Mixture, curing agent, curable composition, method for producing cured body, prepreg, and semiconductor sealing agent

Abstract

The purpose of the present invention is to provide a mixture containing an amino group-containing polyphenylene ether, with which it is possible to obtain a cured product having high heat resistance and low hygroscopicity. A mixture according to the present invention comprises a compound having an active hydrogen group and a compound that reacts with the compound having an active hydrogen group, and is characterized in that the compound having an active hydrogen group contains an amino group-containing polyphenylene ether (A) that contains a constituent component represented by general formula (a).

Description

Mixtures, curing agents, curable compositions, methods for producing cured products, prepregs, and semiconductor encapsulants

[0001] The present invention relates to a mixture, a curing agent, a curable composition, a method for producing a cured product, a prepreg, and a semiconductor encapsulant.

[0002] In recent years, electric vehicles, which reduce carbon dioxide emissions during driving, have been increasing globally, and SiC is attracting attention as a key material for power module chips that can handle the increased voltage of batteries. Compared to silicon, which has been used for a long time, SiC has better energy efficiency and superior functions such as high voltage resistance and high temperature resistance. To fully utilize these functions, semiconductor encapsulants are required to have even higher heat resistance, electrical properties, and low moisture absorption.

[0003] For semiconductor encapsulants, materials primarily used are thermosetting resins such as epoxy resins cured with phenolic or amine-based curing agents. In particular, aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone have been mainly used as amine-based curing agents, and have been used for many years with various applications and modifications. However, these curing materials have been insufficient to meet the recent demands for heat resistance and low moisture absorption.

[0004] On the other hand, polyphenylene ether (PPE) resins such as poly(2,6-cymethyl-1,4-phenylene ether) have excellent heat resistance, insulation properties, and low moisture absorption, and are therefore widely used as materials for products and parts in the electrical and electronic fields, the automotive field, and other industrial materials fields.

[0005] Japanese Patent Publication No. 2004-224860 Japanese Patent Publication No. 2013-245287

[0006] Patent documents 1 and 2 describe the use of PPE as a curing agent for epoxy compositions. However, because PPE has a structure with functional groups only at both ends, it has a small number of functional groups and does not meet the increasingly high demands for heat resistance.

[0007] As mentioned above, conventional technologies have not yielded a curable material that possesses both high heat resistance and low moisture absorption.

[0008] Therefore, the present invention aims to provide a mixture containing an amino group-containing polyphenylene ether that can yield a cured product having high heat resistance and low moisture absorption.

[0009] As a result of diligent research to solve the above problems, the present inventors have found that a cured product with both high heat resistance and low moisture absorption can be obtained by a mixture containing an amino group-containing polyphenylene ether, in which a structure containing a primary or secondary amino group is introduced into the main chain skeleton of the polyphenylene ether. The above mixture can be efficiently manufactured by a simple synthesis method and can use inexpensive general-purpose engineering plastics, making it economically advantageous.

[0010] In other words, the present invention is as follows: [1] A mixture comprising a compound having an active hydrogen group and a compound that reacts with the compound having the active hydrogen group, wherein the compound having the active hydrogen group comprises an amino group-containing polyphenylene ether (A) having a component represented by the following general formula (a). (In formula (a), R １ ~R ４ Each independently contains a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, a cyano group, or an amino group represented by the following general formulas (b), (c), or (d), R １ ~R ４ At least one of these structures contains the aforementioned amino group. (In formulas (b), (c), and (d), X is an alkylene group, an arylene group containing a divalent electron-withdrawing group, and an alkylene group containing a divalent electron-withdrawing group, and Y is a structure that independently contains a primary amino group or a secondary amino group.) [2] The mixture according to [1], wherein the compound that reacts with the compound having the active hydrogen group is a curable resin. [3] The mixture according to [1] or [2], wherein the compound having the active hydrogen group is a curing agent. [4] A curing agent characterized by containing an amino group-containing polyphenylene ether (A) having a component represented by the following general formula (a). (In formula (a), R1 to R4 are each independently a structure containing a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, a cyano group, or an amino group represented by the following general formulas (b), (c), or (d), and at least one of R1 to R4 is a structure containing the amino group. (In formulas (b), (c), and (d), X is an alkylene group, an arylene group containing a divalent electron-withdrawing group, and an alkylene group containing a divalent electron-withdrawing group, and Y is a structure that independently contains a primary amino group or a secondary amino group.) [5] The curing agent according to [4], which is a liquid. [6] The curing agent according to [5], further comprising a liquid amine compound or a liquid phenol compound. [7] A method for producing a cured product, comprising the step of mixing the curing agent according to any one of [4] to [6] with a curable resin and curing it. [8] A curable composition, characterized by comprising an amino group-containing polyphenylene ether (A) containing a component represented by the following general formula (a) and a curable resin. (In formula (a), R1 to R4 are each independently a structure containing a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, a cyano group, or an amino group represented by the following general formulas (b), (c), or (d), and at least one of R1 to R4 is a structure containing the amino group. (In formulas (b), (c), and (d), X is an alkylene group, an arylene group containing a divalent electron-withdrawing group, and an alkylene group containing a divalent electron-withdrawing group, and Y is a structure that independently contains a primary amino group or a secondary amino group.) [9] The curable composition according to [8], wherein the nitrogen content of the amino group-containing polyphenylene ether (A) is 3% by mass or more and 32% by mass or less.

[10] The curable composition according to [9], wherein the curable resin is an epoxy resin (B).

[11] The curable composition according to

[10] , wherein the epoxy group equivalent of the epoxy resin (B) is 100 to 1000 g / eq.

[12] The curable composition according to any one of [8] to

[11] , further comprising an inorganic filler.

[13] A method for producing a cured product, characterized by comprising a step of curing the curable composition according to any one of [8] to

[12] .

[14] A prepreg characterized by comprising the curable composition according to any one of [8] to

[12] . A semiconductor encapsulant characterized by comprising any of the curable compositions of

[15] [8] to

[12] .

[0011] The present invention can provide a mixture containing an amino group-containing polyphenylene ether that can yield a cured product having high heat resistance and low hygroscopicity.

[0012] The following describes in detail embodiments for carrying out the present invention (hereinafter referred to as "this embodiment"). It should be noted that the present invention is not limited to the following embodiments, and can be implemented in various modifications within the scope of its gist.

[0013] [Mixture] The mixture of this embodiment comprises a compound having an active hydrogen group and a compound that reacts with the compound having the active hydrogen group, wherein the compound having the active hydrogen group includes an amino group-containing polyphenylene ether (A) containing the components shown in the following general formula (a). The mixture of this embodiment may consist only of the compound having the active hydrogen group and the compound that reacts with the compound having the active hydrogen group, or it may further contain other components. In this specification, the amino group-containing polyphenylene ether (A) containing the components shown in general formula (a) may be simply referred to as "amino group-containing polyphenylene ether (A)".

[0014] <Compounds Having Active Hydrogen Groups> The compound having active hydrogen groups in this embodiment must contain an amino group-containing polyphenylene ether (A). The compound having active hydrogen groups may consist only of the amino group-containing polyphenylene ether (A), or it may further contain other compounds having active hydrogen groups. Examples of other compounds having active hydrogen groups include phenol compounds. The compound having active hydrogen groups in this embodiment is preferably a curing agent. Details of the curing agent in this embodiment will be described later. Examples of active hydrogen groups include amino groups, hydroxyl groups, carboxyl groups, imino groups, mercapto groups, etc. Among these, amino groups are preferred. The compound having active hydrogen groups and the other compounds having active hydrogen groups may be one type or a combination of two or more types.

[0015] (Amino group-containing polyphenylene ether (A)) The above amino group-containing polyphenylene ether (A) contains the constituent components shown in the following general formula (a). In formula (a), R １ ~R ４ Each independently contains a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, a cyano group, or an amino group represented by the following general formulas (b), (c), or (d), R １ ~R ４At least one of them has a structure containing the amino group represented by the following general formula (b), (c) or (d). In formula (b), (c), (d), X is an alkylene group, an arylene group containing a divalent electron-withdrawing group, or an alkylene group containing a divalent electron-withdrawing group, and Y is, independently of each other, a structure containing a primary amino group or a secondary amino group. The amino group-containing polyphenylene ether (A) may be of one kind or a combination of two or more kinds. When there are a plurality of the above structures having an amino group represented by formula (b), (c), (d) in the amino group-containing polyphenylene ether (A), each structure may be the same or different.

[0016] In formula (a), the following embodiments are preferred. R １ ~R ４ The number of carbon atoms of the alkyl group and the alkyl fluoride group in is preferably 1 to 12, more preferably 1 to 4. R １ ~R ４ As the allyl group of, a 2-propenyl group, a 2-methyl-2-propenyl group, and a 2-hexenyl group are preferred. R １ ~R ４ As the aryl group of (that is, on the main chain side), a phenyl group and a benzyl group are preferred.

[0017] The above formula (a) is preferably the following formula (a'), more preferably formula (1) and formula (2). In formula (a'), R １ ~R ４ 、X and Y are the same as in the above formula (a). In formula (1) and (2), R １ ~R ５Each is independently a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, or a cyano group, each is independently an alkylene group, an arylene group containing a divalent electron-withdrawing group, or an alkylene group containing a divalent electron-withdrawing group, and each is independently a structure containing a primary amino group or a secondary amino group. In formula (2), the two X and two Y may be the same or different. The amino group-containing polyphenylene ether (A) may contain the unit of formula (1) but not the unit of formula (2), may contain the unit of formula (2) but not the unit of formula (1), or may contain both the unit of formula (1) and the unit of formula (2). In formulas (1) and (2), R １ ~R ２ , R ４ ~R ５ It is more preferable that the group is a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, or a cyano group. When both the (1) unit and the (2) unit are included, there are no particular limitations, but the proportion of the (1) unit is preferably in the range of 1 mol% to 99 mol%, more preferably 10 mol% to 99 mol%, and even more preferably 30 mol% to 99 mol%, based on a total of 100 mol% of the (1) and (2) units. If the proportion of the (1) unit is 1 mol% or more, the heat resistance tends to improve, and if it is 99 mol% or less, the heat decomposition resistance tends to be high. If the proportion of the (1) unit is 10 mol% or more, the flexibility of the cured product is sufficient, and if it is 99 mol% or less, the heat decomposition resistance tends to be high. If the proportion of the (1) unit is 30 mol% or more, the mechanical strength of the cured product tends to improve, and if it is 99 mol% or less, the heat decomposition resistance tends to be high. In equations (1) and (2), R １ ~R ５ The number of carbon atoms in the alkyl group and alkyl fluoride in R is preferably 1 to 12, and more preferably 1 to 4. １ ~R ５ The allyl group is preferably a 2-propenyl group, a 2-methyl-2-propenyl group, or a 2-hexernyl group. １ ~R ５The preferred aryl group is a phenyl group or a benzyl group.

[0018] In formulas (b), (1), and (2), the number of carbon atoms in the alkylene group of X is preferably 1 to 12, and more preferably 1 to 6. The divalent electron-withdrawing groups of X are -C(O)- (carbonyl group (keto group)), -S(O)- (sulfoxide), and -S(O). ２ Examples include -(sulfone), and -C(O)-(carbonyl group (keto group)). Examples of the "arylene group" containing a divalent electron-withdrawing group of X include a phenylene group, a naphthylene group, anthracenylene group, and a benzylidene group, with the phenylene group being preferred. The number of carbon atoms in the "alkylene group" containing a divalent electron-withdrawing group of X is preferably 1 to 12, and more preferably 1 to 8. The alkylene group containing a divalent electron-withdrawing group and the arylene group containing a divalent electron-withdrawing group may have a structure in which one divalent electron-withdrawing group and one alkylene group or arylene group are directly bonded. When X has a structure in which one divalent electron-withdrawing group and one alkylene group or arylene group are directly bonded, it is preferable that the divalent electron-withdrawing group is bonded to the benzene ring of formula (a) and the alkylene group or arylene group is bonded to Y of formula (b).

[0019] The above Y has a structure containing a primary amino group or a secondary amino group. The structure of Y is not particularly limited, but the structure represented by the following general formulas (8), (9), (10), and (11) is preferred, the structure represented by the following general formulas (8), (9), and (10) is more preferred, and the structure represented by the following general formulas (8) and (11) is even more preferred. In the above general formula (8), R １８ R represents an alkylene group having 2 to 6 carbon atoms, or an oxybisalkylene group having a total of 2 to 6 carbon atoms, with an alkylene group having 2 to 6 carbon atoms being preferred. １９ Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, or a 2-hydroxyethoxyethyl group, with a hydrogen atom being preferred. n represents an integer from 0 to 5, with 1 or 2 being preferred. In the above general formula (10), R２２ This represents an alkyl group having 1 to 3 carbon atoms, a 2-hydroxyethyl group, or a 2-hydroxypropyl group. In the above general formula (11), n1 represents an integer from 0 to 11. When Y is the above general formula (8), from the viewpoint of controlling the curing reaction of the mixture, it is particularly preferable that X bonded to Y in formulas (1) and (2) is an arylene group containing a divalent electron-withdrawing group (more preferably a structure consisting of one divalent electron-withdrawing group and one arylene group), and that n in formula (8) is 1 or 2. It is preferable that the -X-Y structure in formulas (1) and (2) is an aromatic amine. By adopting the above configuration, the curing reaction can be suppressed in the kneading process to obtain a composition consisting of an epoxy resin, an inorganic filler described later, etc. Furthermore, the moisture absorption rate can be reduced compared to a structure in which Y is an aliphatic amine.

