Polymer, composition, cured product, laminated body, and electronic component

Abstract

One embodiment of the present invention relates to a polymer, a composition, a cured product, a laminated body, or an electronic component, said composition including a polymer containing a repeating unit that is represented by formula (1). [In formula (1): -N(R')-R3-N(R')- is a structure derived from a dimer diamine substituted by an unsubstituted group or a substituted group; R', R1, and R2 each independently represent a hydrogen atom, a halogen atom, a C1-20 hydrocarbon group substituted by an unsubstituted or a substituted group, a C3-20 heterocyclic aliphatic group substituted by an unsubstituted or a substituted group, or a C3-20 heterocyclic aromatic group substituted by an unsubstituted or a substituted group; and -NR1R2 may be a nitrogen-containing heterocyclic group with 5-20 ring-forming atoms in which R1 and R2 are bound to each other.]

Description

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

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

[0002] In recent years, with the pursuit of miniaturization, multifunctionality, and faster communication speeds for electronic devices, there has been a demand for even thinner and more flexible flexible printed wiring boards. For this reason, a technique for constructing a multilayer printed wiring board by laminating a resin film has attracted attention as a method for manufacturing a multilayer printed wiring board. Multilayer printed wiring boards formed by laminating a resin film are known to have weaknesses in mechanical strength, heat resistance, flame retardancy, and thermal conductivity compared to those formed using prepregs manufactured using glass cloth or the like. Recently, techniques for improving these weaknesses have been reported (see, for example, Patent Documents 1 to 3).

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 11-129399 Patent Document 2: International Publication No. 2001 / 097582 Patent Document 3: International Publication No. 2005 / 025857

[0004] In order to improve the mechanical strength, heat resistance, flame retardancy, and thermal conductivity, attempts have been made to add curing agents such as epoxy compounds, cyanate compounds, and acrylic compounds, and inorganic fillers such as silica and alumina, but the effects of these additions have not been sufficient. Furthermore, in the process of manufacturing a multilayer printed wiring board, it is sometimes required to bond each electronic component material using a polymer (or a composition containing a polymer), and in this case, it is required that the polymer or a composition containing a polymer can be uniformly applied to the substrate (excellent application properties), and that the layer obtained from the polymer or the composition containing the polymer has high adhesion to the substrate.

[0005] However, conventional polymers such as the polymers described in the above patent documents have insufficient solubility in common solvents, the polymers or compositions containing the polymers cannot be uniformly applied to a substrate (poor coatability), and the adhesion of layers obtained from the polymers or compositions containing the polymers to a substrate (hereinafter also simply referred to as "adhesion to a substrate") is insufficient.

[0006] One embodiment of the present invention provides a polymer that is excellent in heat resistance, soluble in a general-purpose solvent, and has excellent coatability and adhesion to a substrate, and also provides a composition that can form a cured product (cured product layer) that has excellent heat resistance and has excellent coatability and adhesion to a substrate.

[0007] The present inventors have found that the above-mentioned problems can be solved by the following configuration example. The configuration example of the present invention is as follows.

[0008] [1] A composition comprising a polymer containing a repeating unit represented by the following formula (1):

[0009] [In formula (1), -N(R')-R 3 -N(R')- is a structure derived from unsubstituted or substituted dimer diamine, and R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic group having 3 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, and —NR 1 R 2 is R 1 and R 2 and may be bonded to each other to form a nitrogen-containing heterocyclic group having 5 to 20 ring atoms.]

[0010] [2] The composition according to [1], wherein the polymer further contains a repeating unit represented by the following formula (2):

[0011] [In formula (2), R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic group having 3 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, and R 4 represents a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, -(R41 -O) m -, a divalent silicon-containing group, a group in which two or more selected from these groups are combined, a group in which at least a portion of these groups is substituted with at least one atom selected from oxygen atoms, nitrogen atoms and sulfur atoms, or a group in which a portion of these groups is substituted with a substituent, and R 41 are independently alkylene having 2 to 4 carbon atoms, m is an integer of 1 to 70, and —NR 1 R 2 is R 1 and R 2 and may be a nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which they are bonded to each other, and —N(R′)—R 4 - is R' and R 4 and may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which the ring atoms are bonded to each other, and —N(R′)—R 4 -N(R')- may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which two R's are bonded to each other.

[0012] [3] The composition according to [1] or [2], further comprising a curable compound (C). [4] The composition according to any one of [1] to [3], further comprising a curing aid (D). [5] The composition according to any one of [1] to [4], further comprising a solvent.

[0013] [6] The composition according to [3], wherein the curable compound (C) is at least one selected from the group consisting of epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, oxetane compounds, methylol compounds, (meth)acrylic compounds, oxazoline compounds, and propargyl compounds.

[0014] [7] A cured product obtained by curing the composition according to any one of [1] to [6]. [8] A laminate having a substrate and a cured product layer formed using the composition according to any one of [1] to [6]. [9] An electronic component having the laminate according to [8].

[0015]

[10] A polymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2):

[0016]

[0017] [In formulas (1) and (2), —N(R′)—R 3 -N(R')- is a structure derived from unsubstituted or substituted dimer diamine, and R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic group having 3 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, and R 4 represents a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, -(R 41 -O) m -, a divalent silicon-containing group, a group in which two or more selected from these groups are combined, a group in which at least a portion of these groups is substituted with at least one atom selected from oxygen atoms, nitrogen atoms and sulfur atoms, or a group in which a portion of these groups is substituted with a substituent, and R 41 are independently alkylene having 2 to 4 carbon atoms, m is an integer of 1 to 70, and —NR 1 R 2 is R 1 and R 2 and may be a nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which they are bonded to each other, and —N(R′)—R 4 - is R' and R 4 and may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which the ring atoms are bonded to each other, and —N(R′)—R 4 -N(R')- may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which two R's are bonded to each other.

[0018]

[11] A molded article obtained by molding the polymer according to

[10] .

[12] A laminate having a substrate and a layer formed using the polymer according to

[10] .

[13] An electronic component having the laminate according to

[12] .

[0019]

[14] A polymer containing a repeating unit represented by the following formula (1), or a polymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), and having at least one group selected from a phenolic hydroxyl group, an allyl group, a vinyl group, a (meth)acryloyl group, a maleimide group, a propargyl group, an ethynyl group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a heterocyclic group at a terminal.

[0020]

[0021] [In formulas (1) and (2), —N(R′)—R 3 -N(R')- is a structure derived from unsubstituted or substituted dimer diamine, and R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic group having 3 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, and R 4 represents a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, -(R 41 -O) m -, a divalent silicon-containing group, a group in which two or more selected from these groups are combined, a group in which at least a portion of these groups is substituted with at least one atom selected from oxygen atoms, nitrogen atoms and sulfur atoms, or a group in which a portion of these groups is substituted with a substituent, and R 41 are independently alkylene having 2 to 4 carbon atoms, m is an integer of 1 to 70, and —NR 1 R 2 is R 1 and R 2and may be a nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which they are bonded to each other, and —N(R′)—R 4 - is R' and R 4 and may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which the ring atoms are bonded to each other, and —N(R′)—R 4 -N(R')- may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which two R's are bonded to each other.

[0022] According to one embodiment of the present invention, it is possible to provide a polymer that has excellent heat resistance, is soluble in a general-purpose solvent, and has excellent coatability and adhesion to substrates such as copper substrates and gold substrates. Furthermore, according to one embodiment of the present invention, it is possible to provide a composition that can form a cured product (cured product layer) that has excellent heat resistance and has excellent coatability and adhesion to substrates such as copper substrates and gold substrates.

[0023] FIG. 1 shows the polymer obtained in Example 2. 1 2 is a H-NMR spectrum of the polymer obtained in Example 5. 1 3 is a H-NMR spectrum of the polymer obtained in Example 6. 1 4 is a H-NMR spectrum of the polymer obtained in Example 8. 1 5 is a H-NMR spectrum of the polymer obtained in Example 9. 1 6 shows the H-NMR spectrum of the polymer obtained in Example 10. 1 1 H-NMR spectrum.

[0024] Preferred embodiments of the present invention will be described in detail below. It should be understood that the present invention is not limited to the embodiments described below, but also includes various modifications that are implemented within the scope of the present invention. In this specification, a numerical range described using "to" means that the numerical values ​​before and after "to" are included as the lower and upper limits.

[0025] 1. Polymer and Composition A composition according to one embodiment of the present invention (hereinafter also referred to as "the composition") contains a polymer (hereinafter also referred to as "polymer (1)") having a repeating unit represented by the following formula (1). The polymer (1) contained in the composition may be one type or two or more types.

[0026] A polymer according to one embodiment of the present invention (hereinafter also referred to as "polymer (2)") contains a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2). Polymer (2) may have structural units other than the repeating unit represented by formula (1) and the repeating unit represented by formula (2).

[0027] A polymer according to one embodiment of the present invention (hereinafter also referred to as "polymer (3)") is a polymer having at least one group (hereinafter also referred to as "terminal group") selected from a phenolic hydroxyl group, an allyl group, a vinyl group, a (meth)acryloyl group, a maleimide group, a propargyl group, an ethynyl group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a heterocyclic group at the terminal of polymer (1) or polymer (2). Polymer (3) may have a repeating unit represented by formula (1), a repeating unit represented by the following formula (2), and a structural unit other than the terminal group. In the present invention, "terminal" refers to at least one terminal of the main chain (longest chain) of the polymer, and includes, for example, -NR in formula (1) below. 1 R 2 is not called a terminal. Hereinafter, polymers (1) to (3) will be collectively referred to as "the present polymer."

[0028] The repeating unit represented by formula (1) below is bonded to, for example, another structural unit or a terminal structure as shown below. Examples of the terminal structure include a structure derived from a raw material constituting the repeating unit represented by formula (1) below (e.g., a compound represented by formula (A) or (B) below) or a structure derived from an end-capping agent as shown below, and are preferably the terminal groups described above. The repeating unit represented by formula (2) below is bonded to, for example, a repeating unit represented by formula (1) below or a terminal structure. Examples of the terminal structure include a structure derived from a raw material constituting the repeating unit represented by formula (2) below (e.g., a compound represented by formula (A) or (C) below) or a structure derived from an end-capping agent as shown below, and are preferably the terminal groups described above.

[0029] <<Present Polymer>> The present polymer is a polymer having a repeating unit represented by the following formula (1). By having the present polymer have a repeating unit represented by the following formula (1), it is possible to obtain a polymer having excellent solubility in solvents, and it is possible to improve the coatability onto substrates, etc. Two or more types of present polymers can be used for the purpose of adjusting the solubility in the following solvents, the solubility with other components, and various physical properties of the composition.

[0030] [In formula (1), -N(R')-R 3 -N(R')- is a structure derived from unsubstituted or substituted dimer diamine, and R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic group having 3 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, and —NR 1 R 2 is R 1 and R 2 and may be bonded to each other to form a nitrogen-containing heterocyclic group having 5 to 20 ring atoms.]

[0031] Examples of the structure derived from an unsubstituted or substituted dimer diamine include a divalent dimer acid diamine residue derived from a dimer acid diamine, and a group in which at least a portion of the divalent dimer acid diamine residue is substituted with a substituent.

[0032] Dimer acid diamines are diamines in which the two terminal carboxylic acid groups (-COOH) of dimer acids (cyclic and acyclic dimer acids (mainly containing 36 carbon atoms) obtained as dimers of unsaturated fatty acids (containing 18 carbon atoms)) are substituted with primary aminomethyl groups (-CH-NH) or amino groups (-NH). The dimer acid diamines are compounds derived from dimer acids, which are dimers of unsaturated fatty acids such as oleic acid (see, for example, JP-A-9-12712), and various known dimer diamines can be used without particular limitation.

[0033] Dimer acids are known dibasic acids obtained by the intermolecular polymerization reaction of unsaturated fatty acids. Their industrial production process is largely standardized within the industry. They are typically obtained by dimerizing unsaturated fatty acids having 11 to 22 carbon atoms using a clay catalyst or the like. Industrially obtained dimer acids typically consist primarily of a 36-carbon dibasic acid obtained by dimerizing 18-carbon unsaturated fatty acids, such as oleic acid or linoleic acid. Depending on the degree of purification, however, they may contain arbitrary amounts of monomer acid (18 carbon atoms), trimer acid (54 carbon atoms), and other polymerized fatty acids having 20 to 54 carbon atoms. In one embodiment of the present invention, it is preferable to use dimer acids whose dimer acid content has been increased to 90% by mass or more by molecular distillation. Furthermore, in one embodiment of the present invention, if double bonds remain after the dimerization reaction, dimer acids further subjected to a hydrogenation reaction to reduce the degree of unsaturation are also included in the definition of dimer acids.

[0034] The polymer's structure derived from a dimer acid diamine can impart to it the properties derived from the dimer acid skeleton, specifically the following properties. Because dimer acid diamines are aliphatic macromolecules with molecular weights of approximately 500 to 620 and containing multiple isomeric structures, they can increase the molar volume of the polymer and relatively reduce the amount of polar groups in the polymer. These characteristics of dimer acid diamines are believed to contribute to improving the dielectric properties of the polymer while suppressing a decrease in its heat resistance. Furthermore, when a dimer acid diamine has two freely movable hydrophobic chains with 4 to 9 carbon atoms and two linear aliphatic amino groups with a length close to 8 to 10 carbon atoms, the structure derived from the dimer acid diamine not only imparts flexibility to the polymer but also allows the polymer to have an asymmetric or non-planar chemical structure. This is believed to improve the solubility of the polymer.

[0035] Non-limiting structural formulas of dimer diamines are shown below: In each of the following formulas, m+n=6 to 17, p+q=8 to 19, and the wavy lines represent carbon-carbon single bonds or carbon-carbon double bonds.

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044] The dimer diamine is preferably a compound having an active hydrogen equivalent of 130 to 140 and an amine value of 180 to 220.

[0045] Commercially available dimer acid diamines include, for example, Versamine 551 (manufactured by BASF Japan Ltd.), Versamine 552 (manufactured by Cognix Japan Ltd.; a hydrogenated product of Versamine 551), Priamine 1075, and Priamine 1074 (all manufactured by Croda Japan Ltd.).

[0046] R', R 1 and R 2 Examples of the halogen atom in the formula include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0047] R', R 1 and R 2 Examples of the hydrocarbon group having 1 to 20 carbon atoms in R', R include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group, or a group formed by combining these groups. 1 and R 2 The heterocyclic aliphatic group having 3 to 20 carbon atoms in R' and R' includes a monovalent heterocyclic aliphatic group. 1 and R 2 The heterocyclic aromatic group having 3 to 20 carbon atoms in the formula (I) includes a monovalent heterocyclic aromatic group. These hydrocarbon groups, heterocyclic aliphatic groups, and heterocyclic aromatic groups may be substituted with a substituent.

