Dihydrooxaphosphaphenanthrene derivative serving as flame retardant

Abstract

The purpose of the present invention is to provide a novel flame retardant and a flame-retardant resin composition containing the flame retardant. The present invention relates to the use of a compound represented by general formula (1) or a salt thereof as a flame retardant, said compound being characterized by having a triazine ring and a dihydrooxaphosphaphenanthrene structure in each molecule. (The symbols in the formulas are as defined in the description.)

Description

Dihydrooxaphosphaphenanthrene derivatives as flame retardants.

[0001] The present invention relates to the use of novel 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter also referred to as "HCA") derivatives having a triazine ring in the molecule as flame retardants.

[0002] Synthetic resins are widely used as molded articles, films, fibers, and coating agents due to their excellent moldability, mechanical properties, appearance, and other characteristics. Since synthetic resins are generally flammable, flame retardant treatment is required in many applications, and flame retardants are used to impart flame retardancy. Known examples of such flame retardants include halogen compounds, antimony compounds, inorganic hydroxides, organic phosphorus compounds, and organic nitrogen compounds.

[0003] These flame retardants may be used alone, but some combinations show a synergistic effect when used in combination. For example, it is known that the combination of a halogen-based compound and antimony trioxide, or the combination of an organic phosphorus compound and an organic nitrogen compound, etc., shows a high flame retardant effect.

[0004] However, halogen-based flame retardants pose a risk of toxic gases being generated during molding and burning of synthetic resins containing them, and antimony trioxide is being avoided due to the toxicity of the compound itself. Therefore, flame retardant methods that do not use these flame retardants are desired, and research and development of various new flame retardants, such as organophosphate flame retardants, is being conducted worldwide.

[0005] In order for a flame retardant to fully exert its effect on synthetic resins, it is required that it remain stable without decomposition under high-temperature molding and polymerization conditions, or up to the combustion initiation temperature, and that it does not volatilize. Therefore, flame retardants must not only have excellent thermal stability, but also be devised to prevent volatilization by polymerizing them together with the resin monomer in the case of reactive flame retardants with reactive functional groups, or by increasing the molecular weight of the additive flame retardant itself.

[0006] An object of the present invention is to provide an HCA derivative that exhibits a high flame retardant effect, a method for producing the same, and a flame retardant resin composition containing the same.

[0007] The present inventors have conducted extensive research into the possibility that HCA derivatives having a triazine ring in the molecule may exhibit high flame retardancy, and as a result, have succeeded in synthesizing a compound represented by the following general formula (1), which is a novel HCA derivative with excellent thermal stability, and have found that the problems of volatility, sublimation, and heat resistance are resolved, and that the synergistic effect of nitrogen and phosphorus results in high flame retardancy.

[0008] The present invention is as follows: [1] A compound represented by the following general formula (1):

[0009]

[0010] (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , and R ６ each independently represents a hydrogen atom; an alkyl group which may be substituted by one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group which may be substituted; or R ３ and R ５ , and / or R ４ and R ６ [2] A flame retardant containing a compound represented by the following general formula (1): １is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ２ is a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ３ is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ４is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ５ is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; and R ６ is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or ３ and R ５, and / or R ４ and R ６ are each independently bonded to each other to form a ring group together with the nitrogen atom to which they are bonded. １ is a phenyl group, a tolyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a vanillyl group, a nitrophenyl group, a carboxyphenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl group, or a cyclohexyl group, and R ２ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a phenyl group, a tolyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group; R ３ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group, and R ４is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group, and R ５ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group, and R ６ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group, or R ３ and R ５ , and / or R ４ and R ６are each independently bonded to each other to form, together with the nitrogen atom to which they are bonded, a pyrrolyl group, an indolinyl group, an imidazolyl group, a benzimidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a carbazolyl group, a piperidyl group, a morpholinyl group, or a phenothiazinyl group. １ is a phenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a cyclohexyl group, and R ２ is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a hydroxymethyl group, or a 2-hydroxyethyl group, and R ３ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, and R ４ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, and R ５ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, and R ６ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, or R ３ and R ５ , and / or R ４ and R ６are each independently bonded to each other to form, together with the nitrogen atom to which they are bonded, a benzimidazolyl group, a benzotriazolyl group, a carbazolyl group, or a phenothiazinyl group. [5] A flame-retardant resin composition containing the flame retardant and a resin according to any one of [1] to [4] above. [6] The flame-retardant resin composition according to [5] above, wherein the resin is a thermoplastic resin or a thermosetting resin. [7] The flame-retardant resin composition according to [5] or [6] above, which contains 0.1 to 400 parts by mass of the flame retardant per 100 parts by mass of the resin. [8] A molded article of the flame-retardant resin composition according to any one of [5] to [7] above.