[0020] The amino group-containing polyphenylene ether (A) may further contain the component represented by general formula (3). That is, in addition to the component represented by formula (a), the amino group-containing polyphenylene ether (A) may further contain the component represented by formula (3). (In formula (3), R ６ Each of these is independently an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom, R ７ Each of these is independently a hydrogen atom, an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom.

[0021] In the above formula (3), R ６ Each of these is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably a methyl group or a phenyl group, and even more preferably a methyl group. In formula (3), the two R ６ It is preferable that both have the same structure. ６ Substituents for C1-C6 alkyl groups and C6-C12 aryl groups include C1-C10 saturated or unsaturated hydrocarbon groups, C6-C10 aryl groups, and halogen atoms.

[0022] In the above formula (3), R ７ Each of these is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group. In formula (3), the two R ７ These may be different, but it is preferable that one is a hydrogen atom and the other is an alkyl group having 1 to 6 carbon atoms (preferably a methyl group). ７ Substituents for C1-C6 alkyl groups and C6-C12 aryl groups include C1-C10 saturated or unsaturated hydrocarbon groups, C6-C10 aryl groups, and halogen atoms.

[0023] The amino group-containing polyphenylene ether (A) may further contain the components represented by general formula (4). (In formula (4), R ９ Each of these is independently a hydrogen atom, an optionally substituted C1-C20 alkyl or unsaturated hydrocarbon group, an optionally substituted C6-C12 aryl group, or a halogen atom, and two R ９ Both are not hydrogen atoms, R ８ This is a substructure represented by general formula (5). (In formula (5), R １０ Each of these is independently a linear alkyl group having 1 to 8 carbon atoms, which may be substituted, or two R １０ These are bonded to each other to form a cyclic alkyl structure having 1 to 8 carbon atoms, R １１ Each is independently an alkylene group having 1 to 8 carbon atoms, which may be substituted, and each is independently 0 or 1, R １２ This is a hydrogen atom, an optionally substituted C1-C8 alkyl group, or an optionally substituted phenyl group.

[0024] In the above formula (4), R ９Each of these is preferably independently a hydrogen atom, a C1-C15 alkyl group or unsaturated hydrocarbon group, or a C6-C12 aryl group which may be substituted with a C1-C6 alkyl group, more preferably a hydrogen atom, a C1-C6 alkyl group or unsaturated hydrocarbon group, or a C6-C10 aryl group which may be substituted with a C1-C6 alkyl group, and even more preferably a hydrogen atom or a methyl group. In formula (4), the two R ９ These are preferably different, and more preferably one is a hydrogen atom and the other is an alkyl group or unsaturated hydrocarbon group having 1 to 6 carbon atoms (preferably a methyl group). ９ Examples of substituents in the alkyl or saturated hydrocarbon group having 1 to 20 carbon atoms, or the aryl group having 6 to 12 carbon atoms, include saturated or unsaturated hydrocarbon groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, halogen atoms, and the like.

[0025] The substructure represented by formula (5) above is preferably a group containing secondary and / or tertiary carbons, such as an isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-amyl group, 2,2-dimethylpropyl group, cyclohexyl group, or a structure having a phenyl group at its terminal, more preferably a tert-butyl group or cyclohexyl group, and even more preferably a tert-butyl group.

[0026] In this embodiment, the structure of the amino group-containing polyphenylene ether (A) can be identified by analyzing it using methods such as NMR and mass spectrometry. A specific method for identifying the structure of the polyphenylene ether involves performing field desorption mass spectrometry (FD-MS), which is known to be less prone to fragmentation, and estimating the repeating units based on the spacing of the detected ions. Furthermore, a method for estimating the structure of the polyphenylene ether can be proposed that combine electron ionization (EI) peak analysis of fragment ions with structural analysis by NMR.

[0027] The amino group-containing polyphenylene ether (A) may contain units of formula (1) and units of formula (3). Although not particularly limited, the proportion of units of formula (1) is preferably in the range of 1 mol% to 99 mol%, more preferably in the range of 10 mol% to 99 mol%, and even more preferably in the range of 30 mol% to 99 mol%, with respect to 100 mol% of the total of units of formula (1) and units of formula (3). If the proportion of units of formula (1) is 1 mol% or more, the heat resistance tends to improve, and if it is 99 mol% or less, the heat decomposition resistance tends to be high. If the proportion of units of formula (1) is 10 mol% or more, the flexibility of the cured product is sufficient, and if it is 99 mol% or less, the heat decomposition resistance tends to be high. If the proportion of units of formula (1) is 30 mol% or more, the mechanical strength of the cured product tends to improve, and if it is 99 mol% or less, the heat decomposition resistance tends to be high.

[0028] The amino group-containing polyphenylene ether (A) may contain units of formula (1) and units of formula (4). Although not particularly limited, the proportion of units of formula (1) is preferably in the range of 1 mol% to 99 mol%, more preferably in the range of 10 mol% to 99 mol%, and even more preferably in the range of 30 mol% to 99 mol%, with respect to 100 mol% of the total of units of formula (1) and units of formula (4). If the proportion of units of formula (1) is 1 mol% or more, the gas barrier properties tend to improve, and if it is 99 mol% or less, the thermal decomposition resistance tends to be high. If the proportion of units of formula (1) is 10 mol% or more, the flexibility of the cured product is sufficient, and if it is 99 mol% or less, the thermal decomposition resistance tends to be high. If the proportion of units of formula (1) is 30 mol% or more, the mechanical strength of the cured product tends to improve, and if it is 99 mol% or less, the thermal decomposition resistance tends to be high.

[0029] The amino group-containing polyphenylene ether (A) may contain units of formula (1), formula (3), and formula (4). While not particularly limited, it is preferable that, per 100 mol% of the total of units of formula (1), formula (3), and formula (4), the proportion of unit (1) is in the range of 1 mol% to 98 mol%, the proportion of unit (3) is in the range of 1 mol% to 98 mol%, and the proportion of unit (4) is in the range of 1 mol% to 98 mol%. Within these ranges, the heat resistance tends to improve, and the flexibility of the cured product tends to be sufficient. It is more preferable that the proportion of unit (1) is in the range of 10 mol% to 98 mol%, the proportion of unit (3) is in the range of 1 mol% to 89 mol%, and the proportion of unit (4) is in the range of 1 mol% to 50 mol%. Within these ranges, the mechanical strength of the cured product tends to improve, and the resistance to thermal decomposition tends to be high.

[0030] The proportions of each repeating unit in equations (1), (2), (3), and (4) are, for example, １ H-NMR, １３ This can be determined using analytical methods such as C-NMR.

[0031] The nitrogen content of the amino group-containing polyphenylene ether (A) is preferably 3 to 32% by mass, and more preferably 3 to 20% by mass, from the viewpoint of heat resistance and low water absorption of the cured product. The nitrogen content can be measured, for example, by a total nitrogen assay method. The specific measurement method is as described in the examples.

[0032] The amino group-containing polyphenylene ether (A) may contain repeating units derived from phenol of the following formula (6). (In formula (6), R １３ Each of these is independently an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom, R １４ Each of these is independently a hydrogen atom, an optionally substituted C1-C6 alkyl group, an optionally substituted C6-C12 aryl group, or a halogen atom.

[0033] Since the phenol in formula (6) does not have an unsubstituted ortho position (i.e., hydrogen atoms are not bonded to the two ortho carbon atoms of the carbon atom to which the hydroxyl group is bonded), it can react with other phenolic monomers only at the phenolic hydroxyl group and the para carbon atom. Therefore, the repeating units derived from formula (6) include repeating units having the structure of formula (3).

[0034] The amino group-containing polyphenylene ether (A) may contain a unit derived from phenol of formula (6) and a repeating unit derived from phenol of formula (7) below. (In formula (7), R １６ Each of these is independently a hydrogen atom, an optionally substituted C1-C20 alkyl or unsaturated hydrocarbon group, an optionally substituted C6-C12 aryl group, or a halogen atom, and two R １６ Both are not hydrogen atoms, R １５ This is a substructure represented by general formula (5).

[0035] The phenol of formula (7) can react with another phenolic monomer at either the ortho or para position of the phenol, in addition to the phenolic hydroxyl group. Therefore, repeating units derived from the phenol of formula (7) have the structures of formula (4), formula (12) below, or combinations thereof.

[0036] The amino group-containing polyphenylene ether (A) may contain, in addition to the phenol of formula (6) and the phenol of formula (7), a terpolymer containing a structure derived from the divalent phenol of formula (13) as an impurity (in this specification, this may simply be referred to as "impurity A"). The amino group-containing polyphenylene ether (A) may be a mixture of the above polyphenylene ether and the above impurity A. The molar ratio of impurity A to 100 mol% of polyphenylene ether is preferably 10 mol% or less, and more preferably 5 mol% or less. The above impurity A can be synthesized, for example, as a terpolymer containing a structure derived from the divalent phenol of formula (13) with z=0 by a reaction between the following formula (14), which is generated as a byproduct during the oxidative polymerization of a monovalent phenol, and a polyphenylene ether composed of the monovalent phenol. (In formula (13), R １３ and R １４ This is the same as equation (6). z is 0 or 1, and Y is (In the formula, R ２４ Each of these is independently one of the following: a hydrocarbon group having 1 to 6 carbon atoms (which may be substituted), an aryl group having 6 to 12 carbon atoms (which may be substituted), or a halogen atom. (In formula (14), R １３ and R １４ This is the same as equation (6).

[0037] (Method for producing amino group-containing polyphenylene ether (A)) The method for producing amino group-containing polyphenylene ether (A) is not particularly limited, but it is preferable to include the following steps 1) to 3): 1) Polymerization step of an unmodified polyphenylene ether base 2) Synthesis step of a modified polyphenylene ether by introducing spacers such as alkylene groups, aryl groups containing divalent electron-withdrawing groups, alkylene groups containing divalent electron-withdrawing groups, and halogeno groups into the unmodified polyphenylene ether (synthesis step of a modified polyphenylene ether by halogenating the unmodified polyphenylene ether) 3) Step of introducing amino groups into the modified polyphenylene ether

[0038] 1) Polymerization step of unmodified polyphenylene ether Unmodified polyphenylene ether can be obtained by a method that includes, for example, a step of oxidative polymerization of a monovalent phenol compound represented by formula (6) and / or formula (7). The step of oxidative polymerization preferably involves oxidative polymerization of a raw material containing at least the phenol of formula (6) and / or the phenol of formula (7).

[0039] Examples of monovalent phenol compounds represented by the above formula (6) include 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2-methyl-6-tolylphenol, 2,6-ditolylphenol, 2,3,6-trimethylphenol, 2,3-diethyl-6-n-propylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-dimethyl-3-n-butylphenol, and 2,6-dimethyl-3-t-butylphenol. In particular, 2,6-dimethylphenol, 2,3,6-trimethylphenol, and 2,6-diphenylphenol are preferred because they are inexpensive and readily available. The monovalent phenol compound represented by formula (6) above may be used individually or in combination of multiple types.

[0040] Examples of monovalent phenol compounds represented by formula (7) above include 2-isopropyl-5-methylphenol, 2-cyclohexyl-5-methylphenol, 2-tert-butyl-5-methylphenol, and 2-isobutyl-5-methylphenol. From the viewpoint of suppressing multi-branching and gelation, 2-t-butyl-5-methylphenol and 2-cyclohexyl-5-methylphenol, which have bulky substituents, are more preferred. One monovalent phenol compound represented by formula (7) above may be used alone, or multiple types may be used in combination.

[0041] In a method for producing unmodified polyphenylene ether, an aromatic solvent, which is a good solvent for polyphenylene ether, can be used as the polymerization solvent in the oxidative polymerization step. Here, a good solvent for polyphenylene ether is a solvent that can dissolve polyphenylene ether, and examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene (including o-, m-, and p- isomers), and ethylbenzene, as well as halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; and nitro compounds such as nitrobenzene.

[0042] In the method for producing unmodified polyphenylene ether, known catalyst systems that can generally be used for the production of polyphenylene ether can be used as polymerization catalysts. Commonly known catalyst systems consist of a transition metal ion with redox activity and an amine compound that can form a complex with the transition metal ion. Examples include catalyst systems consisting of a copper compound and an amine compound, a manganese compound and an amine compound, a cobalt compound and an amine compound, etc. Since the polymerization reaction proceeds efficiently under slightly alkaline conditions, a small amount of alkali or further amine compounds may be added.

[0043] The polymerization catalyst described above is a catalyst comprising a copper compound, a halogen compound, and an amine compound as catalyst components, and more preferably a catalyst containing a diamine compound represented by the following formula (15) as the amine compound. In formula (15), R ２５ , R２６ , R ２７ , R ２８ Each of these is independently a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms, and not all of them are hydrogen atoms at the same time. ２９ This is an alkylene group having 2 to 5 carbon atoms and being linear or methyl-branched.