[0048] Examples of the monovalent chain hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group; alkenyl groups such as an ethenyl group, a propenyl group, a butenyl group, and a pentenyl group; and alkynyl groups such as an ethynyl group, a propynyl group, a butynyl group, and a pentynyl group.

[0049] Examples of the monovalent alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; polycyclic cycloalkyl groups such as a norbornyl group and an adamantyl group; monocyclic cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group; and polycyclic cycloalkenyl groups such as a norbornenyl group.

[0050] Examples of the monovalent aromatic hydrocarbon group include aryl groups such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthryl group.

[0051] Examples of the group formed by combining these groups include aralkyl groups such as benzyl, phenethyl, phenylpropyl, and naphthylmethyl.

[0052] Examples of the monovalent heterocyclic aliphatic group include monovalent heterocyclic aliphatic groups derived from heterocycles such as aziridine, oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, pyrroline, piperidine, piperideine, pyrazolidine, imidazolidine, imidazoline, tetrahydrofuran, dioxolane, tetrahydrothiophene, piperazine, tetrahydropyran, dioxane, and morpholine.

[0053] Examples of the monovalent heterocyclic aromatic group include monovalent heterocyclic aromatic groups derived from a heterocycle such as thiophene, benzothiophene, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, indole, isoindole, benzimidazole, purine, indazole, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, furan, benzofuran (1-benzofuran), isobenzofuran (2-benzofuran), oxazole, isoxazole, thiazole, benzoxazole, benzisoxazole, and benzothiazole.

[0054] Substituents in the structure derived from the dimer diamine, and R′, R 1 and R 2The substituents on the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic aromatic group having 3 to 20 carbon atoms in the formula (I) are 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 alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphate group, a hydroxy group, a primary to tertiary amino group, a salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphate group, a salt of a hydroxy group, and a salt of a primary to tertiary amino group.

[0055] R' is preferably a hydrogen atom.

[0056] R 1 or R 2 is a hydrogen atom, an interaction occurs between the hydrogen atom and the heteroatom moiety other than the nitrogen atom to which the hydrogen atom is bonded or the triazine ring moiety, and the polymer is likely to have relatively excellent adhesion to the substrate, which is preferable.

[0057] The number of repeating units of the repeating unit represented by the formula (1) is not particularly limited, but is, for example, 2 to 10,000, preferably 3 to 8,000, and more preferably 3 to 5,000.

[0058] The lower limit of the content of the repeating unit represented by formula (1) in the present polymer is preferably 5 mol%, more preferably 15 mol%, even more preferably 25 mol%, and particularly preferably 40 mol%. The upper limit of the content is preferably 95 mol%, more preferably 90 mol%, even more preferably 85 mol%, and particularly preferably 80 mol%. The present polymer having a content of the repeating unit represented by formula (1) in the above range has excellent solubility in solvents and excellent coatability onto substrates.

[0059] Polymer (1) may contain structural units other than the repeating unit represented by formula (1). The other structural units are not particularly limited as long as they do not impair the effects of the present invention, but it is particularly preferable for them to contain a repeating unit represented by formula (2) below. Furthermore, polymer (2) contains a repeating unit represented by formula (1) above and a repeating unit represented by formula (2) below.

[0060] [In formula (2), R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic group having 3 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, and R 4 represents a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, -(R 41 -O) m -, a divalent silicon-containing group, a group in which two or more selected from these groups are combined, a group in which at least a portion of these groups is substituted with at least one atom selected from oxygen atoms, nitrogen atoms and sulfur atoms, or a group in which a portion of these groups is substituted with a substituent, and R 41 are independently alkylene having 2 to 4 carbon atoms, m is an integer of 1 to 70, and —NR 1 R 2 is R 1 and R 2 and may be a nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which they are bonded to each other, and —N(R′)—R 4 - is R' and R 4 and may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which the ring atoms are bonded to each other, and —N(R′)—R 4 -N(R')- may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which two R's are bonded to each other.

[0061] R′ and R in formula (2) 1 and R 2Specific examples of R′ and R in the formula (1) include 1 and R 2 This is similar to the specific example above.

[0062] R 4 is a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a group in which the aromatic hydrocarbon group is combined with one or more other groups, a group in which at least a portion of these groups is substituted with at least one atom selected from oxygen atoms, nitrogen atoms and sulfur atoms, or a group in which a portion of these groups is substituted with a substituent, -NR'-R in formula (2) 4 Examples of the structure of the —NR′— portion include structures derived from the compounds shown below.

[0063] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0064] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0065] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0066] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0067] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0068] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0069] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0070] R 4 is a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a group in which the alicyclic hydrocarbon group is combined with one or more other groups, a group in which at least a portion of these groups is substituted with at least one atom selected from oxygen atoms, nitrogen atoms and sulfur atoms, or a group in which a portion of these groups is substituted with a substituent, -NR'-R in formula (2)4 Examples of the structure of the —NR′— portion include the structure shown below. Note that the dotted line in the following structure indicates the R 4 and R′ means a bond that bonds to a group different from R′.

[0071]

[0072] R 4 Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms in the formula (I) include divalent groups obtained by removing one hydrogen atom from the above-mentioned monovalent chain hydrocarbon group.

[0073] R 4 is a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a group in which the chain hydrocarbon group is combined with one or more other groups, a group in which at least a portion of these groups is substituted with at least one atom selected from oxygen atoms, nitrogen atoms and sulfur atoms, or a group in which a portion of these groups is substituted with a substituent, -NR'-R in formula (2) 4 Examples of the structure of the —NR′— portion include the structure shown below. Note that the dotted line in the following structure indicates the R 4 and R′ means a bond that bonds to a group different from R′.

[0074] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0075] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0076] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0077] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0078] - (R 41 -O) m In the divalent group represented by -, R 41are independently alkylene having 2 to 4 carbon atoms, and m is an integer of 1 to 70, preferably an integer of 1 to 40.

[0079] R 4 is a divalent silicon-containing group, -NR'-R in formula (2) 4 Examples of the structure of the —NR′— portion include structures derived from KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, and X-22-9409 manufactured by Shin-Etsu Chemical Co., Ltd.

[0080] R 4 is a divalent silicon-containing group, -NR'-R in formula (2) 4 As the structure of the —NR′— portion, for example, the structure shown below is preferred. Note that the dotted line in the following structure indicates the R of the nitrogen atom in —NR′ of formula (2). 4 and R′ means a bond that bonds to a group different from R′.

[0081] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0082] Commercially available products that provide the silicon-containing group represented by the above formula include X-22-161A, X-22-161B, KF-8010, X-22-1660B-3, and KF-8012 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0083] a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, -(R 41 -O) m Specific examples of the divalent group represented by -, the divalent silicon-containing group, or the group in which at least a portion of a group consisting of two or more selected from these groups is substituted with at least one atom selected from oxygen atoms, nitrogen atoms, and sulfur atoms include groups in which a portion of the aromatic hydrocarbon group, alicyclic hydrocarbon group, chain hydrocarbon group, oxyalkylene group, or silicon-containing group is substituted with -O-, -OO-, -C(=O)-, -C(=O)-O-, -S-, -SS-, -SO2-, =N-, -N-C(=O)-, a tertiary amino group, or the like.

[0084] R 4 is a group in which a divalent chain hydrocarbon group having 1 to 20 carbon atoms is partly substituted with —O—, or —(R 41 -O) m When the divalent group is represented by -, -NR'-R in formula (2) 4 Examples of the structure of the —NR′— portion include structures derived from polyoxyalkyleneamines such as the JEFFAMINE-D series, JEFFAMINE-ED series, JEFFAMINE-EDR series, and JEFFAMINE-RT series manufactured by Huntsman.

[0085] R 4 is a group in which a divalent chain hydrocarbon group having 1 to 20 carbon atoms is partly substituted with —O—, or —(R 41 -O) m When the divalent group is represented by -, -NR'-R in formula (2) 4 As the structure of the —NR′— portion, for example, the structure shown below is preferred. Note that the dotted line in the following structure indicates the R of the nitrogen atom in —NR′ of formula (2). 4 and R′ means a bond that bonds to a group different from R′.

[0086] (In the above formula, "-" with no bond destination indicates a methyl group.)

[0087] A divalent chain hydrocarbon group having 1 to 20 carbon atoms, represented by the formula above, partly substituted with —O—, or —(R 41 -O) mExamples of monomers that provide a divalent group represented by - include JEFFAMINE manufactured by Huntsman. D-230 (n=up to 2.5, Mw=230), D-400 (n=up to 6.1, Mw=430), D-2000 (n=up to 33, Mw=2000), D-4000 (n=up to 68, Mw=4000), ED-600 (y=up to 9.0, x+z=up to 3.6, Mw=600), ED-900 (y=up to 12.5, x+z=up to 6.0, Mw=900), ED-2003 (y=up to 39, x+z=up to 6.0, Mw=2000), EDR-148 (x=up to 2.0, Mw=148), RT-1000 (Mw=1000), and the like are particularly preferred. Among these, JEFFAMINE represented by the formula (D) is particularly preferred. D-230, D-400, D-2000, and D-4000 are preferred.

[0088] The divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, the divalent chain hydrocarbon group having 1 to 20 carbon atoms, -(R 41 -O) m The substituent in the divalent group represented by -, the divalent silicon-containing group, a group consisting of a combination of two or more selected from these groups, or a group in which at least a portion of these groups is substituted with at least one atom selected from oxygen atoms, nitrogen atoms, and sulfur atoms and then partially substituted with a substituent 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 alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphate group, a hydroxy group, an oxo group, a primary to tertiary amino group, a salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphate group, a salt of a hydroxy group, and a salt of a primary to tertiary amino group.

[0089] In formula (2), —N(R′)—R 4 - is R' and R 4 and may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 8 ring atoms in which the ring atoms are bonded to each other, and —N(R′)—R 4 When - is such a monocyclic nitrogen-containing heterocyclic group, -NR'-R in formula (2)4 Examples of the structure of the —NR′— portion include the structure shown below. Note that the dotted line in the following structure indicates the R 4 and R′ means a bond that bonds to a group different from R′.

[0090]

[0091] In formula (2), —N(R′)—R 4 -N(R')- may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which two R's are bonded to each other. In this case, -NR'-R in formula (2) 4 Examples of the structure of the —NR′— portion include the structure shown below. Note that the dotted line in the following structure indicates the R 4 and R′ means a bond that bonds to a group different from R′.

[0092]

[0093]

[0094] The number of repeating units of the repeating unit represented by the formula (2) is not particularly limited, but is, for example, 2 to 10,000, preferably 3 to 8,000, and more preferably 3 to 5,000.

[0095] The lower limit of the content of the repeating unit represented by formula (2) in the present polymer is preferably 5 mol%, more preferably 15 mol%, even more preferably 25 mol%, and particularly preferably 40 mol%. The upper limit of the content is preferably 95 mol%, more preferably 85 mol%, even more preferably 80 mol%, and particularly preferably 75 mol%. The present polymer, in which the content of the repeating unit represented by formula (2) falls within the above range, can control the solubility in various solvents and the compatibility with other components such as the curable compound described below.

[0096] Polymers (1) and (2) may contain structural units other than the repeating unit represented by formula (1) and the repeating unit represented by formula (2). The structural units are not particularly limited as long as they do not impair the effects of the present invention, and examples thereof include the terminal groups described above. Furthermore, polymer (3) has the terminal group described above at the end of polymer (1) or polymer (2).

[0097] Examples of the terminal group include a reactive group selected from a phenolic hydroxyl group, an allyl group, a vinyl group, a (meth)acryloyl group, a maleimide group, a propargyl group, and an ethynyl group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group, and a heterocyclic group. The two groups at the ends of the main chain of the polymer may be the same or different.

[0098] Examples of the terminal group include groups derived from terminal blocking agents shown below. Examples of the terminal blocking agent include aminophenol compounds such as 4-(2-aminoethyl)phenol and aminophenol; allyl compounds such as allylamine, diallylamine and 4-allylphenol; vinyl compounds such as chloromethylstyrene, 4-aminostyrene, 4-vinylphenol and 4-isopropenylphenol; (meth)acrylic compounds such as (meth)acryloyl chloride and (meth)acrylic anhydride; maleimide compounds such as 4-hydroxyphenylmaleimide; propargyl compounds such as propargylamine; ethynyl compounds such as 4-ethynylaniline; aromatic hydrocarbon group-containing compounds (e.g., monophenol compounds such as 2-phenylphenol, aromatic monoamino compounds such as aniline and 4-tert-butylaniline), aliphatic hydrocarbon group-containing compounds (e.g., aliphatic monoamino compounds such as 2-ethylhexylamine and di(2-ethylhexyl)amine), and heterocyclic group-containing compounds (e.g., cyclic amine compounds such as 4-methylpiperidine, 1-methylpiperazine and morpholine).

[0099] The terminal group is preferably a reactive group derived from a terminal-capping agent selected from an aminophenol compound, an allyl compound, a vinyl compound, and a (meth)acrylic compound, from the viewpoint of easily obtaining a thermosetting composition capable of reacting with an epoxy resin, etc. Furthermore, the terminal group is preferably a group derived from a terminal-capping agent selected from a monophenol compound, an aromatic monoamino compound, an aliphatic monoamino compound, and a cyclic amine compound, from the viewpoint of use as a thermoplastic material, etc.

[0100] <Physical Properties of the Present Polymer> In order to provide a polymer with excellent heat resistance, the present polymer preferably has a weight average molecular weight (Mw) in terms of polystyrene of 1,000 to 400,000, more preferably 3,000 to 200,000, and a molecular weight distribution (Mw / Mn) of preferably 1.5 to 12.0, more preferably 1.7 to 9.0. Specifically, the Mw can be measured by the method described in the examples below.

[0101] The glass transition temperature (Tg) of the present polymer measured by a differential scanning calorimeter (DSC) is preferably −50 to 200° C., more preferably −50 to 150° C. Specifically, the Tg can be measured by the method described in the examples below.

[0102] The 5% mass loss temperature (Td5) of the present polymer measured by thermogravimetric analysis (TGA) is preferably 200 to 600°C, more preferably 250 to 600°C. The present polymer having a Td5 in the above range can be said to have excellent heat resistance. Specifically, the Td5 can be measured by the method described in the examples below.

