Curable composition

Abstract

The present disclosure provides a curable composition which has excellent solvent solubility and can be cured at a low temperature in the presence of oxygen. This curable composition contains a compound (A) represented by formula (1) and a curing accelerator (B). The curing accelerator (B) is one or more substances selected from the group consisting of a reaction product of m-xylylenediamine, a quaternary phosphonium salt, a phosphonium salt having a carboxyl group, a 2-ethylhexanoate which is a heat-latent base generator and has a carboxyl group, a secondary monoamine, an imidazole compound, and a low-molecular-weight maleimide. # imgabs0 #

Description

Technical Field

[0001] The present disclosure relates to a curable composition. More specifically, the present disclosure relates to a curable composition having excellent solvent solubility and capable of curing at low temperatures in the presence of oxygen. This application claims priority to Japanese Patent Application No. 2022-152875 filed in Japan on September 26, 2022, the contents of which are incorporated herein by reference. Background Art

[0002] Engineering plastics are high-performance materials that have both high heat resistance and mechanical properties, and are used as materials necessary for miniaturization, lightness, high performance, and high reliability of various parts. However, polyimide, for example, is a type of engineering plastic, but it is not easily dissolved in solvents and is not easily melted, so it is difficult to obtain a molded body that matches the intended use.

[0003] In particular, polyetheretherketone (PEEK), also known as super engineering plastic, is a thermoplastic resin with a continuous use temperature of 260°C and excellent heat resistance, flame retardancy and electrical properties. However, due to its melting point of 343°C, it is particularly difficult to melt and dissolve in solvents, resulting in poor processability, making it difficult to obtain a molded body.

[0004] On the other hand, a curable compound that can be molded into a cured product having a PEEK skeleton is known. The curable compound is easily meltable and has excellent solvent solubility, so it has good handling and processability, and can easily obtain a cured product and a molded body having a PEEK skeleton (see Patent Documents 1 to 3).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2021-95542

[0008] Patent Document 2: Japanese Patent Application Publication No. 2021-95544

[0009] Patent Document 3: International Publication No. 2019 / 244693 Summary of the invention

[0010] Problems to be solved by the invention

[0011] Sometimes it is required that the curable compound can be cured at a relatively low temperature. In order to cure at low temperatures, it is considered to use a peroxide as a curing agent. However, peroxides are deactivated by oxygen, so it is difficult to form a cured product with stable quality in a system with oxygen such as an air atmosphere. It should be noted that when peroxides are used as curing agents, it is necessary to carry out under a nitrogen atmosphere. In addition, when peroxides are not used, high temperature treatment of more than 300°C is required.

[0012] Therefore, an object of the present disclosure is to provide a curable composition which has excellent solvent solubility and can be cured at a low temperature in the presence of oxygen.

[0013] Solutions for solving problems

[0014] The inventors of the present disclosure have conducted intensive research to solve the above technical problems, and as a result, have found that a curable composition having excellent solvent solubility and capable of curing at low temperatures in the presence of oxygen can be obtained by using a specific curable compound and a specific curing accelerator in combination. The present disclosure relates to a technical solution completed based on these findings.

[0015] That is, the present disclosure provides a curable composition comprising the following compound (A) and the following curing accelerator (B).

[0016] Compound (A): a compound represented by the following formula (1).

[0017] [Chemical formula 1]

[0018]

[0019] [Where R 1 and R 2 The same or different groups represent a group represented by the following formula (r-1).

[0020] [Chemical formula 2]

[0021]

[0022] [In the formula, Q represents C or CH. Two Qs in the formula are bonded via a single bond or a double bond. R 3 ~R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group. 3 and R 4 Optionally, they are bonded to each other to form a ring. n' represents an integer greater than 0. The bond with a wavy line in the formula is 1 or D 2 Bonding 1 and D 2 are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit comprising a structure represented by the following formula (I) and a structure represented by the following formula (II)]

[0023] [Chemical formula 3]

[0024]

[0025] (Where Ar 1 ~Ar 3are the same or different and represent a group formed by removing two hydrogen atoms from the structural formula of an aromatic ring, or a group formed by removing two hydrogen atoms from the structural formula of two or more aromatic rings bonded via a single bond or a connecting group. X represents -CO-, -S- or -SO2-, and Y is the same or different and represents -S-, -SO2-, -O-, -CO-, -COO- or -CONH-. n represents an integer greater than 0)

[0026] Curing accelerator (B): at least one selected from the group consisting of meta-xylylenediamine reactants, quaternary phosphonium salts, phosphonium salts having a carboxyl group, 2-ethylhexanoate as a thermally latent base generator having a carboxyl group, secondary monoamines, imidazole compounds, and low molecular weight maleimides.

[0027] It is preferred that the curing accelerator (B) contains an organic nucleophilic agent as the quaternary phosphonium salt.

[0028] Preferably, the curable composition further includes a compound (C) having a hindered phenol structure including a hydrazine skeleton.

[0029] It is preferred that the content of the curing accelerator (B) in the curable composition is 0.1 to 2% by mass.

[0030] Preferably, the curable composition can start curing at 200° C. or lower in the presence of oxygen.

[0031] Preferably, the curable composition is cured and used as an insulating film covering a conductive wire.

[0032] Furthermore, the present disclosure provides an insulated wire including a conductive wire and an insulating film covering the conductive wire, wherein the insulating film is a cured product of the curable composition.

[0033] Furthermore, the present disclosure provides a coil including the above-mentioned insulated wire.

[0034] Furthermore, the present disclosure provides a motor including the above-mentioned coil.

[0035] Furthermore, the present disclosure provides a generator including the above-mentioned coil.

[0036] Furthermore, the present disclosure provides an electronic / electrical device including the above-mentioned coil.

[0037] Furthermore, the present disclosure provides a cable including the above-mentioned insulated wire.

[0038] Furthermore, the present disclosure provides an electronic / electrical device including the above-mentioned cable.

[0039] Effects of the Invention

[0040] The curable composition of the present disclosure has excellent solvent solubility and can be cured at low temperatures in the presence of oxygen. Therefore, the curable composition has a wide range of applications in terms of equipment and productivity for curing the curable composition and can be used in various situations. DETAILED DESCRIPTION

[0041] [Curable composition]

[0042] The curable composition of the present disclosure contains at least a compound represented by formula (1) described below (hereinafter sometimes referred to as "compound (A)") and a curing accelerator described below (hereinafter sometimes referred to as "curing accelerator (B)"). The compound (A) and the curing accelerator (B) may be used alone or in combination of two or more.

[0043] (Compound (A))

[0044] The compound (A) is a compound represented by the following formula (1).

[0045] [Chemical formula 1]

[0046]

[0047] In formula (1), R 1 and R 2 The same or different groups represent a group represented by the following formula (r-1).

[0048] [Chemical formula 2]

[0049]

[0050] In formula (r-1), Q represents C or CH. Two Qs in the formula are bonded via a single bond or a double bond. 3 ~R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group. 3 and R 4 They are optionally bonded to each other to form a ring. n' represents an integer greater than 0. The bond with a wavy line in formula (r-1) and D 1 or D 2 Bonding.

[0051] In formula (1), D 1 and D 2 The same or different, represents a single bond or a connecting group.

[0052] In formula (1), L represents a divalent group having a repeating unit including a structure represented by the following formula (I) and a structure represented by the following formula (II).

[0053] [Chemical formula 3]

[0054]

[0055] In formula (I) and formula (II), Ar 1 ~Ar 3 are the same or different and represent a group formed by removing two hydrogen atoms from the structural formula of an aromatic ring, or a group formed by removing two hydrogen atoms from a structural formula formed by bonding two or more aromatic rings via a single bond or a connecting group. X represents -CO-, -S- or -SO2-, and Y is the same or different and represents -S-, -SO2-, -O-, -CO-, -COO- or -CONH-. n represents an integer greater than 0.

[0056] As R 3 ~R 6 The hydrocarbon group in the above-mentioned may include, for example, a saturated or unsaturated aliphatic hydrocarbon group (preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms), an aromatic hydrocarbon group (preferably an aryl group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group), and a group formed by bonding two or more groups selected from the above-mentioned saturated or unsaturated aliphatic hydrocarbon groups and the above-mentioned aromatic hydrocarbon groups.

[0057] R 3 and R 4 They are optionally bonded to each other to form a ring together with adjacent carbon atoms. Examples of the above-mentioned ring include alicyclic rings having 3 to 20 carbon atoms, aromatic rings having 6 to 14 carbon atoms, and the like. Examples of the above-mentioned alicyclic rings having 3 to 20 carbon atoms include: cycloalkane rings having three to twenty members (preferably three to fifteen members, and particularly preferably five to eight members) such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring; cycloalkene rings having three to twenty members (preferably three to fifteen members, and particularly preferably five to eight members) such as cyclopentene ring and cyclohexene ring; perhydronaphthalene ring, norbornane ring, norbornene ring, adamantane ring, tricyclo[5.2.1.0 2,6 ]Decane ring, tetracyclic [4.4.0.1 2,5 .1 7,10 ] bridged cyclic hydrocarbon groups such as a dodecane ring, etc. Examples of the aromatic ring having 6 to 14 carbon atoms include a benzene ring and a naphthalene ring.

[0058] n′ is an integer greater than or equal to 0, for example, an integer from 0 to 3, and preferably 0 or 1.

[0059] As the group represented by the above formula (r-1), a group selected from the groups represented by the following formulae (r-1-1) to (r-1-6) is preferred.

[0060] [Chemical formula 4]

[0061]

[0062] (The bond extending from the nitrogen atom in the formula is connected to D in formula (1) 1 or D 2 Bonding)

[0063] One or more substituents may be bonded to the groups represented by the above formulae (r-1-1) to (r-1-6). Examples of the substituents include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and halogen atoms.