[0011] According to the present invention, a flame-retardant resin composition can be provided by incorporating the HCA derivative into one or more resins such as thermoplastic resins and thermosetting resins.

[0012] IR chart of the compound synthesized in Example 1 (compound of formula (9)) IR ​​chart of the compound synthesized in Example 2 (compound of formula (10)) IR ​​chart of the compound synthesized in Example 3 (compound of formula (11)) IR ​​chart of the compound synthesized in Example 4 (compound of formula (12)) IR ​​chart of the compound synthesized in Example 5 (compound of formula (13)) IR ​​chart of the compound synthesized in Example 6 (compound of formula (14)) IR ​​chart of the compound synthesized in Example 7 (compound of formula (15)) IR ​​chart of the compound synthesized in Example 8 (compound of formula (16)) IR ​​chart of the compound synthesized in Example 9 (compound of formula (17)) IR ​​chart of the compound synthesized in Example 10 (compound of formula (18))

[0013] In this specification, a compound represented by general formula (1) may be referred to as a "compound of formula (1)," and compounds represented by general formulas (2) to (19) may be referred to as a "compound of formula (2)" to a "compound of formula (19)," respectively.

[0014] In the present specification, examples of salts of the compound of formula (1) include salts with inorganic acids, salts with organic acids, salts with inorganic bases, salts with organic bases, salts with amino acids, and the like.

[0015] Examples of salts with inorganic acids include salts with hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrobromic acid, etc. Examples of salts with organic acids include salts with oxalic acid, maleic acid, citric acid, fumaric acid, lactic acid, malic acid, succinic acid, tartaric acid, acetic acid, trifluoroacetic acid, gluconic acid, ascorbic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc. Examples of salts with inorganic bases include sodium salts, potassium salts, calcium salts, magnesium salts, ammonium salts, etc. Examples of salts with organic bases include salts with methylamine, diethylamine, trimethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, tris(hydroxymethyl)methylamine, dicyclohexylamine, N,N'-dibenzylethylenediamine, guanidine, pyridine, picoline, choline, cinchonine, meglumine, etc. Examples of salts with amino acids include salts with lysine, arginine, aspartic acid, glutamic acid, etc. The salt of the compound represented by general formula (1) of the present invention is preferably a salt with an inorganic acid or an organic acid.

[0016] In this specification, the term "alkyl group" refers to a linear or branched alkyl group having one or more carbon atoms, and an alicyclic alkyl group having three or more carbon atoms (for example, a cycloalkyl group, an adamantyl group). When there is no particular limitation on the range of the carbon atoms, preferred examples include linear or branched alkyl groups having 1 to 10 carbon atoms, and alicyclic alkyl groups having 3 to 8 carbon atoms (for example, a cycloalkyl group (e.g., a cyclohexyl group, etc.)).

[0017] In this specification, "optionally substituted" means unsubstituted or substituted with a specific substituent at any substitutable position (any hydrogen atom is replaced with a substituent). The "substituent" is not particularly limited, but when no substituent is particularly specified, it means that the group may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group. The number of substituents is not particularly limited as long as it is a substitutable number, but is usually 1 to 5, preferably 1 to 3. When multiple substituents are present, the respective substituents may be the same or different.