[0044] Examples of copper compounds used as catalyst components are listed below. Suitable copper compounds include cuprous compounds, cupric compounds, or mixtures thereof. Examples of cupric compounds include cupric chloride, cupric bromide, cupric sulfate, and cupric nitrate. Examples of cuprous compounds include cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Among these, particularly preferred metallic compounds are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. These copper salts may also be synthesized at the time of use from oxides (e.g., cuprous oxide), carbonates, hydroxides, and corresponding halogens or acids. A frequently used method is to prepare them by mixing the previously exemplified cuprous oxide with hydrogen halides (or solutions of hydrogen halides).

[0045] Examples of halogen compounds include hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, and tetraethylammonium iodide. These can be used as aqueous solutions or in solutions with a suitable solvent. These halogen compounds can be used individually or in combination of two or more. Preferred halogen compounds are aqueous solutions of hydrogen chloride and aqueous solutions of hydrogen bromide.

[0046] The amount of these compounds used is not particularly limited, but it is preferably 2 to 20 times the amount of halogen atoms relative to the molar amount of copper atoms, and the preferred amount of copper atoms to use per 100 moles of phenol compound added to the polymerization reaction is in the range of 0.02 moles to 0.6 moles.

[0047] Next, we list examples of diamine compounds that are catalyst components. For example, N,N,N',N'-tetramethylethylenediamine, N,N,N'-trimethylethylenediamine, N,N'-dimethylethylenediamine, N,N-dimethylethylenediamine, N-methylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N'-triethylethylenediamine, N,N'-diethylethylenediamine, N,N'-diethylethylenediamine, N-ethylethylenediamine, N,N'-dimethyl-N'-ethylethylenediamine, N,N'-dimethyl-N-ethylethylenediamine, N-n-propylethylenediamine, N,N'-n-propylethylenediamine, N-i-propylethylenediamine, N,N'-i-propylethylenediamine, N-n-butylethylenediamine, N,N'-n-butyl Examples include N-ethylenediamine, N-i-butylethylenediamine, N,N'-i-butylethylenediamine, N-t-butylethylenediamine, N,N'-t-butylethylenediamine, N,N,N',N'-tetramethyl-1,3-diaminopropane, N,N,N'-trimethyl-1,3-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N-methyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,3-diamino-1-methylpropane, N,N,N',N'-tetramethyl-1,3-diamino-2-methylpropane, N,N,N',N'-tetramethyl-1,4-diaminobutane, N,N,N',N'-tetramethyl-1,5-diaminopentane, and N,N,N',N'-tetramethylpropanediamine. Preferred diamine compounds are those in which the alkylene group connecting the two nitrogen atoms has two or three carbon atoms. The amount of these diamine compounds used is not particularly limited, but it is preferably in the range of 0.01 moles to 10 moles per 100 moles of the phenol compound added to the polymerization reaction.

[0048] The polymerization catalyst may contain primary amines and secondary monoamines as constituent components. Examples of secondary monoamines, but not limited to those listed below, include dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-t-butylamine, dipentylamines, dihexylamines, dioctylamines, didecylamines, dibenzylamines, methylethylamine, methylpropylamine, methylbutylamine, cyclohexylamine, N-phenylmethanolamine, N-phenylethanolamine, N-phenylpropanolamine, N-(m-methylphenyl)ethanolamine, N-(p-methylphenyl)ethanolamine, N-(2',6'-dimethylphenyl)ethanolamine, N-(p-chlorophenyl)ethanolamine, N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, and diphenylamine.

[0049] The polymerization catalyst may also contain a tertiary monoamine compound. A tertiary monoamine compound is an aliphatic tertiary amine, including alicyclic tertiary amines. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, and N-methylcyclohexylamine. These tertiary monoamines may be used individually or in combination of two or more. The amount used is not particularly limited, but it is preferably in the range of 15 moles or less per 100 moles of the phenol compound added to the polymerization reaction.

[0050] In the above method for producing unmodified polyphenylene ether, there are no restrictions on the addition of surfactants that have been conventionally known to improve polymerization activity. Examples of such surfactants include trioctylmethylammonium chloride, known by the trade names Aliquat 336 and Capriquat. The amount used is preferably not more than 0.1% by mass relative to 100% by mass of the total amount of the polymerization reaction mixture.

[0051] In the method for producing unmodified polyphenylene ether, the oxygen-containing gas that can be used includes pure oxygen, a mixture of oxygen and an inert gas such as nitrogen in any proportion, air, or a mixture of air and an inert gas such as nitrogen in any proportion. While atmospheric pressure is sufficient for the system pressure during the polymerization reaction, it can be reduced or increased as needed.

[0052] The polymerization temperature is not particularly limited, but if it is too low the reaction will not proceed easily, and if it is too high the reaction selectivity may decrease or a gel may form. Therefore, it is preferably 0°C or higher, more preferably 10°C or higher, preferably 60°C or lower, and more preferably 40°C or lower.

[0053] In the method for producing unmodified polyphenylene ether, polymerization can also be carried out in a poor solvent such as alcohol.

[0054] In the method for producing unmodified polyphenylene ether, there are no particular restrictions on the post-treatment method after the polymerization reaction is completed. Typically, an acid such as hydrochloric acid or acetic acid, or ethylenediaminetetraacetic acid (EDTA) and its salts, nitrilotriacetic acid and its salts, etc., are added to the reaction solution to deactivate the catalyst. In addition, the removal of divalent phenol by-products generated by the polymerization of polyphenylene ether can be carried out using conventionally known methods. If the metal ions that act as catalysts are substantially deactivated as described above, the mixture can be decolorized simply by heating it. Alternatively, it is also possible to add the required amount of a known reducing agent. Examples of known reducing agents include hydroquinone and sodium dithionite.

[0055] In a method for producing unmodified polyphenylene ether, water may be added to extract the compound from which the copper catalyst has been deactivated, followed by liquid-liquid separation into an organic phase and an aqueous phase. The copper catalyst may then be removed from the organic phase by removing the aqueous phase. This liquid-liquid separation step is not particularly limited, but examples include static separation and separation by centrifugation. Known surfactants may be used to promote the above liquid-liquid separation.

[0056] Next, in the method for producing unmodified polyphenylene ether, the organic phase containing the polyphenylene ether after liquid-liquid separation may be concentrated and dried by volatilizing the solvent.

[0057] Methods for volatilizing the solvent contained in the organic phase are not particularly limited, but include methods such as transferring the organic phase to a high-temperature concentration tank and distilling off the solvent to concentrate it, or using equipment such as a rotary evaporator to distill off toluene and concentrate it.

[0058] The drying temperature in the drying process is preferably at least 60°C, more preferably 80°C or higher, even more preferably 120°C or higher, and most preferably 140°C or higher. Drying polyphenylene ether at a temperature of 60°C or higher efficiently reduces the content of high-boiling point volatile components in the unmodified polyphenylene ether powder.

[0059] To efficiently obtain unmodified polyphenylene ether, methods such as increasing the drying temperature, increasing the vacuum level in the drying atmosphere, and stirring during drying are effective, but increasing the drying temperature is particularly preferable from the viewpoint of manufacturing efficiency. In the drying process, it is preferable to use a dryer equipped with a mixing function. Examples of mixing functions include agitation type and tumbling type dryers. This allows for a larger processing volume and maintains high productivity.

[0060] The reduced viscosity of unmodified polyphenylene ether, measured with a 0.5 g / dL chloroform solution at 30°C, is not particularly limited, but is 1.00 dL / g or less, more preferably 0.60 dL / g or less, and even more preferably 0.30 dL / g or less. If the reduced viscosity is 1.00 dL / g or less, the epoxy curability is sufficient; if it is 0.60 dL / g or less, the cured product strength is sufficient; and if it is 0.30 dL / g or less, the fluidity is sufficient and the melt moldability tends to be excellent. The reduced viscosity can be measured by the method described in the examples below.

[0061] 2) Synthesis Process of Modified Polyphenylene Ether The method for synthesizing modified polyphenylene ether is not particularly limited, but examples include introducing acyl groups, especially acyl groups having aromatic hydrocarbon groups; sulfone groups, especially sulfone groups having aromatic hydrocarbon groups; sulfinyl groups, especially sulfinyl groups having aromatic hydrocarbon groups; phosphonyl groups, especially phosphonyl groups having aromatic hydrocarbon groups; etc., to the aromatic ring skeleton of unmodified polyphenylene ether using a Friedel-Crafts acylation reaction. More specifically, in the Friedel-Crafts acylation reaction, unmodified polyphenylene ether is reacted with an acid halide, etc., in the presence of a Lewis acid (metal halide) such as aluminum chloride, tin chloride, or iron chloride.

[0062] Dichloromethane, chloroform, methylene chloride, etc., can be used as reaction solvents. The reaction conditions can be those described in Li, Q.; Liu, L.; Liang, S.; Li, Q.; Jin, B.; Bai, R.; Polym. Chem., 2014, 5, 2425-2432.

[0063] The above-mentioned acid halides are not particularly limited, but include compounds represented by the following general formulas (16) and (17). (In formula (16), Z is a halogen atom other than a fluorine atom, and R ３０ ~R ３４ Each of these is independently a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, a cyano group, or a nitro group, where R ３０~R ３４ At least one of them is a hydrogen atom. (In formula (17), Z is a halogen atom other than a fluorine atom, and R is independent of each other.) ３５ The 'Z' represents an alkyl group having 2 to 10 carbon atoms. The two 'Z's may have the same structure or different structures.

[0064] Examples of acid halides include compounds in which, in the above general formula (16), the side-chain aromatic hydrocarbon group bonded to the carbonyl group is replaced with a polycyclic aromatic hydrocarbon group such as a naphthyl group or an anthracenyl group, instead of a phenyl group. Furthermore, examples of compounds in which, in the above general formula (16), the group bonded to the carbonyl group is replaced with an aryl group (for example, a benzyl group) that allows the carbonyl group and the side-chain aromatic hydrocarbon group to be linked in a manner that an alkyl group is sandwiched between them.

[0065] Furthermore, as an acid halide, in the above general formulas (16) and (17), the [-C(O)-] portion is replaced with [-S(O) ２ Compounds with the -] portion (also called sulfonyl halogens); compounds in the above general formulas (16) and (17) with the -S(O)- portion replaced by the -C(O)- portion (also called sulfinyl halogens).

[0066] The acylated polyphenylene ether obtained by the Friedel-Crafts acylation reaction may be alkylated using a reducing agent. This reduction reaction is preferably carried out after introducing an amino group to the polyphenylene ether.

[0067] While not particularly limited, methods for synthesizing modified polyphenylene ethers include, in addition to Friedel-Crafts acylation, Friedel-Crafts alkylation and chloromethylation reactions to introduce chloromethyl groups into the aromatic ring skeleton of polyphenylene ether. Specifically, the chloromethylation reaction involves generating a chloromethyltin intermediate using tin(IV) chloride, paraformaldehyde, and trimethylsilane, and then reacting this intermediate with the polyphenylene ether to introduce chloromethyl groups.

[0068] The modification rate of the modified polyphenylene ether is not particularly limited, but is preferably 1 mol% to 200 mol%, more preferably 10 mol% to 100 mol%, even more preferably 20 mol% to 100 mol%, and even more preferably 30 mol% to 80 mol. When the modification rate is 1 mol% or higher, the heat resistance tends to improve, and when it is 200 mol or lower, the heat decomposition resistance tends to be high. When the modification rate is 10 mol% or higher, the mechanical strength of the cured product tends to improve, and when it is 100 mol or lower, the toughness of the cured product tends to be high. When the modification rate is 10 mol% or higher, the mechanical strength of the cured product tends to be sufficiently high, and when it is 100 mol or lower, the toughness of the cured product tends to be high. When the modification rate is 30 mol% or higher, the reaction time with epoxy resin (B) tends to be short, and when it is 80 mol or lower, the flexibility of the cured product tends to be high. The modification rate can be measured by the method described in the examples below.

[0069] While not particularly limited, a known method for synthesizing modified polyphenylene ethers is to halogenate the hydrogen atoms (benzyl hydrogen) of the methyl groups at the 2 and 6 positions of PPE. Fluorine, chlorine, bromine, and iodine can be used as halogens, but bromine is preferred due to its high leaving-off ability, low cost, and ease of handling.

[0070] In the process of halogenating the benzyl position of PPE, a portion of the benzene rings at positions 3 and 5 may be substituted with halogen groups. However, since Sn2-type nucleophilic substitution reactions do not occur with halogen groups of the benzene rings, it is preferable to use known reaction conditions that selectively halogenate the benzyl position. Specifically, it is preferable to use carbon tetrachloride or chlorobenzene as the reaction solvent. This is because using these solvents with low halogen solubility keeps the halogen concentration in the reaction system low, resulting in preferential halogenation at the benzyl position. For example, it is known that using polar solvents such as acetonitrile results in halogenation of only the benzene rings. From the viewpoint of ease of handling, it is preferable to avoid carbon tetrachloride and use chlorobenzene.