[0064] The group represented by the above formula (r-1) is preferably a group selected from the groups represented by the above formulae (r-1-1) to (r-1-5), and a group represented by the above formula (r-1-1) or (r-1-5) is particularly preferred.

[0065] As the group represented by the above formula (r-1), among them, a group represented by the following formula (r-1′) is preferred.

[0066] [Chemical formula 5]

[0067]

[0068] (In the formula, Q, R 3 and R 4 Same as above)

[0069] In formula (1), D 1 and D 2 The same or different represents a single bond or a linking group. Examples of the linking group include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imide bond, and a group formed by connecting a plurality of these.

[0070] As D 1 and D 2 Among them, from the perspective of obtaining a cured product having particularly excellent heat resistance, a group containing a divalent aromatic hydrocarbon group is preferred, and particularly preferred are arylene groups having 6 to 14 carbon atoms such as 1,4-phenylene, 1,3-phenylene, 4,4'-biphenylene, 3,3'-biphenylene, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,8-naphthalenediyl, and anthracenediyl.

[0071] As D 1 and D 2 , preferably a group selected from the groups represented by the following formulae (d-1) to (d-4), particularly preferably a group represented by the following formula (d-1) (1,2-phenylene, 1,3-phenylene or 1,4-phenylene), more preferably 1,4-phenylene. It should be noted that the connection position of the bonding bond in the following formula is not particularly limited.

[0072] [Chemical formula 6]

[0073]

[0074] In addition, D 1 and D 2 The divalent aromatic hydrocarbon group is preferably linked to at least one group selected from the group consisting of a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, and an imide bond, and the divalent aromatic hydrocarbon group is particularly preferably linked to an ether bond.

[0075] Therefore, as R in formula (1) 1 -D 1 - Base and R 2 -D 2 - group, preferably a group represented by the following formula (rd-1'-1) or (rd-1'-2). It should be noted that the connection position of the bond in the following formula is not particularly limited.

[0076] [Chemical formula 7]

[0077]

[0078] (In the formula, Q, R 3 and R 4 Same as above)

[0079] Ar 1 ~Ar 3 The same or different groups refer to groups formed by removing two hydrogen atoms from a structural formula of an aromatic ring, or groups formed by removing two hydrogen atoms from a structural formula of two or more aromatic rings bonded via a single bond or a linking group.

[0080] Examples of the aromatic ring include aromatic rings having 6 to 14 carbon atoms such as benzene, naphthalene, anthracene, and phenanthrene. Among them, aromatic hydrocarbon rings such as aromatic rings having 6 to 10 carbon atoms such as benzene and naphthalene are preferred.

[0081] Examples of the linking group include a divalent hydrocarbon group having 1 to 5 carbon atoms and a group in which one or more hydrogen atoms of a divalent hydrocarbon group having 1 to 5 carbon atoms are substituted with a halogen atom.

[0082] Therefore, as Ar 1 ~Ar 3 , the same or different, preferably a group formed by removing two hydrogen atoms from the structural formula of an aromatic ring having 6 to 14 carbon atoms, or a group formed by removing two hydrogen atoms from a structural formula formed by two or more aromatic rings having 6 to 14 carbon atoms bonded via the following structure, wherein the structure is: a single bond, a straight-chain or branched alkylene group having 1 to 5 carbon atoms, or a group formed by replacing one or more hydrogen atoms of a straight-chain or branched alkylene group having 1 to 5 carbon atoms with a halogen atom.

[0083] As Ar 1 ~Ar 3 , wherein the same or different, preferably a group selected from the groups represented by the following formulae (a-1) to (a-5). It should be noted that the connection position of the bonding bond in the following formulae is not particularly limited.

[0084] [Chemical formula 8]

[0085]

[0086] As Ar in formula (I) 1 and Ar 2 Among them, a group formed by removing two hydrogen atoms from the structural formula of an aromatic ring having 6 to 14 carbon atoms is preferred, and a group represented by the above formula (a-1) or (a-2) is particularly preferred.

[0087] X in formula (I) represents -CO-, -S- or -SO2-. Among them, -CO- or -SO2- is preferred as X.

[0088] As Ar in formula (II) 3 Among them, a group selected from the groups represented by the above formulae (a-1), (a-4) and (a-5) is preferred.

[0089] Y in formula (II) is the same or different and represents -S-, -SO2-, -O-, -CO-, -COO- or -CONH-. Among them, -S-, -O- or -SO2- is preferred as Y.

[0090] n in formula (II) represents an integer of 0 or greater, for example, an integer of 0-5, preferably an integer of 1-5, and particularly preferably an integer of 1-3.

[0091] As L in the formula (1), a divalent group represented by the following formula (L-1-1) or (L-1-2) is preferred.

[0092] [Chemical formula 9]

[0093]

[0094] In the above formula, m1 and m2 are the number of repeating units shown in parentheses contained in the molecular chain (= the divalent group represented by the above formula (L-1-1) or (L-1-2)), i.e., the average degree of polymerization, and are, for example, 2 to 50, preferably 3 to 40, more preferably 4 to 30, further preferably 5 to 20, and particularly preferably 5 to 10. It should be noted that the values ​​of m1 and m2 can be determined by GPC measurement and NMR spectrum analysis.

[0095] The number of moles of the group represented by the formula (r-1) per 1 g of the compound (A) (hereinafter sometimes referred to as “functional group concentration”) is, for example, 0.5×10 -4 ~20×10 -4 The upper limit of the functional group concentration is preferably 15×10 -4 mol / g, particularly preferably 10×10 -4 The lower limit of the functional group concentration is preferably 1.0×10 -4 mol / g, particularly preferably 1.5×10 -4 mol / g. If the functional group concentration of compound (A) is within the above range, the solvent solubility is excellent, and a cured product with excellent toughness and heat resistance can be formed. On the other hand, if the functional group concentration is lower than the above range, there is a tendency for the solvent solubility to decrease. In addition, if the functional group concentration is higher than the above range, there is a tendency for it to be difficult to form a cured product with excellent toughness.

[0096] The above functional group concentration can be determined by 1 The area of ​​each peak was determined from the H-NMR spectrum, and the determined value was substituted into the following formula for calculation.

[0097] Functional group concentration = [peak area of ​​the group represented by formula (r-1) / number of protons of the group represented by formula (r-1)] / Σ

[0098] [(area of ​​each peak / number of protons of the group to which each peak belongs)×chemical formula weight corresponding to each peak]

[0099] The number average molecular weight (Mn; standard polystyrene conversion) of the compound (A) is, for example, 1000 to

[0100] 15000-15000, preferably 1500-12000, more preferably 2000-10000, further preferably 2200-

[0101] 8000, particularly preferably 2500-7500.

[0102] The weight average molecular weight (Mw; standard polystyrene conversion) of the compound (A) is, for example, 1000 to

[0103] The lower limit of the weight average molecular weight (Mw) is preferably 1500, more preferably 2500, further preferably 3000, and particularly preferably 4000. The upper limit of the weight average molecular weight (Mw) is preferably

[0104] 40,000, more preferably 35,000, further preferably 25,000.

[0105] The above-mentioned Mn and Mw are determined by gel permeation chromatography (GPC) measurement (solvent: chloroform, standard polystyrene conversion). When the compound (A) has the above-mentioned molecular weight, it has excellent solvent solubility.

[0106] The compound (A) has excellent solvent solubility, and its solubility in 100 g of the solvent at 23° C. is preferably 1 g or more, more preferably 5 g or more, and particularly preferably 10 g or more.

[0107] Compound (A) has excellent solvent solubility, and its solubility in 100 g of solvent at 23°C is

[0108] 1 g or more, preferably 5 g or more, particularly preferably 10 g or more.

[0109] The compound (A) can be produced, for example, by reacting a compound represented by the following formula (2) with a compound represented by the following formula (3).

[0110] [Chemical formula 10]

[0111]

[0112] (Where D 1 , D 2 and L is the same as above)

[0113] [Chemical formula 11]

[0114]

[0115] (In the formula, Q and R 3 ~R 6 Same as above)

[0116] Among the compounds represented by the above formula (2), for example, the compound represented by the following formula (2-1) can be produced through the following steps [1-1] and [1-2].

[0117] Step [1-1]: A compound represented by the following formula (4) is reacted with a compound represented by the following formula (5) in the presence of a base to obtain a compound represented by the following formula (6).

[0118] Step [1-2]: reacting an amino alcohol (a compound represented by the following formula (7)) with a compound represented by the following formula (6).

[0119] [Chemical formula 12]

[0120]

[0121] In the above formula, Ar 1 ~Ar 3, X, Y and n are the same as above. D represents a connecting group, which can be D 1 and D 2 The same examples are given for the linking groups in . m is the average degree of polymerization of the repeating units, and is, for example, 3 to 50, preferably 4 to 30, and particularly preferably 5 to 20. Z represents a halogen atom.

[0122] (Process [1-1])

[0123] Examples of the compound represented by the formula (4) include halides of bisaryl compounds such as benzophenone and 2-naphthylphenyl ketone, and derivatives thereof.

[0124] Examples of the compound represented by the formula (5) include hydroquinone, resorcinol, and bisphenol A.

[0125] Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate; and organic bases such as pyridine and triethylamine. The amount of the base used can be appropriately adjusted depending on the type of the base. For example, the amount of a dibasic base such as calcium hydroxide used is about 1.0 to 2.0 moles relative to 1 mole of the compound represented by formula (5).

[0126] In addition, the reaction can be carried out in the presence of a solvent. As the solvent, for example, an organic solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethyl sulfoxide, or a mixed solvent of two or more thereof can be used.

[0127] The reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, and may be, for example, a nitrogen atmosphere, an argon atmosphere, etc. The reaction temperature is, for example, about 100 to 200°C.