[0018] In this specification, the term "aldehyde" is not particularly limited as long as it is a compound having a formyl group (-CHO). Suitable aldehydes include compounds of the following formula (3):

[0019]

[0020] (In the formula, R １ has the same meaning as above.)

[0021] In the present specification, the term "primary amines" refers to amines having an amino group (-NH ２ There are no particular limitations on the primary amines as long as they have the formula (4).

[0022]

[0023] (In the formula, R ２ has the same meaning as above.)

[0024] In the present specification, the term "amines" refers to, but is not limited to, primary amines, secondary amines, nitrogen-containing heterocycles (cyclic amines), etc. Suitable amines include compounds of the following formula (6) and formula (8). Specific examples of the nitrogen-containing heterocycle include rings derived from the "nitrogen-containing heterocyclic group" described below.

[0025] In this specification, the term "flame-retardant resin composition" refers to a flame-retardant composition containing a flame retardant containing the HCA derivative and one or more resins such as thermoplastic resins and thermosetting resins.

[0026] In this specification, "flame retardant" means that a substance is difficult to ignite, and even if it ignites and combustion continues, the burning rate is very slow or the substance then self-extinguishes.

[0027] The thermoplastic resin is preferably at least one selected from the group consisting of polyolefin resin, polystyrene resin, foamed polystyrene resin, acrylonitrile-styrene resin (AS resin), acrylonitrile-butadiene-styrene resin (ABS resin), methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), acrylonitrile-acrylic rubber-styrene resin (AAS resin), acrylic resin, polyphenylene sulfide resin, polyimide resin, polyether ether ketone resin, polysulfone resin, polyarylate resin, polyether ketone resin, polyether nitrile resin, polythioether sulfone resin, polyether sulfone resin, polybenzimidazole resin, polycarbodiimide resin, polyamide imide resin, polyether imide resin, polyamide resin, liquid crystal polymer, polyurethane resin, polycarbonate resin, polyester resin, vinyl chloride resin, polyphenylene ether resin, and alloy resins thereof, The thermosetting resin is preferably at least one selected from the group consisting of polyurethane resin, phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, diallyl phthalate resin, bismaleimide triazine resin, and modified polyphenylene ether resin.

[0028] (HCA Derivative of the Present Invention) The novel HCA derivative of the present invention is a compound of the following formula (1) or a salt thereof.

[0029]

[0030] Preferred embodiments of each group are as follows: １represents a hydrogen atom; an optionally substituted alkyl group (preferably an alkyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group); or an optionally substituted aryl group.

[0031] R １is preferably a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group, More preferred are phenyl groups, tolyl groups (e.g., 2-tolyl, 3-tolyl, 4-tolyl), vinylphenyl groups (e.g., 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl), hydroxyphenyl groups (e.g., 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 4-hydroxy-3-methoxyphenyl), vanillyl groups, nitrophenyl groups (e.g., 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl), carboxyphenyl groups (e.g., 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl), chlorophenyl groups (e.g., 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl), bromophenyl groups (e.g., 2-bromophenyl, 3-bromophenyl, 4-bromophenyl), 1-naphthyl groups, 2-naphthyl groups, biphenyl groups, and cyclohexyl groups. Particularly preferred are a phenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a cyclohexyl group.

[0032] R ２represents a hydrogen atom; an optionally substituted alkyl group (preferably an alkyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group); or an optionally substituted aryl group.

