 1 independently represents -O-, -S- or -N(R 14 )-,

[0027] R 14is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group in which a part of the hydrocarbon group or halogenated hydrocarbon group is substituted with at least one selected from an oxygen atom and a sulfur atom]

[0028] [Chemistry 2]

[0029] *-R 12 -X 1 -** (a1)

[0030] [In the above formula (a1),

[0031] * indicates that for the R 13 The key,

[0032] ** represents the bonding bond with other structural units in the polymer (A),

[0033] R 12 and X 1 Respectively with R in the formula (1) 12 and X 1 for the same meaning] [2]

[0035] The polymer (A) according to the item [1] further has a repeating structural unit represented by the following formula (2).

[0036] [Chemistry 3]

[0037]

[0038] [In the above formula (2),

[0039] R 21 represents a divalent substituted or unsubstituted nitrogen-containing heteroaromatic ring,

[0040] R 22 represents a divalent group containing a substituted or unsubstituted aromatic hydrocarbon group in the main chain,

[0041] X 2 independently represents -O-, -S- or -N(R 24 )-,

[0042] R 24 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group in which a part of the hydrocarbon group or halogenated hydrocarbon group is substituted with at least one selected from an oxygen atom and a sulfur atom] [3]

[0044] The polymer (A) according to item [1] or [2] has a group Y represented by the following formula (y) at the terminal.

[0045] [Chemistry 4]

[0046] -Y (y)

[0047] [In the above formula (y), Y is a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic ring] [4]

[0049] The polymer (A) according to any one of items [1] to [3], wherein the repeating structural unit represented by the formula (1) is contained in the range of 5 mol% to 95 mol%, when all the structural units contained in the polymer (A) are taken as 100 mol%. [5]

[0051] The polymer (A) according to any one of items [1] to [4], wherein -R 12 - are independently a structure represented by the following formula (5).

[0052] [Chemistry 5]

[0053]

[0054] [In the above formula (5),

[0055] * indicates that for the R 13 The key,

[0056] *** indicates that the X 1 The bond of

[0057] R 51 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, n 52 Integer from 0 to 4, n 53 Integer from 0 to 2] [6]

[0059] The polymer (A) according to Item [5], wherein the structure represented by the formula (5) is the following formula (5-1) or the following formula (5-2).

[0060] [Chemistry 6]

[0061]

[0062] [In the above formula (5-1) and formula (5-2),

[0063] * indicates that for the R 13The key,

[0064] *** indicates that the X 1 The bond of

[0065] R 51 and n 53 With R in formula (5) 51 and n 53 For the same meaning,

[0066] n 54 Integer from 0 to 3, n 55 represents an integer from 0 to 2,

[0067] R 52 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms] [7]

[0069] A composition comprising the polymer (A) according to any one of items [1] to [6] and a curable compound (B) other than the polymer (A). [8]

[0071] The composition according to item [7], wherein the curable compound (B) comprises at least one selected from the group consisting of vinyl compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, thiol compounds, oxazine compounds, cyanate compounds, epoxy compounds, oxetane compounds, hydroxymethyl compounds, benzocyclobutene compounds, propargyl compounds and silane compounds. [9]

[0073] The composition according to item [7] or [8], further comprising at least one selected from the group consisting of hindered phenol compounds, phosphorus compounds, sulfur compounds, metal compounds, and hindered amine compounds.

[10]

[0075] A composition comprising a polymer (A2) having a repeating structural unit represented by the following formula (3) and a repeating structural unit represented by the following formula (4), and a curable compound (B2) other than the polymer (A2).

[0076] [Chemistry 7]

[0077]

[0078] [In the formula (3),

[0079] R 31 represents a divalent organic group having 3 to 10 carbon atoms,

[0080] R 32 independently represent a divalent substituted or unsubstituted aromatic hydrocarbon group,

[0081] R 33 Indicates that there are two R bonds 12 a hydrocarbon group having 1 to 20 carbon atoms and at least one group represented by the following formula (a2)]

[0082] [Chemistry 8]

[0083] *-R 32 -O-** (a2) [In the formula (a2),

[0084] * indicates that for the R 33 The key,

[0085] ** represents the bonding bond with other structural units in the polymer (A2),

[0086] R 32 With R in the formula (3) 32 for the same meaning]

[0087] [Chemistry 9]

[0088]

[0089] [In the above formula (4),

[0090] R 41 represents a divalent organic group having 3 to 10 carbon atoms,

[0091] R 42 represents a divalent group containing a substituted or unsubstituted aromatic hydrocarbon group in the main chain, wherein the oxygen atom in the formula is directly bonded to the aromatic hydrocarbon group]

[11]

[0093] The composition according to Item

[10] , wherein the polymer (A2) has a group Y represented by the following formula (y) at a terminal.

[0094] [Chemistry 10]

[0095] -Y (y)

[0096] [In the above formula (y), Y is a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic ring]

[12]

[0098] The composition according to item

[10] or item

[11] , wherein the curable compound (B2) comprises at least one selected from the group consisting of vinyl compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, thiol compounds, oxazine compounds, cyanate compounds, epoxy compounds, oxetane compounds, methylol compounds, benzocyclobutene compounds, propargyl compounds and silane compounds.

[13]

[0100] The composition according to any one of Items

[10] to

[12] , further comprising an antioxidant.

[14]

[0102] A hardened product, which is a hardened body of the composition according to any one of Items [7] to

[13] .

[15]

[0104] A laminate having a substrate and a cured layer formed using the composition according to any one of Items [7] to

[13] .

[16]

[0106] An electronic component comprising the hardened material according to item

[14] .

[17]

[0108] An electronic component comprising the laminated body according to Item

[15] .

[0109] Effects of the Invention

[0110] According to one embodiment of the present invention, a polymer having a low dielectric constant and a low dielectric loss tangent can be provided, and a composition and a laminate having a low dielectric constant and a low dielectric loss tangent and having a good balance of curability, adhesion, heat resistance and linear expansion coefficient can be obtained. DETAILED DESCRIPTION

[0111] Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, the present invention is not limited to the embodiments described below, and it should be understood that various modifications implemented within the scope of the present invention are also included.

[0112] In the present specification, a numerical range described using “to” means that the numerical values ​​described before and after “to” are included as the lower limit and the upper limit.

[0113] Hereinafter, a polymer, a composition, a cured product, a laminate, or an electronic component according to an embodiment of the present invention will be described in detail.

[0114] "polymer"

[0115] The polymer according to one embodiment of the present invention (hereinafter also referred to as “polymer (A)”) has a repeating structural unit represented by the following formula (1) (hereinafter also referred to as “repeating unit (1)”).

[0116] [Chemistry 11]

[0117]

[0118] [In the formula (1),

[0119] R 11 represents a divalent substituted or unsubstituted nitrogen-containing heteroaromatic ring,

[0120] R 12 independently represent a divalent substituted or unsubstituted aromatic hydrocarbon group,

[0121] R 13 Indicates that the two R 12 In addition, at least one hydrocarbon group having 1 to 20 carbon atoms is bonded to a group represented by the following formula (a1),

[0122] X 1 independently represents -O-, -S- or -N(R 14 )-,

[0123] R 14 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group in which a part of the hydrocarbon group or halogenated hydrocarbon group is substituted with at least one selected from an oxygen atom and a sulfur atom]

[0124] [Chemistry 12]

[0125] *-R 12 -X 1 -** (a1)

[0126] [In the above formula (a1),

[0127] * indicates that for the R 13 The key,

[0128] ** represents the bonding bond with other structural units in the polymer (A),

[0129] R 12 and X 1 Respectively with R in the formula (1) 12 and X 1 for the same meaning]

[0130] In the formula (1), R 11represents a divalent substituted or unsubstituted nitrogen-containing heteroaromatic ring. Specific examples of the nitrogen-containing heteroaromatic ring include a pyrrole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a phthalazine ring, a quinazoline ring, a naphthyridine ring, a carbazole ring, an acridine ring, and a phenazine ring.

[0131] The nitrogen-containing heteroaromatic ring is preferably a pyrimidine ring from the viewpoints of being able to synthesize the polymer (A) with good polymerization reactivity and being able to easily obtain a polymer (A) having excellent solubility in various organic solvents.

[0132] Two bonds to the nitrogen-containing heteroaromatic ring (bonded to X 1 The position of the bonding bond (eg, on) is not particularly limited, but is preferably the meta position from the viewpoint of being able to synthesize the polymer (A) with good polymerization reactivity.

[0133] Examples of the substituent in the nitrogen-containing heteroaromatic ring include a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a group in which a part of these hydrocarbon groups or halogenated hydrocarbon groups is substituted with at least one selected from an oxygen atom and a sulfur atom, a nitro group, a cyano group, an amino group, and a salt of an amino group.

[0134] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0135] Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group.

[0136] Examples of the chain hydrocarbon group 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.

[0137] Examples of the monovalent alicyclic hydrocarbon group 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.

[0138] Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthracenyl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, and naphthylmethyl.

[0139] Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which a part or all of the hydrogen atoms of the monovalent hydrocarbon group having 1 to 20 carbon atoms are substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0140] Examples of the group in which a portion of the monovalent hydrocarbon group having 1 to 20 carbon atoms or the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms is substituted with at least one selected from an oxygen atom and a sulfur atom include, specifically, a group in which a portion of the hydrocarbon group or the halogenated hydrocarbon group is substituted with -O-, -S-, an ester group or a sulfonyl group.

[0141] The amino group is not particularly limited, and may be a primary amino group (—NH 2 ), a secondary amino group (—NHR), or a tertiary amino group (—NR 2 ).

[0142] The substituent (R) in the secondary amino group and the tertiary amino group is not particularly limited, and examples thereof include the monovalent hydrocarbon groups having 1 to 20 carbon atoms.

[0143] The anion constituting the anion site in the salt of the amino group is not particularly limited, and examples thereof include Cl - and the like.

[0144] As the substituent in the nitrogen-containing heteroaromatic ring, from the viewpoint of synthesizing the polymer (A) with good polymerization reactivity and improving the solubility of the monomer serving as the raw material of the polymer (A), preferably, it is a halogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 6 carbon atoms, a nitro group, a cyano group, an amino group or a salt of an amino group, and more preferably, it is a fluorine atom, a chlorine atom, a methyl group, a nitro group, a cyano group, a tert-butyl group, a phenyl group or a primary amino group.

[0145] As becomes the R 11Examples of monomers of raw materials for the part include 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-di 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; 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. In addition, these monomers may be used alone or in combination of two or more.

[0146] In the formula (1) and formula (a1), R 12 and independently represent a divalent substituted or unsubstituted aromatic hydrocarbon group.

[0147] Examples of the divalent unsubstituted aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as a phenylene group, a naphthylene group, and an anthracene group.

[0148] The substituent in the divalent substituted aromatic hydrocarbon group is not particularly limited, and examples thereof include an allyl group, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxyl group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a hydroxyl group, a primary to tertiary amino group, a salt of a carboxyl group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxyl group, or a salt of a primary to tertiary amino group.

[0149] From the viewpoint of increasing the glass transition temperature (Tg) of the polymer (A), -R in the formula (1) and the formula (a1) 12 - is preferably independently a structure represented by the following formula (5).