[0128] (Process [1-2])

[0129] Examples of the compound represented by the formula (7) include 4-aminophenol, 2-amino-6-hydroxynaphthalene, and positional isomers and derivatives thereof.

[0130] The reaction can be carried out in the presence of a solvent. As the solvent, the same solvent as used in step [1] can be used. The reaction temperature is, for example, about 100 to 200°C.

[0131] The content of the compound (A) in the curable composition is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more relative to the total amount 100% by mass of the curable composition. In addition, the content is, for example, 99% by mass or less, preferably 60% by mass or less, and more preferably 50% by mass or less.

[0132] The content ratio of the compound (A) in the curable composition is preferably 40% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more relative to 100% by mass of the total amount of the solid content in the curable composition (e.g., the total amount of each component excluding the solvent). In addition, in the curable composition, the content ratio of the compound (A) relative to the total of 100% by mass of the compound (A), the curing accelerator (B), and the compound (C) described later is preferably within the above range.

[0133] (Curing accelerator (B))

[0134] The curing accelerator (B) is one or more selected from the group consisting of a reactant of meta-xylylenediamine, a quaternary phosphonium salt, a phosphonium salt having a carboxyl group, 2-ethylhexanoate as a thermally latent base generator having a carboxyl group, a secondary monoamine, an imidazole compound, and a low molecular weight maleimide.

[0135] The reactant of the meta-xylylenediamine is a reactant of meta-xylylenediamine and other compounds. The other compounds include compounds having the following functional groups: functional groups reactive with amino groups. Examples of the functional groups include hydroxyl groups, groups containing vinyl groups, epoxy groups, and halide groups. Examples of the compounds having the groups containing vinyl groups include styrene.

[0136] The reaction product of the meta-xylylenediamine is preferably a compound represented by the following formula (B-1).

[0137] [Chemical formula 13]

[0138]

[0139] In formula (B-1), R a Represents a divalent organic group, n a Indicates an integer greater than 1, n b Represents 0 or 1.

[0140] As the above-mentioned divalent organic group, for example, a hydrocarbon group optionally having a substituent can be listed. The above-mentioned hydrocarbon group can be any type of saturated or unsaturated. In addition, the above-mentioned hydrocarbon group can be listed as: a straight-chain hydrocarbon group, a branched hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a group formed by bonding two or more of them. The number of carbon atoms of the above-mentioned divalent organic group is preferably 1 to 10, and more preferably 3 to 8.

[0141] Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, a carboxyl group, a nitro group, a cyano group, an isocyanate group, an isothiocyanate group, and the like.

[0142] n a It represents an integer of 1 or more, and is preferably 1-16, and more preferably 1-12.

[0143] Examples of the compound represented by the formula (B-1) include an adduct of meta-xylylenediamine and styrene (trade name "GASKAMINE 240" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and an adduct of meta-xylylenediamine and epichlorohydrin (trade name "GASKAMINE 328" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like).

[0144] The quaternary phosphonium salt is a salt composed of a phosphonium cation and a counter anion. Examples of the quaternary phosphonium salt include well-known or commonly used compounds such as tetraphenylphosphonium tetra(p-tolyl)borate.

[0145] Among them, as the quaternary phosphonium salt, a compound represented by the following formula (B-2) is preferred.

[0146] [Chemical formula 14]

[0147]

[0148] In formula (B-2), R b represents an alkyl group or an aryl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include: a linear or branched alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl; and a cyclic alkyl group (cycloalkyl group) having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and methylcyclohexyl. In addition, examples of the aryl group include: a phenyl group, a substituted phenyl group (e.g., tolyl, xylyl, mesityl, ethylphenyl, methoxyphenyl, ethoxyphenyl, etc.), and a naphthyl group. R b Among them, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 2 to 6 carbon atoms is more preferred.

[0149] In formula (B-2), R c represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl. c Among them, a linear or branched alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group or an ethyl group is more preferred.

[0150] R b and R c are different groups, preferably Rb The carbon number of R c More carbon atoms.

[0151] In formula (B-2), A - Represents a counter anion. As the above-mentioned counter anion, a known or commonly used counter anion can be used, without particular limitation, and preferably a conjugate base of an acidic phosphate. As the above-mentioned acidic phosphate, known or commonly used acidic phosphates can be listed, without particular limitation, for example, monophosphate (monoalkyl phosphate, etc.), diester phosphate (dialkyl phosphate, etc.), etc. can be listed. More specifically, as the above-mentioned acidic phosphate, a group represented by the following formula (B-2a) is preferred.

[0152] [Chemical formula 15]

[0153]

[0154] In formula (B-2a), R d are the same or different and represent an alkyl group or an aryl group having 1 to 10 carbon atoms. d Specific examples include the following: b The same groups as those listed above. As R in formula (B-2a) d Among them, a linear or branched alkyl group having 1 to 10 carbon atoms is preferred, a linear or branched alkyl group having 1 to 4 carbon atoms is more preferred, and a methyl group or an ethyl group is further preferred.

[0155] The compound represented by the above formula (B-2) can be obtained by a known or customary production method, and is also available as a commercial product such as "HISHICOLIN PX-4MP" (manufactured by Nippon Chemical Industry Co., Ltd.).

[0156] The phosphonium salt having a carboxyl group is a salt composed of a phosphonium cation and a counter anion, and the phosphonium cation and / or the counter anion has a carboxyl group. Among them, it is preferred that the counter anion has a carboxyl group.

[0157] Among them, as the phosphonium salt having a carboxyl group, a compound represented by the following formula (B-3) is preferred.

[0158] [Chemical formula 16]

[0159]

[0160] In formula (B-3), R e are the same or different and represent a linear or branched alkyl group having 1 to 16 carbon atoms, or a phenyl group which may have a substituent on the aromatic ring. e, wherein a linear or branched alkyl group having 1 to 4 carbon atoms is preferred. As the above alkyl group, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl are preferred. The above phenyl group which may have a substituent is preferably phenyl or p-tolyl. R is particularly preferred. e All of them are linear or branched butyl groups.

[0161] In formula (B-3), A - represents a counter anion. As the above counter anion, a known or commonly used counter anion can be used without particular limitation, and an anion having a carboxyl group is preferred. As the above anion having a carboxyl group, an anion of a polycarboxylic acid is preferred. As the above polycarboxylic acid, aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, and aromatic polycarboxylic acids can be listed. Among them, aliphatic polycarboxylic acids are preferred. The above polycarboxylic acids may also be in the form of anhydrides.

[0162] The number of carboxyl groups in the polycarboxylic acid is, for example, 2 to 6, preferably 2 to 4, and more preferably 2. The anion of the polycarboxylic acid is an anion of a monovalent or higher (typically monovalent) carboxyl group anion obtained by dissociating hydrogen atoms of one or more carboxyl groups of the polycarboxylic acid.

[0163] As the anion of the polycarboxylic acid, a group represented by the following formula (B-3a) is preferred.

[0164] [Chemical formula 17]

[0165]

[0166] In formula (B-3a), R f , R g , R h and R i are the same or different, representing a hydrogen atom, a hydroxyl group, a carboxyl group or an organic group, R f ~R i Two or more of the above-mentioned groups are optionally bonded to each other to form a ring. Examples of the above-mentioned organic group include a hydrocarbon group optionally having a substituent. Examples of the above-mentioned substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group, a carboxyl group, a nitro group, a cyano group, an isocyanate group, an isothiocyanate group, etc.

[0167] Specific examples of the aliphatic polycarboxylic acid that can form the group represented by the above formula (B-3a) include: f ~R i Succinic acid with all hydrogen atoms; R f ~R h is a hydrogen atom and R i Malic acid with hydroxyl group; R f and R g is a hydrogen atom, Rh is hydroxyl group, R i Citric acid represented by carboxymethyl; R f and R h is a hydrogen atom, R g and R i butane-1,2,3,4-tetracarboxylic acid, etc. which are carboxyl groups.

[0168] Examples of the alicyclic polycarboxylic acid that can form the group represented by the above formula (B-3a) include: f and R g The carbon atom to which it is bonded and R h and R i The carbon atoms to which the bonding occurs are alicyclic polycarboxylic acids constituting atoms.

[0169] Examples of the alicyclic polycarboxylic acid include a compound represented by the following formula (B-3b) and a compound represented by the following formula (B-3c).

[0170] [Chemical formula 18]

[0171]

[0172] In the above formula (B-3b) and the above formula (B-3c), R j , R k , R l and R m are the same or different and represent a hydrogen atom, a hydroxyl group, a carboxyl group or an organic group. Examples of the organic group include a hydrocarbon group optionally having a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group, a carboxyl group, a nitro group, a cyano group, an isocyanate group, an isothiocyanate group, etc. As the hydrocarbon group, a linear or branched alkyl group having 1 to 4 carbon atoms is preferred. n It represents a divalent organic group, and is preferably a divalent hydrocarbon group, more preferably a divalent hydrocarbon group having 1 to 4 carbon atoms, and particularly preferably a methylene group or an ethylene group.

[0173] As the compound represented by the above formula (B-3b), preferably: R n is a methylene group and R j ~R m A compound composed entirely of hydrogen atoms; R n is methylene, R j ~R m A compound in which one of the atoms is a methyl group and three of the atoms are hydrogen atoms.

[0174] As the compound represented by the above formula (B-3c), preferably: R j ~R m A compound composed entirely of hydrogen atoms; R j ~Rm A compound in which one of the R atoms is a methyl group and three of the R atoms are hydrogen atoms; j ~R m Two of them (especially R k and R l ) is a carboxyl group and two are hydrogen atoms. In the above formula (B-3c), more preferably: R j ~R m A compound composed entirely of hydrogen atoms; R j ~R m Two of them (especially R k and R l ) is a carboxyl group and two are hydrogen atoms.

[0175] Examples of the aromatic polycarboxylic acid include compounds represented by the following formula (B-3d).