[0103] The present polymer is soluble in a general-purpose solvent and has excellent solubility in the general-purpose solvent. Examples of the general-purpose solvent include solvents having a boiling point of 180°C or less at atmospheric pressure, and specific examples include cyclohexanone and cyclopentanone. It can be said that the present polymer is soluble in the general-purpose solvent when 1 g or more of the present polymer dissolves in 100 g of the general-purpose solvent at 25°C. Whether or not the polymer is soluble can be determined by the presence or absence of a precipitate. If the present polymer is soluble in the general-purpose solvent, the present polymer can be dissolved in the general-purpose solvent to prepare a solution, which is preferable because it has excellent coatability and drying properties.

[0104] The dielectric loss tangent (tan δ) of the present polymer is preferably 0.0060 or less, more preferably 0.0050 or less, from the viewpoint of reducing transmission loss when a composition containing the present polymer is prepared, and the lower limit is not particularly limited, but is preferably 0.0005 or more. Specifically, the dielectric loss tangent can be measured by the method described in the examples below.

[0105] <Method for synthesizing the present polymer> The present polymer can be produced, for example, by utilizing a condensation reaction between a conventionally known dihalogenated triazine compound and a compound having a nucleophilic functional group, such as a diamine compound. Specific examples are described in the Examples, and an example is shown below.

[0106] Polymer (1) can be synthesized, for example, by heating and polymerizing a compound represented by formula (A) below and a dimer diamine represented by formula (B) below in a suitable organic solvent such as cyclohexanone, N-methyl-2-pyrrolidone (NMP), or N,N-dimethylacetamide (DMAc) in the presence of an alkali metal compound such as potassium carbonate. Polymer (2) can be synthesized, for example, by heating and polymerizing a compound represented by formula (A) below, a compound represented by formula (B) below, and a compound represented by formula (C) below in a suitable organic solvent such as cyclohexanone, N-methyl-2-pyrrolidone (NMP), or N,N-dimethylacetamide (DMAc) in the presence of an alkali metal compound such as potassium carbonate. Furthermore, during these syntheses, the reaction may be carried out in the presence of the terminal-capping agent, and polymer (3) can be synthesized using the terminal-capping agent during these syntheses.

[0107] [In formula (A), R 1 and R 2 are each independently R in formula (1). 1 and R 2 and X is a halogen atom. 1 R 2 is R 1 and R 2 and may be bonded to each other to form a nitrogen-containing heterocyclic group having 5 to 20 ring atoms.]

[0108] [In formula (B), -N(R')-R 3 -N(R')- is a structure derived from unsubstituted or substituted dimer diamine, and R' independently has the same meaning as R' in formula (1).

[0109] [In formula (C), R 4 and R' each independently represent R in formula (2). 4 and R′, and —N(R′)—R 4 - is R' and R 4 and may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which the ring atoms are bonded to each other, and —N(R′)—R 4-N(R')- may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which two R's are bonded to each other.

[0110] The heating conditions are not particularly limited as long as the polymerization reaction proceeds. However, from the viewpoint of suppressing side reactions, the heating temperature is preferably 0 to 150°C, more preferably 10 to 130°C, and the heating time is preferably 0.5 to 100 hours, more preferably 1 to 24 hours.

[0111] In particular, from the viewpoint of obtaining the present polymer with little coloration, the heating temperature is preferably about 40 to 110°C and the heating time is preferably 4 to 24 hours. Furthermore, from the viewpoint of obtaining the present polymer with a high molecular weight and a small amount of low molecular weight components, the heating temperature is more preferably 50 to 100°C.

[0112] The use ratio of the compound represented by formula (A) to the total of the compounds represented by formula (B) and (C), when the total of the compounds represented by formula (A), formula (B) and formula (C) is taken as 100 mol%, the compound represented by formula (A) is preferably 30 mol% or more and 70 mol% or less, more preferably 35 mol% or more and 60 mol% or less, even more preferably 35 mol% or more and 55 mol% or less, and the compounds represented by formula (B) and (C) are preferably 30 mol% or more and 70 mol% or less, more preferably 40 mol% or more and 65 mol% or less, even more preferably 40 mol% or more and less than 65 mol%. The compound represented by formula (A) may be used alone or in combination with two or more. The compound represented by formula (B) may also be used alone or in combination with two or more, and the compound represented by formula (C) may also be used alone or in combination with two or more.

[0113] Examples of the alkali metal compound include alkali metals such as lithium, potassium, and sodium; alkali metal hydrides such as lithium hydride, potassium hydride, and sodium hydride; alkali metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide; alkali metal carbonates such as lithium carbonate, potassium carbonate, and sodium carbonate; alkali metal bicarbonates such as lithium bicarbonate, potassium bicarbonate, and sodium bicarbonate; alkali metal alkoxides such as sodium ethoxide; alkali metal acetates such as sodium acetate and potassium acetate; alkali metal oxides such as lithium oxide; alkali metal phosphates such as trilithium phosphate, trisodium phosphate, and tripotassium phosphate; and alkali metal fluorides such as cesium fluoride. Among these, potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, and cesium fluoride are preferred. The alkali metal compounds may be used alone or in combination of two or more.

[0114] In addition, an organic base may be used in the reaction, and specific examples thereof include ammonia, trimethylamine, triethylamine, diisopropylmethylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine, etc. One type of organic base may be used, or two or more types may be used.

[0115] The amount of the alkali metal compound used is such that the amount of alkali metal atoms in the alkali metal compound is usually 1 to 3 equivalents, preferably 1 to 2.5 equivalents, and more preferably 1.1 to 2.0 equivalents, relative to one —NH—R′ in the compounds represented by formulas (B) and (C).

[0116] <<Other Components>> The composition may further contain other components other than the polymer (1) within a range that does not impair the effects of the present invention. Examples of such other components include curable compounds (C), curing aids (D), reactive diluents, solvents, fillers, antioxidants, reinforcing agents, lubricants, flame retardants, antibacterial agents, colorants, mold release agents, foaming agents, and other polymers other than the polymer (1) and the curable compound (C) (e.g., known polymers such as polyimides, polyarylenes, ester resins, phenoxy resins, phenolic resins, (meth)acrylic acid ester resins, polystyrene resins, rubber-like resins such as hydrogenated styrene-butadiene-styrene copolymers and hydrogenated styrene-isoprene-styrene copolymers). Each of these other components may be used alone or in combination of two or more.

[0117] <Curable Compound (C)> The present composition may contain a curable compound (C) (hereinafter also referred to as "compound (C)"), and it is preferable that the composition contains compound (C) from the viewpoint of, for example, being able to easily form a cured product having excellent chemical resistance. Note that compound (C) is a compound other than the present polymer. The present polymer has excellent compatibility with compound (C), so that the present composition can be easily obtained without precipitation or phase separation. When the present composition contains compound (C), the present composition may contain one type of compound (C) or two or more types of compound (C).

[0118] The curable compound (C) is a compound that cures upon exposure to heat or light (e.g., visible light, ultraviolet light, near-infrared light, far-infrared light, or an electron beam), and may require a curing aid (D), described below. Examples of such compounds (C) include epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, oxetane compounds, methylol compounds, (meth)acrylic compounds, oxazoline compounds, urethane compounds, and propargyl compounds. Among these, in terms of compatibility with the polymer (1), heat resistance, and other properties, at least one selected from the group consisting of epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, oxetane compounds, methylol compounds, (meth)acrylic compounds, oxazoline compounds, and propargyl compounds is particularly preferred. The term "(meth)acrylic compound" refers to an acrylic compound and / or a methacrylic compound.

[0119] The epoxy compound is a compound having an epoxy group, and includes a bifunctional or higher polyfunctional epoxy compound having two or more epoxy groups or a total of two or more epoxy groups and other reactive groups. Specific examples include epoxy compounds represented by the following formulas (c1-1) to (c1-9). Examples of the other reactive groups include an alkoxysilyl group, a propargyl group, and a (meth)acrylic group. An example of the compound represented by the following formula (c1-6) is the epoxy group-containing NBR particles "XER-81" manufactured by JSR Corporation. Further examples of the epoxy compound include polyglycidyl ether of a dicyclopentadiene-phenol polymer, a phenol novolac-type liquid epoxy compound, a cresol novolac-type epoxy compound, an epoxidized product of a styrene-butadiene block copolymer, and 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

[0120] [In formula (c1-5), n is 0 to 5000, and m is independently 0 to 5000. In formula (c1-9), R' is an alkylene group having 2 to 10 carbon atoms.]

[0121] Examples of the cyanate ester compound include compounds represented by the following formulas (c2-1) to (c2-7).

[0122] [In formulas (c2-6) and (c2-7), n is independently an integer of 0 to 30.]

[0123] Examples of the vinyl compound include compounds represented by the following formulas (b-1-1) to (b-1-5): Further examples of the vinyl compound include styrene-based thermoplastic elastomers, such as styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-butadiene elastomer (SBR), tert-butylstyrene, and vinyl group-containing compounds such as 2-vinyl-4,6-diamino-1,3,5-triazine, TA100 (manufactured by Mitsubishi Gas Chemical Company, Inc.), and ULL-950S (manufactured by LONZA).

[0124] [In formulas (b-1-2) and (b-1-4), n independently represents 1 to 5000. In formula (b-1-5), l, m, and n independently represent 1 to 5000.]

[0125] Examples of the silicone compound include compounds represented by the following formulas (c4-1) to (c4-16). R in formula (c4-1) is selected from the following: when a group having an acryloyl group is selected, it can be treated as the acrylic compound; when a group having a methacryloyl group is selected, it can be treated as the methacrylic compound; and when a group having an oxetane group is selected, it can be treated as the oxetane compound. In formulas (c4-2) to (c4-16), R each independently represents an organic group selected from an alkyl group, an alicyclic saturated hydrocarbon group, an aryl group, and an alkenyl group, and n represents an integer of 0 to 1000 (preferably an integer of 0 to 100). The alkyl group, alicyclic saturated hydrocarbon group, aryl group, and alkenyl group can be selected from R' and R in formula (1), respectively. 1 and R 2 Examples of the groups include the same groups as those exemplified in the explanation of the above.

[0126]

[0127] Examples of the oxazine compound include compounds represented by the following formulas (c5-1) to (c5-5), such as 2,2-bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine)propane.

[0128]

[0129] Examples of the maleimide compound include compounds represented by the following formulas (c6-1) to (c6-5).

[0130] [In formula (c6-2), Et is an ethyl group, and in formula (c6-3), n is an integer of 0 to 30.]

[0131] Examples of the allyl compound include compounds represented by the following formulas (c7-1) to (c7-6). In particular, the allyl compound is preferably a compound having two or more (particularly 2 to 6, more preferably 2 to 3) allyl groups.

[0132]

[0133] Examples of the oxetane compound include compounds represented by the following formulae (c8-1) to (c8-3) and (3-ethyloxetan-3-yl)methyl methacrylate.

[0134] [In formulas (c8-1) and (c8-2), the number of repeating units enclosed in parentheses is independently 0 to 30.]

[0135] Examples of the methylol compound include the methylol compounds described in JP-A-2006-178059 and JP-A-2012-226297. Specific examples include melamine-based methylol compounds such as polymethylolated melamine, 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxymethylmelamine; glycoluril-based methylol compounds such as polymethylolated glycoluril, tetramethoxymethylglycoluril, and tetrabutoxymethylglycoluril; 3,9-bis[2-(3, guanamine-based methylol compounds such as methylol compounds of guanamine, such as 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxospiro[5.5]undecane and 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)propyl]-2,4,8,10-tetraoxospiro[5.5]undecane, and compounds in which all or part of the active methylol groups in the compounds have been alkyl-etherified.

[0136] Examples of the (meth)acrylic compound include trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane PO (propylene oxide)-modified tri(meth)acrylate, tetramethylolpropane tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and tricyclodecane dimethanol. Examples of such an epoxy (meth)acrylate include di(meth)acrylate, an epoxy (meth)acrylate obtained by adding (meth)acrylic acid to a diglycidyl ether of bisphenol A, bisphenol A di(meth)acryloyloxyethyl ether, bisphenol A di(meth)acryloyloxymethyl ethyl ether, bisphenol A di(meth)acryloyloxyethyloxyethyl ether, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,9-bis((meth)acryloyloxy)nonane, and polyester (meth)acrylates (tri- or higher functional).

[0137] Examples of the oxazoline compound include 2,2'-bis(2-oxazoline), 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, and 1,3-bis(4,5-dihydro-2-oxazolyl)benzene.

[0138] Examples of the propargyl compound include compounds represented by the following formulae (c9-1) and (c9-2).

[0139]

[0140] When the present composition contains compound (C), the content of compound (C) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to 100% by mass of the total of compound (C) and the present polymer, and is preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. A content of compound (C) within the above range is preferable from the viewpoint of further improving the toughness, heat resistance, and chemical resistance of the cured product of the present composition, etc.

[0141] <Curing Aid (D)> The present composition may contain a curing aid (D) as needed. Examples of the curing aid (D) include polymerization initiators such as curing agents, thermal reaction initiators (e.g., thermal radical generators, thermal acid generators, thermal base generators), and photoinitiators (e.g., photoradical generators, photoacid generators, photobase generators). The curing aid (D) may be used alone or in combination of two or more.

[0142] Examples of the curing aid (D) when an epoxy compound is used as the compound (C) include curing agents such as amine-based curing agents, acid-based or acid anhydride-based curing agents, basic active hydrogen compounds, imidazoles, polymercaptan-based curing agents, phenolic resins, urea resins, melamine resins, isocyanate-based curing agents, and Lewis acids.

[0143] Examples of the amine curing agent include polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis(hexamethylene)triamine, and 1,3,6-trisaminomethylhexane; cycloaliphatic polyamines such as menthenediamine (MDA), isophoronediamine (IPDA), bis(4-amino-3-methylcyclohexyl)methane, diaminodicyclohexylmethane, bisaminomethylcyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, and norbornane-based diamines typified by NBDA manufactured by Mitsui Chemicals, Inc.; aliphatic polyamines containing an aromatic ring such as metaxylylenediamine (MXDA); and aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and diaminodiethyldiphenylmethane, and derivatives thereof.

[0144] Further, other amine-based curing agents include, for example, Mannich-modified amines obtained by reacting polyamines with aldehydes and / or phenols; amine adducts (polyamine epoxy resin adducts), polyamine-ethylene oxide adducts, polyamine-propylene oxide adducts, cyanoethylated polyamines, and ketimines which are reaction products of aliphatic polyamines and ketones; tetramethylguanidine, triethanolamine, piperidine, pyridine, 4-dimethylaminopyridine, benzyldimethylamine, picoline, 2-(dimethylamino)pyridine, methylamino-2-methylpropanol, methylamino-1 ... and liquid polyamides obtained by reacting dimer acid with polyamines such as diethylenetriamine and triethylenetetramine.