[0071] In this embodiment, known halogenating agents such as elemental halogens and N-halogenated succinimide can be used as the halogen source. The halogenation reaction conditions are preferably carried out under an inert atmosphere such as argon or nitrogen, at a reaction temperature of 80°C or higher, for at least 3 hours. Higher reaction temperatures increase the selectivity for halogenation to the benzyl position. However, at temperatures above 140°C, side reactions such as polymer crosslinking may occur; therefore, the reaction is more preferably carried out at 100°C or higher and less than 135°C.

[0072] In this embodiment, modified PPE can be obtained by adding methanol, ethanol, acetone, etc., to the solution after the halogenation reaction to precipitate the polymer, washing with the same solvent, and drying. Methanol is more preferably used as the solvent.

[0073] In this embodiment, the degree of halogenation of modified PPE can be determined, for example, by nuclear magnetic resonance (NMR) using deuterated chloroform as the solvent. The halogenation of the benzene ring and the halogenation of the benzyl position can be determined based on the characteristic peaks in NMR to determine the relative abundance of each unit structure. For detailed unit structures, for example, the heteronuclide single coherence method (HSQC) can be used to identify them.

[0074] PPE has methyl groups at the 2 and 6 positions, and there are six hydrogen atoms at the benzyl position where substitution can occur. However, in most cases, one hydrogen atom is substituted for a halogen group per methyl group, and there are also a certain number of cases where two hydrogen atoms are substituted for halogen groups. On the other hand, no cases were observed where three hydrogen atoms were substituted for halogen groups per methyl group.

[0075] In this embodiment, there are no particular restrictions on the degree of halogenation of the benzene ring, but it is preferably between 0 and 1.0. If this value becomes too high, the degree of halogenation to the benzyl position will relatively decrease, leading to an excessive amount of halogen being used. Furthermore, when used as a encapsulant, if halogen is released during the molding process, it can cause corrosion of metal parts.

[0076] 3) Steps to introduce amino groups into modified polyphenylene ether The method for introducing amino groups into the modified polyphenylene ether described above is not particularly limited, but examples include reacting the modified polyphenylene ether with an amine compound in the absence of a solvent or in the presence of a solvent using an aromatic nucleophilic substitution reaction or a nucleophilic substitution reaction.

[0077] The amine compound is not particularly limited, but structures represented by the following general formulas (18), (19), (20), and (21) are preferred, and structures represented by the following general formulas (18), (19), and (20) are more preferred. In the above general formula (18), R １８ R represents an alkylene group having 2 to 6 carbon atoms, or an oxybisalkylene group having a total of 2 to 6 carbon atoms. １９ Each of these independently represents a hydrogen atom, a C1-C3 alkyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, or a 2-hydroxyethoxyethyl group. n represents an integer from 1 to 5. R ２３ This represents an alkyl group having 1 to 3 carbon atoms, a 2-hydroxyethyl group, or a 2-hydroxypropyl group. In the general formula (21) above, n1 represents an integer from 0 to 11.

[0078] While there are no particular limitations on the method for introducing amino groups into modified polyphenylene ethers, methods other than aromatic nucleophilic substitution reactions include amination by reduction of nitro groups. Specific reduction methods include reduction using metal catalysts such as tin and zinc, catalytic reduction using Pd / C with hydrogen gas as the reducing agent, hydrazine reduction, and reduction using osmium-activated carbon.

[0079] The solvent is not particularly limited, but aprotic organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, tetrahydrofuran, and dimethyl sulfoxide, as well as nonpolar solvents such as toluene and xylene, may be used. The reaction temperature is not particularly limited, but is usually 25 to 200°C, and the reaction time is usually 1 to 72 hours.

[0080] Other components besides those shown in formulas (1), (2), (3), and (4) include units derived from crosslinking agents added to adjust film strength and molecular weight. Examples of crosslinking agents include terephthalic acid dichloride and oxalyl chloride, which can carry out the Friedel-Crafts reaction at two locations.

[0081] <Compounds that react with compounds having active hydrogen groups> In this embodiment, compounds that react with compounds having active hydrogen groups refer to compounds that can chemically react with the above-mentioned compounds having active hydrogen groups to form a covalent bond. Specific examples of compounds that react with the above-mentioned compounds having active hydrogen groups include curable resins, isocyanates, halogen compounds, etc. From the viewpoint of achieving sufficient heat resistance of the cured product, it is preferable that the compound that reacts with the above-mentioned compounds having active hydrogen groups is a curable resin.

[0082] (Curable Resin) The curable resin described above is a resin that can be cured by a chemical curing reaction, and may be a thermosetting resin or a photocurable resin. From the viewpoint of ease of the manufacturing process of the cured product, the curable resin is preferably a thermosetting resin. Examples of thermosetting resins include epoxy resins, maleimide resins, cyanate ester resins, etc., and epoxy resins are preferred from the viewpoint of availability and curability of the cured product.

[0083] -Epoxy resin (B)- As epoxy resin (B), monomers, oligomers, and polymers in general that have two or more epoxy groups in one molecule can be used. Non-halogenated epoxy resins are particularly preferred as epoxy resin (B).

[0084] Examples of epoxy resins (B) include biphenyl-type epoxy resins; bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and tetramethylbisphenol F-type epoxy resin; stilbene-type epoxy resins; novolac-type epoxy resins such as phenol novolac-type epoxy resin and cresol novolac-type epoxy resin; polyfunctional epoxy resins such as triphenolmethane-type epoxy resin and alkyl-modified triphenolmethane-type epoxy resin; phenol aralkyl-type epoxy resins having a phenylene skeleton, and phenol aralkyl-type epoxy resins having a biphenylene skeleton. Examples include phenol aralkyl epoxy resins such as oxy resins; naphthol-type epoxy resins such as dihydroxynaphthalene-type epoxy resins and epoxy resins obtained by glycidyl etherification of dihydroxynaphthalene dimers; triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; bridged cyclic hydrocarbon compound-modified phenol-type epoxy resins such as dicyclopentadiene-modified phenol-type epoxy resins; and polyglycidylamine-type epoxy resins such as triglycidylamine-type epoxy resins and tetraglycidylamine-type epoxy resins. The epoxy resin (B) is not limited to these, as long as it is a commonly used epoxy resin. These may be used individually or in combination of two or more types.

[0085] The epoxy resin (B) more preferably contains at least one of bisphenol-type epoxy resin, biphenyl-type epoxy resin, novolac-type epoxy resin (e.g., o-cresol novolac epoxy resin), phenol aralkyl-type epoxy resin, and triphenolmethane-type epoxy resin. Furthermore, from the viewpoint of suppressing warping of the cured product, it is particularly preferable to contain at least one of phenol aralkyl-type epoxy resin and novolac-type epoxy resin. To further improve fluidity, biphenyl-type epoxy resin is particularly preferred, and to control the elastic modulus at high temperatures, phenol aralkyl-type epoxy resin having a biphenylene skeleton is particularly preferred.

[0086] As the epoxy resin (B), for example, one can be used that contains at least one selected from the group consisting of epoxy resins represented by the following general formula (22), epoxy resins represented by the following general formula (23), epoxy resins represented by the following general formula (24), epoxy resins represented by the following general formula (25), epoxy resins represented by the following general formula (26), and epoxy resins represented by the following general formula (27). In general formula (22), Ar1 represents a phenylene group or a naphthylene group, and if Ar1 is a naphthylene group, the glycidyl ether group may be bonded to either the α or β position. Ar2 represents one of the groups phenylene, biphenylene, or naphthylene. Ra and Rb each independently represent a hydrocarbon group having 1 to 10 carbon atoms. g is an integer from 0 to 5, and h is an integer from 0 to 8. n3 represents the degree of polymerization, and its average value is greater than 1 and less than or equal to 10. In general formula (23), each of the multiple Rc elements independently represents either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. I is an integer from 1 to 4, and n4 represents the degree of polymerization, with an average value from 0 to 10. In general formula (24), the multiple Rd and Re elements each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. I is an integer from 1 to 4, and n6 represents the degree of polymerization, with an average value from 0 to 10. In general formula (25), each of the multiple Rf elements independently represents either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. I is an integer from 1 to 4, and n7 represents the degree of polymerization, with an average value from 0 to 10. In general formula (26), each of the multiple Rg groups independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a glycidyl ether group, or a phenyl group. I is an integer from 1 to 4, J is an integer from 1 to 3, and n8 represents the degree of polymerization, the average value of which is greater than 1 and less than or equal to 10. In general formula (27), each of the multiple Rh elements independently represents either a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. n9 represents the degree of polymerization, and its average value is between 0 and 10.

[0087] The number-average molecular weight of epoxy resin (B) is not particularly limited and can be appropriately selected from viewpoints such as fluidity and curability. For example, the number molecular weight is about 100 to 2000. Furthermore, from the viewpoint of fluidity, the ICI viscosity of epoxy resin (B) at 150°C is preferably 0.1 to 20.0 poise.

[0088] The epoxy equivalent of epoxy resin (B) is preferably 100 to 1000 g / eq, more preferably 100 to 400 g / eq, and even more preferably 150 to 300 g / eq. When the composition contains multiple epoxy resins, it is preferable that the total epoxy equivalent of the multiple epoxy resins is equal to the above values.

[0089] - Maleimide Resins - Maleimide resins can be any monomer, oligomer, or polymer having two or more maleimide groups in one molecule. The nitrogen atom of the maleimide group can be bonded to a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic ring, or a fused ring of an aromatic ring and an aliphatic ring. Specifically, you can use "MIR-3000" (manufactured by Nippon Kayaku Co., Ltd.), "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Yamato Kasei Co., Ltd.), "BMI-5100" (manufactured by Yamato Kasei Co., Ltd.), "BMI-80" (manufactured by Kei-I Kasei Co., Ltd.), "BMI-6100" (manufactured by Designer Molecules Inc.), "BMI-689" (manufactured by Designer Molecules Inc.), and maleimide resins disclosed in the Japan Institute of Invention and Innovation, Technical Report No. 2020-500211.

[0090] [Curing agent] The curing agent of this embodiment essentially contains an amino group-containing polyphenylene ether (A). The amino group-containing polyphenylene ether (A) in the curing agent of this embodiment is the same as the amino group-containing polyphenylene ether (A) in the mixture of this embodiment described above. The curing agent of this embodiment is a curing agent that reacts with a compound that reacts with the compound having an active hydrogen group as described above. The curing agent may consist only of an amino group-containing polyphenylene ether (A), or may consist only of an amino group-containing polyphenylene ether (A) and a liquid amine compound or a liquid phenol compound, or may consist only of an amino group-containing polyphenylene ether (A) and a liquid amine compound, or may further contain other components.

[0091] The curing agent in this embodiment is preferably a liquid. Here, "liquid" means that it is liquid at 20°C. "Liquid" means, for example, that its viscosity is 100 cp or less. A liquid curing agent can be applied to liquid encapsulants. Furthermore, its impregnation into carbon fibers is improved.

[0092] The curing agent of this embodiment is preferably a liquid containing a liquid amine compound or a liquid phenol compound, and more preferably a liquid containing a liquid amine compound (for example, a liquid containing a liquid amine compound but not a liquid phenol compound). The liquid amine compound and the liquid phenol compound are liquid at 20°C. This configuration allows for the production of a liquid curing agent, improving its applicability to liquid encapsulants and impregnation into carbon fibers. From the viewpoint of improving the efficiency of the curing reaction, the curing agent of this embodiment is preferably a liquid that does not contain any liquids other than the liquid amine compound or the liquid phenol compound. The total content of the amino group-containing polyphenylene ether (A), liquid amine compound, and liquid phenol compound in the curing agent of this embodiment is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, based on 100% by mass of the curing agent.

[0093] (Liquid Amine Compounds) The above liquid amine compounds include aliphatic polyamines such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine, and hexamethylenediamine; metaphenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 2-methyl-4,6-bis(methylthio)-1,3-benzenediamine, and 4-methyl-2,6-bis(methylthio)-1,3-be Examples include aromatic amines with one aromatic ring, such as lenzendiamine and 2,4-diaminoanisole; aromatic amines with two aromatic rings, such as 2,4-diaminodiphenylmethane, 4,4-diaminodiphenylsulfone, 4,4'-methylenebis(2-ethylaniline), 3,3'-diethyl-4,4'-diaminophenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminophenylmethane, and 3,3',5,5'-tetraethyl-4,4'-diaminophenylmethane; and polyamine compounds including dicyandiamide (DICY) and organic acid dihydrazides. These may be used individually or in combination of two or more. Among these, aliphatic polyamines, aromatic diamines, and polyoxypropylenediamines are preferred from the viewpoint of excellent heat resistance and hygroscopicity of the cured product, and excellent solubility in amino group-containing polyphenylene ether (A).

[0094] Regarding aromatic amines, those having an alkylenedieniline structure are preferred, and liquid 4,4'-methylenebis(2-ethylaniline) is particularly preferred in terms of reactivity and curing properties. Furthermore, the combined use of 3,5-diethyl-2,4-diaminotoluene and 3,5-diethyl-2,6-diaminotoluene is preferred because it allows for the production of a liquid sealant with low viscosity. Additionally, 2-methyl-4,6-bis(methylthio)-1,3-benzenediamine and 4-methyl-2,6-bis(methylthio)-1,3-benzenediamine can also be preferably used because they possess a desirable combination of viscosity, reactivity, and curing properties. These may be used alone or in combination with 4,4'-methylenebis(2-ethylaniline), 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, etc.