[0176] [Chemical formula 19]

[0177]

[0178] In the above formula (B-3d), R o , R p , R q and R r The same or different groups represent a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group, an alkyl group or an alkoxy group.

[0179] Specific examples of the compound represented by the formula (B-3d) include phthalic acid, 4-methylphthalic acid, 4-hydroxyphthalic acid, 4-aminophthalic acid, and 4-methoxyphthalic acid.

[0180] It should be noted that the quaternary phosphonium salt may be a compound corresponding to the phosphonium salt having a carboxyl group, and the phosphonium salt having a carboxyl group may be a compound corresponding to the quaternary phosphonium salt.

[0181] Among them, the quaternary phosphonium salt and the phosphonium salt having a carboxyl group are compounds represented by the above formula (B-2) or compounds represented by the above formula (B-3), and A is particularly preferred. - The compound is a conjugate base of the above acidic phosphate or an anion of the above polycarboxylic acid. In this case, there is a tendency for the compatibility with the solvent to be excellent.

[0182] As the 2-ethylhexanoic acid salt having a carboxyl group which is a heat-latent base generator, a salt composed of a 2-ethylhexanoic acid anion and an amidine cation is preferred.

[0183] Examples of the amidine that can form the amidine include compounds represented by the following formula (B-4).

[0184] [Chemical formula 20]

[0185]

[0186] In the above formula (B-4), Cy represents an alicyclic ring having one nitrogen atom and a carbon atom between two nitrogen atoms in formula (B-4) as constituent atoms. The above alicyclic ring is optionally substituted with a monovalent organic group on the carbon atom constituting the above alicyclic ring. The above alicyclic ring is preferably a four- to eight-membered ring, and more preferably a five- to seven-membered ring.

[0187] Examples of the monovalent organic group include alkyl groups having 1 to 6 carbon atoms (methyl, ethyl, isopropyl, n-butyl, tert-butyl, n-hexyl, etc.), hydroxyalkyl groups having 1 to 6 carbon atoms (hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxyisopropyl, 3-hydroxytert-butyl, 6-hydroxyhexyl, etc.), and dialkylamino groups having 2 to 12 carbon atoms (dimethylamino, methylethylamino, diethylamino, diisopropylamino, tert-butylmethylamino, di-n-hexylamino, etc.).

[0188] Specific examples of the compound represented by the formula (B-4) include 1,5-diazabicyclo[4,3,0]-nonene-5 (DBN), 1,5-diazabicyclo[4,4,0]-decene-5, 1,8-diazabicyclo[5,4,0]-undecene-7, 5-hydroxypropyl-1,8-diazabicyclo[5,4,0]-undecene-7, and 5-dibutylamino-1,8-diazabicyclo[5,4,0]-undecene-7. Among them, DBN and 1,8-diazabicyclo[5,4,0]-undecene-7 are particularly preferred.

[0189] The activation temperature of the 2-ethylhexanoic acid salt having a carboxyl group as the above-mentioned heat-latent base generator is preferably 85 to 130°C, more preferably 90 to 120°C, and further preferably 95 to 110°C.

[0190] The secondary monoamine is an amine having a secondary amino group as the only amino group in the molecule. As the secondary monoamine, a compound in which two hydrocarbon groups are bonded to a nitrogen atom is preferred. As the hydrocarbon group, a straight-chain or branched hydrocarbon group can be cited. As the hydrocarbon group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 2 to 4 carbon atoms is more preferred. The two hydrocarbon groups may be the same or different.

[0191] Specific examples of the secondary monoamines include N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine, N,N-dibutylamine, N,N-dipentylamine, N,N-dihexylamine, N,N-diheptylamine, N,N-dioctylamine, N,N-dinonylamine, N,N-didecylamine, N,N-diundecylamine, N,N-didodecylamine, N-methyl-N-propylamine, N-ethyl-N-propylamine, and N-propyl-N-butylamine.

[0192] Examples of the imidazole compound include compounds represented by the following formula (B-5).

[0193] [Chemical formula 21]

[0194]

[0195] In the above formula (B-5), R s , R t , R u and R v are the same or different and represent a hydrogen atom or a hydrocarbon group optionally having a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a hydroxyl group, a carboxyl group, a nitro group, a cyano group, an isocyanate group, an isothiocyanate group, and the like.

[0196] Examples of the hydrocarbon group include an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a group in which two or more of these groups are bonded to each other.

[0197] Specific examples of the imidazole compound include 2-ethyl-4-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, and 1-cyanoethyl-2-methylimidazole.

[0198] Examples of the low molecular weight maleimide include compounds having carbon atoms of 100 or less (preferably 10 to 50). Among them, the low molecular weight maleimide is preferably a compound represented by the following formula (B-6).

[0199] [Chemical formula 22]

[0200]

[0201] In the above formula (B-6), R W It represents a linear or branched alkylene group, a cycloalkylene group, an arylene group, or a group in which two or more of them are bonded via a single bond or a linking group.

[0202] The linking group is not particularly limited, and examples thereof include ether bonds (-O-), thioether bonds (-S-), sulfonyl bonds (-SO2-), amide bonds (-NHCO-), ester bonds (-COO-), acyl bonds (-CO-), etc. The number of carbon atoms in the linear or branched alkylene group is preferably 1 to 12, more preferably 2 to 8. The number of carbon atoms in the cycloalkylene group is preferably 4 to 6. The arylene group preferably has 6 carbon atoms (phenylene group).

[0203] Examples of the compound represented by the above formula (B-6) include: w The aliphatic bismaleimide compound is a linear or branched alkylene compound. Examples of the aliphatic bismaleimide compound include 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 1,6-bismaleimide-(2,4,4-trimethyl)hexane, N,N'-decamethylenebismaleimide, N,N'-decamethylenebismaleimide, N,N'-octamethylenebismaleimide, N,N'-heptamethylenebismaleimide, N,N'-hexamethenebismaleimide, Methylbismaleimide, N,N'-pentamethylenebismaleimide, N,N'-tetramethylenebismaleimide, N,N'-trimethylenebismaleimide, N,N'-ethylenebismaleimide, N,N'-(oxydimethylene)bismaleimide, 1,13-bismaleimide-4,7,10-trioxatridecane, 1,11-bis(maleimide)-3,6,9-trioxatridecane, and the like.

[0204] Examples of the compound represented by the above formula (B-6) include: w Aromatic bismaleimide compound containing the above arylene group The number of aromatic rings in the above aromatic bismaleimide compound is not particularly limited.

[0205] Examples of the aromatic bismaleimide compound having one aromatic ring include 4-methyl-1,3-phenylenebismaleimide, 1,3-phenylenebismaleimide, 1,4-phenylenebismaleimide, 1,2-phenylenebismaleimide, naphthalene-1,5-dimaleimide, and 4-chloro-1,3-phenylenebismaleimide.

[0206] Examples of the aromatic bismaleimide compound having two aromatic rings include 4,4'-diphenylmethane bismaleimide, N,N'-(4,4'-biphenylene) bismaleimide, N,N'-(sulfonyl di-p-phenylene) bismaleimide, N,N'-(oxy di-p-phenylene) bismaleimide, N,N'-(3,3'-dimethyl-4,4'-biphenylene) bismaleimide, N,N'-(benzylidene di-p-phenylene) bismaleimide, 3,3'-dichloro-4,4 '-Diphenylmethane bismaleimide, 3,3'-dimethyl-4,4'-diphenylmethane bismaleimide, 3,3'-dimethoxy-4,4'-diphenylmethane bismaleimide, 4,4'-diphenyl sulfide bismaleimide, 4,4'-diphenyl ether bismaleimide, 3,3'-benzophenone bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 1,1'-[1,4-butanediylbis(oxy-p-phenylene)]bismaleimide, etc.

[0207] Examples of the aromatic bismaleimide compound having three or more aromatic rings include: 2,2-bis[4-(4-maleimide phenoxy) phenyl] propane, bis[4-maleimide (4-phenoxyphenyl)] sulfone, 1,1'-[1,4-phenylene bis(oxy-4,1-phenylene)] bismaleimide, 1,1'-[sulfonyl bis(4,1-phenyleneoxy-3,1-phenylene)] bismaleimide, bis[4-( 3-maleimidophenoxy)phenyl]ketone, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, 1,1'-[oxybis(4,1-phenylenethio-4,1-phenylene)]bismaleimide, 1,1'-[(2,2',3,3',5,5',6,6'-octafluoro[1,1'-biphenyl]-4,4'-diyl)bis(oxy-3,1-phenylene)]bismaleimide, etc.

[0208] Among the aromatic bismaleimide, a compound represented by the following formula (B-6a) is preferred from the viewpoint of having better compatibility with a solvent and better low-temperature curability.

[0209] [Chemical formula 23]

[0210]

[0211] In the above formula (B-6a), n c represents an integer of 1 or more, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. As the compound represented by the above formula (B-6a), n c For compounds with different values ​​of nc The values ​​of have a distribution of compounds.

[0212] The molecular weight of the low molecular weight maleimide is not particularly limited, but is preferably 200 to 10,000, more preferably 200 to 8,000, and even more preferably 250 to 6,000.

[0213] The melting point (Tm) of the low molecular weight maleimide is preferably 155°C or less (e.g., 60 to 155°C), more preferably 150°C or less, and further preferably 145°C or less. If the melting point is 155°C or less, the curing of the curable composition can be promoted at a lower temperature. It should be noted that the melting point refers to the endothermic peak temperature measured by DSC.

[0214] The curing accelerator (B) is preferably an organic nucleophile. Among them, the curing accelerator (B) preferably contains an organic nucleophile which is the quaternary phosphonium salt.

[0215] The content of the curing accelerator (B) in the curable composition is preferably 0.03 to 30% by mass, more preferably 0.07 to 10% by mass, and even more preferably 0.1 to 2% by mass, based on 100% by mass of the total amount of the curable composition.