[0145] Examples of the acid or acid anhydride curing agent include polycarboxylic acids such as adipic acid, azelaic acid, and decanedicarboxylic acid; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), pyromellitic anhydride, and 3,3',4,4'-benzophenonetetracarboxylic anhydride; maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and alkenyl anhydride. Examples of the acid anhydride include cyclic aliphatic acid anhydrides such as succinic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenetetracarboxylic anhydride, methylhimic anhydride, trialkyltetrahydrophthalic anhydride, and poly(phenylhexadecanedioic) anhydride; aliphatic acid anhydrides such as polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, dodecenylsuccinic anhydride, and poly(ethyloctadecanedioic) anhydride; and halogenated acid anhydrides such as chlorendic anhydride and tetrabromophthalic anhydride.

[0146] Examples of the basic active hydrogen compound include dicyandiamide and organic acid dihydrazides.

[0147] Examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-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.

[0148] Examples of the polymercaptan curing agent include partial epoxy adducts of 2,2'-bismercaptoethyl ether; esters of thioglycolic acid such as pentaerythritol tetrathioglycolate, dipentaerythritol hexathioglycolate, and trimethylolpropane tristhioglycolate; and compounds containing a mercapto group such as polysulfide rubber having a mercapto group at its terminal.

[0149] Examples of the isocyanate curing agent include isocyanate compounds such as toluene diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate; and blocked isocyanate compounds obtained by masking an isocyanate group by reacting it with a blocking agent such as phenol, alcohol, or caprolactam.

[0150] Examples of the Lewis acid include diaryliodonium salts and triarylsulfonium salts.

[0151] Furthermore, when an epoxy compound is used as the compound (C), examples of the curing aid (D) that can be used include onium salt compounds, sulfone compounds, sulfonate ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, and nitrobenzyl compounds, as well as organic halides and photoacid generators such as disulfones.

[0152] Furthermore, when an epoxy compound is used as the compound (C), photobase generators such as (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, 9-anthrylmethyl N,N-diethylcarbamate, (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine, 1-(anthraquinone-2-yl)ethyl imidazolecarboxylate, 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate, and 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propionate can also be used as the curing aid (D).

[0153] Examples of the curing aid (D) when a cyanate ester compound is used as the compound (C) include organic metal salts such as zinc octylate, zinc naphthenate, cobalt naphthenate, copper naphthenate, iron acetylacetonate, nickel octylate, and manganese octylate; phenolic compounds such as phenol, xylenol, cresol, resorcinol, catechol, octylphenol, and nonylphenol; alcohols such as 1-butanol and 2-ethylhexanol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-methylimidazole, 1-methyl-4 ... Examples of the curing aid that can be used include imidazoles such as benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole, as well as derivatives of these imidazoles, such as adducts of carboxylic acids or acid anhydrides, amines such as benzyldimethylamine and 4-methyl-N,N-dimethylbenzylamine, and phosphorus compounds such as phosphine compounds and phosphine oxide compounds. Furthermore, photoacid generators and photobase generators, which were described as the curing aid (D) when the epoxy compound is used, can also be used.

[0154] When a vinyl compound is used as compound (C), examples of the curing aid (D) include compounds (polymerization agents) that generate cationic or radical active species by heat or light. Examples of cationic polymerization agents include diaryliodonium salts and triarylsulfonium salts. Examples of radical polymerization agents include benzoin-based compounds such as benzoinacetophenone, acetophenone-based compounds such as 2,2-dimethoxy-2-phenylacetophenone, sulfur-based compounds such as 2,4-diethylthioxanthone, azo compounds such as azobisisobutyronitrile, and organic peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide.

[0155] Further, as the curing aid (D) when a vinyl compound is used as the compound (C), for example, acetophenone, propiophenone, benzophenone, xanthol, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothioxanthone and the like photoradical generators can also be used.

[0156] When a silicone compound is used as compound (C), examples of the curing aid (D) that can be used include platinum group metal catalysts such as platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, platinum-based catalysts such as platinum bisacetoacetate; palladium-based catalysts; and rhodium-based catalysts; zinc benzoate; and zinc octoate.

[0157] Furthermore, examples of the curing aid (D) when a silicone compound is used as the compound (C) include acetophenone, propiophenone, benzophenone, xanthol, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 2,2'-diethoxyacetophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, and 3-chloro-8 -nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylaminophenyl)ketone, benzyl methoxyketal, 2-chlorothioxanthone, diethylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-{4-(methylthio)phenyl}-2-morpholino-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanon-1-one, 1-{4-(2-hydroxyethoxy)-phenyl}-2-methyl-1-propan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, photoinitiators such as cyclohexyl phenyl ketone can also be used.

[0158] When an oxazine compound is used as compound (C), examples of the curing aid (D) that can be used include phenol and its derivatives, cyanate esters, Bronsted acids such as p-toluenesulfonic acid, adipic acid, p-toluenesulfonic acid esters, aromatic amine compounds such as melamine, bases such as 2-ethyl-4-methylimidazole, boron trifluoride, Lewis acids, etc. Furthermore, photoacid generators and photobase generators described above as the curing aid (D) when an epoxy compound is used can also be used.

[0159] When a maleimide compound is used as compound (C), examples of the curing aid (D) that can be used include bases such as imidazole, 1-methylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazoline, N,N-diisopropylethylamine, 1,4-dimethylpiperazine, quinoline, triazole, benzotriazole, and DBU, phosphorus compounds such as triphenylphosphine, curing agents such as azobisisobutyronitrile, and organic peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and dicumyl peroxide. Furthermore, the photoacid generators and photobase generators described above as the curing aid (D) when an epoxy compound is used can also be used.

[0160] As the curing aid (D) when an allyl compound or a propargyl compound is used as the compound (C), for example, azo initiators such as azobisisobutyronitrile and 2,2'-azobisisobutyrate dimethyl, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, peroxides such as dicumyl peroxide, acetophenone-based compounds such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,1'-hydroxycyclohexyl phenyl ketone, benzoin-based compounds such as benzoin ethyl ether, benzophenone-based compounds such as benzophenone, phosphorus-based compounds such as acylphosphine oxide, sulfur-based compounds such as thioxanthone, benzyl-based compounds such as benzyl, 9,10-phenanthrenequinone, and peroxycarbonate-based curing agents can be used. Furthermore, a photoacid generator or a photobase generator, which have been explained as the curing aid (D) when the epoxy compound is used, can also be used.

[0161] When an oxetane compound or a methylol compound is used as the compound (C), for example, a photo- or thermal cation generator can be used as the curing aid (D).

[0162] Examples of the photocation generator include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds. Specific examples of the onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds include the compounds described in paragraphs

[0074] to

[0079] of JP-A-2014-186300.

[0163] Specific examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, and s-triazine derivatives such as phenyl-bis(trichloromethyl)-s-triazine, 4-methoxyphenyl-bis(trichloromethyl)-s-triazine, styryl-bis(trichloromethyl)-s-triazine, naphthyl-bis(trichloromethyl)-s-triazine, and 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis-(trichloromethyl)-1,3,5-triazine.

[0164] Examples of the thermal cation generator include benzyl(4-hydroxyphenyl)(methyl)sulfonium tetrakis(pentafluorophenyl)borate, (4-hydroxyphenyl)(dimethyl)sulfonium tetrakis(pentafluorophenyl)borate, 4-acetoxyphenyl(dimethyl)sulfonium tetrakis(pentafluorophenyl)borate, (4-hydroxyphenyl)methyl(4-methylbenzyl)sulfonium tetrakis(pentafluorophenyl)borate, and benzyl(4-hydroxyphenyl)(methyl)sulfonium hexafluorophosphate.

[0165] When the present composition contains a curing aid (D), the content of the curing aid (D) is preferably within a range in which the present composition is cured well to obtain a cured product. Specifically, the content of the curing aid (D) is typically 0.1 to 30 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 15 parts by mass, per 100 parts by mass of the present polymer and compound (C) combined.

[0166] <Solvent> The present composition may contain a solvent, if necessary. Examples of the solvent include amide-based solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; ester-based solvents such as γ-butyrolactone and butyl acetate; ketone-based solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, and benzophenone; ether-based solvents such as 1,2-methoxyethane, diphenyl ether, tetrahydrofuran, 4-methyltetrahydropyran, and dioxane; polyfunctional solvents such as 1-methoxy-2-propanol and propylene glycol methyl ether acetate; sulfone-based solvents such as sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, and diphenyl sulfone; and methylene chloride, benzene, toluene, xylene, dialkoxybenzenes (the number of carbon atoms in the alkoxy group is 1 to 4), and trialkoxybenzenes (the number of carbon atoms in the alkoxy group is 1 to 4). These solvents may be used alone or in combination of two or more.

[0167] The content of the solvent in the present composition is not particularly limited, but is, for example, preferably 0 parts by mass or more and 2000 parts by mass or less, more preferably 0 parts by mass or more and 1000 parts by mass or less, relative to 100 parts by mass of the total of the present polymer and compound (C).

[0168] <Filler> The composition may contain a filler as needed. The polymer contained in the composition has a triazine ring structure, resulting in a planar structure with strong pi-electron interactions. This is believed to give the polymer a high ability to coordinate to fillers and the like. Furthermore, the main chain contains a structure derived from dimer diamine, and the flexible, long main chain is believed to be able to conform to the particle surface and interparticle gaps of fillers and the like. Therefore, when the composition contains a filler, it is believed that a composition with excellent dispersibility of the filler can be easily obtained. As such, the polymer is believed to have excellent coordination ability and dispersibility, as well as excellent dispersion stability, and therefore also functions as a good dispersant.

[0169] The filler may be any conventionally known filler, and may be appropriately selected from conventionally known fillers depending on the intended use of the composition. One type of filler may be used alone, or two or more types may be used.

[0170] The filler may be, for example, at least one selected from the group consisting of metal, carbon, metal carbide, metal oxide, and metal nitride, with metal oxide and metal nitride being preferred. Examples of metal oxides include magnesium oxide, aluminum oxide (alumina), silicon oxide (solid silica, hollow silica), calcium oxide, zinc oxide, yttrium oxide, zirconium oxide, cerium oxide, ytterbium oxide, and sialon (ceramics composed of silicon, aluminum, oxygen, and nitrogen). Examples of metal nitrides include boron nitride, aluminum nitride, and silicon nitride.

[0171] The shape of the filler is not particularly limited, and may be in the form of particles, whiskers, fibers, plates, or aggregates thereof.

[0172] Examples of commercially available fillers include silica having a silanol group (—SiOH) at its terminal, such as ADMAFINE SC2500-SQ manufactured by Admatechs Co., Ltd.; silica having an aminophenyl group, such as ADMAFINE SC2500-SXJ manufactured by the same company; silica having a phenyl group, such as ADMAFINE SC2500-SPJ manufactured by the same company; boron nitride powder, such as XGP, SGP, and MGP manufactured by Denka Co., Ltd.; boron nitride powder, such as UHP-1K and UHP-2K manufactured by Showa Denko K.K.; spherical alumina powder, such as DAW-01, DAW-01DC, DAW-03, and DAW-05 manufactured by Denka Co., Ltd.; and spherical alumina powder, such as CB-P02, CB-P05, and CB-P07 manufactured by Showa Denko K.K.; of these, ADMAFINE SC2500-SQ and ADMAFINE SC2500-SPJ can be preferably used.

[0173] When the present composition contains a filler, the content of the filler may be appropriately selected depending on the application of the present composition, but is preferably 0.1 to 10,000 parts by mass, more preferably 10 to 9,000 parts by mass, per 100 parts by mass of the present polymer.

[0174] <Reactive Diluent> The present composition may contain a reactive diluent as needed. The reactive diluent is preferably a liquid compound that reacts with the curable compound (C) and dissolves or uniformly mixes other components when the composition is prepared. Such a reactive diluent may be appropriately selected from conventionally known reactive diluents depending on the type of curable compound (C) in the present composition. The reactive diluent may be used alone or in combination of two or more types.

[0175] As the reactive diluent, for example, when the curable compound (C) is an epoxy compound, a monofunctional liquid epoxy compound that can easily react with epoxy, a liquid acid anhydride, or the like can be used.

[0176] When the present composition contains a reactive diluent, the content of the reactive diluent may be appropriately selected depending on the application of the present composition, but is preferably 20 to 150 parts by mass, more preferably 50 to 120 parts by mass, per 100 parts by mass of the curable compound (C).

[0177] <Antioxidant> Examples of the antioxidant include hindered phenol compounds, phosphorus compounds, sulfur compounds, metal compounds, and hindered amine compounds. Among these, hindered phenol compounds are preferred. The antioxidants may be used alone or in combination of two or more.

[0178] 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-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-3,5-triazine, pentaerythritol tetrakis[3-(3,5-t-butyl-4-hydroxyphenyl)propionate], 1,1,3-tris[2-methyl-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-5-t-butylphenyl]butane, 2,2-thiazolinone ... o-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0179] When the present composition contains an antioxidant, the content of the antioxidant is, for example, preferably 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the total of the present polymer and compound (C).

[0180] <<Method for preparing the present composition>> The method for preparing the present composition is not particularly limited, and for example, the composition can be prepared by uniformly mixing the polymer (1) and, if necessary, the other components. The present composition can also be in the form of a liquid, a paste, or the like. In particular, since the present polymer has excellent compatibility with the compound (C), it can be dissolved in the liquid compound (C) to form a solventless composition.

[0181] 2. Cured Product A cured product according to one embodiment of the present invention is a cured product of the present composition described above, and is obtained by curing the present composition described above. The shape of the cured product is not particularly limited, and it may be formed into an appropriate shape depending on the application, purpose, etc.

[0182] The curing method of the present composition is not particularly limited, but typically, a method of thermal curing by heating or a method of photocuring by irradiation with light is used. These methods can also be used in combination. In the case of thermal curing, the heating temperature is preferably 50 to 350°C, more preferably 100 to 300°C, and even more preferably 100 to 280°C. The heating time is preferably 0.5 to 36 hours, more preferably 0.5 to 24 hours. In the case of photocuring, examples of the light to be irradiated include visible light, ultraviolet light, near infrared light, far infrared light, and electron beams.