[0095] When the curing agent of this embodiment contains a liquid amine compound, the mass ratio of the liquid amine compound to 100% by mass of the cured product is preferably 1 to 90% by mass, more preferably 1 to 70% by mass, and even more preferably 1 to 50% by mass, from the viewpoint of excellent heat resistance and hygroscopicity of the cured product and excellent solubility in amino group-containing polyphenylene ether (A).

[0096] The curing agent of this embodiment can also be used as a curing agent containing the amino group-containing polyphenylene ether (A) in the mixture of this embodiment described above.

[0097] [Curable Composition] The curable composition of this embodiment contains an amino group-containing polyphenylene ether (A) and a curable resin. The amino group-containing polyphenylene ether (A) is the amino group-containing polyphenylene ether (A) in the mixture of this embodiment described above. The curable resin is the curable resin in the compound that reacts with the compound having an active hydrogen group in the mixture of this embodiment described above, and is preferably the epoxy resin (B) in the compound that reacts with the compound having an active hydrogen group in the mixture of this embodiment described above.

[0098] When epoxy resin (B) is used as the curable resin, the amount of amino group-containing polyphenylene ether (A) used in the curable composition of this embodiment is preferably 0.5 to 1.5 equivalents per equivalent of epoxy groups in epoxy resin (B). If the amount is less than 0.5 equivalents or more than 1.5 equivalents per equivalent of epoxy groups, curing may be incomplete, and good cured physical properties may not be obtained. The mass ratio of the curable composition of this embodiment is preferably 20 to 80% by mass of amino group-containing polyphenylene ether (A) and 20 to 80% by mass of epoxy resin (B), when the total of amino group-containing polyphenylene ether (A) and epoxy resin (B) is taken as 100% by mass. The ratio of the total mass of (A) and (B) to 100% by mass of the curable composition of this embodiment is preferably 5% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more. In another embodiment, the total mass ratio of (A) and (B) to 100% by mass of the curable composition of this embodiment is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.

[0099] In the curable composition of this embodiment, when α is the nitrogen content (mass%) of the amino group-containing polyphenylene ether (A) and β is the epoxy group equivalent (g / eq) of the epoxy resin (B), the β / α value is preferably 5 to 250, more preferably 10 to 150, and even more preferably 15 to 110, from the viewpoint of curability.

[0100] The curable composition of this embodiment may optionally contain other components.

[0101] (Other components) Other components include, for example, a curing accelerator and an inorganic filler, which will be described later, and it is preferable to include an inorganic filler.

[0102] -Curing accelerator- Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diazabicyclo(5,4,0)undecene-7; phosphines such as triphenylphosphine; and metal compounds such as tin octylate. The curing accelerator is used in amounts of 0.02 to 5.0 parts by mass per 100 parts by mass of epoxy resin (B), as needed. The gelation time can be adjusted by using the curing accelerator.

[0103] - Inorganic Fillers - Specifically, examples of the above inorganic fillers include silica, alumina, titanium white, aluminum hydroxide, talc, clay, mica, glass fiber, etc. The product may contain only one type of inorganic filler, or two or more types.

[0104] Silica is preferred as the inorganic filler mentioned above. Examples of silica include molten crushed silica, molten spherical silica, crystalline silica, and secondary agglomerated silica. Among these, molten spherical silica is particularly preferred.

[0105] The inorganic filler described above is usually in the form of particles. The particle shape is preferably approximately spherical. The average particle size of the inorganic filler is not particularly limited, but is typically 1 to 100 μm, preferably 1 to 50 μm, and more preferably 1 to 20 μm. An appropriate average particle size ensures adequate fluidity during curing. The average particle size of the inorganic filler can be determined by acquiring volume-based particle size distribution data using a laser diffraction / scattering particle size distribution analyzer (for example, the LA-950 wet particle size distribution analyzer manufactured by Horiba, Ltd.) and processing that data. The measurement is usually performed dry.

[0106] Inorganic fillers such as silica may be pre-treated with a coupling agent such as a silane coupling agent. This suppresses aggregation of the inorganic filler and allows for better fluidity. It also increases the affinity between the inorganic filler and other components, improving the dispersibility of the inorganic filler. This is thought to contribute to improved mechanical strength of the cured product and suppression of microcrack formation.

[0107] As coupling agents used for surface treatment of inorganic fillers, known coupling agents such as various silane compounds including epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and methacrylicsilane, as well as titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be used. Among these, primary aminosilanes such as γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane can be preferably used. By modifying the surface of the inorganic filler with groups (such as amino groups) that can react with epoxy resin (B), the dispersibility of the inorganic filler can be improved. Furthermore, by appropriately selecting the type of coupling agent used for surface treatment of the inorganic filler and appropriately adjusting the amount of coupling agent used, the fluidity and strength after curing can be controlled.

[0108] Surface treatment of an inorganic filler with a coupling agent can be carried out, for example, as follows: First, the inorganic filler and the coupling agent are mixed and stirred using a mixer. A known mixer, such as a ribbon mixer, can be used for mixing and stirring. The mixer can be operated in one of the following ways: (i) The inorganic filler (B) and the coupling agent may be placed in the mixer beforehand and the blades may be turned; or (ii) Only the inorganic filler (B) may be placed in the mixer first, and while the blades are turned, the coupling agent may be added to the mixer little by little using a spray nozzle or the like.

[0109] During mixing and stirring, it is preferable to maintain low humidity inside the mixer (for example, humidity of 50% or less). Low humidity prevents moisture from adhering to the surface of the inorganic filler. Furthermore, it prevents moisture from contaminating the coupling agent and causing it to react with other coupling agents.

[0110] Next, the resulting mixture is removed from the mixer and subjected to an aging treatment to promote the coupling reaction. The aging treatment is carried out, for example, by leaving it for one day or more (preferably 1 to 7 days) under conditions of 20±5°C and 40-50% RH. By carrying out the treatment under these conditions, the coupling agent can be uniformly bonded to the surface of the inorganic filler. After the aging treatment, the mixture is sieved to remove coarse particles, thereby obtaining an inorganic filler that has undergone surface treatment (coupling treatment).

[0111] (Method for producing the curable composition) The curable composition of this embodiment can be easily obtained by a method similar to that of conventionally known methods. For example, an epoxy resin (B), an amino group-containing polyphenylene ether (A), and other components such as a curing accelerator and / or inorganic filler as needed can be thoroughly kneaded using an extruder, kneader, roll, etc., at a rotation speed of 50 to 500 rpm at a temperature of 80 to 250°C until uniform to obtain the curable composition. The kneading temperature is preferably within a temperature range in which the curable composition does not harden, specifically 50°C to 250°C or lower, more preferably 50°C to 200°C or lower, and even more preferably 50°C to 180°C or lower.

[0112] [Mixed Matter] In this specification, "mixed matter" refers to a mixture containing the curing agent of this embodiment described above and other components. For example, if the other components contained in the mixed matter are compounds that react with the compound having an active hydrogen group of this embodiment described above, it corresponds to the mixture of this embodiment described above. Also, if the other components contained in the mixed matter are curable resins, it corresponds to the mixture of this embodiment described above and the curable resin composition of this embodiment described above. Also, if the other components contained in the mixed matter do not correspond to compounds that react with the compound having an active hydrogen group of this embodiment described above, it does not correspond to the mixture of this embodiment described above. The curing agent in the mixed matter described above is the same as the curing agent in this embodiment described above (for example, a curing agent containing the amino group-containing polyphenylene ether (A) described above). Also, the other components in the mixed matter described above are compounds that react with the compound having an active hydrogen group in the mixture of this embodiment described above (for example, curable resins), other components in the curable composition of this embodiment described above (for example, inorganic fillers, curing accelerators), organic solvents, etc.

[0113] The compound of this embodiment is preferably liquid at 20°C. Being liquid allows for application to liquid encapsulants and improves impregnation into carbon fibers. Other components of the compound of this embodiment include curable resins. When epoxy resin (B), which is a curable resin, is included as another component of the compound of this embodiment, the amount of curing agent used (preferably the amount of amino group-containing polyphenylene ether (A)) is preferably 0.5 to 1.5 equivalents per equivalent of epoxy groups in epoxy resin (B). If the amount is less than 0.5 equivalents or more than 1.5 equivalents per equivalent of epoxy groups, curing may be incomplete, and good cured properties may not be obtained. The total mass ratio of the curing agent and curable resin to 100% by mass of the compound of this embodiment is preferably 5% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, from the viewpoint of excellent heat resistance and hygroscopicity of the cured product. In another embodiment, the total mass ratio of the curing agent and curable resin to 100% by mass of the kneaded mixture of this embodiment is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may also be 100% by mass.

[0114] The compound of this embodiment can be easily obtained by a method similar to that known conventionally. For example, it is prepared by mixing and stirring the raw materials. Mixing and stirring can be done using a roll mill, but is not limited to this. If solid raw materials are included, it is preferable to liquefy or fluidize them by heating or other means before mixing. The components may be mixed simultaneously, or some components may be mixed first and the remaining components may be mixed later, or the method may be modified as appropriate.

[0115] [Method for manufacturing a cured body and a cured product] The method for manufacturing a cured product in this embodiment includes a step of curing the curable composition of this embodiment described above. The method for manufacturing a cured body in this embodiment also includes a step of mixing the curing agent of this embodiment described above and the curable resin described above and curing them. The curable resin is a compound that reacts with the compound having an active hydrogen group in the mixture of this embodiment described above, and is preferably an epoxy resin (B). Here, "cured product" refers to a product obtained by curing a curable composition containing the amino group-containing polyphenylene ether (A) and a curable resin. Also, "cured body" refers to a product obtained by mixing a curing agent containing the amino group-containing polyphenylene ether (A) and a curable resin and curing them. For example, when a curable composition is prepared and left to stand for a while before curing, it is a cured product, and when raw materials are mixed to prepare a curable composition and the curable composition is cured continuously, it can become a cured body.

[0116] In the above-described manufacturing method, curing is preferably performed by heating. For example, the curable composition of this embodiment described above, or a mixture of a curing agent and a curable resin, can be molded using a post-molding casting or transfer molding machine, and then heated at 80 to 250°C for 2 to 10 hours to produce a cured product or cured body. For example, a liquid sealing material containing the curing agent or mixture of this embodiment can be applied to the part to be sealed (the surface to be sealed) using a dispenser, printing machine, etc. Here, the temperature at the time of application is preferably 50 to 200°C. After that, sealing is completed by heating and curing at a predetermined temperature for a predetermined time, specifically at 100 to 250°C for 20 minutes to 10 hours. It can also be applied to a compression molding method. The required amount of liquid composition is dropped into a mold, and it can be molded by compression from the mold. Here, the mold temperature is 100 to 200°C, the curing time is 5 to 60 minutes, and the post-curing temperature is 100 to 250°C and the post-curing time is 20 minutes to 10 hours.

[0117] In the method for producing the cured product of this embodiment, other components other than the curing agent and the compound that reacts with the curable resin may be used. As other components, the inorganic filler and / or curing accelerator described above in the curable composition of this embodiment can be used.

[0118] The method for manufacturing the cured body of this embodiment may substantially include a step of mixing a curing agent and a curable resin and curing them. For example, the manufacturing method may involve pre-mixing and stirring raw materials such as a curing agent and a compound that reacts with a compound having an active hydrogen group to form a kneaded mixture before curing.

[0119] [Cured product] The cured product of this embodiment may be a cured product obtained by curing the mixture, curable composition, curing agent, or kneaded product of this embodiment described above, a cured product obtained by the method for producing the cured product of this embodiment described above, or a cured product obtained by the method for producing the cured product of this embodiment described above.

[0120] The glass transition temperature of the cured product in this embodiment is preferably 200°C or higher, more preferably 210°C or higher. It may also be 400°C or lower. Furthermore, the moisture absorption rate is preferably 2% or lower, and more preferably less than 1.5%. If the glass transition temperature is 200°C or higher and the moisture absorption rate is 2% or lower, stable reliability can be obtained under high-temperature and high-moisture conditions. The glass transition temperature and moisture absorption rate can be measured by the method described in the examples below.

[0121] [Varnish] The mixture, curable composition, curing agent, or kneaded product of this embodiment can be converted into a varnish by adding an organic solvent. Examples of solvents that can be used include amide solvents such as γ-butyrolactones, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolidinone; sulfones such as tetramethylene sulfone; ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, and propylene glycol monobutyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic solvents such as toluene and xylene. The solvent is used in a range such that the solid content concentration excluding the solvent in the resulting varnish is usually 10 to 80% by mass, preferably 15 to 70% by mass.

[0122] [Prepreg] The prepreg of this embodiment includes the curable composition of this embodiment described above. Preferably, the prepreg further contains reinforcing fibers, and may be a prepreg obtained by impregnating the reinforcing fibers with the curable composition. For example, the prepreg of this embodiment can be obtained by heating and melting the curable composition of this embodiment and impregnating it with reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers. Alternatively, the prepreg of this embodiment can be obtained by impregnating the reinforcing fibers with the varnish and then heating and drying them. After cutting the prepreg into a desired shape and laminating it, a fiber-reinforced composite material can be obtained by applying pressure to the laminate using a press molding method, autoclave molding method, sheet winding molding method, etc., and then heating and curing it. Copper foil or organic film can also be laminated when laminating the prepreg. It is also preferable that the same applies to a prepreg obtained by impregnating the reinforcing fibers with the mixture, curing agent, or kneaded mixture of this embodiment described above.