[0033] R ２is preferably a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group, More preferably, it is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a phenyl group, a tolyl group (e.g., 2-tolyl, 3-tolyl, 4-tolyl), a vinylphenyl group (e.g., 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl), a hydroxyphenyl group (e.g., 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 4-hydroxy-3-methoxyphenyl), a carboxyphenyl group (e.g., 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl), a nitrophenyl group (e.g., 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl), a chlorophenyl group (e.g., 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl), a bromophenyl group (e.g., 2-bromophenyl, 3-bromophenyl, 4-bromophenyl), a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group. More preferred are a phenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a hydroxymethyl group, or a 2-hydroxyethyl group, and particularly preferred are a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a hydroxymethyl group, or a 2-hydroxyethyl group.

[0034] R ３represents a hydrogen atom; an optionally substituted alkyl group (preferably an alkyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group); or an optionally substituted aryl group.

[0035] R ３is preferably a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group, More preferably, it is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group (e.g., 2-tolyl, 3-tolyl, 4-tolyl), a benzyl group, a vinylphenyl group (e.g., 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl), a hydroxyphenyl group (e.g., 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 4-hydroxy-3-methoxyphenyl), a carboxyphenyl group (e.g., 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl), a nitrophenyl group (e.g., 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl), a chlorophenyl group (e.g., 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl), a bromophenyl group (e.g., 2-bromophenyl, 3-bromophenyl, 4-bromophenyl), a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group. Particularly preferred are a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group.

[0036] R ４represents a hydrogen atom; an optionally substituted alkyl group (preferably an alkyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group); or an optionally substituted aryl group.

[0037] R ４is preferably a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group, More preferably, it is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group (e.g., 2-tolyl, 3-tolyl, 4-tolyl), a benzyl group, a vinylphenyl group (e.g., 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl), a hydroxyphenyl group (e.g., 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 4-hydroxy-3-methoxyphenyl), a carboxyphenyl group (e.g., 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl), a nitrophenyl group (e.g., 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl), a chlorophenyl group (e.g., 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl), a bromophenyl group (e.g., 2-bromophenyl, 3-bromophenyl, 4-bromophenyl), a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group. Particularly preferred are a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group.

[0038] R ５represents a hydrogen atom; an optionally substituted alkyl group (preferably an alkyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group); or an optionally substituted aryl group.

[0039] R ５is preferably a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group, More preferably, it is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group (e.g., 2-tolyl, 3-tolyl, 4-tolyl), a benzyl group, a vinylphenyl group (e.g., 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl), a hydroxyphenyl group (e.g., 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 4-hydroxy-3-methoxyphenyl), a carboxyphenyl group (e.g., 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl), a nitrophenyl group (e.g., 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl), a chlorophenyl group (e.g., 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl), a bromophenyl group (e.g., 2-bromophenyl, 3-bromophenyl, 4-bromophenyl), a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group. Particularly preferred are a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group.

[0040] R ６represents a hydrogen atom; an optionally substituted alkyl group (preferably an alkyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group); or an optionally substituted aryl group.

[0041] R ６is preferably a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group, More preferably, it is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group (e.g., 2-tolyl, 3-tolyl, 4-tolyl), a benzyl group, a vinylphenyl group (e.g., 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl), a hydroxyphenyl group (e.g., 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 4-hydroxy-3-methoxyphenyl), a carboxyphenyl group (e.g., 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl), a nitrophenyl group (e.g., 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl), a chlorophenyl group (e.g., 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl), a bromophenyl group (e.g., 2-bromophenyl, 3-bromophenyl, 4-bromophenyl), a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group. Particularly preferred are a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group.

[0042] R ３ and R ５ , and / or R ４ and R ６may each independently be bonded to each other to form a ring group together with the nitrogen atom to which they are bonded.

[0043] R ３ and R ５ , and / or R ４ and R ６ However, the ring group formed by bonding to each other independently together with the nitrogen atom to which they are bonded is a nitrogen-containing heterocyclic group, and examples thereof include (i) an aromatic heterocyclic group, (ii) a non-aromatic heterocyclic group, (iii) a 6- to 10-membered bridged cyclic non-aromatic heterocyclic group, and (iv) a 6- to 12-membered spirocyclic non-aromatic heterocyclic group, each of which may contain, as ring-constituting atoms, 1 to 4 heteroatoms selected from a nitrogen atom, a sulfur atom, and an oxygen atom in addition to a nitrogen atom and a carbon atom.