[0183] One embodiment of the cured product is, for example, a film, which can be obtained by melt molding or casting the composition to form a film-shaped cured product.

[0184] The use of the film is not particularly limited, but it can be suitably used as an optical film, specifically as a liquid crystal display element substrate, a light guide plate, a polarizing film, a retardation film, etc.

[0185] The thickness of the film is not particularly limited and may be appropriately selected depending on the intended use, but is, for example, 0.5 μm to 3 mm, preferably 1 μm to 1 mm.

[0186] 3. Molded Article A molded article according to one embodiment of the present invention is obtained by molding the polymer (2). One embodiment of the molded article is, for example, a film. The film can be obtained as a film-shaped molded article by, for example, melt molding or cast molding the polymer (2). The uses and thickness of the film are the same as those described in the section on cured products.

[0187] 4. Laminate A laminate according to one embodiment of the present invention has a substrate and a cured layer formed using the present composition, or a substrate and a layer formed using the polymer (2) (hereinafter also referred to as a "polymer layer"). The laminate may have two or more substrate layers, two or more cured layer or polymer layer, or a substrate and a conventionally known layer other than a cured layer or polymer layer. When the laminate has two or more substrate layers, cured layer or polymer layer, or other layer, these may be the same layer (plate) or different layers (plates).

[0188] Examples of the substrate include metal substrates, inorganic substrates (substrates other than metal substrates), and resin substrates, from the viewpoints of adhesiveness and practicality. Examples of the metal substrate include metal substrates containing copper, aluminum, gold, silver, nickel, palladium, etc. as components. Examples of the inorganic substrate include inorganic substrates containing silicon, silicon carbide, silicon nitride, alumina, glass, gallium nitride, etc. as components. Examples of the resin substrate include resin substrates containing liquid crystal polymers, polyimides, polyphenylene sulfide, polyamide (nylon), polyethylene terephthalate, polyethylene naphthalate, polyolefins, etc. as components.

[0189] The cured product layer can be formed, for example, by applying the composition to a substrate and then thermally curing and / or photocuring the composition. The polymer layer can be formed, for example, by disposing polymer (2) on a substrate and then melting the polymer (2). The thickness of the cured product layer or polymer layer is not particularly limited, but is, for example, 1 μm to 3 mm.

[0190] <Applications> The present polymer, the present composition, the cured product, the molded product, and the laminate can be suitably used as structural materials used in the transportation industry, such as the aircraft industry and the automobile industry, and as electrical and electronic materials used in the electrical and electronics industry. Specifically, they can be suitably used in, for example, sealing materials for electrical and electronic components, interlayer insulating films, various primers for stress relaxation, adhesion, bonding, insulation, etc.; laminates (e.g., printed wiring boards, interlayer adhesives, solder resists, solder pastes); adhesives (e.g., thermally conductive adhesives, adhesive sheets); pressure-sensitive adhesives (e.g., insulating tape, conductive tape); structural adhesives and prepregs used in various structural materials; various coating agents; optical components (e.g., optical films such as wave plates and retardation plates, various special lenses such as conical lenses, spherical lenses, and cylindrical lenses, and lens arrays); insulating films for printed wiring boards, etc.

[0191] 5. Electronic Component An electronic component according to one embodiment of the present invention includes the laminate described above. The electronic component may include two or more laminates. When two or more laminates are included, the laminates may be the same or different.

[0192] Examples of the electronic components include circuit boards, semiconductor packages, and display substrates. The cured material layer or polymer layer in the laminate can be used as a surface protection film, rewiring layer, or planarization film for these electronic components. Since the cured material layer or polymer layer can maintain insulation even under high temperature and high humidity, the electronic components can protect circuit patterns from external environments such as dust, heat, and humidity, and have excellent insulation reliability between circuit patterns, allowing them to operate stably for many years.

[0193] For example, a rewiring layer can be formed by filling metal between the patterns of the cured material layer or polymer layer by plating or the like, and if necessary, stacking further cured material layers or polymer layers and repeating the metal filling process, thereby producing an electronic component having a base material and a rewiring layer including metal wiring and an insulating film.

[0194] Hereinafter, one embodiment of the present invention will be described in detail based on examples, but the present invention is not limited to the following examples.

[0195] [1] Polymer Synthesis (Example 1) 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (19.0 g), dimer diamine (Priamine 1075 (manufactured by Croda Japan Co., Ltd.)) (21.1 g), 1,3-bisaminomethylcyclohexane (5.6 g), and potassium carbonate (12.0 g) were weighed into a four-neck separable flask equipped with a stirrer, and cyclohexanone (74.7 g) and water (32.0 g) were added thereto, and the mixture was reacted at 100°C for 20 hours under a nitrogen atmosphere. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral. The solvent was then concentrated to obtain a solution of polymer (10) represented by the following formula (10) with a solid content of 30% by mass. As mentioned above, dimer diamine is not a single substance, and therefore the structure derived from dimer diamine shown in the following formula represents its representative structure. The same applies to the formulas described in the following examples.

[0196]

[0197] Example 2 A solution of the target polymer (11) with a solid content of 30% by mass was obtained in the same manner as in Example 1, except that the components used in Example 1 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (24.8 g), Priamine 1075 (11.0 g), 1,3-bisaminomethylcyclohexane (11.7 g), potassium carbonate (15.6 g), cyclohexanone (88.7 g), water (22.1 g).

[0198] The obtained polymer (11) 1 The H-NMR spectrum is shown in Figure 1. 1 From the peaks around 1.5 ppm and 0.5 ppm in the H-NMR spectrum, it was confirmed that the obtained polymer (11) was a polymer having the structure represented by the above formula (10). 1 H-NMR was measured as follows. 1 H-NMR was also measured in the same manner.

[0199] < 1 H-NMR measurement of polymer 1The H-NMR measurement was carried out using a nuclear magnetic resonance spectrometer ("ECX400P" manufactured by JEOL Ltd.) and deuterated chloroform as the measurement solvent.

[0200] Example 3 A solution of the target polymer (12) represented by the following formula (12) with a solid content of 30% by mass was obtained in the same manner as in Example 1, except that the components used in Example 1 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (17.4 g), Priamine 1075 (19.3 g), 4,4′-methylenebis(2-methylcyclohexylamine) (isomer mixture) (8.6 g), potassium carbonate (11.0 g), cyclohexanone (73.9 g), water (31.7 g).

[0201]

[0202] 1 From the H-NMR spectrum, it was confirmed that the obtained polymer (12) was a polymer having the structure represented by the above formula (12).

[0203] Example 4 A solution of the target polymer (13) represented by the following formula (13) with a solid content of 30% by mass was obtained in the same manner as in Example 1, except that the components used in Example 1 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (15.0 g), Priamine 1075 (16.7 g), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (12.8 g), potassium carbonate (17.3 g), cyclohexanone (117.6 g), water (60.6 g).

[0204]

[0205] 1 From the H-NMR spectrum, it was confirmed that the obtained polymer (13) was a polymer having the structure represented by the above formula (13).

[0206] ​​Example 5 A solution of the target polymer (14) represented by the following formula (14) with a solid content of 30 mass % was obtained in the same manner as in Example 1, except that the components used in Example 1 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (8.4 g), Priamine 1075 (13.1 g), poly(propylene glycol) diamine (JEFFAMINE-D2000 [manufactured by Huntsman]) (21.0 g), potassium carbonate (5.3 g), cyclohexanone (69.5 g), and water (29.8 g).

[0207]

[0208] The obtained polymer (14) 1 The H-NMR spectrum is shown in FIG. 1 From the H-NMR spectrum, it was confirmed that the obtained polymer (14) was a polymer having the structure represented by the above formula (14).

[0209] Example 6 A solution of the target polymer (15) with a solid content of 30% by mass was obtained in the same manner as in Example 5, except that the components used in Example 5 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (6.6 g), Priamine 1075 (7.5 g), poly(propylene glycol) diamine (JEFFAMINE-D2000) (27.9 g), potassium carbonate (4.2 g), cyclohexanone (68.6 g), and water (29.4 g).

[0210] The obtained polymer (15) 1 The H-NMR spectrum is shown in FIG. 1 From the H-NMR spectrum, it was confirmed that the obtained polymer (15) was a polymer having the structure represented by the above formula (14).

[0211] Example 7 A solution of the target polymer (16) represented by the following formula (16) with a solid content of 30% by mass was obtained in the same manner as in Example 1, except that the components used in Example 1 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (10.2 g), Priamine 1075 (20.3 g), silicone oil modified at both ends with amino groups (X-22-161B [manufactured by Shin-Etsu Chemical Co., Ltd.]) (12.6 g), potassium carbonate (6.4 g), cyclohexanone (70.4 g), and water (30.2 g).

[0212]

[0213] Example 8 A solution of the target polymer (17) with a solid content of 30% by mass was obtained in the same manner as in Example 7, except that the components used in Example 7 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (8.1 g), Priamine 1075 (14.3 g), silicone oil modified with amino terminals (X-22-161B) (20.1 g), potassium carbonate (5.1 g), cyclohexanone (69.3 g), and water (29.7 g).

[0214] The obtained polymer (17) 1 The H-NMR spectrum is shown in FIG. 1 From the peak in the vicinity of 0 ppm in the H-NMR spectrum (—Si—CH, 0.13 ppm, see the National Institute of Advanced Industrial Science and Technology: Spectral Database of Organic Compounds), it was confirmed that the obtained polymer (17) was a polymer having a structure represented by the above formula (16).

[0215] Example 9 A solution of the target polymer (18) with a solid content of 30% by mass was obtained in the same manner as in Example 7, except that the components used in Example 7 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (10.0 g), Priamine 1075 (16.5 g), silicone oil modified at both ends with amino groups (X-22-161A [manufactured by Shin-Etsu Chemical Co., Ltd.]) (16.5 g), potassium carbonate (6.3 g), cyclohexanone (70.3 g), and water (30.1 g).

[0216] The obtained polymer (18) 1The H-NMR spectrum is shown in FIG. 1 The structure of the obtained polymer (18) was confirmed from the peak in the vicinity of 0 ppm in the H-NMR spectrum (—Si—CH, 0.13 ppm, see the National Institute of Advanced Industrial Science and Technology: Spectral Database of Organic Compounds).

[0217] Example 10 A solution of the target polymer (19) with a solid content of 30% by mass was obtained in the same manner as in Example 7, except that the components used in Example 7 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (11.6 g), Priamine 1075 (15.4 g), silicone oil modified at both ends with amino groups (KF-8010 [manufactured by Shin-Etsu Chemical Co., Ltd.]) (16.5 g), potassium carbonate (7.3 g), cyclohexanone (71.1 g), and water (30.4 g).

[0218] The obtained polymer (19) 1 The H-NMR spectrum is shown in FIG. 1 The structure of the obtained polymer (19) was confirmed from the peak in the vicinity of 0 ppm in the H-NMR spectrum (—Si—CH, 0.13 ppm, see the National Institute of Advanced Industrial Science and Technology: Spectral Database of Organic Compounds).

[0219] Example 11 A solution of the target polymer (22) represented by the following formula (22) with a solid content of 30 mass % was obtained in the same manner as in Example 5, except that the components used in Example 5 were changed as follows: 4,6-dichloro-N,N-diphenyl-1,3,5-triazin-2-amine (PDCT) (10.4 g), Priamine 1075 (12.3 g), poly(propylene glycol) diamine (JEFFAMINE-D2000) (19.7 g), potassium carbonate (5.0 g), cyclohexanone (69.2 g), and water (29.7 g).

[0220]

[0221] Example 12 A solution of the target polymer (23) represented by the following formula (23) with a solid content of 30 mass % was obtained in the same manner as in Example 5, except that the components used in Example 5 were changed as follows: 4,6-dichloro-N,N-dimethyl-1,3,5-triazin-2-amine (MDCT) (7.1 g), Priamine 1075 (13.7 g), poly(propylene glycol) diamine (JEFFAMINE-D2000) (21.9 g), potassium carbonate (5.6 g), cyclohexanone (69.7 g), and water (29.9 g).

[0222]

[0223] Example 13 A solution of the target polymer (24) represented by the following formula (24) with a solid content of 30 mass % was obtained in the same manner as in Example 5, except that the components used in Example 5 were changed as follows: 4,6-dichloro-1,3,5-triazin-2-amine (ADCT) (6.2 g), Priamine 1075 (14.0 g), poly(propylene glycol)diamine (JEFFAMINE-D2000) (22.5 g), potassium carbonate (5.7 g), cyclohexanone (69.8 g), and water (29.9 g).

[0224]

[0225] (Example 80) In a four-necked separable flask equipped with a stirrer, 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (17.8 g), dimer diamine (Priamine 1075) (19.8 g), 1,3-bis(4-piperidyl)propane (7.8 g), and potassium carbonate (10.4 g) were weighed out, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (25) represented by the following formula (25) having a solid content of 30% by mass.

[0226]

[0227] (Example 81) 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (20.1 g), dimer diamine (Priamine 1075) (22.4 g), piperazine (3.6 g), and potassium carbonate (11.8 g) were weighed into a four-necked separable flask equipped with a stirrer, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (26) represented by the following formula (26) with a solid content of 30% by mass.

[0228]

[0229] (Example 82) In a four-necked separable flask equipped with a stirrer, 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (19.9 g), dimer diamine (Priamine 1075) (22.0 g), homopiperazine (4.1 g), and potassium carbonate (11.6 g) were weighed out, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (27) represented by the following formula (27) having a solid content of 30% by mass.

[0230]

[0231] (Example 83) 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (19.6 g), dimer diamine (Priamine 1075) (21.7 g), 4-(aminomethyl)piperidine (4.6 g), and potassium carbonate (11.4 g) were weighed into a four-necked separable flask equipped with a stirrer, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (28) represented by the following formula (28) with a solid content of 30% by mass.

[0232]

[0233] (Example 84) 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (18.5 g), dimer diamine (Priamine 1075) (20.5 g), N,N'-diethyl-1,6-diaminohexane (6.6 g), and potassium carbonate (10.8 g) were weighed into a four-necked separable flask equipped with a stirrer, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (29) represented by the following formula (29) with a solid content of 30% by mass.

[0234]

[0235] (Example 85) In a four-necked separable flask equipped with a stirrer, 2-methyl-2-phenylamino-4,6-dichloro-s-triazine (AMDCT) (19.0 g), dimer diamine (Priamine 1075) (20.0 g), N,N'-diethyl-1,6-diaminohexane (6.4 g), and potassium carbonate (10.5 g) were weighed out, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (50) represented by the following formula (50) having a solid content of 30% by mass.