[0216] The content ratio of the above-mentioned one or more selected from the group consisting of the reactant of meta-xylylenediamine, quaternary phosphonium salt, phosphonium salt having a carboxyl group, 2-ethylhexanoate having a carboxyl group as a thermally latent base generator, secondary monoamine and imidazole compounds in the above-mentioned curable composition is preferably 0.03 to 10% by mass, more preferably 0.07 to 5% by mass, and further preferably 0.1 to 2% by mass relative to the total amount 100% by mass of the above-mentioned curable composition. The content ratio of the above-mentioned low molecular weight maleimide in the above-mentioned curable composition is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and further preferably 15 to 25% by mass relative to the total amount 100% by mass of the above-mentioned curable composition.

[0217] The content of the curing accelerator (B) is preferably 0.1 to 200 parts by mass, more preferably 0.2 to 100 parts by mass, and even more preferably 1 to 50 parts by mass, based on 100 parts by mass of the total amount of the compound (A).

[0218] The content of one or more selected from the group consisting of the reactant of meta-xylylenediamine, quaternary phosphonium salt, phosphonium salt having a carboxyl group, 2-ethylhexanoate having a carboxyl group as a thermally latent base generator, secondary monoamine and imidazole compounds is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 7 parts by mass, and further preferably 1 to 4 parts by mass relative to 100 parts by mass of the total amount of the compound (A). The content of the low molecular weight maleimide in the curable composition is preferably 50 to 200 parts by mass, more preferably 70 to 150 parts by mass, and further preferably 80 to 120 parts by mass relative to 100 parts by mass of the total amount of the compound (A).

[0219] (Compound (C))

[0220] The curable composition preferably further comprises a compound having a hindered phenol structure including a hydrazine skeleton (sometimes referred to as "compound (C)"). The compound (C) has excellent compatibility with the solvent, and even when the curable composition is applied to a metal substrate such as copper, a cured product with stable quality can be formed from the curable composition. The compound (C) may be used alone or in combination of two or more.

[0221] Examples of the hindered phenol structure in the compound (C) include a structure having a bulky alkyl group such as a tert-butyl group at the ortho position to the hydroxyl group in the phenol skeleton.

[0222] As the compound (C), a compound represented by the following formula (C-1) is preferred.

[0223] [Chemical formula 24]

[0224]

[0225] In the above formula (C-1), R x represents a divalent organic group, preferably a divalent hydrocarbon group, more preferably an alkylene group. The divalent organic group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 2 carbon atoms.

[0226] The content of the compound (C) in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on 100% by mass of the total amount of the curable composition.

[0227] The content of the compound (C) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 3 parts by mass, based on 100 parts by mass of the total amount of the compound (A).

[0228] (Solvent)

[0229] The curable composition may also contain a solvent. As the solvent, a known or commonly used organic solvent may be used without particular limitation, and examples thereof include: chain ketones such as methyl ethyl ketone and methyl isobutyl ketone; cyclic ketones such as cyclopentanone and cyclohexanone; amides such as formamide, acetamide, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, and N,N-dimethylacetamide (DMAc); halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, trifluorotoluene, and hexafluoro-2-propanol; sulfoxides such as dimethyl sulfoxide (DMSO), diethyl sulfoxide, and benzylphenyl sulfoxide; tetrahydrofuran (THF); aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as anisole; and mixtures of two or more thereof.

[0230] The solvent is preferably one having a large difference between the exothermic starting temperature of the compound (A) and the boiling point (= boiling point under normal pressure) of the solvent, from the viewpoint of suppressing the curing reaction of the compound (A) and making the solvent easily volatilize.

[0231] Among the above solvents, anisole is preferred from the viewpoint of excellent solubility of the compound (A) and the curing accelerator (B).

[0232] In addition to containing the above-mentioned components, the above-mentioned curable composition may also contain other components as required. As other components, known or customary additives may be used, for example, curable compounds other than compound (A), polymerization initiators, catalysts, fillers, organic resins (silicone resins, epoxy resins, fluororesins, etc.), stabilizers (antioxidants other than compound (C), ultraviolet light absorbers, light stabilizers, heat stabilizers, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcing materials, nucleating agents, coupling agents, lubricants, waxes, plasticizers, release agents, impact resistance modifiers, hue modifiers, fluidity modifiers, colorants (dyes, pigments, etc.), dispersants, defoamers, deaerators, antibacterial agents, preservatives, viscosity modifiers, thickeners, curing agents, curing accelerators other than curing accelerators (B), crosslinking agents, etc., may be listed. The above-mentioned other components may be used only one, or two or more.

[0233] It should be noted that, in the case of containing a curable compound other than compound (A), the ratio of compound (A) to the total amount 100% by mass of curable compounds is preferably 60% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more. In addition, in the case of containing a curing accelerator other than curing accelerator (B), the ratio of curing accelerator (B) to the total amount 100% by mass of curing accelerator is preferably 60% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more. In addition, in the case of containing an antioxidant other than compound (C), the ratio of compound (C) to the total amount 100% by mass of antioxidant is preferably 60% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more.

[0234] Examples of the polymerization initiator include radical polymerization initiators. Examples of the radical polymerization initiator include photoradical polymerization initiators and thermal radical polymerization initiators.

[0235] Examples of the photoradical polymerization initiator include benzophenone, benzylacetophenone, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfide, methyl o-benzoylbenzoate, ethyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2-methyl-1-[4-(methyl)phenyl]-2-morpholinopropanone-1, 1-hydroxycyclohexyl phenyl ketone, 2-dimethylamino-2-(4-morpholino)benzoyl-1-phenylpropane, and 2-amino-2-benzoyl-1-propane. -phenyl alkane compounds, tetrakis (tert-butylperoxycarbonyl) benzophenone, benzil, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, aminobenzene derivatives such as 4,4'-bis (diethylamino) benzophenone, imidazole compounds such as 2,2'-bis (2-chlorophenyl) -4,5,4',5'-tetraphenyl-1,2'-biimidazole, halogenated methylated triazine compounds such as 2,6-bis (trichloromethyl) -4- (4-methoxynaphthalen-1-yl) -1,3,5-triazine, halogenated methylated oxadiazole compounds such as 2-trichloromethyl-5- (2-benzofuran-2-yl-vinyl) -1,3,4-oxadiazole, etc. In addition, a photosensitizer may be added as needed.

[0236] Examples of the thermal radical polymerization initiator include azo compounds such as azobisisobutyronitrile and organic peroxides. Examples of the organic peroxides include hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, peroxyketals, ketone peroxides, and the like (specifically, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoyl)peroxyhexane, tert-butyl peroxybenzoate, tert-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzoyl peroxide, 1,4-di(2-tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, and 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate).

[0237] The curable composition can be cured at low temperatures even without using a polymerization initiator. Therefore, the content of the polymerization initiator in the curable composition can be 2 parts by mass or less, or 1 part by mass or less, 0.5 part by mass or less, 0.1 part by mass or less, or 0.02 part by mass or less relative to 100 parts by mass of the total amount of the compound (A).

[0238] The curable composition preferably has no precipitate or insoluble matter at 60° C. Moreover, it is particularly preferred that the curable composition has no precipitate or insoluble matter at room temperature (eg, 25° C.).

[0239] The curable composition preferably starts to cure at 300° C. or lower (preferably 250° C. or lower, more preferably 200° C. or lower) in the presence of oxygen. That is, the exothermic starting temperature is preferably within the above range.

[0240] The solvent solubility of the above-mentioned curable composition is excellent, and it can be cured at low temperatures in the presence of oxygen. Therefore, from the equipment aspect and productivity aspect that make the above-mentioned curable composition solidify, it has a wide range of application and can be used in various situations. In addition, even if the above-mentioned curable composition is solidified in contact with metal substrates such as copper, the quality (dielectric constant, glass transition temperature, flexibility, adhesion, etc.) of the cured product is not easy to be unstable. Therefore, the above-mentioned curable composition is not limited to the type of the substrate used, and multiple substrates can be coated.

[0241] The curable composition can be prepared by mixing the above-mentioned components, heating and stirring at a temperature of, for example, 80°C or lower, preferably at room temperature (about 25°C to 80°C), particularly preferably at 50 to 70°C.

[0242] The curable composition is subjected to heat treatment to react the compound (A) with each other, thereby solidifying to form a cured product. It is also possible to provide a drying process to volatilize the solvent before heat treatment is applied. In addition, heat treatment can be carried out at normal pressure, or under reduced pressure or under pressure. In addition, heat treatment can also be carried out under an inert gas atmosphere such as nitrogen or argon, but the curable composition is fully cured even in the presence of oxygen, and is therefore preferably carried out in an air atmosphere such as in the presence of oxygen.

[0243] The heating treatment temperature is not particularly limited. From the viewpoint that the curable composition can be cured at low temperatures, the heating treatment temperature is preferably 300°C or lower (e.g., 60 to 300°C), more preferably 250°C or lower (e.g., 80 to 250°C), and even more preferably 200°C or lower (e.g., 100 to 200°C). It should be noted that the heating may be performed while maintaining a constant temperature or in stages.

[0244] The heating method has no specific

[0245] The method is not particularly limited, and a known or customary method can be used.

[0246] Furthermore, the curable composition may be temporarily stopped during the curing reaction to form a semi-curable

[0247] Cured material (B stage). Semi-cured material temporarily shows fluidity by heating and can move with

[0248] Furthermore, by further performing a heat treatment, a substrate having a height difference can be formed.

[0249] Cured material with super heat resistance, flame retardancy and good dielectric properties.

[0250] The degree of curing of the semi-cured product is, for example, 85% or less (for example, 10 to 85%, particularly preferably

[0251] The preferred range is 15 to 75%, and more preferably 20 to 70%).