[0150] [Chemistry 13]

[0151]

[0152] [In the above formula (5),

[0153] * indicates that for the R 13 The key,

[0154] *** indicates that the X 1 The bond of

[0155] R 51 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, n 52 Integer from 0 to 4, n 53 Integer from 0 to 2]

[0156] From the viewpoint of improving heat resistance (Tg of polymer (A)) while maintaining a low dielectric constant and a low dielectric loss tangent, the structure represented by formula (5) is preferably the following formula (5-1) or the following formula (5-2).

[0157] [Chemistry 14]

[0158]

[0159] [In the above formula (5-1) and formula (5-2),

[0160] * indicates that for the R 13 The key,

[0161] *** indicates that the X 1 The bond of

[0162] R 51 and n 53 With R in formula (5) 51 and n 53 For the same meaning,

[0163] n 54 Integer from 0 to 3, n 55 represents an integer from 0 to 2,

[0164] R 52 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms]

[0165] As the R 51 and R 52 Examples of the alkyl group having 1 to 10 carbon atoms in the group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group.

[0166] As the R 51and R 52 Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and an octyloxy group.

[0167] As the R 51 and R 52 Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0168] The 52 represents an integer of 0 to 4, preferably an integer of 1 to 3. 53 represents an integer of 0 to 2, preferably 0 or 1. 54 represents an integer of 0 to 3, preferably an integer of 0 to 2, wherein n 55 It represents an integer of 0 to 2, and is preferably 0 or 1.

[0169] In the formula (1), R 13 Indicates that except for the two R 12 In addition, at least one hydrocarbon group having 1 to 20 carbon atoms and the group represented by the formula (a1) is bonded. The structure of the hydrocarbon group is not particularly limited, and may include an aromatic ring or an alicyclic ring.

[0170] In the R 13 In the case where the portion obtained by removing the group represented by the formula (a1) is defined as Z, -R in the repeating unit (1) 12 -R 13 -R 12 - can be represented by the following formula (1'): That is, the repeating unit (1) has a branched structure.

[0171] Furthermore, the branched structure is preferably formed by the tertiary carbon or quaternary carbon in the Z.

[0172] [Chemistry 15]

[0173]

[0174] [In the formula (1'), n 1 Indicates an integer greater than 1]

[0175] As the-R 12 -R 13 -R 12 - The raw material monomer of the partial structure represented by - includes, for example, a compound represented by the following formula (6).

[0176] [Chemistry 16]

[0177]

[0178] [In the above formula (6),

[0179] Z represents n having 1 to 20 carbon atoms 61 Valence hydrocarbon group,

[0180] R 61 independently represent 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,

[0181] n 61 represents an integer greater than or equal to 2 and less than or equal to 4,

[0182] n 62 independently represents an integer from 1 to 5, n 63 Integer from 0 to 4, 1 ≦ n 62 +n 63 ≦5]

[0183] The compound represented by the formula (6) is preferably a compound represented by the following formula (6-1) or the following formula (6-2).

[0184] [Chemistry 17]

[0185]

[0186] [In the above formula (6-1) and formula (6-2), Z, R 61 and n 61 With Z, R in the formula (6) 61 and n 61 for the same meaning]

[0187] Specific examples of the compound represented by the formula (6) include the following compounds.

[0188] [Chemistry 18]

[0189]

[0190] X in the formula (1) and formula (a1) 1 independently represents -O-, -S- or -N(R 14 )-. In X 1 When X is -O-, it is preferred in terms of flexibility, solubility, and heat resistance. 1 -N(R 14 )-, it is preferred in terms of adhesion and the like.

[0191] R 14It is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group in which a part of the hydrocarbon group or halogenated hydrocarbon group is substituted with at least one selected from an oxygen atom and a sulfur atom.

[0192] As R 14 The monovalent hydrocarbon group having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms are exemplified by the above R 11 The monovalent hydrocarbon group having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms exemplified in the substituent in the nitrogen-containing heteroaromatic ring of 14 A group in which a part of a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms is substituted by at least one selected from an oxygen atom and a sulfur atom, specifically, a group in which a part or all of the hydrocarbon group or the halogenated hydrocarbon group is substituted by an ester group or a sulfonyl group.

[0193] As R 14 From the viewpoint of being able to synthesize the polymer (A) with good polymerization reactivity, a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferred.

[0194] In addition, in formula (1), both X are -N(R 14 )-, two R 14 Can be the same or different.

[0195] The ** in the formula (a1) represents a bond to other structural units in the polymer (A). Here, the other structural units may be other repeating units (1), or may be repeating structural units represented by the formula (2) described later, other structural units, or terminal groups Y. In addition, when the ** in a repeating unit (1) represents a bond to another repeating unit (1), the ** and R in the other repeating unit (1) are 11 Bonded but not to X 1 Bond.

[0196] When all structural units contained in the polymer (A) are set to 100 mol%, the content ratio of the repeating unit (1) is preferably in the range of 5 mol% to 95 mol%, more preferably in the range of 10 mol% to 90 mol%, and further preferably in the range of 20 mol% to 80 mol%.

[0197] The polymer (A) preferably has a repeating structural unit represented by the following formula (2) (hereinafter also referred to as "repeating unit (2)") in addition to the repeating unit (1).

[0198] [Chemistry 19]

[0199]

[0200] [In the above formula (2),

[0201] R 21 represents a divalent substituted or unsubstituted nitrogen-containing heteroaromatic ring,

[0202] R 22 represents a divalent group containing a substituted or unsubstituted aromatic hydrocarbon group in the main chain,

[0203] X 2 Indicates -O-, -S- or -N(R 24 )-,

[0204] R 24 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group in which a part of the hydrocarbon group or halogenated hydrocarbon group is substituted with at least one selected from an oxygen atom and a sulfur atom]

[0205] In the formula (2), R 21 represents a divalent substituted or unsubstituted nitrogen-containing heteroaromatic ring.

[0206] R 21 The specific examples or preferred forms of R in the formula (1) are 11 The same as the content illustrated in . In addition, regarding the 21 The monomers of the raw materials of the part may also be the same as R in the formula (1) 11 The same monomers as exemplified in .

[0207] In the formula (2), R 22 It represents a divalent group containing a substituted or unsubstituted aromatic hydrocarbon group in the main chain. As the divalent group, it is preferable to contain a group represented by the following formula (2-1).

[0208] [Chemistry 20]

[0209]

[0210] [In formula (2-1),

[0211] Ar 1 and Ar 2 are each independently an unsubstituted or substituted aromatic hydrocarbon group;

[0212] L is a single bond, -O-, -S-, -N(R 8 )-, -C(O)-, -C(O)-O-, -C(O)-NH-, -S(O)-, -S(O)2-, -P(O)- or a divalent organic group [R 8is 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];

[0213] y is an integer of 0 to 5; when y is 2 or more, a plurality of Ar 1 and L may be the same or different;

[0214] R 6 and R 7 are each independently a single bond, a methylene group or an alkylene group having 2 to 4 carbon atoms]

[0215] As Ar 1 and Ar 2 The aromatic hydrocarbon groups represented are each independently preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group, a naphthyl group or an anthracenyl group, and particularly preferably a phenyl group or a naphthyl group.

[0216] Ar 1 and Ar 2 The aromatic hydrocarbon groups represented by may each have 1 to 8 substituents. In terms of being able to synthesize the polymer (A) with good polymerization reactivity, Ar 1 and Ar 2 The number of substituents possessed by the represented aromatic hydrocarbon groups is preferably 0 to 8, more preferably 0 to 4, and still more preferably 0 to 2.

[0217] As the Ar 1 and Ar 2 The substituent in is not particularly limited, and examples thereof include an allyl group, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxyl group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a hydroxyl group, a primary to tertiary amino group, a salt of a carboxyl group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxyl group, or a salt of a primary to tertiary amino group.

[0218] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0219] Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include monovalent chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups, and monovalent aromatic hydrocarbon groups. Monovalent chain hydrocarbon groups are preferred in terms of polymerizability and low dielectric properties of the polymer.

[0220] Examples of the chain hydrocarbon group 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.

[0221] The divalent organic group in L is preferably a divalent organic group having 1 to 20 carbon atoms, and examples thereof include a substituted or unsubstituted methylene group, an alkylene group having 2 to 20 carbon atoms, a halogenated alkylene group having 2 to 20 carbon atoms, a divalent cardo structure, or a group represented by the following formula (L1).

[0222] [Chemistry 21]

[0223]

[0224] [In formula (L1), R c is an unsubstituted or substituted divalent alicyclic hydrocarbon group having 5 to 30 ring members]

[0225] Examples of the substituted methylene group in L include alkyl-substituted methylene groups having 1 to 5 carbon atoms, such as 1-methylmethylene, 1-ethylmethylene, 1,1-dimethylmethylene, 1-ethyl-1-methylmethylene, and 1,1-bistrifluoromethylmethylene.

[0226] Examples of the alkylene group having 2 to 20 carbon atoms in L include ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, neopentylene, 4-methyl-pentane-2,2-diyl, nonane-1,9-diyl, and decane-1,1-diyl.

[0227] Examples of the halogenated methylene group in L include groups in which a part or all of the hydrogen atoms of the methylene group are substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0228] Examples of the halogenated alkylene group having 2 to 20 carbon atoms in L include groups in which a part or all of the hydrogen atoms of the alkylene group having 2 to 20 carbon atoms are substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0229] Examples of the divalent carboxylic acid structure in L include a divalent group derived from fluorene (that is, a group obtained by removing two hydrogen atoms from a compound having a fluorene skeleton) represented by the following formula (L2).

[0230] [Chemistry 22]

[0231]

[0232] [In formula (L2), R8 and R9 are each independently a hydrogen atom, a fluorine atom or a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, and k is independently an integer of 0 to 4]

[0233] Examples of the divalent carbolic acid structure include structures derived from compounds represented by the following formula.

[0234] [Chemistry 23]

[0235]

[0236] As R c Examples of the unsubstituted or substituted divalent alicyclic hydrocarbon group having 5 to 30 ring members include an unsubstituted or substituted monocyclic alicyclic hydrocarbon group having 5 to 15 ring members, an unsubstituted or substituted monocyclic fluorinated alicyclic hydrocarbon group having 5 to 15 ring members, an unsubstituted or substituted polycyclic alicyclic hydrocarbon group having 7 to 30 ring members, and an unsubstituted or substituted polycyclic fluorinated alicyclic hydrocarbon group having 7 to 30 ring members.

[0237] Examples of the unsubstituted or substituted monocyclic alicyclic hydrocarbon group having 5 to 15 ring members 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 a part or all of the hydrogen atoms of these groups are substituted with a monovalent chain hydrocarbon group having 1 to 20 carbon atoms.

[0238] Examples of the unsubstituted or substituted monocyclic fluorinated alicyclic hydrocarbon group having 5 to 15 ring members include groups in which a part or all of the hydrogen atoms of the groups exemplified as the monocyclic alicyclic hydrocarbon group having 5 to 15 ring members are substituted with fluorine atoms.