[0123] [Semiconductor Encapsulator] The semiconductor encapsulant of this embodiment includes the curable composition of this embodiment described above. Preferably, the semiconductor encapsulant includes the cured product described above. Preferably, the semiconductor encapsulant is a semiconductor encapsulant for power modules. The cured product using amino group-containing polyphenylene ether (A) has excellent properties of high heat resistance and low moisture absorption, making it suitable for use as a semiconductor encapsulant. Furthermore, it can be suitably used as an insulating material for electrical and electronic components, as well as for various composite materials including laminates (printed wiring glass fiber reinforced composite materials) and CFRP (carbon fiber reinforced composite materials), as well as for various adhesives, various paints, structural members, etc. The cured product using amino group-containing polyphenylene ether (A) has excellent properties of high heat resistance and low moisture absorption, making it suitable for use as a semiconductor encapsulant for power modules. Power modules are used for power conversion, such as changing frequency, voltage, DC current to AC current, or AC current to DC current. Specifically, these components play a role in driving motors, charging batteries, and supplying a stable power supply to electric vehicles, home appliances, and other devices. Power modules, which handle higher voltages and currents than ordinary semiconductor modules, tend to generate heat and become hot, requiring high heat resistance and low moisture absorption when encapsulated with resin. The semiconductor encapsulant containing the mixture, curing agent, or kneaded product of the above embodiment can also be suitably used for the above applications.

[0124] The embodiment will be described in detail below with reference to examples and comparative examples, but this embodiment is not limited to these examples. The evaluation method and measurement method used in this embodiment are as follows.

[0125] (Reduced viscosity) A 0.5 g / dL chloroform solution of unmodified polyphenylene ether was prepared, and the reduced viscosity (ηsp / c) (dL / g) at 30°C was determined using an Ubbelohde viscous tube.

[0126] (Revision Rate) Modified polyphenylene ether, in which spacers such as alkylene groups, arylene groups containing divalent electron-withdrawing groups, and alkylene groups containing divalent electron-withdrawing groups are introduced into unmodified polyphenylene ether, is dissolved in deuterated chloroform, and tetramethylsilane is used as an internal standard. １ ¹H-NMR measurements were performed (Brker Biospin AvanceNEO600, frequency: 600 MHz, pulse program: zg30, number of integrations: 16, temperature: 25°C). The denaturation rate (mol%) of the denatured polyphenylene ether was calculated from the signal of the aromatic ring unit of formula (3) of the undenatured polyphenylene ether and the signal of the aromatic ring unit after denaturation. For example, in the undenatured polyphenylene ether obtained in the example, the signal derived from the aromatic ring unit of the repeating unit of formula (3), i.e., the 2,6-dimethylphenol-derived structure (2,6-dimethylphenylene unit), and the signal derived from the aromatic ring unit of the 2,6-dimethylphenol-derived structure of the compound in which a 4-fluorobenzoyl group was introduced at the 3rd or 5th position of 2,6-dimethylphenol were analyzed as follows. The peaks of each repeating unit appear in the following regions. The peak (2H) originating from the hydrogen atoms of the aromatic ring of the unmodified 2,6-dimethylphenylene unit appears at 6.40–6.60 ppm, while the peak (1H) originating from the hydrogen atoms of the aromatic ring of the 2,6-dimethylphenylene unit in compounds in which a 4-fluorobenzoyl group has been introduced at the 3rd or 5th position of 2,6-dimethylphenol appears at 5.90–6.30 ppm. By examining the integral value of the above signals, the denaturation rate can be calculated from the following formula (4): X = 100 × Z / (Y / 2 + Z) ... Formula (4) X: Denaturation rate Y: Integral value of the peak originating from the aromatic ring of the 2,6-dimethylphenylene unit Z: Integral value of the peak originating from the aromatic ring of the 2,6-dimethylphenylene unit in compounds in which a 4-fluorobenzoyl group has been introduced at the 3rd or 5th position of 2,6-dimethylphenol

[0127] (Glass Transition Point) The cured film was cut into 1 cm x 5 cm pieces and heated stepwise from 30°C to 350°C at a heating rate of 5°C / min using a dynamic viscoelastic device (DMA: Hitachi High-Tech Corporation, product name: DMA7100), and measurements were taken at a frequency of 2 Hz. The maximum temperature at which the tanδ value was maximized during the measurement was defined as the glass transition point.

[0128] (Moisture absorption rate) The weight increase rate was measured after 24 hours at 121°C / 100%. A moisture absorption rate of less than 1.5% was classified as A, 1.5% to less than 2% as B, and 2% or more as C.

[0129] (Ethylenediamine solubility of curing agent components) The amino group-containing polyphenylene ether (A) described in the examples and comparative examples was mixed with the liquid amine compound in the proportions shown in Tables 4 and 5, and ethylenediamine was added to evaluate the solubility at room temperature. Complete dissolution was considered good, and residual insoluble matter was considered poor. The ethylenediamine solubility of the liquid amine compound was not confirmed.

[0130] (Curing Film Properties) Amino group-containing polyphenylene ether (A), liquid amine compound, and thermosetting resin (C) were dissolved in an organic solvent and evaluated whether a curing film could be obtained by heating at 80°C for 2 hours and 180°C for 4 hours. If a curing film was obtained, it was considered good; if no film was formed, it was considered poor.

[0131] (Degree of bromination) Bromination analysis of aromatic ring alkyl substituents of polyphenylene ether is performed by dissolving brominated polyphenylene ether in deuterated chloroform and using tetramethylsilane as an internal standard. １ The analysis was performed using 1H-NMR (Brker Biospin AvanceNEO600, frequency: 600MHz, pulse program: zg30, number of integrations: 16, temperature: 25°C). The degree of bromination was calculated by comparing the integral values ​​of 6.35–6.6 ppm (2H) and 6.6–6.8 ppm (1H).

[0132] (Nitrogen content α) 0.5 g of the sample was weighed, and 30 mL of sulfuric acid, 25 g of potassium sulfate and 1 g of copper sulfate as catalysts were added. The mixture was heated to decompose the organic matter. Next, sodium hydroxide was added to the decomposed sample to make it alkaline, and then it was separated by distillation. The distilled ammonia was absorbed into the sulfuric acid. An appropriate amount of this distillate was taken, and the ammonium ions were quantified by indophenol blue spectrophotometric analysis. The value converted to nitrogen content was defined as the nitrogen content (mass%). A JASCO V-630 spectrophotometer was used for measurement. The nitrogen content (mass%) of the amino group-containing PPE prepared by the method described below is shown in Table 1.

[0133]

[0134] (Preparation of unmodified polyphenylene ether) (Unmodified PPE-1-1) A 40-liter jacketed polymerization tank equipped with a sparger, stirring turbine blades and baffles at the bottom for introducing oxygen-containing gas, and a reflux condenser in the vent gas line at the top of the polymerization tank was filled with 4.57 g of cupric oxide, 24.18 g of 47% by mass aqueous solution of hydrogen bromide, 11.00 g of di-t-butylethylenediamine, 62.72 g of di-n-butylamine, 149.92 g of butyldimethylamine, 20.65 kg of toluene, and 3.12 kg of 2,6-dimethylphenol, while blowing nitrogen gas at a flow rate of 0.5 L / min. The mixture was stirred until a homogeneous solution was formed and the internal temperature of the polymerization tank reached 25°C. Next, dry air was introduced into the polymerization tank through the sparger at a rate of 32.8 NL / min to start polymerization. Dry air was passed through for 140 minutes to obtain the polymerization mixture. During polymerization, the internal temperature was controlled to 40°C. At the end of polymerization, the polymerization mixture (polymerization solution) was in a homogeneous solution state. The supply of dry air was stopped, and 10 kg of a 2.5% by mass aqueous solution of tetrasodium ethylenediaminetetraacetate (reagent manufactured by Dojin Chemical Research Institute) was added to the polymerization mixture. The polymerization mixture was stirred at 70°C for 150 minutes, then allowed to stand for 20 minutes, and the organic phase and aqueous phase were separated by liquid-liquid separation. The separated organic phase yielded a toluene solution containing 13.1% by mass of polyphenylene ether. The above solution was placed in a jacketed stirring tank, and heated by flowing a heat transfer medium at 120°C through the jacket. The generated toluene-based vapor was cooled by a condenser to remove the toluene from the system, and the polymer concentration in the stirring tank was concentrated to 30% by mass. Methanol was mixed in such a ratio of 1.0 to the polymer solution, and the polymer was precipitated. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. Furthermore, the wet polyphenylene ether was washed with methanol in an amount such that the ratio of methanol to wet polyphenylene ether was 2.5. This washing operation was repeated three times. Then, the wet polyphenylene ether was held at 140°C and 1 mmHg for 120 minutes to obtain dry, unmodified polyphenylene ether. The reduced viscosity of the obtained unmodified polyphenylene ether was 0.57 dL / g.

[0135] (Unmodified PPE-1-2) A 1.5-liter jacketed reactor equipped with a sparger for introducing oxygen-containing gas at the bottom, stirring turbine blades and baffles, and a reflux condenser in the vent gas line at the top of the reactor, contained 0.2512 g of cupric chloride dihydrate, 1.1062 g of 35% hydrochloric acid, 3.6179 g of di-n-butylamine, 9.5937 g of N,N,N',N'-tetramethylpropanediamine, 673.80 g of methanol, and 180.0 g of 2,6-dimethylphenol. Oxygen was then introduced into the reactor from the sparger at a rate of 180 ml / min while vigorously stirring, and the polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain a temperature of 40°C. The polymerization solution gradually took on the form of a slurry. No adhesion to the reactor was observed during polymerization. 120 minutes after the start of oxygen introduction, the flow of oxygen-containing gas was stopped. Next, the obtained slurry was filtered under reduced pressure using a glass filter to obtain wet polyphenylene ether. The wet polyphenylene ether was then washed with methanol in an amount such that the ratio of methanol to wet polyphenylene ether was 2.5. This washing operation was repeated three times. Then, the wet polyphenylene ether was held at 140°C and 1 mmHg for 120 minutes to obtain dry, unmodified polyphenylene ether. The reduced viscosity of the obtained unmodified polyphenylene ether was 0.07 dL / g.

[0136] (Unmodified PPE-2-1) A 40-liter jacketed polymerization tank equipped with a sparger, stirring turbine blades and baffles at the bottom for introducing oxygen-containing gas, and a reflux condenser in the vent gas line at the top of the polymerization tank, was prepared by blowing nitrogen gas at a flow rate of 0.5 L / min. 4.57 g of cupric oxide, 24.18 g of 47% by mass aqueous solution of hydrogen bromide, 11.00 g of di-t-butylethylenediamine, 62.72 g of di-n-butylamine, 149.92 g of butyldimethylamine, 20.65 kg of toluene, and 3.12 kg of 2,6-dimethylphenol were added, and the mixture was stirred until a homogeneous solution was formed and the internal temperature of the polymerization tank reached 25°C. Next, dry air was introduced into the polymerization tank through the sparger at a rate of 32.8 NL / min to start polymerization. Dry air was passed through for 140 minutes to obtain the polymerization mixture. The internal temperature was controlled to 40°C during polymerization. At the end of polymerization, the polymerization mixture (polymerization solution) was in a homogeneous solution state. The supply of dry air was stopped, and 10 kg of a 2.5 mass% aqueous solution of tetrasodium ethylenediaminetetraacetate (reagent manufactured by Dojin Chemical Research Institute) was added to the polymerization mixture. The polymerization mixture was stirred at 70°C for 150 minutes, then allowed to stand for 20 minutes, and the organic phase and aqueous phase were separated by liquid-liquid separation. The separated organic phase yielded a toluene solution containing 13.1 mass% polyphenylene ether. The above solution was placed in a jacketed stirring tank, and heated by flowing a heat transfer medium at 120°C through the jacket. The generated toluene-based vapor was cooled by a condenser to remove the toluene from the system, and the mixture was concentrated until the polymer concentration in the stirring tank reached 30 mass%. Methanol was mixed in such a ratio of 1.0 to the polymer solution, and the polymer was precipitated. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. Furthermore, the wet polyphenylene ether was washed with methanol in an amount such that the ratio of methanol to wet polyphenylene ether was 2.5. This washing operation was repeated three times. Then, the wet polyphenylene ether was held at 140°C and 1 mmHg for 120 minutes to obtain dry, unmodified polyphenylene ether. The reduced viscosity of the obtained unmodified polyphenylene ether was 0.57 dL / g.