[0044] Examples of the "aromatic heterocyclic group" include 5- to 14-membered aromatic heterocyclic groups which may contain, as ring-constituting atoms, a nitrogen atom and 1 to 4 heteroatoms selected from a nitrogen atom, a sulfur atom, and an oxygen atom in addition to carbon atoms.

[0045] Specific examples of the "aromatic heterocyclic group" include 5- or 6-membered monocyclic aromatic heterocyclic groups such as pyrrolyl, imidazolyl, pyrazolyl, triazolyl, and tetrazolyl; and 8- to 14-membered fused aromatic heterocyclic groups (fused polycyclic (preferably bi- or tricyclic) aromatic heterocyclic groups) such as benzimidazolyl, benzotriazolyl, imidazopyridyl, pyrrolopyridyl, pyrazolopyridyl, imidazopyrazinyl, imidazopyrimidinyl, pyrrolopyrimidinyl, pyrazolopyrimidinyl, pyrazolotriazinyl, indolyl, isoindolyl, 1H-indazolyl, purinyl, carbazolyl, β-carbolinyl, phenanthridinyl, phenothiazinyl, and phenoxazinyl.

[0046] Examples of the "non-aromatic heterocyclic group" include 3- to 14-membered non-aromatic heterocyclic groups containing, as ring-constituting atoms, a nitrogen atom, 1 to 4 heteroatoms selected from a nitrogen atom, a sulfur atom, and an oxygen atom in addition to carbon atoms.

[0047] Specific examples of the "non-aromatic heterocyclic group" include 3- to 10-membered monocyclic non-aromatic heterocyclic groups (preferably 5- to 8-membered monocyclic non-aromatic heterocyclic groups) such as aziridinyl, azetidinyl, pyrrolinyl, pyrrolidinyl, imidazolinyl, imidazolidinyl, oxazolinyl, oxazolidinyl, pyrazolinyl, pyrazolidinyl, thiazolinyl, thiazolidinyl, tetrahydroisothiazolyl, tetrahydrooxazolyl, tetrahydroisoxazolyl, piperidyl, piperazinyl, tetrahydropyridyl, dihydropyridyl, tetrahydropyrimidinyl, tetrahydropyridazinyl, morpholinyl, thiomorpholinyl, azepanyl, diazepanyl, azepinyl, azocanyl, and diazocanyl; Tetrahydrotriazolopyridyl, tetrahydrotriazolopyrazinyl, tetrahydropyrazolopyrazinyl, dihydropyrazolopyrrolyl, tetrahydropyrazolopyridyl, tetrahydroimidazolopyridyl, dihydroimidazolopyridyl, dihydroimidazolopyrrolyl, tetrahydroimidazolopyrazinyl, dihydropyrimidopyrrolyl, dihydropyridopyrrolyl, tetrahydropyridopyridyl, tetrahydrooxazolopyrazinyl, tetrahydropyridopyridyl, tetrahydrotriazolodiazepinyl, octahydro-1,4-oxazinopyrazinyl, dihydrobenzimidazolyl, dihydrobenzoxazolyl, dihydrobenzothiazolyl, dihydrobenzisothiazolyl Examples of the fused non-aromatic heterocyclic group include 9- to 14-membered fused non-aromatic heterocyclic groups (fused polycyclic (preferably bicyclic) non-aromatic heterocyclic groups) such as zolyl, tetrahydroisoquinolyl, tetrahydroquinolyl, 4H-quinolidinyl, indolinyl, isoindolinyl, tetrahydrobenzoazepinyl, tetrahydroquinoxalinyl, tetrahydrophenanthridinyl, hexahydrophenothiazinyl, hexahydrophenoxazinyl, tetrahydrophthalazinyl, tetrahydronaphthyridinyl, tetrahydroquinazolinyl, tetrahydrocinnolinyl, tetrahydrocarbazolyl, tetrahydro-β-carbolinyl, tetrahydroacridinyl, tetrahydrophenazinyl, and octahydroisoquinolyl.