[0239] Examples of the unsubstituted or substituted polycyclic alicyclic hydrocarbon group having 7 to 30 ring members include norbornane, norbornene, adamantane, tricyclo[5.2.1.0 2,6 ]Decane, tricyclo[5.2.1.0 2,6 ]heptane, pinane, camphane, decahydronaphthalene, tricyclo[2.2.1.0 2,6 ] A group formed by two hydrogen atoms bonded to one carbon atom of a polycyclic alicyclic hydrocarbon such as nortricyclane, perhydroanthracene, perhydroazulene, cyclopentano-hydrophenanthrene, and bicyclo[2.2.2]-2-octene; a group formed by replacing a part or all of the hydrogen atoms of these groups with a monovalent chain hydrocarbon group having 1 to 20 carbon atoms.

[0240] Examples of the unsubstituted or substituted polycyclic fluorinated alicyclic hydrocarbon group having 7 to 30 ring members include groups in which a part or all of the hydrogen atoms of the groups exemplified as the polycyclic alicyclic hydrocarbon group having 7 to 30 ring members are substituted with fluorine atoms.

[0241] -N(N8 )-R 8 is 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. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms include Ar 1 The monovalent hydrocarbon group having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms exemplified in .

[0242] From the viewpoint of the structural stability of the polymer (A), L is preferably a single bond, -O-, -S-, -C(O)-, -S(O)-, -S(O)2-, -C(O)-NH-, -C(O)-O-, a methylene group, an alkyl-substituted methylene group having 1 to 5 carbon atoms, an alkylene group having 2 to 5 carbon atoms, a halogenated methylene group, a halogenated alkylene group having 2 to 10 carbon atoms, or a divalent carboxylic acid structure.

[0243] From the same viewpoint, y is preferably 0-4, more preferably 0-3, and particularly preferably 0-1.

[0244] As R 6 and R 7 Examples of the alkylene group having 2 to 4 carbon atoms include ethylene, n-propylene, isopropylene, n-butylene and sec-butylene.

[0245] As R 6 and R 7 , from the viewpoint of synthesizing the polymer (A) with good polymerization reactivity, each independently preferably is a single bond, a methylene group or an ethylene group.

[0246] As becomes the R 22Monomers of raw materials for the part of the raw materials include, for example, dihydroxyphenyl compounds such as hydroquinone, resorcinol, catechol, and phenylhydroquinone; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-allylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 4,4'-(1,3-dimethylbutylene)bisphenol, 1,1-bis(4-hydroxyphenyl)-nonane, bis(4-hydroxyphenyl)sulfone, 1,1- Bisphenol compounds such as bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 4,4'-cyclododecylene bisphenol, 4,4'-decylene bisphenol, 4,4'-dihydroxy-2,2',3,3',5,5'-hexamethylbiphenyl; PRIPLAST 1901, 1838, 3186, 3192, 3197, 3199 (Croda Japan These monomers may be used alone or in combination of two or more.

[0247] X in the formula (2) 2 are independently -O-, -S- or -N(R 24 )-.X 2 The specific examples or preferred forms of X in the formula (1) are 1 The contents shown in the example are the same.

[0248] In the case where ** in the repeating unit (1) represents a bond to the repeating unit (2), the ** and R in the repeating unit (2) are 21 Bonded but not to X 2 Bond.

[0249] When all structural units contained in the polymer (A) are set to 100 mol%, the content ratio of the repeating unit (2) is preferably in the range of 5 mol% to 95 mol%, more preferably in the range of 10 mol% to 90 mol%, and further preferably in the range of 20 mol% to 80 mol%.

[0250] The polymer (A) preferably has a group Y represented by the following formula (y) at the terminal (hereinafter also referred to as “terminal group Y”).

[0251] [Chemistry 24]

[0252] -Y (y)

[0253] [In the above formula (y), Y is a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic ring]

[0254] In addition, when the terminal group Y is bonded to the repeating unit (1), 1 Bonded but not to R 11 Similarly, when the terminal group Y is bonded to the repeating unit (2), 2 Bonded but not to R 21 Bond.

[0255] In order to improve dielectric properties, the terminal group Y is preferably an aromatic hydrocarbon group or an aliphatic hydrocarbon group or a nitrogen-containing heteroaromatic ring with low polarity. When it also contains an ethylenically unsaturated double bond, heat resistance and curability can be expected because the crosslinking density can be increased.

[0256] Examples of the group having 3 to 50 carbon atoms and containing an ethylenically unsaturated double bond include aromatic ring-containing groups such as 3-isopropenylphenyl, 4-isopropenylphenyl, 2-allylphenyl, 2-methoxy-4-allylphenyl, 4-(1-propenyl)-2-methoxyphenyl, 4-vinylbenzyl, 3-vinylbenzyl, and 2-vinylbenzyl, allyl, acrylic, methacrylic, and methallyl.

[0257] Examples of the aromatic hydrocarbon group having 6 to 50 carbon atoms include aryl groups such as phenyl, biphenylyl, tolyl, xylyl, naphthyl, and anthracenyl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, and naphthylmethyl.

[0258] Examples of the aliphatic hydrocarbon group 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.

[0259] Examples of the unsubstituted nitrogen-containing heteroaromatic ring include 11 The same ring as the ring exemplified in .

[0260] The substituents in the unsubstituted or substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, the unsubstituted or substituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, and the unsubstituted nitrogen-containing heteroaromatic ring are groups other than hydroxyl groups. Specific examples thereof include the following: 1 The same groups as those exemplified as the substituents in .

[0261] In addition to providing R in the formula (1) 11 or R 12 -R 13 -R 12 In addition to the monomer, at least one monomer for forming an end group Y selected from the group consisting of monovalent phenols, monovalent amines, monovalent thiols, monovalent aromatics, monovalent aliphatic halides, monovalent acid halides and monovalent acid anhydrides is used as a raw material for reaction, thereby obtaining a polymer (A) having its terminal sealed by the end group Y.

[0262] When synthesizing a polymer (A) in which the terminal group Y contains a double bond, for example, in order to avoid 11 The monomers of the raw materials are R 12 and R 13 When the monomers of the raw materials of the part are polymerized, the double bonds in the monomers for forming the terminal group Y react with each other to form a gel. 11 The monomers of the raw materials are R 12 and R 13 After polymerization of some of the raw material monomers, a monomer for forming the terminal group Y is added to carry out a reaction.

[0263] As the monomer for forming the terminal group Y, for example, monovalent phenol compounds such as tert-butylphenol, nonylphenol, 4-isopropenylphenol, 4-vinylphenol, 2-allylphenol, isoeugenol, tocotrienol, α-tocopherol, 4-hydroxyphenylmaleimide, and 2-phenylphenol; monovalent amine compounds such as 4-hexylaniline and diallylamine; monovalent thiol compounds such as 1-octanethiol; monovalent aliphatic halides such as allyl chloride, 4-(chloromethyl)styrene, and 3-(chloromethyl)styrene; monovalent acid halides such as acryloyl chloride, methacryloyl chloride, crotonyl chloride, and cinnamoyl chloride; monovalent acid anhydrides such as acrylic anhydride, crotonic anhydride, and methacrylic anhydride. In addition, these monomers can be used alone or in combination of two or more.

[0264] The polymer (A) may have other structural units as needed in addition to the repeating unit (1), the repeating unit (2) and the terminal group Y. Therefore, regarding the repeating unit (1), for example, the repeating units (1) may be bonded to each other or to the repeating unit (2), the other structural unit or the terminal group Y.

[0265] When the polymer (A) has a plurality of repeating units (1), the plurality of R 11 They may be the same or different. 12 , R 13 The same applies to the repeating unit (2) and other structural units.

[0266] As monomers for deriving the other structural units, for example, compounds for deriving structural units containing carbonate bonds, thiocarbonate bonds or selenocarbonate bonds such as diphenyl carbonate, diphenyl thiocarbonate, diphenyl selenocarbonate, phosgene, thiophosgene, and selenophosgene; dihydroxy compounds such as benzyl alcohol and cyclohexanedimethanol; phosphine oxide compounds such as bis(fluorophenyl)phenylphosphine oxide, bis(fluorophenyl)naphthylphosphine oxide, and bis(fluorophenyl)anthracenephosphine oxide; dihalides of dicarboxylic acids such as phthalic acid dichloride, isophthalic acid dichloride, and terephthalic acid dichloride. In addition, these monomers may be used alone or in combination of two or more.

[0267] <Method for synthesizing polymer (A)>

[0268] The synthesis method of the polymer (A) is not particularly limited, and a known method can be used. For example, the polymer (A) can be synthesized by mixing the R 11 The monomer of the raw material of part of R 12 and R 13 The monomer of the raw material of part of the present invention may be optionally converted into the monomer containing the R 21 The monomer of the raw material of part of R 22 and R 13 The monomers of the raw materials of the part, the monomers for forming the terminal group Y and the monomers for deriving the other structural units are heated together with a polymerization inhibitor, an alkali metal or an alkali metal compound, etc. to form a monomer containing R 21 The monomer of the raw material of part of R 22 and R 13 The monomers of the raw materials of the part, the monomers for deriving the other structural units or the monomers for forming the terminal group Y may also be included in the R 11 The monomers of the raw materials are the same as those of the R 12 The monomers of some raw materials are polymerized and then heated and mixed to react.

[0269] Alkali metals and alkali metal compounds

[0270] In the synthesis process of the polymer (A), when a compound having a hydroxyl group such as a phenol compound is used as a raw material, the alkali metal and the alkali metal compound react with the compound having a hydroxyl group to form an alkali metal salt.

[0271] Examples of such alkali metals and alkali metal compounds include:

[0272] Alkali metals such as lithium, sodium, and potassium;

[0273] Alkali metal hydrides such as lithium hydride, sodium hydride, potassium hydride, etc.

[0274] Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.

[0275] Alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, etc.

[0276] Alkali metal bicarbonates such as lithium bicarbonate, sodium bicarbonate, potassium bicarbonate.

[0277] Among these, alkali metal carbonates are preferred, and potassium carbonate is more preferred.

[0278] When synthesizing polymer (A), when using a compound having a hydroxyl group, the amount of alkali metal and the alkali metal compound used is preferably 1, more preferably 1.1, and further preferably 1.2, with 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 the upper limit of the ratio is preferably 3, more preferably 2, and further preferably 1.8.

[0279] Organic solvent

[0280] Examples of the organic solvent include:

[0281] Ether solvents such as tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether, anisole, phenethyl ether, diphenyl ether, dialkoxybenzene, trialkoxybenzene, etc.;

[0282] Nitrogen-containing solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone;

[0283] Ester solvents such as γ-butyrolactone;

[0284] Sulfur-containing solvents such as sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, and diphenyl sulfone;

[0285] Ketone solvents such as benzophenone, 2-heptanone, cyclohexanone, and methyl ethyl ketone;

[0286] Halogen solvents such as dichloromethane, chloroform, and chlorobenzene;

[0287] Aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

[0288] 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.

[0289] 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.

[0290] The lower limit of the reaction time in the synthesis is preferably 1 hour, more preferably 2 hours, and still more preferably 3 hours, and the upper limit is preferably 100 hours, more preferably 50 hours, and still more preferably 24 hours.

[0291] In order to suppress gelation of the polymerization solution, the lower limit of the reaction temperature when adding the monomer for forming the terminal group Y after polymerization is preferably 0°C, more preferably 10°C, and the upper limit is preferably 130°C, more preferably 110°C.