[0252] It should be noted that the degree of curing of the semi-cured product can be measured by DSC before curing (uncured).

[0253] The heat release of the curable composition and the heat release of its semi-cured product are calculated according to the following formula. Curing degree (%) = [1-(heat release of semi-cured product / heat release of uncured curable composition)] × 100 The cured product of the above curable composition has excellent heat resistance.

[0254] The 5% weight loss temperature (Td5 ) is, for example, 300°C or higher, preferably 400°C

[0255] 5% weight loss temperature

[0256] (T d5 ) is, for example, 600°C, preferably 550°C, and particularly preferably 530°C.

[0257] The 5% weight reduction temperature can be measured by TG / DTA (simultaneous measurement of differential thermal and thermogravimetric).

[0258] Therefore, the curable composition is molded by a known conventional molding method and then (according to

[0259] A molded body consisting of a cured product or a semi-cured product of the curable composition can be produced by subjecting the curable composition to a heat treatment (if drying treatment is required).

[0260] The curable composition can be preferably used in electronic information equipment, home appliances, automobiles, precision

[0261] Machinery, aircraft, space industry equipment, energy field (oil field excavation pipelines / pipes, fuel containers)

[0262] Composite materials (fiber reinforced plastics, prepregs, etc.) used under severe ambient temperature conditions

[0263] Molding materials, shielding materials, conductive materials (e.g., thermal conductive materials, etc.), insulating materials, adhesives

[0264] In addition, it can be preferably used as a sealing agent,

[0265] Paint, ink, sealant, anti-corrosion agent, molding material, forming material [thrust washer, oil filter

[0266] Cleaners, seals, bearings, gears, cylinder head covers, bearing retainers, intake manifolds, pedals, etc.

[0267] Automobile parts; semiconductor / liquid crystal manufacturing equipment parts such as substrates, electrical insulating materials (insulating films, etc.), laminates, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, silicon wafer carriers, IC chip trays, electrolytic capacitor trays, insulating films, etc.; optical parts such as lenses; compressor parts such as pumps, valves, and seals; aircraft cabin interior parts; medical equipment parts such as sterilization equipment, columns, and piping, and food / beverage manufacturing equipment parts; materials for forming components for electrical / electronic equipment such as housings for personal computers, mobile phones, etc., and keyboard supports that are components for supporting keyboards inside personal computers], etc.

[0268] [cured material]

[0269] By molding the above-mentioned curable composition and drying it as needed, the coagulant of the above-mentioned curable composition (preferably the coagulant of compound (A)) can be given a desired shape to obtain a molded body composed of the above-mentioned coagulant. The molded body composed of the above-mentioned coagulant temporarily embodies fluidity or adhesion by heating, and can be secondary molded and bonded to other components. In addition, if the coagulant given a desired shape is heat-treated, a molded body composed of a cured product or a semi-cured product (preferably a cured product or a semi-cured product of compound (A)) of the above-mentioned curable composition is obtained. It should be noted that the shape of the molded body is not particularly limited, and the shape can be appropriately selected according to the purpose.

[0270] [Insulated wire]

[0271] The curable composition is particularly preferably cured and used as an insulating film covering a conductive wire. Thus, an insulated electric wire including a conductive wire and the insulating film covering the conductive wire can be obtained.

[0272] The insulating film includes a cured product of the curable composition. In the total amount of the insulating film, the proportion of the cured product of the compound (A) is, for example, 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, more preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more. It should be noted that the upper limit of the above ratio is 100% by weight. That is, the insulating film may also be composed only of a cured product of the compound (A).

[0273] The insulating film can be obtained, for example, by applying the curable composition on the surface of the conductive wire and firing the obtained coating film.

[0274] The curable composition may be applied to the conductor by a known or commonly used coating method, such as dipping, etc. Dipping is a method of immersing the conductor in the curable composition to adhere the curable composition to the surface of the conductor to form a coating film.

[0275] When applying to the wire, the temperature of the curable composition is preferably maintained at a temperature lower than the exothermic starting temperature of the compound (A). At the above temperature, the curing reaction of the compound (A) does not proceed, so the thickening of the curable composition can be suppressed and a coating film with uniform thickness can be formed when applied to the wire.

[0276] In addition, the application of the curable composition to the guide wire can be repeated several times until the thickness of the coating reaches the desired thickness. Compound (A) does not generate water when solidified. Therefore, even if the coating is fired after being laminated to the desired thickness, no voids or pinholes caused by water will be generated. In addition, if the coating is fired after being laminated, the number of firings can be reduced, saving electricity and energy. It should be noted that the coating is preferably dried between the application of the curable composition and the next application. The drying of the coating can be carried out, for example, by heating at a temperature exceeding room temperature and lower than the exothermic starting temperature of the compound (A).

[0277] The dried coating film is fired, specifically, fired by heating at a temperature equal to or higher than the exothermic starting temperature of the compound (A), whereby curing of the compound (A) can be initiated, thereby forming an insulating film composed of a cured product of the compound (A).

[0278] The above-mentioned conductive wire is a wiring formed by a raw material having conductivity. Examples of the above-mentioned raw material having conductivity include copper, copper alloy, aluminum, aluminum alloy, stainless steel, etc. Among them, copper is preferred from the perspective of obtaining high conductivity. Therefore, as the conductive wire, a copper wire is preferred. The above-mentioned conductive wire may also have a coating (e.g., a tin coating) on ​​its surface for inhibiting corrosion.

[0279] The diameter of the conductive wire is, for example, 0.5 to 2.0 mm. The cross-sectional shape of the conductive wire may be appropriately selected according to the intended use without particular limitation, and examples thereof include circular, rectangular, and square shapes.

[0280] The relative dielectric constant of the cured product (or the insulating film) at 10 GHz is, for example, 2.70 or less, preferably 2.65 or less, and more preferably 2.60 or less. It should be noted that the lower limit of the relative dielectric constant is, for example, 2.20. If the relative dielectric constant is within the above range, the insulating film has excellent insulating properties.

[0281] The insulating film has excellent insulating properties, and thus can exhibit a sufficient insulating function even if the insulating film is thin (for example, even if the thickness is 30 μm or less). The lower limit of the thickness of the insulating film is, for example, 10 μm.

[0282] [Coil]

[0283] The insulated wire can be used to obtain a coil. The coil includes the insulated wire. More specifically, the coil has a structure in which the insulated wire is wound. The coil is preferably used in electronic / electrical equipment [e.g., a motor (e.g., a motor of a hybrid vehicle, an electric vehicle, etc.), a generator, etc., which has a device for converting electrical energy into mechanical energy], etc.

[0284] The insulating film of the insulated wire has excellent insulating properties and can ensure high insulation even if it is thinned. Therefore, the coil can maintain the insulating properties and achieve miniaturization and lightness by thinning the insulating film. In addition, the insulating film of the insulated wire has high adhesion to the conductor and will not be peeled off due to the load when the coil is wound, so the coil including the insulated wire has high reliability in terms of electrical properties.

[0285] [cable]

[0286] The insulated wire can be used to obtain a cable. The cable includes the insulated wire. More specifically, the cable has a structure in which one or more insulated wires are bundled and a protective outer coating (= sheath) is applied on the surface. The cable can be preferably used as a connecting part of electronic / electrical equipment (e.g., a charging cord of a smartphone, a LAN cable of an electronic device, a charging cord of a home appliance, etc.).

[0287] The insulating film of the insulated wire has excellent insulating properties and can ensure high insulation even if it is thinned. Therefore, the cable can maintain the insulating properties and achieve miniaturization and lightness by thinning the insulating film. In addition, the insulating film of the insulated wire has high adhesion to the conductor, so the cable has high reliability in terms of electrical properties.

[0288] Moreover, the electronic / electrical equipment equipped with the above-mentioned cable also has high reliability in terms of electrical characteristics. The above-mentioned electronic / electrical equipment is, for example, equipment equipped with connection components such as power cords and LAN cables, and can include chargers for smartphones, electronic devices such as smartphones including the above-mentioned chargers, and household appliances.

[0289] Each scheme disclosed in this specification may also be combined with any other feature disclosed in this specification. Each structure and combination of structures in each embodiment is an example, and appropriate addition, omission, replacement and other changes of structures can be made without departing from the scope of the present disclosure. In addition, each invention disclosed in this disclosure is not limited by the embodiments and the following examples, but only by the patent claims.

[0290] Example

[0291] Hereinafter, one embodiment of the present disclosure will be described in more detail based on examples, but the present disclosure is not limited to these examples.

[0292] Preparation Example 1 (Preparation of Compound (1-1))

[0293] (Process 1-1)

[0294] 37.25 g of 4,4'-difluorobenzophenone, 32.48 g of bisphenol A, 29.50 g of anhydrous potassium carbonate, 214.4 g of N-methylpyrrolidone and 90.4 g of toluene were added to a reactor equipped with a stirring device, a nitrogen inlet pipe and a Dean-Stark device, and the mixture was heated while stirring under a nitrogen atmosphere, and the toluene was refluxed at 130-140°C for 4 hours. Thereafter, the mixture was further heated and toluene was distilled off at 170-180°C. Furthermore, the mixture was stirred at 170-180°C for 10 hours, and then returned to room temperature.

[0295] (Process 1-2)

[0296] After that, 6.520 g of 4-aminophenol, 8.260 g of anhydrous potassium carbonate, 27.9 g of N-methylpyrrolidone and 117.4 g of toluene were added to the reactor to which the reaction product was added, and the mixture was heated again under a nitrogen atmosphere while stirring, and the toluene was refluxed at 130 to 140 ° C for 3 hours. After that, heating was performed, and toluene was distilled off at 170 to 180 ° C, and the above temperature was further maintained and stirred for 4 hours. After that, it was cooled to room temperature, and the reaction solution was added to 3000 mL of methanol, and a powdered solid was obtained by filtration. After the powdered solid was repeatedly washed with methanol and water, it was dried under reduced pressure at 80 ° C overnight to obtain a powdered solid diamine-1 (Diamine-1, a compound shown in the following formula).