[0137] (Unmodified PPE-2-2) A 1.5-liter jacketed reactor equipped with a sparger for introducing oxygen-containing gas at the bottom, stirring turbine blades and baffles, and a reflux condenser in the vent gas line at the top of the reactor, contained 0.2512 g of cupric chloride dihydrate, 1.1062 g of 35% hydrochloric acid, 3.6179 g of di-n-butylamine, 9.5937 g of N,N,N',N'-tetramethylpropanediamine, 673.80 g of methanol, and 180.0 g of 2,6-dimethylphenol. Oxygen was then introduced into the reactor from the sparger at a rate of 180 ml / min while vigorously stirring, and the polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain a temperature of 40°C. The polymerization solution gradually took on the form of a slurry. No adhesion to the reactor was observed during polymerization. 120 minutes after the start of oxygen introduction, the flow of oxygen-containing gas was stopped. Next, the obtained slurry was filtered under reduced pressure using a glass filter to obtain wet polyphenylene ether. The wet polyphenylene ether was then washed with methanol in an amount such that the ratio of methanol to wet polyphenylene ether was 2.5. This washing operation was repeated three times. Then, the wet polyphenylene ether was held at 140°C and 1 mmHg for 120 minutes to obtain dry, unmodified polyphenylene ether. The reduced viscosity of the obtained unmodified polyphenylene ether was 0.07 dL / g.

[0138] (Unmodified PPE-3-1) A 1.5-liter jacketed reactor equipped with a sparger for introducing oxygen-containing gas at the bottom, stirring turbine blades and baffles, and a reflux condenser in the vent gas line at the top of the reactor, contained 0.2512 g of cupric chloride dihydrate, 1.1062 g of 35% hydrochloric acid, 3.6179 g of di-n-butylamine, 9.5937 g of N,N,N',N'-tetramethylpropanediamine, 706 g of methanol, and 180.0 g of 2,6-dimethylphenol. Oxygen was then introduced into the reactor from the sparger at a rate of 180 ml / min while vigorously stirring, and the polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain a temperature of 40°C. The polymerization solution gradually took on the form of a slurry. No adhesion to the reactor was observed during polymerization. 120 minutes after the start of oxygen introduction, the flow of oxygen-containing gas was stopped. Next, the obtained slurry was filtered under reduced pressure using a glass filter to obtain wet polyphenylene ether. The wet polyphenylene ether was then washed with methanol in an amount such that the ratio of methanol to wet polyphenylene ether was 2.5. This washing operation was repeated three times. Then, the wet polyphenylene ether was held at 140°C and 1 mmHg for 120 minutes to obtain dry, unmodified polyphenylene ether. The number-average molecular weight (Mn) of the obtained unmodified polyphenylene ether was 1200 by the method described above.

[0139] (Preparation of Modified Polyphenylene Ether) (Modified PPE-1-1) In a 5 L four-necked flask purged with argon, 90 g of the unmodified polyphenylene ether PPE-1-1 obtained above and 2250 mL of dichloromethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (109 g) and 4-fluorobenzoyl chloride (129 g) in dichloromethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure, and modified (fluorobenzoylated) polyphenylene ether was recovered as the product. Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the denaturation rate was 100 mol% using the method described above.

[0140] (Modified PPE-1-2) The procedure was carried out in the same manner as for Modified PPE-1, except that unmodified polyphenylene ether was used as PPE-1-2 (90 g), aluminum chloride (59 g), and 4-fluorobenzoyl chloride (70 g). Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the denaturation rate was 50 mol% using the method described above.

[0141] (Modified PPE-1-3) In a 5 L four-necked flask purged with argon, 90 g of the unmodified polyphenylene ether PPE-1-2 obtained above and 2250 mL of dichloroethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (59 g) and 4-nitrobenzoyl chloride (82 g) in dichloroethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 80°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover modified (nitrobenzoylated) polyphenylene ether as the product. Structural identification of denatured polyphenylene ethers １ Results obtained by 1H-NMR measurement showed that the denaturation rate was 50 mol% using the method described above.

[0142] (Modified PPE-1-4) The procedure was carried out in the same manner as for Modified PPE-1-3, except that aluminum chloride (83 g) and 4-nitrobenzoyl chloride (115 g) were used. Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the denaturation rate was 70 mol% using the method described above.

[0143] (Modified PPE-1-7) The procedure was carried out in the same manner as for Modified PPE-1-1, except that the unmodified polyphenylene ether was replaced with PPE-2 (90 g), aluminum chloride (177 g), and 4-fluorobenzoyl chloride (210 g). Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the denaturation rate was 150 mol% using the method described above.

[0144] (Modified PPE-2-1) In a 5 L four-necked flask purged with argon, 90 g of the unmodified polyphenylene ether PPE-2-1 obtained above and 2250 mL of dichloromethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (109 g) and 4-fluorobenzoyl chloride (129 g) in dichloromethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 40°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover modified (fluorobenzoylated) polyphenylene ether as the product. Structural identification of denatured polyphenylene ethers １ Results obtained by 1H-NMR measurement showed that the denaturation rate was 100 mol% using the method described above.

[0145] (Modified PPE-2-2) The procedure was carried out in the same manner as for Modified PPE-2-1, except that unmodified polyphenylene ether was used as PPE-2-2 (90 g), aluminum chloride (59 g), and 4-fluorobenzoyl chloride (70 g). Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the denaturation rate was 50 mol% using the method described above.

[0146] (Modified PPE-2-3) In a 5 L four-necked flask purged with argon, 90 g of the unmodified polyphenylene ether PPE-2-2 obtained above and 2250 mL of dichloroethane were added and stirred. To the polyphenylene ether solution prepared above, a 750 mL solution of aluminum chloride (59 g) and 4-nitrobenzoyl chloride (82 g) in dichloroethane was added dropwise over 45 minutes at room temperature. After the addition was complete, the reaction solution was heated using a mantle heater and reacted at 80°C for 24 hours, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to methanol (18 L) to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in chloroform (1.4 L), and the solution was added to methanol (10 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover modified (nitrobenzoylated) polyphenylene ether as the product. Structural identification of denatured polyphenylene ethers １ Results obtained by 1H-NMR measurement showed that the denaturation rate was 50 mol% using the method described above.

[0147] (Modified PPE-2-4) The procedure was carried out in the same manner as for Modified PPE-2-3, except that aluminum chloride (83 g) and 4-nitrobenzoyl chloride (115 g) were used. Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the denaturation rate was 70 mol% using the method described above.

[0148] (Modified PPE-2-5) The procedure was carried out in the same manner as for Modified PPE-2-1, except that unmodified polyphenylene ether was replaced with PPE-2-2 (90 g), aluminum chloride (177 g), and 4-fluorobenzoyl chloride (210 g). Structural identification of the modified polyphenylene ether was performed. １ Results obtained by 1H-NMR measurement showed that the denaturation rate was 150 mol% using the method described above.

[0149] (Modified PPE-3-1) In a 500 mL four-neck flask substituted with argon, the unmodified polyphenylene ether PPE-3-1 (40 g) obtained above and chlorobenzene (250 mL) were added, and stirred to form a uniform transparent solution. N-bromosuccinimide (13 g) and azobisisobutyronitrile (2 g) were added, and the reaction was carried out for 6 hours while heating the liquid temperature to 120 °C and maintaining it under strong stirring in an oil bath. After allowing the reaction solution to cool, it was added to 2 L of methanol to precipitate the polymer, and the crude product was recovered by filtration. Further, the recovered crude product was dissolved in chlorobenzene (500 mL), and the solution was added to methanol (4 L) for precipitation purification. The precipitate was filtered under reduced pressure to recover the modified polyphenylene ether as the product. The bromination degree of the obtained modified polyphenylene ether was １ As a result of measurement by 1H-NMR, it was found that the modification rate was 20 mol% by the above-described method.

[0150] (Modified PPE-3-2) The operation was carried out in the same manner as in modified PPE-3-1 except that N-bromosuccinimide was changed to 22 g. The bromination degree of the obtained modified polyphenylene ether was １ As a result of measurement by 1H-NMR, it was found that the modification rate was 30 mol% by the above-described method.

[0151] (Modified PPE-3-3) The operation was carried out in the same manner as in modified PPE-3-1 except that N-bromosuccinimide was changed to 31 g. The bromination degree of the obtained modified polyphenylene ether was １ As a result of measurement by 1H-NMR, it was found that the modification rate was 40 mol% by the above-described method.

[0152] (Modified PPE-3-4) The operation was carried out in the same manner as in modified PPE-3-1 except that N-bromosuccinimide was changed to 41 g. The bromination degree of the obtained modified polyphenylene ether was １ As a result of measurement by 1H-NMR, it was found that the modification rate was 50 mol% by the above-described method.

[0153] (Modified PPE-3-5) The operation was carried out in the same manner as in Modified PPE-3-1, except that N-bromosuccinimide was used in an amount of 49 g. The bromination degree of the obtained modified polyphenylene ether was １ determined by 1H-NMR measurement. As a result, it was found that the modification rate was 60 mol% by the above-described method.

[0154] (Modified PPE-3-6) The operation was carried out in the same manner as in Modified PPE-3-1, except that N-bromosuccinimide was used in an amount of 58 g. The bromination degree of the obtained modified polyphenylene ether was １ determined by 1H-NMR measurement. As a result, it was found that the modification rate was 70 mol% by the above-described method.

[0155] (Production of Amino Group-Containing Polyphenylene Ether (A)) (Amino Group-Containing PPE-1-1) 100 g of Modified PPE-1-1 was dissolved in 1.0 L of N,N-dimethylformamide in a 2-L four-necked flask purged with argon, and 500 g of ethylenediamine was added as an amine compound and stirred. The temperature was raised using an oil bath, and the mixture was heated under reflux at 100 °C for 24 hours, and then the reaction solution was allowed to cool to room temperature. The reaction solution was added to 10 L of ion-exchanged water to precipitate the polymer, and the crude product was recovered by filtration. Further, the recovered crude product was dissolved in 1.0 L of N,N-dimethylformamide, and the solution was added to 10 L of ion-exchanged water for precipitation purification. The precipitate was filtered under reduced pressure and dried under reduced pressure at 50 °C for 24 hours to recover amino group-containing polyphenylene ether (A) as a product. The obtained polymer was dissolved in N,N-dimethylformamide-d ７ and 19F-NMR measurement (ECS400 manufactured by JEOL, frequency: 400 MHz, number of integrations: 512 times, temperature: 25 °C) was carried out using hexafluorobenzene as an internal standard. Since disappearance of the peak derived from the fluorobenzoyl group of the raw material was confirmed, amination was confirmed. Also, by measurement with an infrared spectrophotometer (MIRacle 10 manufactured by Shimadzu), the peak (1240 cm １９ -1) derived from fluorobenzoylated polyphenylene ether disappeared, and the appearance of the peak (1530 cm －１ -1) derived from the amino group was confirmed. －１

[0156] (Amino group-containing PPE-1-2) The procedure was carried out in the same manner as for amino group-containing PPE-1-1, except that modified polyphenylene ether was replaced with modified PPE-1-2 (100 g) and diethylenetriamine (250 g).

[0157] (Amino group-containing PPE-1-3) The procedure was carried out in the same manner as for amino group-containing PPE-1-1, except that the modified polyphenylene ether was replaced with modified PPE-1-2 (100 g) and ethylenediamine (250 g).

[0158] (Amino group-containing PPE-1-4) In a 2 L four-necked flask purged with argon, 30 g of modified PPE-3 was dissolved in 1.0 L of tetrahydrofuran, and 3 g of osnium-carbon and 180 g of hydrazine monohydrate were added and stirred. The mixture was heated in an oil bath and refluxed at 75°C for 12 hours, after which the reaction solution was allowed to cool to room temperature. Osnium-carbon was removed by filtration, and the filtrate was concentrated under reduced pressure. The concentrate was added to 10 L of deionized water and purified by precipitation. The precipitate was filtered under reduced pressure, and the amino group-containing polyphenylene ether (A) was recovered as the product by vacuum drying at 40°C for 12 hours. The obtained polymer was measured using an infrared spectrophotometer (Shimadzu MIRacle 10) and a peak (1347 cm) derived from nitrobenzoyl polyphenylene ether was identified. －１ 1529cm －１ ) disappears, and the peak derived from the amino group (1598 cm) －１ ) Its appearance was confirmed.

[0159] (Amino group-containing PPE-1-5) The procedure was carried out in the same manner as for amino group-containing PPE-1-4, except that modified PPE-1-4 (30 g), osnium-carbon (5 g), and hydrazine monohydrate (250 g) were used.

[0160] (Amino group-containing PPE-1-8) The procedure was carried out in the same manner as for amino group-containing PPE-1-1, except that the modified polyphenylene ether was modified to modified PPE-1-7 (100 g).

[0161] (Amino group-containing PPE-1-9) The procedure was carried out in the same manner as for amino group-containing PPE-1-1, except that the modified polyphenylene ether was modified PPE-1-2 (100 g) and 4-aminobenzylamine (250 g).