[0292] The lower limit of the reaction time when the monomer for forming the terminal group Y is added after polymerization is preferably 1 hour, more preferably 2 hours, and further preferably 3 hours, and the upper limit is preferably 48 hours, more preferably 24 hours, and further preferably 10 hours.

[0293] Polymerization inhibitors

[0294] The polymerization inhibitor can be used for the usual purpose of obtaining a target molecular weight by controlling a polymerization reaction, etc. For example, examples of quinones include p-benzoquinone, 2-tert-butyl-p-benzoquinone, 2,5-diphenyl-p-benzoquinone, chloranil, and trimethylquinone.

[0295] Examples of the hindered phenolic compound include 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-3,5-triazine, pentaerythritol tetrakis[3-(3,5-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 2,6-di-tert-butyl-p-cresol (2,6-di-tert-butyl-p-cresol, BHT), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene[manufactured by ADEKA Co., Ltd., AO-330], etc.

[0296] Examples of the hindered amine compound include 4-cyclohexylcarbonyloxy-2,2,6,6-tetramethylpiperidinyloxy, 4-benzoyloxy-2,2,6,6-tetramethylpiperidinyloxy, 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxy [Adekastab LA-7RD manufactured by ADEKA Co., Ltd.], and IRGASTAB UV 10 (4,4′-[(1,10-dioxo-1,10-decanediyl)bis(oxy)]bis[2,2,6,6-tetramethyl]-1-piperidinyloxy).

[0297] Examples of the amine compound include phenothiazine, 3,7-dicumylphenothiazine, N,N′-diphenyl-1,4-phenylenediamine, and N,N′-di-2-naphthyl-1,4-phenylenediamine.

[0298] [Physical properties of polymer (A)]

[0299] The lower limit of the polystyrene-equivalent weight average molecular weight (Mw) of the polymer (A) is preferably 1,000, more preferably 2,000, and still more preferably 3,000, and the upper limit is preferably 500,000, more preferably 100,000, still more preferably 50,000, and particularly preferably 30,000.

[0300] The polymer (A) having Mw within the above range is preferably preferred because it has a good balance and excellent adhesion, heat resistance, impregnation into glass cloth, and moldability such as resin flow. In addition, Mw in the present invention is a value measured by gel permeation chromatography (GPC) under the conditions described in the following examples.

[0301] In terms of reducing transmission loss when a composition containing the polymer (A) is prepared, the dielectric loss tangent (tan δ) of the polymer (A) is preferably 0.0025 or less, more preferably 0.0020 or less, and further preferably 0.0012 or less, and the lower limit thereof is not particularly limited, but is preferably 0.0005 or more. Specifically, the dielectric loss tangent can be measured by the method described in the following Examples.

[0302] The First Composition

[0303] The first composition of one embodiment of the present invention (hereinafter also referred to as "the present composition (1)") is not particularly limited as long as it contains the polymer (A), but preferably contains a curable compound (B) other than the polymer (A). The present composition (1) may further contain other components such as a curing aid.

[0304] <Polymer (A)>

[0305] The polymer (A) used in the present composition (1) may be one kind or two or more kinds. In addition, the present composition (1) may be a mixture of two or more kinds of polymers (A).

[0306] When two or more polymers (A) are used, polymers (A) having different molecular weights within the molecular weight range of the polymer (A) may be mixed, for example, depending on required physical properties and the like.

[0307] When the solid content in the present composition (1) as a whole is set to 100% by mass, the content ratio of the polymer (A) in the present composition (1) is, for example, preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 50% by mass or more, and is preferably 99.95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less.

[0308] When the content of the polymer (A) is within the above range, it is preferred in that the adhesiveness, heat resistance, curability, electrical properties, and the like of the cured product obtained from the present composition (1) can be further improved.

[0309] <Curing compound (B)>

[0310] The curable compound (B) (hereinafter also referred to as "compound (B)") is a compound other than the polymer (A) and is a compound that is cured by irradiation with heat or light (e.g., visible light, ultraviolet light, near infrared light, far infrared light), and may also be a compound that requires a curing aid described later. Examples of such compound (B) include vinyl compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, thiol compounds, oxazine compounds, cyanate compounds, epoxy compounds, oxetane compounds, methylol compounds, benzocyclobutene compounds, propargyl compounds, and silane compounds. Among these, in terms of compatibility and reactivity with the polymer (A), at least one of vinyl compounds, maleimide compounds, and allyl compounds is particularly preferred.

[0311] The compound (B) may be used alone or in combination of two or more.

[0312] Examples of the vinyl compound include compounds represented by the following formulae (b-1-1) to (b-1-5).

[0313] Examples of the vinyl compound include styrene-based thermoplastic elastomers, vinyl-containing compounds such as styrene butadiene styrene copolymers (Styrene Butadiene Styrene, SBS), hydrogenated styrene butadiene styrene copolymers (Styrene Ethylene Butylene Styrene, SEBS), styrene isoprene styrene copolymers (Styrene Isoprene Styrene, SIS), hydrogenated styrene isoprene styrene copolymers, styrene butadiene elastomers (Styrene Butadiene Rubber (Styrene Butadiene Rubber, SBR)), tert-butylstyrene, and 2-vinyl-4,6-diamino-1,3,5-triazine.

[0314] Examples of the vinyl compound include TA100 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and ULL-950S (manufactured by Lonza Corporation).

[0315] [Chemistry 25]

[0316]

[0317] [In formula (b-1-2) and formula (b-1-4), n is independently 1 to 5000; in formula (b-1-5), l, m and n are independently 1 to 5000]

[0318] Examples of the maleimide compound include compounds represented by the following formula (b-2-1) to formula (b-2-8).

[0319] [Chemistry 26]

[0320]

[0321] [In formula (b-2-4), formula (b-2-5), formula (b-2-7) and formula (b-2-8), n is independently 1 to 50]

[0322] Examples of the allyl compound include compounds represented by the following formula (b-3-1) to formula (b-3-6).

[0323] [Chemistry 27]

[0324]

[0325] Examples of the acrylic compound include compounds represented by the following formula (b-4-1) to formula (b-4-7).

[0326] [Chemistry 28]

[0327]

[0328] [In formula (b-4-1), formula (b-4-2), formula (b-4-3) and formula (b-4-6), n is independently 1 to 50; in formula (b-4-3), m is 1 to 50; in formula (b-4-6), R is a divalent hydrocarbon group having 1 to 20 carbon atoms]

[0329] Examples of the methacrylic compound include bisphenol A epoxy methacrylate, phenol novolac epoxy methacrylate, trimethylolpropane methacrylate, dipentaerythritol hexamethacrylate, and SA-9000 (manufactured by Saudi Basic Industries (Sabic)).

[0330] Examples of the thiol compound include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(2-(3-mercaptobutyryloxy)ethyl)-1,3,5-triazine-2,4,6-trione, 2-(dibutylamino)-1,3,5-triazine-4,6-dithiol, and 6-diallylamino-1,3,5-triazine-2,4-dithiol.

[0331] Examples of the silane compound include KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.) and KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0332] Examples of the oxazine compound include compounds represented by the following formula (b-5-1) to formula (b-5-5).

[0333] [Chemistry 29]

[0334]

[0335] Examples of the cyanate compound include compounds represented by the following formula (b-6-1) to formula (b-6-7).

[0336] [Chemistry 30]

[0337]

[0338] [In formula (b-6-6) and formula (b-6-7), n is independently 0 to 30]

[0339] Examples of the epoxy compound include compounds represented by the following formula (b-7-1) to formula (b-7-5).

[0340] Examples of the epoxy compound include polyglycidyl ethers of dicyclopentadiene-phenol polymers, phenol novolac-type liquid epoxy compounds, cresol novolac-type epoxy compounds, epoxides of styrene-butadiene block copolymers, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, XER-81 (manufactured by JSR Co., Ltd., epoxy-containing nitrile butadiene rubber (NBR) particles), and JP-100 (manufactured by Nippon Soda Co., Ltd.).

[0341] [Chemistry 31]

[0342]

[0343] [In formula (b-7-5), n is 0 to 5000]

[0344] Examples of the oxetane compound include compounds represented by the following formula (b-8-1) to formula (b-8-3).

[0345] [Chemistry 32]

[0346]

[0347] [In formula (b-8-1) and formula (b-8-2), n is independently 0 to 30]

[0348] Examples of the methylol compound include methylol compounds described in JP-A-2006-178059 and JP-A-2012-226297. Specific examples include melamine-based methylol compounds such as polymethylolated melamine, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxymethyl melamine; glycoluril-based methylol compounds such as polymethylolated glycoluril, tetramethoxymethyl glycoluril, and tetrabutoxymethyl glycoluril; compounds obtained by methylolating guanamines such as 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxyspiro[5.5]undecane and 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)propyl]-2,4,8,10-tetraoxyspiro[5.5]undecane; and compounds obtained by alkyl etherifying all or part of the active methylol groups in the above compounds.

[0349] Examples of the benzocyclobutene compound include compounds described in Japanese Patent Application Laid-Open No. 2005-60507.

[0350] Examples of the propargyl compound include compounds represented by the following formula (b-9-1) to (b-9-2).

[0351] [Chemistry 33]

[0352]

[0353] [Content ratio of compound (B)]

[0354] When the solid content in the present composition (1) as a whole is set to 100 mass%, the content ratio of the compound (B) in the present composition (1) is, for example, preferably 0.05 mass% or more, more preferably 10 mass% or more, and further preferably 20 mass% or more, and is preferably 90 mass% or less, more preferably 80 mass% or less, and further preferably 50 mass% or less.

[0355] When the content of the compound (B) is within the above range, it is preferred in that the strength, heat resistance, and other aspects of the cured product obtained from the present composition (1) can be further improved.

[0356] In addition, when the total solid content of the polymer (A) and the compound (B) in the present composition (1) is set to 100 mass%, the content ratio of the compound (B) is preferably 1 mass% or more, more preferably 5 mass% or more, and further preferably 10 mass% or more, and is preferably 99 mass% or less, more preferably 95 mass% or less, and further preferably 90 mass% or less.

[0357] When the content of the compound (B) is within the above range, it is preferred in that the toughness, heat resistance, and the like of the cured product obtained from the present composition (1) can be further improved.

[0358] The Second Composition

[0359] The second composition of one embodiment of the present invention (hereinafter also referred to as "the present composition (2)") contains a polymer (A2) having a repeating structural unit represented by the following formula (3) (hereinafter also referred to as "repeating unit (3)") and a repeating structural unit represented by the following formula (4) (hereinafter also referred to as "repeating unit (4)"), and a curable compound (B2) other than the polymer (A2). The present composition (2) may further contain other components such as a curing aid.