[0297] [Chemical formula 25]

[0298]

[0299] (Process 2)

[0300] To a reactor equipped with a stirring device, a nitrogen inlet pipe and a Dean-Stark device, 49.70 g of diamine-1 obtained in step 1-2, 6.03 g of maleic anhydride, 316.0 g of N-methylpyrrolidone and 178.3 g of toluene were added, and stirred at room temperature for 5 hours under a nitrogen atmosphere. After that, 1.086 g of p-toluenesulfonic acid was added as a catalyst, and after heating to 140 ° C, stirring was continued for 8 hours, and toluene was refluxed to remove water. After the reaction solution was returned to room temperature, the reaction solution was added to 3000 mL of methanol, thereby obtaining a powdered solid. After the powdered solid was repeatedly washed with methanol and water, it was dried under reduced pressure at 80 ° C overnight to obtain 48.8 g of compound (1-1) (a compound represented by the following formula (1-1)).

[0301] [Chemical formula 26]

[0302]

[0303] For the obtained compound (1-1), the functional group concentration was calculated based on the integral intensity ratio of the signals in the 1 1H-NMR spectrum. In addition, the number-average molecular weight and the weight-average molecular weight were determined by GPC measurement. Moreover, the exothermic onset temperature was determined by DSC measurement, and the 5% thermal weight loss temperature (T d5 5%) was determined by TGA measurement. As a result, the functional group concentration was 587.3 μmol / g, the number-average molecular weight was 3500, the weight-average molecular weight was 5900, the exothermic onset temperature was 268 °C, and T d5 5% was 515 °C.

[0304] It should be noted that the measurements were carried out under the following conditions.

[0305] <NMR measurement>

[0306] Measurement device: JEOL ECA500 or BRUKER AVANCE600 MHz.

[0307] Measurement solvent: deuterated DMSO, deuterated chloroform, or a mixed solution of deuterated chloroform / pentafluorophenol = 2 / 1 (wt / wt).

[0308] Chemical shift: based on TMS.

[0309] <GPC measurement>

[0310] Device: pump "LC-20AD" (manufactured by Shimadzu Corporation).

[0311] Detector: RID-10A (manufactured by Shimadzu Corporation) or MODEL302TDA (manufactured by Viscotek) and UV2501 (manufactured by Viscotek).

[0312] Solvent: THF or chloroform.

[0313] Chromatographic column: (Shodex KF-803)×1, (Shodex KF802)×1, and (Shodex KF801)×2.

[0314] Flow rate: 1.0 ml / min.

[0315] Temperature: 40 °C.

[0316] Sample concentration: 0.1% (wt / vol).

[0317] Standard polystyrene conversion

[0318] <DSC measurement>

[0319] Apparatus: DSC 6200 (manufactured by Seiko Instruments Inc.).

[0320] Heating rate: 10 °C / min.

[0321] Atmosphere: Nitrogen atmosphere.

[0322] <TGA measurement>

[0323] Apparatus: TG / DTA 6200 (manufactured by Seiko Instruments Inc.).

[0324] Heating rate: 10 °C / min.

[0325] Atmosphere: Nitrogen atmosphere.

[0326] <DMA measurement>

[0327] Apparatus: DMA 7100 (manufactured by Hitachi High-Tech Science Corporation).

[0328] Heating rate: 5 °C / min.

[0329] Measurement frequency: 1 Hz.

[0330] Examples and Comparative Examples

[0331] The compound (1-1) obtained in Preparation Example 1 above, anisole as a solvent, and the components (organic nucleophilic reagents, antioxidants, etc.) shown in each table were mixed in the blending amounts shown in each table and stirred for 1.5 hours to prepare the curable compositions of each example. It should be noted that the temperature during mixing and stirring was first carried out at room temperature, and in the case where there were some dissolved residues and precipitates in each component, it was carried out at 60 °C.

[0332] <Evaluation>

[0333] The curable compositions prepared in the examples and comparative examples were evaluated as follows.

[0334] (1) Anisole compatibility

[0335] The anisole compatibility during the preparation of the curable composition was evaluated according to the following evaluation criteria. The results are shown in the table.

[0336] [Evaluation criteria]

[0337] ○: All components were completely dissolved under stirring at room temperature.

[0338] Δ: After heating and stirring at 60°C, some dissolved residues and precipitates were present.

[0339] ×: After heating and stirring at 60°C, it was hardly dissolved or dispersed.

[0340] (2) Exothermic starting temperature

[0341] Regarding the exothermic starting temperature of the curable composition, DSC measurement was performed after removing the solvent. Then, the exothermic starting temperature was evaluated according to the following evaluation criteria. The results are shown in the table. It should be noted that some of the examples with poor evaluation of the above-mentioned anisole compatibility were not evaluated and are represented by "-" in the table.

[0342] [Evaluation criteria]

[0343] ◎: Heat generation started at 200°C or lower, and complete curing was confirmed.

[0344] ○: Heat generation started at a temperature exceeding 200° C. and not higher than 250° C., and complete curing was confirmed.

[0345] Δ: Heat generation started at a temperature exceeding 250° C. and not higher than 300° C., and complete curing was confirmed.

[0346] ×1: The start of heat generation at 300°C or lower was not confirmed.

[0347] ×2: After the heat release begins, the reaction is deactivated.

[0348] (3) Curing

[0349] The curable composition is applied to the substrate in a manner of 40 μm thick after curing using an applicator to form a curable film. It should be noted that, as a substrate, a glass plate (commercially available float glass, thickness 4 mm), an aluminum foil (trade name "Aluminium Tough Sheet", 200 square, manufactured by AS ONE Co., Ltd.) or a copper plate (commercially available oxygen-free copper, thickness 1 mm) is used. Then, the above-mentioned substrate with the film formed is stored at 250°C, the solvent is removed and cured to form a cured product. The type of substrate used, the curing time and the curing atmosphere are shown in Table 4.

[0350] (4) Glass transition temperature and residual heat release

[0351] The cured product formed in the evaluation of curability was separated from the substrate and subjected to DMA measurement (dynamic viscoelasticity measurement) or DSC (differential scanning calorimetry) measurement. The DMA measurement was performed on the cured product on the film, and the DSC measurement was performed on the cured product on the copper plate.

[0352] The DMA measurement uses a solid viscoelasticity measuring device (product name "DMA7100", manufactured by Hitachi High-Tech Science Co., Ltd.) in an air atmosphere, a heating rate of 5°C / min, a measuring temperature range of 25 to 400°C, a deformation mode: tension, and a frequency of 1 Hz. The DSC measurement uses a differential scanning calorimeter (trade name "DSC6200", (manufactured by Seiko Instruments Co., Ltd.) in a nitrogen gas flow, a heating rate of 10°C / min, and a measuring temperature range of 30 to 400°C. Then, the inflection point of the obtained temperature thermal history curve is taken as the glass transition temperature, and the heat release between the glass transition temperature and 400°C is taken as the residual heat release. The glass transition temperature and residual heat release are evaluated according to the following evaluation criteria. The results are shown in the table.

[0353] [Evaluation Criteria of Glass Transition Temperature]

[0354] ○: 160℃ or above.

[0355] ×: less than 160°C.

[0356] [Evaluation criteria for residual heat generation]

[0357] ○: less than 5 mJ / mg.

[0358] ×: 5 mJ / mg or more.

[0359] [Table 1]

[0360] (Table 1)

[0361]

[0362] [Table 2]

[0363] (Table 2)

[0364]

[0365]

[0366] [Table 3]

[0367] (Table 3)

[0368]

[0369] [Table 4]

[0370] (Table 4)

[0371]

[0372] The components shown in the table are as follows.

[0373] <Organic nucleophiles>

[0374] GASKAMINE 240: Trade name “GASKAMINE 240”, manufactured by Mitsubishi Gas Chemical Co., Ltd., an addition product of meta-xylylenediamine and styrene.

[0375] PX-4MP: trade name “HISHICOLIN PX-4MP”, manufactured by Nippon Chemical Industry Co., Ltd., methyl tri-n-butylphosphonium dimethyl phosphate.

[0376] TBP-3S: trade name “TBP-3S”, manufactured by Hokko Industry Co., Ltd., tetrabutylphosphonium 2-carboxycyclohexanecarboxylate.

[0377] U-CAT SA-102: trade name “U-CAT SA-102”, manufactured by SAN-APRO Co., Ltd., 2-ethylhexanoate of 1,8-diazabicyclo[5,4,0]-undecene-7.

[0378] GASKAMINE 328: Trade name “GASKAMINE 328”, manufactured by Mitsubishi Gas Chemical Co., Ltd., an addition product of meta-xylylenediamine and epichlorohydrin.

[0379] 2E4MZ: 2-ethyl-4-methylimidazole.

[0380] 1B2MZ: 1-benzyl-2-methylimidazole.

[0381] U-CAT 3512T: trade name “U-CAT 3512T”, manufactured by SAN-APRO CORPORATION, aromatic urea.

[0382] U-CAT 3513N: Trade name "U-CAT 3513N", manufactured by SAN-APRO Co., Ltd., aliphatic urea.

[0383] U-CAT SA-1: trade name “U-CAT SA-1”, manufactured by SAN-APRO Co., Ltd., phenolate of 1,8-diazabicyclo[5,4,0]-undecene-7.

[0384] DMAc: dimethylacetamide.

[0385] 4,4'-DAS: 4,4'-diaminodiphenyl sulfone, manufactured by MITSUI FINE CHEMICALS Co., Ltd.