[0162] (Amino group-containing PPE-2-1) In a 2 L four-necked flask purged with argon, 100 g of modified PPE-2-1 was dissolved in 1.0 L of N,N-dimethylformamide, and 500 g of ethylenediamine was added as the amine compound and stirred. The mixture was heated using an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to 10 L of deionized water to precipitate the polymer, and the crude product was recovered by filtration. Furthermore, the recovered crude product was dissolved in 1.0 L of N,N-dimethylformamide, and the solution was added to 10 L of deionized water for precipitation purification. The precipitate was filtered under reduced pressure and dried under reduced pressure at 50°C for 24 hours to recover amino group-containing polyphenylene ether (A) as the product. The obtained polymer was N,N-dimethylformamide-d ７ Dissolve in and use hexafluorobenzene as an internal standard. １９ F-NMR measurements (JEOL ECS400, frequency: 400 MHz, number of integrations: 512, temperature: 25°C) confirmed the disappearance of the peak originating from the fluorobenzoyl group of the raw material, thus confirming amination. In addition, infrared spectrophotometer (Shimadzu MIRacle 10) measurements revealed a peak originating from fluorobenzoyl polyphenylene ether (1240 cm⁻¹). －１ ) disappears, and the peak derived from the amino group (1530 cm) －１ ) Its appearance was confirmed.

[0163] (Amino group-containing PPE-2-2) The procedure was carried out in the same manner as for amino group-containing PPE-2-1, except that the modified polyphenylene ether was modified PPE-2-2 (100 g) and ethylenediamine (250 g).

[0164] (Amino group-containing PPE-2-3) In a 2 L four-necked flask purged with argon, 30 g of modified PPE-2-3 was dissolved in 1.0 L of tetrahydrofuran, and 3 g of osnium-carbon and 180 g of hydrazine monohydrate were added and stirred. The mixture was heated in an oil bath and refluxed at 75°C for 12 hours, after which the reaction solution was allowed to cool to room temperature. Osnium-carbon was removed by filtration, and the filtrate was concentrated under reduced pressure. The concentrate was added to 10 L of deionized water and purified by precipitation. The precipitate was filtered under reduced pressure, and the amino group-containing polyphenylene ether (A) was recovered as the product by drying under reduced pressure at 40°C for 12 hours. The obtained polymer was measured using an infrared spectrophotometer (Shimadzu MIRacle 10) and a peak (1347 cm) derived from nitrobenzoyl polyphenylene ether was identified. －１ 1529cm －１ ) disappears, and the peak derived from the amino group (1598 cm) －１ ) Its appearance was confirmed.

[0165] (Amino group-containing PPE-2-4) Modified PPE-4 (30 g), osnium-carbon (5 g), and hydrazine monohydrate (250 g) were used, and the procedure was carried out in the same manner as for amino group-containing PPE-2-3.

[0166] (Amino group-containing PPE-2-5) The procedure was carried out in the same manner as for amino group-containing PPE-2-1, except that the modified polyphenylene ether was modified PPE-2-2 (100 g) and 4-aminobenzylamine (250 g).

[0167] (Amino group-containing PPE-2-6) The procedure was carried out in the same manner as for amino group-containing PPE-2-1, except that the modified polyphenylene ether was modified to PPE-2-5 (100 g).

[0168] (Amino group-containing PPE-3-1) In a 2 L four-necked flask purged with argon, 40 g of modified PPE-3-1 was dissolved in 250 mL of N-methyl-2-pyrrolidone, and 200 g of 4-aminobenzylamine was added as the amine compound and the mixture was stirred. The mixture was heated in an oil bath and incubated at 100°C for 24 hours under reflux, after which the reaction solution was allowed to cool to room temperature. The reaction solution was added to 1 L of deionized water to precipitate the polymer, and the crude product was recovered by filtration. The recovered crude product was then dissolved in 250 mL of N,N-dimethylformamide, and the solution was added to 1 L of methanol for precipitation and purification. The precipitate was filtered under reduced pressure, and the amino group-containing polyphenylene ether was recovered as the product by vacuum drying at 50°C for 24 hours. The nitrogen content (%) of the obtained amino group-containing polyphenylene ether was determined by the total nitrogen measurement method, and the result was 3.8% by the method described above. Furthermore, the nitrogen content (%) / number-average molecular weight (Mn) was 0.0026.

[0169] (Amino group-containing PPE-3-2 to 3-4, 3-6 to 3-7) The same procedure as for amino group-containing PPE-3-1 was performed, except that the type of modified PPE was changed as shown in Table 1, to obtain amino group-containing PPE-3-2 to 3-4, 3-6 to 3-7.

[0170] (Amino group-containing PPE-3-5) The same procedure as for amino group-containing PPE-3-1 was carried out, except that ethylenediamine (200 g) was added as the amine compound, to obtain amino group-containing PPE-3-5.

[0171] Table 1 shows examples of the production of amino group-containing polyphenylene ethers. １ ¹H-NMR confirmed the absence of a 4.5-5.0 ppm peak originating from alcoholic hydroxyl groups.

[0172] (Liquid amine compounds) Polyoxypropylenediamine: (Manufactured by Tokyo Chemical Industry Co., Ltd., Mw = 230) Tetraethylenepentamine: (Merck KGaA, Mw = 189) 4,4'-diamino-3,3'-diethyldiphenylmethane (Manufactured by Tokyo Chemical Industry Co., Ltd., Mw = 226) Ethylenediamine: (Manufactured by Tokyo Chemical Industry Co., Ltd., Mw = 60)

[0173] (Thermosetting resins) -Epoxy resins- jER828: (Manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent: approx. 190 g / eq) NC-3000L: (Manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin, epoxy equivalent: approx. 272 ​​g / eq) HP4700: (Manufactured by DIC Corporation, naphthalene type tetrafunctional epoxy resin, epoxy equivalent: 162 g / eq) -Maleimide resins- BMI-5100: (Manufactured by Yamato Kasei Co., Ltd.)

[0174] (Compounds other than amino group-containing polyphenylene ether (A)) HF-1M: (Manufactured by Meiwa Chemicals, phenol novolac resin, hydroxyl group equivalent: approx. 106 g / eq) SA90: (Manufactured by SABIC Innovative Plastics, bifunctional polyphenylene ether resin, hydroxyl group equivalent: approx. 789 g / eq) 4,4'-diaminodiphenylmethane: (Manufactured by Tokyo Chemical Industries, aromatic amine compound, amino group equivalent: 99 g / eq)

[0175] (Curing accelerator) 2E4MZ: (Manufactured by Shikoku Chemicals Co., Ltd., 2-ethyl-4-imidazole)

[0176] Using the amino group-containing polyphenylene ether (A) obtained by the method described above, and compounds other than amino group-containing polyphenylene ether (A), various epoxy resins and curing accelerators were blended in the proportions (parts by mass) shown in Tables 2 and 3, dissolved in dimethylformamide, and cured films were prepared using a hot air dryer under conditions of 80°C for 2 hours and 200°C for 4 hours. The results of the physical property measurements of the obtained cured products are shown in Tables 2 and 3. In Examples 1-1 to 1-11, Examples 3-1 to 3-8, and Comparative Examples 1-5 to 1-6, the mass ratio was adjusted so that the molar ratio of epoxy resin to amino group-containing polyphenylene ether (A) or other compounds was 1:1. In Comparative Examples 1-1 to 1-2, cured products for which physical property measurements could be performed could not be obtained with a molar ratio of epoxy resin to amino group-containing polyphenylene ether (A) or other compounds of 1:1, so in Comparative Examples 1-3 to 1-4, cured products were prepared with a mass ratio of epoxy resin to amino group-containing polyphenylene ether (A) or other compounds of 1:1.

[0177]

[0178]

[0179] As shown in Tables 2 and 3, in Examples 1-1 to 1-11 and Examples 3-1 to 3-8, the cured products obtained from the compositions of this embodiment were found to exhibit high heat resistance and low moisture absorption. On the other hand, in Comparative Examples 1-3 to 1-4, the heat resistance was low, and in Comparative Examples 1-5 to 1-6, both the heat resistance and moisture absorption rate were insufficient. In each resin composition of Examples 1-5 to 1-7 and 1-10, silica (S-CO: molten spherical silica (Micron Corporation), average particle size 20 μm, specific surface area 1.7 m²) was added in 100 parts by weight. ２ For resin compositions to which 10 parts by mass, 25 parts by mass, 100 parts by mass, 300 parts by mass, and 400 parts by mass of ( / g) were added, it was confirmed that the Tg and water absorption rate of the resin components were maintained in the same manner as the results in Table 2.

[0180] (Examples 2-1 to 2-10, Example 3-10, Comparative Example 2-1) The amino group-containing polyphenylene ether (A) and liquid amine compound obtained in the production examples were blended in the proportions (parts by mass) shown in Tables 4 and 5, and the solubility of ethylenediamine was evaluated.

[0181]

[0182]

[0183] As shown in Tables 4 and 5, in Examples 2-1 to 2-10 and Example 3-10, the curing agent obtained from the composition of this embodiment showed solubility in ethylenediamine. On the other hand, in Comparative Example 2-1, it did not show solubility in ethylenediamine and could not be liquefied.

[0184] (Examples 2-11 to 2-20, Example 3-11, Comparative Examples 2-2 to 2-5) The amino group-containing polyphenylene ether (A), liquid amine compound, and epoxy resin obtained in the production example were blended in the proportions (parts by mass) shown in Tables 6 and 7, dissolved in dimethylformamide, and a film-like cured product was prepared using a hot air dryer under conditions of 80°C for 2 hours and 200°C for 4 hours. The results of the physical property measurements of the obtained cured products are shown in Tables 6 and 7. In Comparative Example 2-5, the unmodified PPE-2-2 did not dissolve in dimethylformamide, so it was dissolved in toluene to prepare the cured product.

[0185]

[0186]

[0187] As shown in Tables 6 and 7, in Examples 2-11 to 2-20 and Example 3-11, the cured products obtained from the curable composition of this embodiment were found to exhibit high heat resistance and low moisture absorption. On the other hand, in Comparative Examples 2-2 to 2-4, it was found that the heat resistance was low and the moisture absorption rate was high. In Comparative Example 2-5, the curability was low, and therefore no cured product could be obtained. 100 parts by weight of each resin composition in Examples 2-16, 2-17, and 2-19 were used, and silica (S-CO: molten spherical silica (Micron Corporation), average particle size 20 μm, specific surface area 1.7 m²) was used. ２ For resin compositions to which 10 parts by mass, 25 parts by mass, 100 parts by mass, 300 parts by mass, and 400 parts by mass of ( / g) were added, it was confirmed that the Tg and water absorption rate of the resin components were maintained in the same manner as the results in Table 6.

Claims

1. A mixture comprising a compound having an active hydrogen group and a compound that reacts with the compound having the active hydrogen group, wherein the compound having the active hydrogen group contains an amino group-containing polyphenylene ether (A) having a component represented by the following general formula (a). (In formula (a), R １ ~R ４ Each independently contains a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, a cyano group, or an amino group represented by the following general formulas (b), (c), or (d), R １ ~R ４ At least one of these structures contains the aforementioned amino group. (In formulas (b), (c), and (d), X is an alkylene group, an arylene group containing a divalent electron-withdrawing group, or an alkylene group containing a divalent electron-withdrawing group, and Y is a structure that independently contains either a primary amino group or a secondary amino group.) 2. The mixture according to claim 1, wherein the compound that reacts with the compound having the active hydrogen group is a curable resin.

3. The mixture according to claim 1, wherein the compound having the active hydrogen group is a curing agent.

4. A curing agent comprising an amino group-containing polyphenylene ether (A) containing the components shown in the following general formula (a), characterized by reacting with a compound that reacts with a compound having an active hydrogen group. (In formula (a), R １ ~R ４ Each independently contains a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, a cyano group, or an amino group represented by the following general formulas (b), (c), or (d), R １ ~R ４ At least one of these structures contains the aforementioned amino group. (In formulas (b), (c), and (d), X is an alkylene group, an arylene group containing a divalent electron-withdrawing group, or an alkylene group containing a divalent electron-withdrawing group, and Y is a structure that independently contains either a primary amino group or a secondary amino group.) 5. The curing agent according to claim 4, which is a liquid.

6. The curing agent according to claim 5, further comprising a liquid amine compound or a liquid phenol compound.

7. A method for producing a cured product, characterized by comprising the step of mixing the curing agent described in claim 4 with a curable resin and curing the mixture.

8. A curable composition comprising an amino group-containing polyphenylene ether (A) containing a constituent represented by the following general formula (a) and a curable resin. (In formula (a), R １ ~R ４ are each independently a hydrogen atom, a halogen atom, an alkyl group, a fluorinated alkyl group, an allyl group, an aryl group, a cyano group, or a structure containing an amino group represented by the following general formula (b), (c) or (d), and at least one of R １ ~R ４ is a structure containing the amino group.) (In formulas (b), (c), (d), X is an alkylene group, an arylene group containing a divalent electron-withdrawing group, or an alkylene group containing a divalent electron-withdrawing group, and Y is each independently a structure containing a primary amino group or a secondary amino group.) 9. The curable composition according to claim 8, wherein the nitrogen content of the amino group-containing polyphenylene ether (A) is 3% by mass or more and 32% by mass or less.

10. The curable composition according to claim 9, wherein the curable resin is epoxy resin (B).

11. The curable composition according to claim 10, wherein the epoxy group equivalent of the epoxy resin (B) is 100 to 1000 g / eq.

12. The curable composition according to claim 8, further comprising an inorganic filler.

13. A method for producing a cured product, characterized by comprising a step of curing the curable composition described in claim 8.

14. A prepreg characterized by comprising the curable composition of claim 8.

15. A semiconductor encapsulant characterized by comprising the curable composition of claim 8.

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