[0360] [Chemistry 34]

[0361]

[0362] [In the formula (3),

[0363] R 31 represents a divalent organic group having 3 to 10 carbon atoms,

[0364] R 32 independently represent a divalent substituted or unsubstituted aromatic hydrocarbon group,

[0365] R 33 Indicates that there are two R bonds 32 a hydrocarbon group having 1 to 20 carbon atoms and at least one group represented by the following formula (a2)]

[0366] [Chemistry 35]

[0367] *-R 32 -O-** (a2)

[0368] [In the formula (a2),

[0369] * indicates that for the R 33 The key,

[0370] ** represents the bonding bond with other structural units in the polymer (A2),

[0371] R 32With R in the formula (3) 32 for the same meaning]

[0372] [Chemistry 36]

[0373]

[0374] [In the above formula (4),

[0375] R 41 represents a divalent organic group having 3 to 10 carbon atoms,

[0376] R 42 represents a divalent group containing a substituted or unsubstituted aromatic hydrocarbon group in the main chain, wherein the oxygen atom in the formula is directly bonded to the aromatic hydrocarbon group]

[0377] <Polymer (A2)>

[0378] The polymer (A2) has the repeating unit (3) and the repeating unit (4).

[0379] In the repeating unit (3), R 31 represents a divalent organic group having 3 to 10 carbon atoms. The divalent organic group having 3 to 10 carbon atoms is not particularly limited, and examples thereof include phenyl, tolyl, xylyl, and naphthyl. Among these, xylyl is preferred.

[0380] R in the repeating unit (3) 32 R independently represents a divalent substituted or unsubstituted aromatic hydrocarbon group. 32 The details are similar to those of R in the repeating unit (1). 12 same.

[0381] R in the repeating unit (3) 33 Indicates that the bond has the two R 32 A hydrocarbon group having 1 to 20 carbon atoms and at least one group represented by the following formula (a2). 33 and the details of the group represented by the formula (a2) are respectively the same as those of R in the repeating unit (1). 12 The same as the group represented by the above formula (a1).

[0382] From the viewpoint of increasing the glass transition temperature (Tg), the repeating unit (3) preferably contains two or more species in the polymer (A2).

[0383] In the repeating unit (4), R 41 represents a divalent organic group having 3 to 10 carbon atoms. The divalent organic group having 3 to 10 carbon atoms is not particularly limited, and examples thereof include phenyl, tolyl, xylyl, and naphthyl. Among these, xylyl is preferred.

[0384] R in the repeating unit (4) 42 represents a divalent group containing a substituted or unsubstituted aromatic hydrocarbon group in the main chain. 42 The details of R in the repeating unit (2) are the same as 22 same.

[0385] When all structural units contained in the polymer (A2) are set to 100 mol%, the content ratio of the repeating unit (3) is preferably in the range of 5 mol% to 95 mol%, more preferably in the range of 10 mol% to 90 mol%, and further preferably in the range of 20 mol% to 80 mol%.

[0386] In addition, when all the structural units contained in the polymer (A2) are set to 100 mol%, the content ratio of the repeating unit (4) is preferably in the range of more than 5 mol% and less than 95 mol%, more preferably more than 10 mol% and less than 90 mol%, and further preferably more than 20 mol% and less than 80 mol%.

[0387] The polymer (A2) preferably has a group Y represented by the formula (y) at the terminal (terminal group Y). The details of the terminal group Y are as described above.

[0388] In addition, when the terminal group Y is bonded to the repeating unit (3), for example, it is bonded to O (oxygen atom) but not to R. 31 Similarly, when the terminal group Y is bonded to the repeating unit (4), it is bonded to O (oxygen atom) but not to R. 41 Bond.

[0389] The polymer (A2) may have other structural units as needed in addition to the repeating unit (3), the repeating unit (4) and the terminal group Y. Therefore, regarding the repeating unit (3), for example, the repeating units (3) may be bonded to each other or to the repeating unit (4), the other structural unit or the terminal group Y.

[0390] When the polymer (A2) has a plurality of repeating units (3), the plurality of R 31 They may be the same or different. 32 , R 33 The same applies to the repeating unit (4) and other structural units.

[0391] As monomers for deriving the other structural units, for example, compounds derived from structural units containing carbonate bonds, thiocarbonate bonds or selenocarbonate bonds such as diphenyl carbonate, diphenyl thiocarbonate, diphenyl selenocarbonate, phosgene, thiophosgene, and selenophosgene; dihydroxy compounds such as benzyl alcohol and cyclohexanedimethanol; phosphine oxide compounds such as bis(fluorophenyl)phenylphosphine oxide, bis(fluorophenyl)naphthylphosphine oxide, and bis(fluorophenyl)anthracenephosphine oxide; dihalides of dicarboxylic acids such as phthalic acid dichloride, isophthalic acid dichloride, and terephthalic acid dichloride. In addition, these monomers may be used alone or in combination of two or more.

[0392] The synthesis method of the polymer (A2) is not particularly limited, and a known method can be used. For example, the polymer (A2) can be synthesized by the same method as that of the above-mentioned polymer (A).

[0393] The physical properties of the polymer (A2) are preferably the same as those of the polymer (A).

[0394] The polymer (A2) used in the present composition (2) may be one kind or two or more kinds. In addition, the present composition (2) may be a mixture of two or more kinds of polymers (A2).

[0395] When two or more polymers (A2) are used, polymers (A2) having different molecular weights within the molecular weight range of the polymer (A2) may be mixed, for example, depending on required physical properties.

[0396] When the solid content in the present composition (2) as a whole is set to 100 mass%, the content ratio of the polymer (A2) in the present composition (2) is, for example, preferably 10 mass% or more, more preferably 20 mass% or more, and further preferably 50 mass% or more, and is preferably 99.95 mass% or less, more preferably 90 mass% or less, and further preferably 80 mass% or less.

[0397] When the content of the polymer (A2) is within the above range, it is preferred in that the adhesiveness, heat resistance, curability, electrical properties, and the like of the cured product obtained from the present composition (2) can be further improved.

[0398] <Curing compound (B2)>

[0399] The curable compound (B2) (hereinafter also referred to as "compound (B2)") is a compound other than the polymer (A2) and is a compound that is cured by irradiation with heat or light (e.g., visible light, ultraviolet light, near infrared light, far infrared light), and may also be a curing aid that requires the following description. Examples of such compounds (B2) include vinyl compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, thiol compounds, oxazine compounds, cyanate compounds, epoxy compounds, oxetane compounds, methylol compounds, benzocyclobutene compounds, propargyl compounds, and silane compounds. Among these, in terms of compatibility and reactivity with the polymer (A2), at least one of vinyl compounds, maleimide compounds, and allyl compounds is particularly preferred.

[0400] The compound (B2) may be used alone or in combination of two or more. More specific examples of the compound (B2) are the same as those for the compound (B).

[0401] [Content ratio of compound (B2)]

[0402] When the solid content in the present composition (2) as a whole is set to 100 mass%, the content ratio of the compound (B2) in the present composition (2) is, for example, preferably 0.05 mass% or more, more preferably 10 mass% or more, and further preferably 20 mass% or more, and is preferably 90 mass% or less, more preferably 80 mass% or less, and further preferably 50 mass% or less.

[0403] When the content of the compound (B2) is within the above range, it is preferred in that the strength, heat resistance, and other aspects of the cured product obtained from the present composition (2) can be further improved.

[0404] In addition, when the total solid content of the polymer (A2) and the compound (B2) in the present composition (2) is set to 100 mass%, the content ratio of the compound (B2) is preferably 1 mass% or more, more preferably 5 mass% or more, and further preferably 10 mass% or more, and is preferably 99 mass% or less, more preferably 95 mass% or less, and further preferably 90 mass% or less.

[0405] When the content of the compound (B2) is within the above range, it is preferred in that the toughness, heat resistance, and the like of the cured product obtained from the present composition (2) can be further improved.

[0406] <Other ingredients>

[0407] The present composition (1) and the present composition (2) (hereinafter, these are also collectively referred to as "the present composition") may contain other components in addition to the polymer (A) and the compound (B) within a range that does not impair the effects of the present invention.

[0408] Examples of the other components include curing aids, solvents, additives for imparting various functions, inorganic fillers, organic fillers, and polymers other than polymer (A) or polymer (A2). These other components may be used alone or in combination of two or more.

[0409] [Hardening aid]

[0410] The present composition may also contain a hardening aid as necessary.

[0411] Examples of the curing aid include polymerization initiators such as thermal or photo-radical initiators, cationic curing agents, and anionic curing agents.

[0412] Examples of the thermal radical initiator include organic peroxides such as dicumyl peroxide, 1,1-di(tert-butylperoxy)cyclohexane, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, and benzoyl peroxide; and azo compounds such as azobisbutyronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane)]), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis(isobutyrate), and 2,2'-azobis(2-methylbutyronitrile).

[0413] Examples of cationic hardeners include SP70, SP172, CP66 manufactured by ADEKA Co., Ltd., CI2855, CI2823 manufactured by Nippon Soda Co., Ltd., SI100, SI150 manufactured by Sanshin Chemical Industry Co., Ltd., phosphonium salts such as diallyl iodonium salts, trialkyl sulfonium salts, and butyl triphenyl phosphonium thiocyanate using BF4, PF6, and SbF6 as counter anions, and boron trifluoride.

[0414] Examples of the anionic curing agent include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-methyl-4-methylimidazole, 2-methylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazoline-(1)]-ethyl-S-triazine, and 2,4-diamino-6-[2-ethyl-4-methylimidazoline-(1)]-ethyl-S-triazine; phosphorus compounds such as triphenylphosphine; and amine compounds such as 4,4'-diaminodiphenylmethane.

[0415] In addition, examples of curing aids when using a silane compound as compound (B) or compound (B2) include platinum-based catalysts such as platinum black, platinum tetrachloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and diacetylacetate platinum; palladium-based catalysts; platinum group metal catalysts such as rhodium-based catalysts; zinc benzoate and zinc octoate.

[0416] When the oxazine compound is used as the compound (B) or the compound (B2), examples of the curing aid include phenol and its derivatives, cyanate esters, Brunst acids such as p-toluenesulfonic acid, adipic acid, p-toluenesulfonic acid esters, 4,4'-diaminodiphenyl sulfone, aromatic amine compounds such as melamine, bases such as 2-ethyl-4-methylimidazole, boron trifluoride, and curing agents such as Lewis acids.

[0417] When the present composition contains a curing aid, the content ratio of the curing aid is preferably within a range in which the present composition can be cured well to obtain a cured product. Specifically, it is preferably 0.000001 parts by mass or more, more preferably 0.001 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the total solid content of the polymer (A) or polymer (A2) and the compound (B) or compound (B2).

[0418] [Solvent]

[0419] The present composition may contain a solvent as necessary.

[0420] Examples of the solvent include: amide solvents such as N,N-dimethylformamide; ester solvents such as γ-butyrolactone and butyl acetate; ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone and 2-heptanone; ether solvents such as 1,2-methoxyethane, anisole and tetrahydrofuran; polyfunctional solvents such as 1-methoxy-2-propanol and propylene glycol methyl ether acetate; sulfone solvents such as dimethyl sulfoxide; dichloromethane, benzene, toluene, xylene and trialkoxybenzene (the number of carbon atoms in the alkoxy group: 1 to 4).

[0421] When the present composition contains a solvent, the content ratio of the solvent in the present composition is not particularly limited. For example, it is preferably from 0 to 2000 parts by mass, and more preferably from 0 to 100 parts by mass, relative to 100 parts by mass of the total solid content of the polymer (A) or polymer (A2) and the compound (B) or compound (B2).

[0422] When the polymer (A) or polymer (A2) or compound (B) or compound (B2) has high solubility in a solvent, the content of the solvent in the present composition may be 50 parts by mass or more and 200 parts by mass or less.