[0236]

[0237] (Example 86) 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (19.0 g), dimer diamine (Priamine 1075) (21.1 g), N,N'-dimethyl-1,6-diaminohexane (5.9 g), and potassium carbonate (11.1 g) were weighed into a four-necked separable flask equipped with a stirrer, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (51) represented by the following formula (51) with a solid content of 30% by mass.

[0238]

[0239] (Example 87) In a four-necked separable flask equipped with a stirrer, 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (8.8 g), 2-methyl-2-phenylamino-4,6-dichloro-s-triazine (AMDCT) (9.3 g), dimer diamine (Priamine 1075) (19.5 g), 1,3-bis(4-piperidyl)propane (7.7 g), and potassium carbonate (11.1 g) were weighed out, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After completion of the reaction, the aqueous phase was separated with a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (52) having each structural unit represented by the following formula (52) with a solid content of 30% by mass.

[0240] [In formula (52), * represents bonding to **.]

[0241] Example 88 Into a four-neck separable flask equipped with a stirrer, 4,6-dichloro-N,N-diphenyl-1,3,5-triazin-2-amine (PDCT) (11.2 g), 2-methyl-2-phenylamino-4,6-dichloro-s-triazine (AMDCT) (9.0 g), dimer diamine (Priamine 1075) (18.9 g), N,N'-diethyl-1,6-diaminohexane (6.1 g), and potassium carbonate (10.7 g) were weighed, and cyclohexanone (60.0 g) and water (25.7 g) were added, followed by reaction under a nitrogen atmosphere at 100°C for 20 hours. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until it became neutral. The solvent was then concentrated to obtain a solution of polymer (53) having each structural unit represented by formula (53) below with a solid content of 30 mass%.

[0242] [In formula (53), * represents bonding to **.]

[0243] (Example A1) 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.6 g), dimer diamine (Priamine 1075) (30.1 g), diallylamine (0.44 g), and potassium carbonate (7.9 g) were weighed into a four-necked separable flask equipped with a stirrer, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (39) represented by the following formula (39) with a solid content of 30% by mass.

[0244]

[0245] Example A2 A solution of the target polymer (40) represented by the following formula (40) with a solid content of 30 mass % was obtained in the same manner as in Example A1, except that the components used in Example A1 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.5 g), dimer diamine (Priamine 1075) (29.9 g), methacrylic anhydride (0.69 g), potassium carbonate (7.9 g).

[0246]

[0247] Example A3 A solution of the target polymer (41) represented by the following formula (41) with a solid content of 30% by mass was obtained in the same manner as in Example A1, except that the components used in Example A1 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.6 g), dimer diamine (Priamine 1075) (30.1 g), acryloyl chloride (0.41 g), potassium carbonate (7.9 g).

[0248]

[0249] Example A4 A solution of the target polymer (42) represented by the following formula (42) with a solid content of 30% by mass was obtained in the same manner as in Example A1, except that the components used in Example A1 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.6 g), dimer diamine (Priamine 1075) (30.1 g), chloromethylstyrene (m-, p-mixture) (0.43 g), potassium carbonate (7.9 g).

[0250]

[0251] Example A5 A solution of the target polymer (43) represented by the following formula (43) with a solid content of 30% by mass was obtained in the same manner as in Example A1, except that the components used in Example A1 were changed as follows: 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.9 g), dimer diamine (Priamine 1075) (30.2 g), 4-(2-aminoethyl)phenol (0.16 g), potassium carbonate (8.1 g).

[0252]

[0253] (Example A6) Trichlorotriazine (11.0 g), dimer diamine (Priamine 1075) (30.1 g), and potassium carbonate (7.9 g) were weighed into a four-neck separable flask equipped with a stirrer, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 2 hours at 60 ° C. under a nitrogen atmosphere. After completion of the reaction, diallylamine (9.0 g) and a 1 mass% cyclohexane solution of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (5.2 g) were added, and the mixture was further reacted for 13 hours at 100 ° C. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (44) represented by the following formula (44) with a solids content of 30 mass%.

[0254]

[0255] (Example A7) Trichlorotriazine (10.0 g), dimer diamine (Priamine 1075) (24.8 g), and potassium carbonate (11.5 g) were weighed into a four-neck separable flask equipped with a stirrer, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 2 hours at 60 ° C. under a nitrogen atmosphere. After completion of the reaction, 4-(2-aminoethyl)phenol (11.7 g) and a 1% by mass cyclohexane solution of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (5.2 g) were added, and the mixture was further reacted for 13 hours at 100 ° C. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (45) represented by the following formula (45) with a solids content of 30% by mass.

[0256]

[0257] (Example A8) 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.4 g), dimer diamine (Priamine 1075) (29.8 g), 4-hydroxyphenylmaleimide (0.84 g), and potassium carbonate (8.5 g) were weighed into a four-neck separable flask equipped with a stirrer, and cyclohexanone (40.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After completion of the reaction, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral, and the solvent was concentrated to obtain a solution of polymer (46) represented by the following formula (46) with a solid content of 30 mass%.

[0258]

[0259] Comparative Example 1 A commercially available flexible bismaleimide oligomer, ULTIMID3000A (manufactured by ABC Nanotech., LTD.), was used as Comparative Example 1 (polymer (30)).

[0260] Comparative Example 2 Commercially available jER872 (manufactured by Mitsubishi Chemical Corporation), which is a flexible bisphenol A type epoxy resin, was used as Comparative Example 2 (polymer (31)).

[0261] Comparative Example 3 2,4-Dichloro-6-phenoxy-1,3,5-triazine (24.3 g), 2,2-bis(4-hydroxyphenyl)propane (23.0 g), and potassium carbonate (15.3 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (77.3 g) and water (33.1 g) were added thereto, followed by reaction at 100° C. for 20 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was coagulated with methanol, filtered, and washed with methanol to obtain 31 g (yield 78%) of the target polymer (32) consisting of repeating units represented by the following formula (32):

[0262]

[0263] Comparative Example 4 2,4-Dichloro-6-phenoxy-1,3,5-triazine (26.1 g), bis(4-hydroxyphenyl)ether (21.8 g), and potassium carbonate (16.4 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (78.1 g) and water (33.5 g) were added thereto, followed by reaction for 20 hours at 100° C. under a nitrogen atmosphere. After completion of the reaction, the mixture was coagulated with methanol, filtered, and washed with methanol to obtain 30 g (yield 75%) of the target polymer (33) consisting of repeating units represented by the following formula (33):

[0264]

[0265] Comparative Example 5 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (24.4 g), 4,4'-diaminobenzanilide (23.0 g), and potassium carbonate (15.4 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (77.4 g) and water (33.2 g) were added thereto, followed by reaction for 20 hours at 100°C under a nitrogen atmosphere. After completion of the reaction, the mixture was coagulated with methanol, filtered, and washed with methanol to obtain 30 g (yield 75%) of the target polymer (34) consisting of repeating units represented by the following formula (34):

[0266]

[0267] Comparative Example 6 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (29.9 g), bis(aminomethyl)norbornane (19.1 g), and potassium carbonate (18.9 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (80.1 g) and water (34.3 g) were added thereto, followed by reaction for 20 hours at 100° C. under a nitrogen atmosphere. After completion of the reaction, the mixture was coagulated with methanol, filtered, and washed with methanol to obtain 29 g (yield 73%) of the target polymer (35) consisting of repeating units represented by the following formula (35):

[0268]

[0269] Comparative Example 7 2-phenylamino-4,6-dichloro-s-triazine (26.2 g), 1,12-diaminododecane (21.7 g), and potassium carbonate (16.5 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (78.3 g) and water (33.5 g) were added thereto, followed by reaction for 20 hours at 100° C. under a nitrogen atmosphere. After completion of the reaction, the mixture was coagulated with methanol, filtered, and washed with methanol to obtain 31 g (yield 78%) of the target polymer (36) consisting of repeating units represented by the following formula (36):

[0270]

[0271] Comparative Example 8: 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (15.5 g), 4,4'-dichlorodiphenyl sulfone (14.4 g), and potassium carbonate (9.3 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methylpyrrolidone (128 g) and toluene (50 g) were added and stirred. After refluxing the toluene under nitrogen for several hours, the toluene was distilled off and the mixture was further reacted at 190°C for 6 hours. After completion of the reaction, the mixture was diluted with N-methylpyrrolidone (398 g). The salt was filtered off using filter paper, and the filtrate was coagulated with 10.5 kg of methanol. The coagulated powder was filtered off, washed again with a small amount of methanol, and then filtered. The residue was dried under reduced pressure at 120°C for 12 hours using a vacuum dryer to obtain 23 g (yield 89%) of the target polymer (37) consisting of repeating units represented by the following formula (37):

[0272]

[0273] Comparative Example 9 According to the method described in Macromolecules, 3, 533-535 (1970), the target polymer (38) consisting of a repeating unit represented by the following formula (38) was obtained.

[0274]

[0275] [2] Evaluation of Polymer Properties Using each polymer obtained as described above, the weight average molecular weight (Mw), glass transition temperature (Tg) or softening point, 5% mass loss temperature (Td5), dielectric dissipation factor (Df), solubility in cyclohexanone, coatability, adhesion to substrates (copper foil adhesion and gold substrate adhesion), and room temperature tackiness were evaluated according to the following methods. When each polymer was obtained in solution form (Examples 1 to 13, 80 to 88, and A1 to A8), the Mw, Tg, softening point, and Td5 were evaluated as follows after obtaining a single film according to the following methods. The results of these evaluations are shown in Table 1. In the table, "-" indicates that the corresponding evaluation item was not measured.

[0276] <Preparation of Polymer Monolayer Films> A solution of each polymer was applied to a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]), pre-dried at 70°C for 3 minutes, then at 130°C for 3 minutes, and then evaporated under a nitrogen atmosphere at 150°C for 30 minutes and then at 250°C for 3 hours to form a coating film. The copper foil-attached coating film thus formed was immersed in a 40% iron(III) chloride solution to remove the copper foil, washed with pure water, and then dried at 80°C to prepare a polymer monolayer film.

[0277] <Weight-average molecular weight (Mw)> The weight-average molecular weight (Mw) of each polymer was measured using a GPC apparatus (HLC-8320 model, 8420 model, manufactured by Tosoh Corporation) under the following THF conditions when the obtained polymer was soluble in tetrahydrofuran (THF) (Examples 1 to 13, Examples 80 to 88, and Examples A1 to A8), and under the following N-methyl-2-pyrrolidone conditions when the obtained polymer was insoluble in THF (Comparative Examples 3 to 9). Note that for Comparative Example 7, a portion was insoluble in N-methyl-2-pyrrolidone, but the soluble portion was used to measure Mw.

[0278] THF conditions Column: "TSKgel α-M" manufactured by Tosoh Corporation and "TSKgel guard column α" manufactured by Tosoh Corporation connected together Developing solvent: THF Column temperature: 40°C Flow rate: 1.0 mL / min Sample concentration: 0.75% by mass Sample injection amount: 50 μL Detector: differential refractometer Standard material: monodisperse polystyrene

[0279] N-methyl-2-pyrrolidone conditions Developing solvent: N-methyl-2-pyrrolidone (LiBr 10 mM added) Column temperature: 40°C Flow rate: 1.0 mL / min Sample concentration: 0.75 mass% Sample injection volume: 50 μL Detector: differential refractometer Standard material: monodisperse polystyrene

[0280] <Glass transition temperature (Tg)> The glass transition temperature (Tg) of each polymer was determined as the temperature corresponding to the intersection between the baseline and the tangent at the inflection point in the DSC temperature rise curve of a thermogram obtained using a differential scanning calorimeter (a DSC apparatus "Thermo Plus DSC8230" manufactured by Rigaku Corporation) under a nitrogen atmosphere at a heating rate of 20°C / min. The inflection point was determined as the temperature corresponding to the peak in the DDSC curve, which is a differential curve of the DSC temperature rise curve. The DDSC curve was also referred to as appropriate to confirm the DSC baseline.

[0281] <Softening Point: TMA Inflection Point> For polymers for which measurement based on the glass transition temperature (Tg) was difficult or the glass transition temperature was unclear, the softening point was determined from the TMA inflection point. The softening point was determined as the temperature corresponding to the intersection of the tangent to the baseline and the tangent to the line (post-inflection line) shown on the graph after the polymer was significantly deformed at a certain temperature in the thermal displacement curve of a thermogram obtained at a heating rate of 5°C / min using a thermomechanical analyzer ("TMA7100" manufactured by Hitachi High-Tech Science Corporation).

[0282] <5% Mass Loss Temperature (Td5)> The 5% mass loss temperature (Td5) of each polymer was determined as the temperature at which the polymer's mass had cumulatively decreased by 5% by mass from a thermal mass curve obtained using a differential thermobalance ("G209 F1 Libra" manufactured by NETZSCHT) under a nitrogen atmosphere at a heating rate of 10°C / min. Note that Td5 is an index of heat resistance, and a higher Td5 value indicates better heat resistance.

[0283] <Dielectric Loss Tangent (Df)> A test piece (width: 6 cm × length: 6 cm) was cut out from the prepared polymer monolayer film, and the dielectric loss tangent (Df) of the test piece at 10 GHz was measured using a cavity resonator method (manufactured by AET Corporation, dielectric constant measurement system, TE mode resonator).

[0284] <Solubility> The cyclohexanone solutions of the polymers obtained in Examples 1 to 13, Examples 80 to 88, and Examples A1 to A8 were visually inspected, and the cases where no precipitate was observed were evaluated as "A", and the cases where a precipitate was observed visually were evaluated as "B". The solubility of each of the polymers in cyclohexanone in Comparative Examples 1 to 9 was evaluated by adding each polymer to cyclohexanone to a concentration of 1% by mass, stirring, and then evaluating the case where no precipitate was observed visually as "A", and the case where a precipitate was observed visually as "B".

[0285] <Coatability> A cyclohexanone solution of the polymer obtained in Examples 1 to 13, Examples 80 to 88, and Examples A1 to A8 was applied to a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) with an applicator so that the resulting coating film had a thickness of 20 to 30 μm, and the foil was pre-dried at 70°C for 3 minutes and then at 130°C for 3 minutes, and the coating unevenness was visually confirmed and evaluated. Each polymer in Comparative Examples 1 to 9 was dissolved in N-methylpyrrolidone to a concentration shown in the "Polymer solution concentration" column in Table 1, and the resulting solution was applied to a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) with an applicator so that the resulting coating film had a thickness of 20 to 30 μm, and the resulting coating film was pre-dried at 70°C for 3 minutes and then at 130°C for 3 minutes, and the coating unevenness was visually confirmed and evaluated according to the following criteria. "A": There is no repellency on the copper foil, and a uniform film is formed with no unevenness in thickness, and the coating film does not peel off from the copper foil. "B": There is repellency on the copper foil, the coating film peels off from the copper foil, and / or there is an uneven coating film with uneven thickness.