[0386] 3,3'-DAS: 3,3'-diaminodiphenyl sulfone, manufactured by MITSUI FINE CHEMICALS Co., Ltd.

[0387] <Maleimide>

[0388] BMI-2300: trade name "BMI-2300", manufactured by Yamato Chemical Industry Co., Ltd., phenylmethanemaleimide, a compound represented by formula (B-6a).

[0389] <Metal Deactivator / Antioxidant>

[0390] Irganox MD 1024: trade name “Irganox MD 1024”, manufactured by BASF Japan Co., Ltd., 2′,3-bis[[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl]]propionohydrazide, a compound represented by formula (C-1).

[0391] CDA-10: trade name “ADK STAB CDA-10”, manufactured by ADEKA Corporation, 2′,3-bis[[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl]]propionohydrazide, a compound represented by formula (C-1).

[0392] CDA-1M: Trade name "ADK STAB CDA-1M", manufactured by ADEKA Co., Ltd.

[0393] CDA-6: Trade name "ADK STAB CDA-6", manufactured by ADEKA Co., Ltd.

[0394] <Free Radical Generator>

[0395] PERCUMYL D: Trade name "PERCUMYL D", manufactured by NOF Co., Ltd.

[0396] PERCUMYL Z: Trade name "PERCUMYL Z", manufactured by NOF Co., Ltd.

[0397] PERHEXA HC: Trade name "PERHEXA HC", manufactured by NOF Corporation.

[0398] <Adhesion / Heat Resistance Imparting Agent>

[0399] TANAC P: Trade name “TANAC P”, manufactured by Shikoku Chemical Industry Co., Ltd.

[0400] VD-5: Trade name “VD-5”, manufactured by Shikoku Chemical Industry Co., Ltd.

[0401] MA-DGIC: Trade name “MA-DGIC”, manufactured by Shikoku Chemical Industry Co., Ltd.

[0402] TEPIC-VL: Trade name “TEPIC-VL”, manufactured by Shikoku Chemical Industry Co., Ltd.

[0403] TAIC: Trade name “TAIC”, manufactured by Shikoku Chemical Industry Co., Ltd.

[0404] TG-G: Trade name “TG-G”, manufactured by Shikoku Chemical Industry Co., Ltd.

[0405] DAG-G: Trade name “DAG-G”, manufactured by Shikoku Chemical Industry Co., Ltd.

[0406] As shown in Table 1, in the curable composition of the embodiment, the curable compound and the curing accelerator have excellent compatibility with anisole, and the exothermic starting temperature in the air atmosphere is low. Therefore, the curable composition of the embodiment is evaluated to have excellent solvent solubility and can be cured at low temperature in the presence of oxygen. On the other hand, as shown in Tables 2 and 3, when a curing accelerator other than the curing accelerator (B) is used, it is evaluated that the compatibility with anisole is poor (Comparative Examples 4 to 6, 11 to 16), or the exothermic starting temperature is high (Comparative Examples 7 to 10, 13, 14, 17 to 19). In addition, when a free radical generator is used as the curing accelerator (B), although it is confirmed that heat is released at the beginning, it is inactivated (Comparative Examples 1 to 3).

[0407] In addition, as shown in Table 4, even when the curable compositions of Examples 5 and 6 form a cured product on a copper plate, the glass transition temperature and residual heat release are high, the quality stability is excellent, and it is evaluated as being able to be used for a variety of substrates. On the other hand, although the curable composition of Comparative Example 1 has a high glass transition temperature and residual heat release under a nitrogen atmosphere, it has a low residual heat release under an air atmosphere and is evaluated as being unusable. It should be noted that the cured product of the curable composition of Comparative Example 1 under an air atmosphere is very brittle, and DMA measurement cannot be performed, and the glass transition temperature cannot be measured.

[0408] Modifications of the invention disclosed herein will be described below.

[0409] [Supplementary Note 1] A curable composition comprising the following compound (A) and the following curing accelerator (B).

[0410] Compound (A): a compound represented by the following formula (1).

[0411] [Chemical formula 1]

[0412]

[0413] [Where R 1 and R 2 The same or different groups represent a group represented by the following formula (r-1).

[0414] [Chemical formula 2]

[0415]

[0416] [In the formula, Q represents C or CH. Two Qs in the formula are bonded via a single bond or a double bond. R 3 ~R 6 are the same or different and represent a hydrogen atom or a hydrocarbon group. 3 and R 4 Optionally, they are bonded to each other to form a ring. n' represents an integer greater than 0. The bond with a wavy line in the formula is 1 or D 2 Bonding 1 and D 2 are the same or different and represent a single bond or a linking group. L represents a divalent group having a repeating unit comprising a structure represented by the following formula (I) and a structure represented by the following formula (II)]

[0417] [Chemical formula 3]

[0418]

[0419] (Where Ar 1 ~Ar 3 are the same or different and represent a group formed by removing two hydrogen atoms from the structural formula of an aromatic ring, or a group formed by removing two hydrogen atoms from the structural formula of two or more aromatic rings bonded via a single bond or a connecting group. X represents -CO-, -S- or -SO2-, and Y is the same or different and represents -S-, -SO2-, -O-, -CO-, -COO- or -CONH-. n represents an integer greater than 0)

[0420] Curing accelerator (B): at least one selected from the group consisting of meta-xylylenediamine reactants, quaternary phosphonium salts, phosphonium salts having a carboxyl group, 2-ethylhexanoate as a thermally latent base generator having a carboxyl group, secondary monoamines, imidazole compounds, and low molecular weight maleimides.

[0421] [Supplementary Note 2] The curable composition according to Supplementary Note 1, wherein the curing accelerator (B) contains an organic nucleophilic reagent as the quaternary phosphonium salt.

[0422] [Supplement 3] The curable composition according to Supplement 1 or 2, further comprising a compound (C) having a hindered phenol structure including a hydrazine skeleton.

[0423] [Appendix 4] The curable composition according to any one of Appendices 1 to 3, wherein the content of the curing accelerator (B) in the curable composition is 0.1 to 2% by mass.

[0424] [Supplement 5] The curable composition according to any one of Supplements 1 to 4, wherein the curable composition can start curing at 200° C. or less in the presence of oxygen.

[0425] [Appendix 6] The curable composition according to any one of Appendices 1 to 5, wherein the curable composition is cured and used as an insulating film covering a conductive wire.

[0426] [Supplementary Note 7] An insulated electric wire comprising a conductive wire and an insulating film covering the conductive wire, wherein the insulating film is a cured product of the curable composition according to Supplementary Note 6.

[0427] [Supplementary Note 8] A coil comprising the insulated wire as described in Supplementary Note 7.

[0428] [Supplementary Note 9] A motor comprising the coil as described in Supplementary Note 8.

[0429] [Supplementary Note 10] A generator comprising the coil as described in Supplementary Note 8.

[0430] [Supplementary Note 11] An electronic / electrical device comprising the coil as described in Supplementary Note 8.

[0431] [Supplementary Note 12] An electric cable comprising the insulated wire as described in Supplementary Note 7.

[0432] [Supplementary Note 13] An electronic / electrical device comprising the cable as described in Supplementary Note 12.

Claims

1. A curable composition comprising the following compound (A) and the following curing accelerator (B), Compound (A): a compound represented by the following formula (1), [Chemical formula 1] In formula (1), R 1 and R 2 are the same or different and represent a group represented by the following formula (r-1), [Chemical formula 2] In formula (r-1), Q represents C or CH; two Qs in formula (r-1) are bonded via a single bond or a double bond; R 3 ~R 6 The same or different, representing a hydrogen atom or a hydrocarbon group; R 3 and R 4 optionally bonded to each other to form a ring; n' represents an integer greater than 0; the bond with a wavy line in formula (r-1) and D 1 or D 2 Bonding; D 1 and D 2 are the same or different, representing a single bond or a linking group; L represents a divalent group having a repeating unit comprising a structure represented by the following formula (I) and a structure represented by the following formula (II); [Chemical formula 3] In formula (I) and formula (II), Ar 1 ~Ar 3 are the same or different, and represent a group formed by removing two hydrogen atoms from the structural formula of an aromatic ring, or a group formed by removing two hydrogen atoms from a structural formula formed by two or more aromatic rings bonded via a single bond or a connecting group; X represents -CO-, -S- or -SO2-, and Y is the same or different, and represents -S-, -SO2-, -O-, -CO-, -COO- or -CONH-; n represents an integer greater than 0; Curing accelerator (B): at least one selected from the group consisting of meta-xylylenediamine reactants, quaternary phosphonium salts, phosphonium salts having a carboxyl group, 2-ethylhexanoate as a thermally latent base generator having a carboxyl group, secondary monoamines, imidazole compounds, and low molecular weight maleimides.

2. The curable composition according to claim 1, wherein The curing accelerator (B) contains an organic nucleophile as the quaternary phosphonium salt.

3. The curable composition according to claim 1 or 2, wherein The curable composition further includes a compound (C) having a hindered phenol structure including a hydrazine skeleton.

4. The curable composition according to claim 1 or 2, wherein The content ratio of the curing accelerator (B) in the curable composition is 0.1 to 2% by mass.

5. The curable composition according to claim 1 or 2, wherein The curable composition can begin to cure at a temperature below 200° C. in the presence of oxygen.

6. The curable composition according to claim 1 or 2, wherein The curable composition is cured to be used as an insulating film covering a conductive line. 7 . An insulated wire comprising a conductive wire and an insulating film covering the conductive wire, wherein the insulating film is a cured product of the curable composition according to claim 6 .

8. A coil comprising the insulated electric wire according to claim 7.

9. A motor comprising the coil according to claim 8.

10. A generator comprising the coil according to claim 8.

11. An electronic / electrical device comprising the coil according to claim 8.

12. A cable comprising the insulated wire according to claim 7.

13. An electronic / electrical device comprising the cable according to claim 12.

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