[0423] [additive]

[0424] Examples of additives used for the purpose of imparting various functions include antioxidants, flame retardants, and adhesion promoters. Specific compounds include, for example, hindered phenol compounds, phosphorus compounds, sulfur compounds, metal compounds, and hindered amine compounds. Among these, hindered phenol compounds are preferred.

[0425] The hindered phenol compound is preferably a compound having a molecular weight of 500 or more. Examples of the hindered phenol compound having a molecular weight of 500 or more include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-3,5-triazine, pentaerythritol tetrakis[3-(3,5-tert-butyl-4-hydroxyphenyl)propionate], 1,1,3-tris[2-methyl-4-〔3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy〕-5-tert-butylphenyl]butane, 2,2- Thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 3,9-bis[2-〔3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy〕-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 2,6-di-tert-butyl-p-cresol (BHT), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione [ADEKA (co., Ltd.), AO-020], 4,4',4"-(1-methylpropanyl-3-ylidene)tris(6-tert-butylm-cresol) is(6-tert-butyl-m-cresol))[manufactured by ADEKA Co., Ltd., AO-030], 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol[manufactured by ADEKA Co., Ltd., AO-040], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene[manufactured by ADEKA Co., Ltd., AO-330]. .

[0426] Examples of hindered amine compounds include 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-oxyl (Adekastab LA-7RD, manufactured by ADEKA Co., Ltd.); Irgastab UV 10 (4,4'-[(1,10-dioxy-1,10-decanediyl)bis(oxy)]bis[2,2,6,6-tetramethyl]-1-piperidinyloxy) (CAS.2516-92-9), Tinuvin 123 (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-N-oxyl) (both manufactured by BASF); FA-711HM, FA-712HM (2,2,6,6-tetramethylpiperidinyl methacrylate, manufactured by Showa Denko Materials Co., Ltd.); Tinuvin 111FDL, Tinuvin 144, Tinuvin 152, Tinuvin 292, Tinuvin 765, Tinuvin TINUVIN 770DF, TINUVIN 5100, SANOL LS-2626, CHIMASSORB 119FL, CHIMASSORB 2020FDL, CHIMASSORB 944FDL, TINUVIN 622LD (all manufactured by BASF); LA-52, LA-57, LA-62, LA-63P, LA-68LD, LA-77Y, LA-77G, LA-81, LA-82 (1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate), LA-87 (all manufactured by ADEKA (Co., Ltd.)

[0427] When the present composition contains the additive, the content ratio of the additive is preferably, for example, 0.001 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the total solid content of the polymer (A) or polymer (A2) and the compound (B) or compound (B2).

[0428] [Inorganic filler]

[0429] Examples of the inorganic filler include silicas such as natural silica, fused silica, and amorphous silica; white carbon, titanium dioxide, aerosol, alumina, talc, natural mica, synthetic mica, clay, barium sulfate, E-glass, A-glass, C-glass, L-glass, D-glass, S-glass, and M-glass G20.

[0430] When the present composition contains an inorganic filler, the content of the inorganic filler 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 content of the polymer (A) or polymer (A2) and the compound (B) or compound (B2). In addition, the inorganic filler may be dispersed in the solvent through the polymer (A).

[0431] [Organic fillers]

[0432] Examples of the organic filler include fluorine-based resins or fluorine-based particles such as polytetrafluoroethylene (PTFE), polyperfluoroalkoxy resins, polyfluorinated ethylene propylene resins, and polytetrafluoroethylene-polyethylene copolymers, polystyrene resins or particles, rubber-like resins or particles such as polybutadiene and styrene butadiene resins, and hollow particles having divinylbenzene or divinylbiphenyl as a shell.

[0433] When the present composition contains an organic filler, the content of the organic filler is preferably, for example, 0.1 to 300 parts by mass relative to 100 parts by mass of the total solid content of the polymer (A) or polymer (A2) and the compound (B) or compound (B2). The organic filler may be dispersed in a solvent through the polymer (A) or polymer (A2).

[0434] [Method for preparing the present composition]

[0435] The present composition can be prepared, for example, by uniformly mixing the polymer (A) or the polymer (A2), the compound (B) or the compound (B2) and the other components. There are no particular restrictions on the mixing order, mixing conditions, etc., and a known mixer can be used for mixing.

[0436] Hardened

[0437] A cured product according to one embodiment of the present invention (hereinafter also referred to as “the present cured product”) is a cured product of the present composition described above, and can be obtained by curing the present composition described above.

[0438] The present cured product may be, for example, a partially cured product of the present composition obtained by drying the solvent from the present composition.

[0439] The curing method of the present composition is not particularly limited, and generally, a method of heat curing by heating or a method of photocuring by irradiation with light can be used. Furthermore, these methods can also be used in combination.

[0440] In the case of thermal curing, the heating temperature is preferably 50° C. or higher, more preferably 100° C. or higher, and further preferably 120° C. or higher, and is preferably 250° C. or lower, and more preferably 220° C. or lower. The heating time is preferably 0.1 hour or higher, more preferably 0.5 hour or higher, and is preferably 36 hours or lower, and more preferably 5 hours or lower.

[0441] In the case of photocuring, examples of the light to be irradiated include visible light, ultraviolet light, near infrared light, and far infrared light.

[0442] Glass transition temperature (Tg)

[0443] The lower limit of Tg of the cured product is preferably 100° C., more preferably 110° C., and the upper limit is, for example, 300° C. When Tg is within the above range, melt molding can be more easily performed, and a cured product having excellent heat resistance can be easily obtained.

[0444] Regarding Tg, a test piece (width: 3 mm×length: 1 cm) was prepared and measured using a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments, model “EXSTAR 4000”) from 50°C to 300°C under nitrogen at a heating rate of 10°C / min and 1 Hz, and tanδ at this time was defined as the glass transition temperature (Tg). In addition, when there are two or more tanδ, the lowest value is defined as Tg.

[0445] In terms of reducing transmission loss, the dielectric loss tangent (tan δ) of the cured product is preferably 0.0025 or less, more preferably 0.0018 or less, and further preferably 0.0015 or less. The lower limit is not particularly limited, but is preferably 0.0005 or more. Specifically, the dielectric loss tangent can be measured by the method described in the following examples.

[0446] The coefficient of thermal expansion (CTE) of the present hardened material is preferably less than 70 ppm / K, more preferably less than 50 ppm / K, and further preferably less than 20 ppm / K. The lower limit is not particularly limited, but is preferably greater than 17 ppm / K. Specifically, the linear expansion coefficient can be measured by the method described in the following examples. If the CTE is within the above range, the difference in linear expansion coefficient between the present hardened material and a metal species such as copper wiring can be reduced.

[0447] The shape of the present cured product is not particularly limited, and may be in an appropriate shape depending on the application or purpose, and an example thereof may be a film. For example, the present composition may be melt-molded or cast to obtain a cured product in the form of a film.

[0448] The thickness of the film is not particularly limited and may be appropriately selected depending on the intended use, and is, for example, 10 μm or more, preferably 30 μm or more, and, for example, 2 mm or less, preferably 1 mm or less.

[0449] Layered

[0450] A laminate according to one embodiment of the present invention (hereinafter also referred to as “the present laminate”) includes, for example, a substrate and a cured layer formed using the present composition.

[0451] The present laminate may have two or more substrates, may have two or more hardened material layers, may have other layers known before other than the substrate and hardened material layers, etc. When the present laminate has two or more substrates or hardened material layers, or other layers, these may be the same layers (plates) or different layers (plates).

[0452] The present laminate may be a prepreg obtained by impregnating the present composition into a substrate such as glass cloth, polyaramid nonwoven fabric, polyester nonwoven fabric, and curing the substrate.

[0453] As the substrate, from the viewpoint of adhesiveness or practicality, there can be mentioned an inorganic substrate, a metal substrate, a resin substrate, etc. In addition, the substrate may be a prepreg.

[0454] Examples of the inorganic substrate include inorganic substrates having silicon, silicon carbide, silicon nitride, aluminum oxide, glass, gallium nitride, and the like as components.

[0455] Examples of the metal substrate include metal substrates containing copper, aluminum, gold, silver, nickel, palladium, and the like as components.

[0456] Examples of the resin substrate include resin substrates containing liquid crystal polymers, polyimides, polyphenylene sulfide, polyetheretherketone, polyamide (nylon), polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymers, polyolefins, and the like as components.

[0457] The hardened material layer can be formed, for example, by hardening by the method described in the hardened material column.

[0458] The thickness of the hardened material layer is not particularly limited, and is, for example, 1 μm to 3 mm.

[0459] "use"

[0460] The polymer (A), the present composition, the present cured product and the present laminate can be suitably used for structural materials used in transport industries such as aircraft industry or automobile industry, electrical and electronic materials used in electrical and electronic industry, etc. Specifically, for example, they can be suitably used for: sealing materials, interlayer insulating films, and primers for stress relaxation of electrical and electronic parts; laminate applications (for example: prepregs, copper-clad laminates, (multi-layer) printed wiring boards, interlayer adhesives, solder resists, and solder pastes); adhesive applications (for example: adhesive sheets for forming insulating layers, thermally conductive adhesives, and adhesive sheets); structural adhesives and prepregs used in various structural materials; various coatings and optical parts applications (for example: optical films such as wavelength plates and phase difference plates; various special lenses such as conical lenses, spherical lenses, and cylindrical lenses; lens arrays), and insulating films for printed wiring boards.

[0461] Electronic Parts

[0462] An electronic component of one embodiment of the present invention has the present hardened product or the present laminate. The electronic component may have two or more present hardened products or two or more present laminates, or may have one or more present hardened products and one or more present laminates. When having two or more present hardened products or the present laminates, these may be the same or different.

[0463] As the electronic parts, circuit substrates, semiconductor packages or display substrates can be listed. The present cured product (cured film) can be used as prepregs, copper-clad laminates, printed wiring boards, adhesive sheets for forming insulating layers, surface protective films, rewiring layers or planarization films for these electronic parts. The present cured product can maintain insulation even under high temperature and high humidity, so the electronic parts can protect the circuit pattern from the influence of external environments such as dust, heat, and moisture, and the insulation reliability between the circuit patterns is excellent, and can work stably all year round.

[0464] For example, metal is filled between patterns formed on the present hardened product (cured film) by plating or the like, and if necessary, the present hardened product (cured film) is further laminated and filled with metal, and the above operation is repeated to form a redistribution layer, thereby manufacturing an electronic component having a substrate and a redistribution layer including metal wiring and an insulating film.

[0465] Example

[0466] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples at all.

[0467] [Synthesis example 1]

[0468] 2,2-bis(4-hydroxy-3-methylphenyl)propane (51.27 g), α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (21.23 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g) and potassium carbonate (51.31 g) were measured in a four-necked separable flask equipped with a stirring device, and N-methyl-2-pyrrolidone (113.92 g) was added, and the mixture was reacted at 130° C. for 6 hours under a nitrogen atmosphere. After the reaction, chloromethylstyrene (38.55 g) was added dropwise while the container was cooled to 10° C., and the mixture was reacted at 65° C. for 6 hours. N-methyl-2-pyrrolidone (258.1 g) was added to the obtained reaction solution for dilution, and the salt was removed from the diluted solution by filtration, and the obtained solution was then added to methanol (4960 g). The precipitated solid was separated by filtration, washed with a small amount of methanol, separated by filtration again and recovered, and then dried in a vacuum dryer at 80°C under reduced pressure for 12 hours to obtain a polymer (A-1) represented by the following formula (yield 112.84 g, yield 91%).