[0286] <Copper foil adhesion> A cyclohexanone solution of the polymer obtained in Examples 1 to 13, Examples 80 to 88, and Examples A1 to A8 was applied to a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) so that the thickness of the resulting polymer layer would be 20 to 30 μm. The foil was pre-dried at 70° C. for 3 minutes, then at 130° C. for 3 minutes, and further dried at 150° C. for 30 minutes, then at 250° C. for 3 hours in a nitrogen atmosphere to evaporate the solvent, thereby obtaining a laminate consisting of a polymer layer and copper foil. A solution of 2 g of each polymer from Comparative Examples 1 to 9 dissolved in 8 g of N-methylpyrrolidone was applied to copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) so that the resulting polymer layer had a thickness of 20 to 30 μm. The solution was then pre-dried at 70°C for 3 minutes, then at 130°C for 3 minutes, and then at 150°C for 30 minutes, then at 250°C for 3 hours under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a laminate consisting of a polymer layer and copper foil. The resulting laminate was cut into a 5 mm wide x 10 cm long piece and stretched at 90° using an Instron 5567 (manufactured by Instron) at 500 mm / min in the 90° direction. The adhesion strength between the polymer layer and the copper foil was evaluated in accordance with IPC-TM-650 2.4.9. Adhesion strengths of 0.2 N / mm or greater were evaluated as "A," and adhesion strengths of less than 0.2 N / mm were evaluated as "B."

[0287] <Adhesion to Gold Substrate> A cyclohexanone solution of the polymer obtained in Examples 1 to 13, Examples 80 to 88, and Examples A1 to A8 was spin-coated onto a gold sputtered wafer so that the resulting coating film had a thickness of 10 to 20 μm, and the coating was pre-dried at 70° C. for 5 minutes and then at 150° C. for 5 minutes, and then the solvent was evaporated under a nitrogen atmosphere at 250° C. for 1 hour to form a coating film. A solution obtained by dissolving 2 g of each polymer in 8 g of N-methyl-2-pyrrolidone was spin-coated onto a gold sputtered wafer so that the resulting coating film had a thickness of 10 to 20 μm, and the coating was pre-dried at 70° C. for 5 minutes and then at 150° C. for 5 minutes, and then the solvent was evaporated under a nitrogen atmosphere at 250° C. for 1 hour to form a coating film. A stud pin with epoxy resin attached was fixed to the coating surface so that the formed coating and epoxy resin were in contact, and the coating was cured at 160°C for 1 hour. The adhesion between the gold-sputtered wafer and the formed coating was evaluated using a thin film adhesion strength tester (manufactured by QuadGroup) at a measurement condition of 20 N / s. The case where the epoxy resin of the stud pin broke was evaluated as "A", and the case where the coating peeled off at the interface with the gold-sputtered wafer was evaluated as "B".

[0288] <Room Temperature Tackiness> A cyclohexanone solution of the polymer obtained in Examples 5, 6, 11, 12, A6, and A7 was applied to a polyimide film so that the resulting coating film would have a thickness of 10 to 20 μm, and the applied film was pre-dried at 70° C. for 5 minutes, then at 150° C. for 5 minutes. The solvent was then evaporated under a nitrogen atmosphere at 250° C. for 1 hour to form a coated polyimide film laminate. A solution obtained by dissolving 2 g of each of the polymers obtained in Comparative Examples 1 to 9 in 8 g of N-methyl-2-pyrrolidone was applied to a polyimide film with an applicator so that the resulting coating film would have a thickness of 10 to 20 μm. The solution was pre-dried at 70° C. for 5 minutes, then at 150° C. for 5 minutes, and the solvent was then evaporated under a nitrogen atmosphere at 250° C. for 1 hour to form a coated polyimide film laminate. Each coated polyimide film was placed on a stainless steel plate with the coating surface of the coated polyimide film laminate in contact with the stainless steel plate, and the laminate was pressed together with a manual roller to prepare a sample. The adhesion of the coated polyimide film to the stainless steel plate was visually determined, and the results were evaluated as "A" if the polyimide film adhered to the stainless steel plate and "B" if it did not.

[0289]

[0290] Synthesis Example 1 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.2 g), dimer diamine (Priamine 1075) (30.8 g), and potassium carbonate (8.7 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (71.9 g) and water (30.8 g) were added thereto, followed by reaction for 20 hours at 100° C. under a nitrogen atmosphere. After completion of the reaction, the mixture was coagulated with methanol, filtered, and washed with methanol to obtain 31 g (yield 76%) of the target polymer (21) consisting of repeating units represented by the following formula (21):

[0291]

[0292] [2] Composition (I) (Example 20) Polymer (21) and cyclohexanone were placed in a glass bottle so that the solids concentration was 30% by mass, and polymer (21) was dissolved. 16.7 g of the resulting polymer solution (amount of polymer (21): 5 g), 5 g of 2,2-bis(4-cyanatophenyl)propane (Tokyo Chemical Industry Co., Ltd.) as a curing compound, 0.5 g of zinc octylate (Fujifilm Wako Pure Chemical Industries, Ltd.) as a curing aid, and cyclohexanone as an additional solvent were added so that the solids concentration was 35% by mass, and the mixture was thoroughly stirred with a mix rotor to prepare a uniformly mixed composition without phase separation. The prepared composition was applied to copper foil (CF-T9DA-SV [Fukuda Metal Foil & Powder Co., Ltd.]) using a bar coater, and heated in an oven at 250°C for 3 hours under nitrogen to obtain a cured copper foil. The obtained copper foil with the cured product was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured product was washed four times with ion-exchanged water to prepare a film sample for evaluation having a thickness of 30±5 μm.

[0293] (Examples 21 to 33, 40 to 43 and Comparative Examples 20 to 23) Compositions were prepared and evaluation film samples were produced in the same manner as in Example 20, except that the components shown in Table 2 were used in the mass ratio (mass ratio of polymer to curable compound) shown in Table 2. In Example 25 and Comparative Example 23, cyanate compound A and epoxy compound D were used as the curable compounds in a mass ratio of 50:50.

[0294] Example 34 Into a glass bottle, 16.7 g of the polymer solution of polymer (10) obtained in Example 1 (amount of polymer (10): 5 g), 5 g of 2,2-bis(4-cyanatophenyl)propane (Tokyo Chemical Industry Co., Ltd.) as a curing compound, 0.5 g of zinc octylate (Fujifilm Wako Pure Chemical Industries Co., Ltd.) as a curing aid, and cyclohexanone as an additional solvent were added so that the solids concentration was 35% by mass, and the mixture was thoroughly stirred with a mix rotor to prepare a homogeneously mixed composition without phase separation. The prepared composition was applied to copper foil (CF-T9DA-SV [Fukuda Metal Foil & Powder Co., Ltd.]) using a bar coater, and heated in an oven at 250 ° C for 3 hours under nitrogen to obtain a cured copper foil. The obtained copper foil with the cured product was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured product was washed four times with ion-exchanged water to prepare a film sample for evaluation having a thickness of 30±5 μm.

[0295] (Examples 35 to 39, Examples 44 to 49, and Examples 90 to 109) Compositions were prepared in the same manner as in Example 34, except that the components shown in Table 2 were used in the mass ratios (mass ratios of polymer to curable compound) shown in Table 2, and film samples for evaluation were produced.

[0296] [3] Composition (II) (Example 50) Polymer (21) and cyclohexanone were placed in a glass bottle so that the solids concentration was 30% by mass, and polymer (21) was dissolved. 9.3 g of the obtained polymer solution (amount of polymer (21): 2.79 g), 1.2 g of Admafine SC2500-SQ (manufactured by Admatechs Co., Ltd.) as a filler, and cyclohexanone as an additional solvent were added so that the solids concentration was 35% by mass, and the mixture was thoroughly stirred with a mix rotor to prepare a uniformly mixed composition without phase separation. The prepared composition was applied to copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) using a bar coater, and heated in an oven at 250 ° C for 3 hours under nitrogen to obtain a cured copper foil. The obtained copper foil with the cured product was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured product was washed four times with ion-exchanged water to prepare a film sample for evaluation having a thickness of 30±5 μm.

[0297] (Examples 51 to 59 and Comparative Examples 30 to 34) Compositions were prepared in the same manner as in Example 50, except that the components shown in Table 4 were used in the mass ratios shown in Table 4, and film samples for evaluation were produced.

[0298] Example 60: In a glass bottle, 9.3 g of the solution of polymer (14) obtained in Example 5 (amount of polymer (14): 2.79 g), 1.2 g of Admafine SC2500-SQ (manufactured by Admatechs Co., Ltd.) as a filler, and cyclohexanone as an additional solvent were added to a solids concentration of 35% by mass, and the mixture was thoroughly stirred with a mix rotor to prepare a homogeneously mixed composition without phase separation. The prepared composition was applied to copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) using a bar coater and heated in an oven at 250°C for 3 hours under nitrogen to obtain a copper foil with a cured product. The obtained copper foil with a cured product was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured product was washed four times with ion-exchanged water to prepare a film sample for evaluation with a thickness of 30±5 μm.

[0299] (Examples 61 to 72) Except for using the components shown in Table 4 in the mass ratio (mass ratio of polymer to filler) shown in Table 4, compositions were prepared in the same manner as in Example 60, and film samples for evaluation were produced.

[0300] [4] Composition (III) (Example B1) Polymer (21) and cyclohexanone were placed in a glass bottle so that the solids concentration was 30% by mass, and the polymer (21) was dissolved to obtain a solution of polymer (21). The solution of polymer (21) (0.63 g, 0.19 g of polymer (21)) and 2,2-bis(4-glycidyloxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) (10.1 g) as a curing compound were thoroughly stirred in a glass bottle using a mixer rotor to obtain solution X. Furthermore, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride (cis-, turns-mixture) (8.9 g) as a reactive diluent and 1-benzyl-2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.10 g) as a curing aid were thoroughly stirred in a glass bottle using a mixer rotor to obtain solution Y. The obtained solutions X and Y were mixed in a mix rotor to prepare composition Z. The prepared composition Z was applied to a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) using a bar coater and heated in an oven at 200°C for 3 hours under nitrogen to obtain a copper foil with a cured film. The obtained copper foil with a cured film was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured film was washed four times with ion-exchanged water to prepare a film sample for evaluation with a thickness of 30±5 μm.

[0301] (Examples B2 to B3) Except for using the components in the types and mass ratios (mass ratios of polymer / curable compound / reactive diluent / curing aid) shown in Table 5, compositions were prepared in the same manner as in Example B1, and film samples for evaluation were produced.

[0302] (Example B4) A solution of polymer (39) (0.63 g) and 2,2-bis(4-glycidyloxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) (10.1 g) as a curable compound were thoroughly stirred in a glass bottle using a mixer rotor to obtain solution X. Furthermore, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride (cis-, turns-mixture) (8.9 g) as a reactive diluent and 1-benzyl-2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.10 g) as a curing aid were thoroughly stirred in a glass bottle using a mixer rotor to obtain solution Y. The obtained solution X and solution Y were mixed using a mixer rotor to prepare composition Z. The prepared composition Z was applied to a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) using a bar coater, and the foil was heated in an oven at 200°C for 3 hours under nitrogen to obtain a copper foil with a cured film. The obtained copper foil with a cured film was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured film was washed four times with ion-exchanged water to prepare a film sample for evaluation having a thickness of 30±5 μm.

[0303] (Examples B5 to B8) Except for using the types and mass ratios of each component shown in Table 5 (mass ratio of polymer / curable compound / reactive diluent / curing aid), compositions were prepared in the same manner as in Example B4, and film samples for evaluation were produced.

[0304] (Example B9) Polymer (43) (0.26 g), 2,2-bis(4-glycidyloxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) (4.18 g) as a curable compound, and DAW-01DC (manufactured by Denka Co., Ltd.) (12.0 g) were thoroughly stirred in a glass bottle using a mixer rotor to obtain Solution X. In addition, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride (cis-, turns-mixture) (3.7 g) as a reactive diluent and 1-benzyl-2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.042 g) as a curing aid were thoroughly stirred in a glass bottle using a mixer rotor to obtain Solution Y. The obtained Solution X and Solution Y were mixed using a mixer rotor to prepare Composition Z. The prepared composition Z was applied to a copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) using a bar coater, and the foil was heated in an oven at 200°C for 3 hours under nitrogen to obtain a copper foil with a cured film. The obtained copper foil with a cured film was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured film was washed four times with ion-exchanged water to prepare a film sample for evaluation having a thickness of 30±5 μm.

[0305] (Example B10) A composition was prepared in the same manner as in Example B9, except that the components were used in the types and mass ratios shown in Table 5 (mass ratios of polymer / curable compound / reactive diluent / curing aid / filler), and a film sample for evaluation was produced.

[0306] [5] Composition (IV) (Example D1) Polymer (21), curable compound, filler, curing aid, and other polymers were placed in a glass bottle in the mass ratios shown in Table 5. Toluene / methyl ethyl ketone = 1 / 1 (mass ratio) was added as an additional solvent so that the solids concentration was 65 mass%, and the mixture was thoroughly mixed and stirred with a mix rotor to prepare a composition. The prepared composition was applied to copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) using a bar coater and heated in an oven at 200 ° C for 3 hours under nitrogen to obtain a copper foil with a cured film. The obtained copper foil with a cured film was immersed in a 40% aqueous solution of iron (III) chloride to remove the copper foil, and the obtained cured film was washed four times with ion-exchanged water to prepare a film sample for evaluation with a thickness of 30 ± 5 μm.

[0307] (Examples D2 to D20 and Comparative Examples 35 to 36) Compositions were prepared in the same manner as in Example D1, except that the components shown in Table 5 were used in the mass ratios shown in Table 5 (mass ratios of polymer, curable compound, curing aid, filler, and other polymer), and evaluation film samples were produced.

[0308] <Appearance of Composition> The appearance of the composition prepared using the composition (I) was visually observed. The composition was evaluated as "A" when the components used in the preparation were compatible and no precipitation or phase separation was observed, and as "B" when precipitation or phase separation was observed. The results are shown in Table 2.