[0469] [Chemistry 37]

[0470] Polymer (A-1)

[0471]

[0472] The above formula indicates that the polymer (A-1) is a polymer having the above structural unit. In the above formula, * indicates a bond with any **, and the polymer (A-1) has a group represented by the above formula (Y) at the polymer terminal. The same is true in the following synthesis examples.

[0473] [Synthesis example 2]

[0474] The same procedure as in Synthesis Example 1 was used to synthesize a polymer (A-2) represented by the following formula (yield 108.17 g, yield 89%), except that the raw materials used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (51.27 g), 4,4'-(2-hydroxybenzylidene)bis(2,3,6-trimethylphenol) (18.78 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), potassium carbonate (51.31 g), and chloromethylstyrene (38.55 g).

[0475] [Chemistry 38]

[0476] Polymer (A-2)

[0477]

[0478] [Synthesis example 3]

[0479] The same procedure as in Synthesis Example 1 was used to synthesize a polymer (A-3) represented by the following formula (yield 106.28 g, yield 90%), except that the raw materials used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (51.27 g), 1,1,1-tris(4-hydroxyphenyl)ethane (15.32 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), potassium carbonate (51.31 g), and chloromethylstyrene (38.55 g).

[0480] [Chemistry 39]

[0481] Polymer (A-3)

[0482]

[0483] [Synthesis Example 4]

[0484] The same procedure as in Synthesis Example 1 was used to synthesize a polymer (A-4) represented by the following formula (yield 104.48 g, yield 89%), except that the raw materials used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (51.27 g), tris(4-hydroxyphenyl)methane (14.62 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), potassium carbonate (51.31 g), and chloromethylstyrene (38.55 g).

[0485] [Chemistry 40]

[0486] Polymer (A-4)

[0487]

[0488] [Synthesis Example 5]

[0489] The same procedure as in Synthesis Example 1 was used to synthesize a polymer (A-5) represented by the following formula (yield 118.31 g, yield 91%), except that the raw materials used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (51.27 g), 1,1,1-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (27.24 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), potassium carbonate (51.31 g), and chloromethylstyrene (38.55 g).

[0490] [Chemistry 41]

[0491] Polymer (A-5)

[0492]

[0493] [Synthesis example 6]

[0494] The same procedure as in Synthesis Example 1 was used to synthesize a polymer (A-6) represented by the following formula (yield 121.50 g, yield 88%), except that the raw materials used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (51.27 g), 4,4',4",4"'-(propane-2,2-diylbis(cyclohexane-4,1,1-triyl))tetraphenol (28.84 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), potassium carbonate (55.98 g), and chloromethylstyrene (49.15 g).

[0495] [Chemistry 42]

[0496] Polymer (A-6)

[0497]

[0498] [Synthesis Example 7]

[0499] The same procedure as in Synthesis Example 1 was used to synthesize polymer (A-7) (yield 110.00 g, yield 92%) except that the raw materials used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (57.68 g), 1,1,1-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (13.62 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), potassium carbonate (48.98 g), and chloromethylstyrene (33.25 g). Polymer (A-7) has the same structure as that of polymer (A-5) except that the content ratio of each repeating unit is different.

[0500] [Synthesis example 8]

[0501] The same procedure as in Synthesis Example 1 was used to synthesize polymer (A-8) (yield 141.97 g, yield 88%) except that the raw materials used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (32.04 g), 1,1,1-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (68.10 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), potassium carbonate (58.31 g), and chloromethylstyrene (54.45 g). Polymer (A-8) has the same structure as that of polymer (A-5) except that the content ratio of each repeating unit is different.

[0502] [Synthesis Example 9]

[0503] The same procedure as in Synthesis Example 1 was used to synthesize a polymer (A-9) represented by the following formula (yield 112.84 g, yield 89%), except that the raw materials used were changed to 4,4'-dihydroxy-2,2',3,3',5,5'-hexamethylbiphenyl (54.07 g), α,α,α'-tri(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (21.23 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), potassium carbonate (51.31 g), and chloromethylstyrene (38.55 g).

[0504] [Chemistry 43]

[0505] Polymer (A-9)

[0506]

[0507] [Synthesis Example 10]

[0508] The same procedure as in Synthesis Example 1 was used to synthesize a polymer (A-10) represented by the following formula (yield 97.96 g, yield 88%), except that the raw materials used were changed to 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (56.77 g), α,α,α'-tri(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (15.92 g), 4,6-dichloro-2-phenylpyrimidine (31.07 g), potassium carbonate (38.48 g), and chloromethylstyrene (28.91 g).

[0509] [Chemistry 44]

[0510] Polymer (A-10)

[0511]

[0512] [Synthesis Example 11]

[0513] The same procedure as in Synthesis Example 1 was used to synthesize a polymer (A-11) represented by the following formula (yield 98.83 g, yield 92%), except that the raw materials used were changed to 4,4'-(cyclododecane-1,1-diyl)diphenol (52.88 g), α,α,α'-tri(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene (15.92 g), 4,6-dichloro-2-phenylpyrimidine (31.07 g), potassium carbonate (38.48 g), and chloromethylstyrene (28.91 g).

[0514] [Chemistry 45]

[0515] Polymer (A-11)

[0516]

[0517] [Synthesis Example 12]

[0518] The same procedure as in Synthesis Example 1 was used to synthesize a polymer (A'-12) represented by the following formula (yield 100.40 g, yield 92%), except that the raw materials used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (64.09 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), potassium carbonate (46.65 g), and chloromethylstyrene (27.95 g).

[0519] [Chemistry 46]

[0520] Polymer (A'-12)

[0521]

[0522] [Synthesis Example 13]

[0523] The same procedure as in Synthesis Example 1 was used to synthesize a polymer (A'-13) represented by the following formula (yield 93.06 g, yield 89%), except that the raw materials used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (64.09 g), 4,6-dichloro-2-phenylpyrimidine (31.08 g), 4,6-dichloropyrimidine (6.86 g), potassium carbonate (46.65 g), and chloromethylstyrene (22.01 g).

[0524] [Chemistry 47]

[0525] Polymer (A'-13)

[0526]

[0527] [Synthesis Example 14]

[0528] A polymer (A'-14) represented by the following formula was obtained by synthesizing in the same manner as in the production example described in JP-A-2020-200425 except that the raw material used was changed to 1,1,1-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane.

[0529] [Chemistry 48]

[0530] Polymer (A'-14)

[0531]

[0532] [Synthesis Example 15]

[0533] The same procedure as in Synthesis Example 1 was used to synthesize a polymer (A-15) represented by the following formula (yield 133.27 g, yield 88%), except that the raw materials used were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (51.27 g), 4,4',4",4"'-(propane-2,2-diylbis(cyclohexane-4,1,1-triyl))tetrakis(2-methylphenol) (31.63 g), 4,6-dichloro-2-phenylpyrimidine (41.43 g), potassium carbonate (55.98 g), and chloromethylstyrene (49.15 g).

[0534] [Chemistry 49]

[0535] Polymer (A-15)

[0536]

[0537] [Weight average molecular weight (Mw), number average molecular weight (Mn)]

[0538] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymers synthesized in Synthesis Examples 1 to 15 and SA-9000 used in the following Comparative Examples were measured using a GPC apparatus ("HLC-8320" manufactured by Tosoh Co., Ltd.) under the following conditions. The results are shown in Table 1.

[0539] Column: A column that combines "TSK gel α-M" manufactured by Tosoh Corporation and "TSK gel guard column α" manufactured by Tosoh Corporation

[0540] ·Developing solvent: N-methyl-2-pyrrolidone

[0541] Column temperature: 40℃

[0542] Flow rate: 1.0mL / min

[0543] Sample concentration: 0.75 mass%

[0544] Sample injection volume: 50μL

[0545] Detector: Refractometer

[0546] ·Standard material: monodisperse polystyrene

[0547] ·Concentration of the sample for measurement: 0.1 mass%

[0548] <Glass transition temperature (Tg) of polymer>

[0549] The polymer to be measured (polymers synthesized in Synthesis Examples 1 to 15 and SA-9000) 100 parts by mass, Percumyl D (manufactured by NOF Corporation) 0.5 parts by mass, and toluene 100 parts by mass were mixed to prepare a varnish for evaluation. Next, the prepared varnish for evaluation was applied to a copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metal Co., Ltd.) using a Baker applicator (gap: 75 μm), and dried at 100°C for 5 minutes to form a coating film. A copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metal Co., Ltd.) was overlapped on the obtained coating film, vacuum pressed at 150°C for 5 minutes, and then calcined at 200°C under nitrogen for 2 hours to prepare a cured film with copper foil. The produced cured film with copper foil was immersed in a 40 mass % ferric chloride solution, the copper foil was removed from the cured film with copper foil, and then washed with water and dried at 80° C. for 30 minutes to produce a film for measuring glass transition temperature (Tg) having a thickness of 50 μm.

[0550] A test piece (width: 3 mm×length: 1 cm) was cut out from the produced Tg measurement film, and measured using a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments Co., Ltd., model “EXSTAR 4000”) from 50°C to 300°C at a heating rate of 10°C / min and 1 Hz, and tanδ at this time was defined as the glass transition temperature (Tg). The results are shown in Table 1.

[0551] <Dielectric loss tangent>

[0552] The same method as the Tg measurement film was used to cut a test piece (width: 6 cm × length: 6 cm) from the prepared cured film, and the dielectric loss tangent of the test piece at 10 GHz was measured using a cavity resonator method (AET (stock) manufacturing, dielectric constant measurement system TE mode resonator). The case where the dielectric loss tangent is less than 0.0025 is set to "0", and the case where it is greater than 0.0025 is set to "×". The results are shown in Table 1.

[0553] <Peel strength of polymer>

[0554] The polymer to be measured (polymers synthesized in Synthesis Examples 1 to 15 and SA-9000) 100 parts by mass, Percumyl D (manufactured by NOF Corporation) 0.5 parts by mass, and toluene 100 parts by mass were mixed to prepare a varnish for evaluation. Next, the prepared varnish for evaluation was applied to a copper foil (model: CF-V9S-SV, manufactured by Fukuda Metal Co., Ltd.) using a Baker applicator (gap: 75 μm), heated at 100°C for 5 minutes, and then dried at 130°C for 5 minutes to form a coating film. A copper foil (model: CF-V9S-SV, manufactured by Fukuda Metal Co., Ltd.) was overlapped on the obtained coating film, vacuum pressed at 150°C for 5 minutes, and then calcined at 200°C under nitrogen for 2 hours to prepare a cured film with copper foil (copper foil: 18 μm, cured film 10 μm), which was used as a sample for peel strength.

[0555] A test piece (width: 5 mm × length: 10 cm) was cut out from the prepared peel strength sample, and the copper foil with the cured film (the laminated portion of one copper foil and the cured film in the peel strength sample) was stretched in a 90-degree direction at 500 mm / min using "Instron 5567" manufactured by Instron, and the peel strength was measured according to "IPC-TM-650 2.4.9". The peel strength was 0.70 N / mm or more as "0", and the peel strength was less than 0.70 N / mm as "×". The results are shown in Table 1.

[0556]

[0557] [Examples 1 to 23, Comparative Examples 1 to 8]

[0558] The components described in the combination species column described in Table 2-1 and Table 2-2 (hereinafter collectively referred to as "Table 2") were mixed using a mixing rotor in a ratio (parts by mass) described in the composition formulation ratio column, and the concentration was adjusted using toluene so that the solid content concentration became 50 parts by mass, thereby preparing a composition.

[0559] <Production of Cured Film>

[0560] The composition obtained in the above-mentioned examples and comparative examples was applied to a copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metal Co., Ltd.) using a Baker applicator (gap: 125 μm), and then heated at 100°C for 5 minutes, and then dried at 140°C for 5 minutes to form a coating film. A copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metal Co., Ltd.) was stacked on the obtained coating film, vacuum pressed at 160°C for 10 minutes, and then calcined at 200°C under nitrogen for 2 hours to prepare a cured film with copper foil (copper foil: 18 μm, cured film 50 μm to 100 μm). The obtained cured film with copper foil was immersed in a 40% by mass ferric chloride solution, the copper foil was removed, and then washed with water and dried in an oven at 80°C for 30 minutes to prepare a cured film with a thickness of 50 μm.

[0561] <Glass transition temperature (Tg)>

[0562] A test piece (width: 3 mm × length: 1 cm) was cut out from the produced cured film, and a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments, "EXSTAR 4000") was used to measure the temperature from 50°C to 300°C at a heating rate of 10°C / min and 1 Hz, and tanδ at this time was defined as the glass transition temperature (Tg). The results are shown in Table 2. In addition, when there are two or more tanδ, the lowest value is defined as Tg.

[0563] <Dielectric loss tangent>

[0564] A test piece (width: 6 cm × length: 6 cm) was cut out from the prepared cured film, and the dielectric loss tangent of the test piece at 10 GHz was measured using a cavity resonator method (AET (stock) manufacturing, dielectric constant measurement system TE mode resonator). The case where the dielectric loss tangent is less than 0.0025 is set to "0", and the case where it is greater than 0.0025 is set to "×". The results are shown in Table 2.

[0565] <Peel strength>

[0566] 70 parts by mass of polymer (polymers synthesized in Synthesis Examples 1 to 15 and SA-9000), 30 parts of TAIC or DVB960, 0.5 parts by mass of Percumyl D (manufactured by NOF Corporation), and 100 parts by mass of toluene were mixed to prepare a varnish for evaluation. Next, the prepared varnish for evaluation was applied to a copper foil (model: CF-V9S-SV, manufactured by Fukuda Metal Co., Ltd.) using a Baker applicator (gap: 125 μm), heated at 100°C for 5 minutes, and then dried at 130°C for 5 minutes to form a coating film. Copper foil (model: CF-V9S-SV, manufactured by Fukuda Metal Co., Ltd.) was overlapped on the obtained coating film, vacuum pressed at 150°C for 5 minutes, and then calcined at 200°C under nitrogen for 2 hours to prepare a cured film with copper foil (copper foil: 18 μm, cured film 10 μm), which was used as a sample for peel strength.

[0567] A test piece (width: 5 mm × length: 10 cm) was cut out from the prepared peel strength sample, and the copper foil with the cured film (the laminated portion of one copper foil and the cured film in the peel strength sample) was stretched in a 90-degree direction at 500 mm / min using "Instron 5567" manufactured by Instron, and the peel strength was measured in accordance with "IPC-TM-650 2.4.9". The peel strength was 0.70 N / mm or more as "0", and the peel strength was less than 0.70 N / mm as "×". The results are shown in Table 2.

[0568] <Coefficient of Linear Expansion (CTE)>

[0569] 70 parts by mass of polymer (polymers synthesized in Synthesis Examples 1 to 15 and SA-9000), 30 parts of TAIC or DVB960, 0.5 parts by mass of Percumyl D (manufactured by NOF Corporation), and 100 parts by mass of toluene were mixed to prepare a varnish for evaluation. Next, the prepared varnish for evaluation was applied to a copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metal Co., Ltd.) using a Baker applicator (gap: 125 μm), heated at 100°C for 5 minutes, and then dried at 140°C for 5 minutes to form a coating film. Copper foil (model: CF-T49A-DS-HD2, manufactured by Fukuda Metal Co., Ltd.) was overlapped on the obtained coating film, vacuum pressed at 160°C for 10 minutes, and then calcined at 200°C under nitrogen for 2 hours to prepare a cured film with copper foil (copper foil: 18 μm, cured film 50 μm to 100 μm). The produced cured film with copper foil was immersed in a 40 mass % ferric chloride solution, the copper foil was removed from the cured film with copper foil, and then washed with water and dried at 80° C. for 30 minutes to produce a film for CTE measurement.

[0570] The linear expansion coefficient of the prepared CTE measurement film was measured using a SSC-5200 thermomechanical analysis (TMA) measuring device manufactured by Seiko Instruments. At this time, the linear expansion coefficient was calculated based on the gradient of the TMA curve at 80°C to 120°C when the CTE measurement film was heated to a temperature 20°C higher than its glass transition temperature at 5°C / min and then lowered. The case where CTE is less than 70ppm / K is set to "0", and the case where it is more than 70ppm / K is set to "×". The results are shown in Table 2.

[0571]

[0572]

[0573] The abbreviations used in Tables 1 and 2 are described below.

[0574] <Polymer>

[0575] ·SA-9000: Made by Saudi Basic Industries (Sabic), terminal-modified polyphenylene ether <hardening compound>

[0576] TAIC: Manufactured by Mitsubishi Chemical Corporation, triallyl isocyanurate

[0577] ·DVB960: manufactured by Nippon Steel Chemical & Materials Co., Ltd., divinylbenzene (divinylbenzene 96% by mass) <Initiator>

[0578] ·DCP: dicumyl peroxide, Percumyl D, manufactured by NOF Corporation.

Claims

1. A polymer (A) having a repeating structural unit represented by the following formula (1). [Chemistry 1] [In the formula (1), R 11 represents a divalent substituted or unsubstituted nitrogen-containing heteroaromatic ring, R 12 independently represent a divalent substituted or unsubstituted aromatic hydrocarbon group, R 13 Indicates that the two R 12 In addition, at least one hydrocarbon group having 1 to 20 carbon atoms is bonded to a group represented by the following formula (a1), X 1 independently represents -O-, -S- or -N(R 14 )-, R 14 A hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group in which a part of the hydrocarbon group or halogenated hydrocarbon group is substituted with at least one selected from an oxygen atom and a sulfur atom.] [Chemistry 2] *-R 12 -X 1 -** (a1) [In the above formula (a1), * indicates that for the R 13 The key, ** represents the bonding bond with other structural units in the polymer (A), R 12 and X 1 Respectively with R in the formula (1) 12 and X 1 have the same meaning.] 2. The polymer (A) according to claim 1, further comprising a repeating structural unit represented by the following formula (2). [Chemistry 3] [In the formula (2), R 21 represents a divalent substituted or unsubstituted nitrogen-containing heteroaromatic ring, R 22 represents a divalent group containing a substituted or unsubstituted aromatic hydrocarbon group in the main chain, X 2 independently represents -O-, -S- or -N(R 24 )-, R 24 A hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group in which a part of the hydrocarbon group or halogenated hydrocarbon group is substituted with at least one selected from an oxygen atom and a sulfur atom.] 3 . The polymer (A) according to claim 1 , which has a group Y represented by the following formula (y) at the terminal. [Chemistry 4] -Y (y) [In the above formula (y), Y is a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic ring.] 4. The polymer (A) according to claim 1, wherein When all the structural units contained in the polymer (A) are taken as 100 mol %, the repeating structural unit represented by the formula (1) is contained in the range of 5 mol % to 95 mol %.

5. The polymer (A) according to claim 1, wherein In the formula (1) and formula (a1), -R 12 - are independently a structure represented by the following formula (5). [Chemistry 5] [In the above formula (5), * indicates that for the R 13 The key, *** indicates that the X 1 The bond of R 51 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, n 52 Integer from 0 to 4, n 53 Indicates an integer from 0 to 2. ] 6. The polymer (A) according to claim 5, wherein The structure represented by the formula (5) is the following formula (5-1) or the following formula (5-2). [Chemistry 6] [In the above formula (5-1) and formula (5-2), * indicates that for the R 13 The key, *** indicates that the X 1 The bond of R 51 and n 53 With R in formula (5) 51 and n 53 For the same meaning, n 54 Integer from 0 to 3, n 55 represents an integer from 0 to 2, R 52 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms.] 7 . A composition comprising the polymer (A) according to claim 1 and a curable compound (B) other than the polymer (A).

8. The composition according to claim 7, wherein The curable compound (B) includes at least one selected from the group consisting of vinyl compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, thiol compounds, oxazine compounds, cyanate compounds, epoxy compounds, oxetane compounds, methylol compounds, benzocyclobutene compounds, propargyl compounds and silane compounds.

9. The composition according to claim 7, further comprising at least one selected from the group consisting of hindered phenol compounds, phosphorus compounds, sulfur compounds, metal compounds and hindered amine compounds.

10. A composition comprising a polymer (A2) having a repeating structural unit represented by the following formula (3) and a repeating structural unit represented by the following formula (4), and a curable compound (B2) other than the polymer (A2). [Chemistry 7] [In the formula (3), R 31 represents a divalent organic group having 3 to 10 carbon atoms, R 32 independently represent a divalent substituted or unsubstituted aromatic hydrocarbon group, R 33 Indicates that there are two R bonds 12 A hydrocarbon group having 1 to 20 carbon atoms and at least one group represented by the following formula (a2). [Chemistry 8] *-R 32 -O-** (a2) [In the formula (a2), * indicates that for the R 33 The key, ** represents the bonding bond with other structural units in the polymer (A2), R 32 With R in the formula (3) 32 have the same meaning.] [Chemistry 9] [In the above formula (4), R 41 represents a divalent organic group having 3 to 10 carbon atoms, R 42 It represents a divalent group containing a substituted or unsubstituted aromatic hydrocarbon group in the main chain, wherein the oxygen atom in the formula is directly bonded to the aromatic hydrocarbon group.] 11. The composition according to claim 10, wherein The polymer (A2) has a group Y represented by the following formula (y) at the terminal. [Chemistry 10] -Y (y) [In the above formula (y), Y is a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic ring.] 12. The composition according to claim 10, wherein The curable compound (B2) includes at least one selected from the group consisting of vinyl compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, thiol compounds, oxazine compounds, cyanate compounds, epoxy compounds, oxetane compounds, methylol compounds, benzocyclobutene compounds, propargyl compounds and silane compounds.

13. The composition according to claim 10, further comprising an antioxidant.

14. A hardened product, which is a hardened product of the composition according to claim 7 or 10. 15 . A laminate comprising a substrate and a cured layer formed using the composition according to claim 7 or 10.

16. An electronic component comprising the cured product according to claim 14.

17. An electronic component comprising the laminate according to claim 15.

Images