[0309] <Reactivity> The compositions prepared from Composition (I) and Composition (III) were applied to copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) using a Baker-type applicator (gap: 125 μm) so that the resulting cured film had a thickness of 20 to 30 μm. The coating was then pre-dried at 70°C for 3 minutes, then at 130°C for 3 minutes, and then at 150°C for 30 minutes, followed by evaporation of the solvent in a nitrogen atmosphere at 250°C for 3 hours, to obtain a copper foil-attached cured film. The resulting copper foil-attached cured film was immersed in 1.5 L of methyl ethyl ketone (MEK) at room temperature for 10 minutes and then vacuum dried at 120°C for 3 hours. The mass change rate was calculated using the following formula, with a mass change rate of 80% or greater designated "A" and a mass change rate of less than 80% designated "B." The mass change rate increased as the reaction between the polymer and the curable compound progressed. The results are shown in Tables 2 and 6. Mass change rate (%) = mass of cured film with copper foil after vacuum drying / mass of cured film with copper foil before immersion in MEK × 100

[0310] <5% Mass Loss Temperature (Td5)> The 5% mass loss temperature (Td5) of each evaluation film sample prepared using composition (I) and composition (III) was determined as the temperature at which the mass of the evaluation film sample cumulatively decreased by 5% by mass from a thermal mass curve obtained under a nitrogen atmosphere at a heating rate of 10°C / min using a differential thermobalance ("G209 F1 Libra" manufactured by NETZSCHT). The results are shown in Tables 2 and 4.

[0311] <Tensile elongation> The tensile elongation was measured by cutting the evaluation film samples prepared from the compositions (I) and (II) into a No. 7 dumbbell shape as described in JIS K 6251:2017, and conducting a tensile test at room temperature and 5.0 mm / min using a small tabletop testing machine ("EZ-LX" manufactured by Shimadzu Corporation). The results are shown in Tables 2 and 4. Note that when the evaluation film samples obtained in Comparative Examples 30 and 31 were used, the film collapsed (film collapse) during the measurement of the tensile elongation, making it impossible to measure the tensile elongation.

[0312] <Adhesion to Gold Substrate> The composition prepared with composition (I) was spin-coated onto a gold-sputtered wafer to form a coating film having a thickness of 10 to 20 μm. The coating film was then pre-dried at 70°C for 5 minutes, then at 150°C for 5 minutes, and then evaporated under a nitrogen atmosphere at 250°C for 1 hour to form a coating film. A stud pin with an epoxy resin attached was fixed to the coating film surface so that the formed coating film and the epoxy resin were in contact with each other. The coating film was cured at 160°C for 1 hour, and the adhesion between the gold-sputtered wafer and the formed coating film was evaluated using a thin film adhesion strength tester (manufactured by QuadGroup) at a measurement condition of 20 N / s. The results were evaluated as "A" if the epoxy resin on the stud pin broke, and "B" if the coating film peeled off at the interface with the gold-sputtered wafer. The results are shown in Table 2.

[0313] <Adhesion> Of the compositions prepared using composition (I), the compositions obtained in Examples 38 to 39, 44 to 45, 104 to 106, and Comparative Examples 21 and 22 were applied to copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]) using an applicator so that the resulting coating film had a thickness of 20 to 30 μm. The foil was pre-dried at 70°C for 5 minutes, then at 150°C for 5 minutes, and then the solvent was evaporated at 220°C for 1 hour in a nitrogen atmosphere to form a coating film. A 50 μm-thick polyimide film (manufactured by DuPont-Toray Co., Ltd., "Kapton 200H") was laminated to the coating film side of the coated copper foil using a resin manual roller at room temperature (Examples 38 to 39, 44 to 45, 104 to 105) or 80°C (Example 106, Comparative Examples 21 and 22) to prepare samples. The adhesiveness was evaluated by peeling the polyimide film from the prepared sample. The samples were evaluated as "A" if they had adhesiveness due to lamination, i.e., if they were tacky and could be temporarily attached like adhesive tape, and as "B" if they were not tacky and could not be temporarily attached and could be peeled off. The results are shown in Table 3.

[0314] <Dispersibility> The compositions (II) to (IV) were each allowed to stand for 3 hours after preparation, and the dispersibility was evaluated by assigning an "A" when no filler precipitation was observed with the naked eye and a "B" when filler precipitation was observed. The results are shown in Tables 4 and 6. In Comparative Examples 33 and 34, the polymer did not dissolve in cyclohexanone during the preparation of the compositions, and was insoluble (polymer insoluble).

[0315] <Freestanding film> When preparing a film sample for evaluation from the copper foil with a cured product obtained using the composition (II), the evaluation film sample obtained by removing the copper foil from the copper foil with a cured product was rated as "A" if it was a film that could be handled, as "B" if the evaluation film sample was a brittle and easily crumbled film, and as "film collapse" if the evaluation film sample collapsed and no film was obtained. The results are shown in Table 4. Note that when the compositions prepared in Comparative Examples 33 and 34 were used, film formation was not possible (film formation impossible), and copper foil with a cured product itself could not be obtained.

[0316] <Copper Foil Adhesion> The prepared composition (II) was applied to copper foil (CF-T9DA-SV [manufactured by Fukuda Metal Foil & Powder Co., Ltd.]), pre-dried at 70°C for 3 minutes, then at 130°C for 3 minutes, and then pre-dried at 150°C for 30 minutes, then at 250°C for 3 hours under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a laminate consisting of a polymer layer (thickness: 30±5 μm) and copper foil. The obtained laminate was cut into a piece 5 mm wide x 10 cm long and pulled at a 90° angle at 500 mm / min using an Instron 5567 (manufactured by Instron Corporation) in accordance with IPC-TM-650 2.4.9. Adhesion strengths of 0.2 N / mm or more were evaluated as "A," and adhesion strengths of less than 0.2 N / mm were evaluated as "B."

[0317] <Dispersion Stability> The compositions prepared in Examples B9 and B10, and composition (IV) were allowed to stand for 3 days, and the dispersion stability was evaluated as follows: "A" indicates that no filler precipitation was observed with the naked eye and the solution had fluidity; and "B" indicates that filler precipitation was observed and the solution had no fluidity.

[0318]

[0319]

[0320]

[0321]

[0322]

[0323] The abbreviations for the curable compounds, curing aids, reactive diluents, fillers, other polymers, and solvents in Tables 2 to 5 are as follows:

[0324] <Curable Compounds> Cyanate compound A: 2,2-bis(4-cyanatophenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) Cyanate compound B: 1,3-bis[2-(4-cyanatophenyl)propan-2-yl]benzene Epoxy compound A: 2,2-bis(4-glycidyloxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.) Epoxy compound B: jER872 (manufactured by Mitsubishi Chemical Corporation) Epoxy compound C: XD-1000 (manufactured by Nippon Kayaku Co., Ltd.) Epoxy compound D: Denacol EX-991L (manufactured by Nagase ChemteX Corporation) Epoxy compound E: jER604 (manufactured by Mitsubishi Chemical Corporation) Epoxy compound F: Teisun Resin SG-P3 (manufactured by Nagase ChemteX Corporation) Epoxy compound G: Teisun Resin SG-80H (manufactured by Nagase Chemtec Corporation) Maleimide compound A: Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (manufactured by Tokyo Chemical Industry Co., Ltd.) Maleimide compound B: ULTIMID 3000A (manufactured by ABC NANOTECH., LTD.) Acrylic compound: 1,9-bis(acryloyloxy)nonane (manufactured by Tokyo Chemical Industry Co., Ltd.) Allyl compound: Triallyl isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.) Vinyl compound A: Divinylbenzene (manufactured by Tokyo Chemical Industry Co., Ltd., m- and p-mixture) Vinyl compound B: RICON 100 (manufactured by CRAY VALLEY) Methylol compound: 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine (manufactured by Tokyo Chemical Industry Co., Ltd.) Oxazoline compound: 1,3-bis(4,5-dihydro-2-oxazolyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) Oxazine compound: 2,2-bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine)propane (compound synthesized with reference to Macromolecules 2003, 36, 8320-8329) Oxetane compound: (3-ethyloxetan-3-yl)methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0325] <Curing aid> Zinc octylate: zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) Imidazole: 1-benzyl-2-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) Organic peroxide: dicumyl peroxide (manufactured by NOF Corporation) Borate salt: 4-acetoxyphenyl(dimethyl)sulfonium=tetrakis(pentafluorophenyl)borate (manufactured by Sanshin Chemical Industry Co., Ltd.) DMAP: 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0326] <Reactive diluents> Reactive diluent A: 4-methylcyclohexane-1,2-dicarboxylic anhydride (cis-, turns-mixture) (manufactured by Tokyo Chemical Industry Co., Ltd.) Reactive diluent B: o-cresyl glycidyl ether (manufactured by Yokkaichi Chemical Industry Co., Ltd.)

[0327] <Filler> Silica A: ADMAFINE SC2500-SQ (manufactured by Admatechs Co., Ltd.) Silica B: ADMAFINE SC2500-SXJ (manufactured by Admatechs Co., Ltd.) Silica C: ADMAFINE SC2500-SQ-SPJ (manufactured by Admatechs Co., Ltd.) Boron nitride: Boron nitride UHP-1K (manufactured by Showa Denko K.K.) Alumina A: DAW-01DC (manufactured by Denka Co., Ltd.) Alumina B: CB-P02 (manufactured by Showa Denko K.K.)

[0328] <Other polymers> Ester resin: HPC-8000-65T (manufactured by DIC Corporation) Phenol resin: PHENOLITE TD-2090 (manufactured by DIC Corporation) Rubber A: Tuftec M1913 (manufactured by Asahi Kasei Corporation) Rubber B: Tuftec MP10 (manufactured by Asahi Kasei Corporation)

[0329] <Solvent> S1: toluene / methyl ethyl ketone=1 / 1 (mass ratio)

[0330] The present polymer has excellent heat resistance, is soluble in common solvents, and exhibits excellent coatability and adhesion to substrates such as copper substrates and gold substrates. Furthermore, the present composition, obtained by appropriately combining the present polymer with various curable compounds, fillers, etc., can form a cured product (cured product layer) that exhibits excellent heat resistance and excellent coatability and adhesion to substrates such as copper substrates and gold substrates. Therefore, the present polymer and the present composition can be suitably used in a wide range of fields, such as structural materials used in the transportation industry, including the aircraft industry and the automobile industry, and electrical and electronic materials used in the electrical and electronics industry.

Claims

1. A composition comprising a polymer containing a repeating unit represented by the following formula (1): 【Chemistry 1】 In formula (1), -N(R')-R 3 -N(R')- is a structure derived from a dimer diamine which is unsubstituted or substituted by a substituent, and R', R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic group having 3 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, 1 R 2 is R 1 and R 2 and may be bonded to each other to form a nitrogen-containing heterocyclic group having 5 to 20 ring atoms.

2. The composition according to claim 1 , wherein the polymer further contains a repeating unit represented by the following formula (2): 【Chemistry 2】 In formula (2), R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic group having 3 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, R 4 represents a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, -(R 41 -O) m -, a divalent silicon-containing group, a group in which two or more selected from these groups are combined, a group in which at least a portion of these groups is substituted with at least one atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, or a group in which a portion of these groups is substituted with a substituent, and R 41 are independently alkylene having 2 to 4 carbon atoms, m is an integer of 1 to 70, -NR 1 R 2 is R 1 and R 2 and may be a nitrogen-containing heterocyclic group having 5 to 20 ring-constituting atoms bonded to each other, -N(R')-R 4 - is R' and R 4 and may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which the ring members are bonded to each other, -N(R')-R 4 --N(R')-- may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which two R's are bonded to each other.

3. The composition according to claim 1 or 2, further comprising a curable compound (C).

4. The composition according to claim 1 or 2, further comprising a curing aid (D).

5. The composition of claim 1 or 2 further comprising a solvent.

6. The composition according to claim 3, wherein the curable compound (C) is at least one selected from the group consisting of epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, oxetane compounds, methylol compounds, (meth)acrylic compounds, oxazoline compounds, and propargyl compounds.

7. A cured product obtained by curing the composition according to claim 1 or 2.

8. A laminate comprising a substrate and a cured layer formed using the composition according to claim 1 or 2.

9. An electronic component comprising the laminate according to claim 8 .

10. A polymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): 【Chemistry 3】 【Chemistry 4】 In formulas (1) and (2), -N(R')-R 3 -N(R')- is a structure derived from a dimer diamine which is unsubstituted or substituted by a substituent, and R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic group having 3 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, R 4 represents a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, -(R 41 -O) m -, a divalent silicon-containing group, a group in which two or more selected from these groups are combined, a group in which at least a portion of these groups is substituted with at least one atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, or a group in which a portion of these groups is substituted with a substituent, and R 41 are independently alkylene having 2 to 4 carbon atoms, m is an integer of 1 to 70, -NR 1 R 2 is R 1 and R 2 and may be a nitrogen-containing heterocyclic group having 5 to 20 ring-constituting atoms bonded to each other, -N(R')-R 4 - is R' and R 4 and may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which the ring members are bonded to each other, -N(R')-R 4 --N(R')-- may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which two R's are bonded to each other.

11. A molded article obtained by molding the polymer according to claim 10.

12. A laminate comprising a substrate and a layer formed using the polymer according to claim 10.

13. An electronic component comprising the laminate according to claim 12.

14. A polymer containing a repeating unit represented by the following formula (1), or a polymer containing a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), A polymer having at least one group selected from a phenolic hydroxyl group, an allyl group, a vinyl group, a (meth)acryloyl group, a maleimide group, a propargyl group, an ethynyl group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a heterocyclic group at its terminal: 【Chemistry 5】 【Chemistry 6】 In formulas (1) and (2), -N(R')-R 3 -N(R')- is a structure derived from a dimer diamine which is unsubstituted or substituted by a substituent, and R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic group having 3 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, R 4 represents a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, -(R 41 -O) m -, a divalent silicon-containing group, a group in which two or more selected from these groups are combined, a group in which at least a portion of these groups is substituted with at least one atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, or a group in which a portion of these groups is substituted with a substituent, and R 41 are independently alkylene having 2 to 4 carbon atoms, m is an integer of 1 to 70, -NR 1 R 2 is R 1 and R 2 and may be a nitrogen-containing heterocyclic group having 5 to 20 ring-constituting atoms bonded to each other, -N(R')-R 4 - is R' and R 4 and may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which the ring members are bonded to each other, -N(R')-R 4 --N(R')-- may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which two R's are bonded to each other.

15. The composition of claim 1 or 2, further comprising a filler.

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