[0048] Specific examples of the "6- to 10-membered bridged non-aromatic heterocyclic group" include 3,8-diazabicyclo[3.2.1]octyl, 2,5-diazabicyclo[2.2.2]octyl, 7-azabicyclo[2.2.1]heptanyl, quinuclidinyl, and the like.

[0049] Specific examples of the "6- to 12-membered spirocyclic non-aromatic heterocyclic group" include 2,8-diazaspiro[4.5]decyl, 2,7-diazaspiro[3.5]nonyl, 2,6-diazaspiro[3.3]heptyl, and the like.

[0050] R ３ and R ５ , and / or R ４ and R ６ are each independently bonded to each other to form a ring group together with the nitrogen atom to which they are bonded, is preferably a pyrrolyl group, an indolinyl group, an imidazolyl group, a benzimidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a carbazolyl group, an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidyl group, an azepanyl group, a morpholinyl group, a thiomorpholinyl group, or a phenothiazinyl group, more preferably a benzimidazolyl group, a benzotriazolyl group, a carbazolyl group, or a phenothiazinyl group.

[0051] As the compound of formula (1), the following compounds are suitable.

[0052] [Compound (1A)] In the formula (1), R １ , R ２ , R ３ , R ４ , R ５ , and R ６ are each independently a hydrogen atom; an alkyl group which may be substituted by one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group which may be substituted; or R ３ and R ５ , and / or R ４ and R６ are each independently bonded to each other to form a ring group together with the nitrogen atom to which they are attached.

[0053] [Compound (1B)] In the formula (1), R １ is a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ２ is a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ３is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ４ is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ５ is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; and R ６is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or ３ and R ５ , and / or R ４ and R ６ are each independently bonded to each other to form a ring group together with the nitrogen atom to which they are attached.

[0054] [Compound (1C)] In the formula (1), R １ is a phenyl group, a tolyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a vanillyl group, a nitrophenyl group, a carboxyphenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl group, or a cyclohexyl group, and R ２ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a phenyl group, a tolyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group; R ３is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group; R ４ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group; R ５ is a hydrogen atom, and R ６ is a hydrogen atom.

[0055] [Compound (1D)] In the formula (1), R １ is a phenyl group, a tolyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a vanillyl group, a nitrophenyl group, a carboxyphenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl group, or a cyclohexyl group, and R ２is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a phenyl group, a tolyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group; R ３ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group, and R ４ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group, and R ５is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group, and R ６ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group, or R ３ and R ５ , and / or R ４ and R ６ are each independently bonded to each other to form, together with the nitrogen atom to which they are attached, a pyrrolyl group, an indolinyl group, an imidazolyl group, a benzimidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a carbazolyl group, a piperidyl group, a morpholinyl group, or a phenothiazinyl group.

[0056] [Compound (1E)] In the formula (1), R １ is a phenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a cyclohexyl group, and R ２ is a phenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a hydroxymethyl group, or a 2-hydroxyethyl group, and R ３is a phenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, and R ４ is a phenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, and R ５ is a hydrogen atom, and R ６ is a hydrogen atom.

[0057] [Compound (1F)] In the formula (1), R １ is a phenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a cyclohexyl group, and R ２ is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a hydroxymethyl group, or a 2-hydroxyethyl group, and R ３ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, and R ４ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, and R ５ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, and R ６ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, or R３ and R ５ , and / or R ４ and R ６ are each independently bonded to each other to form, together with the nitrogen atom to which they are attached, a benzimidazolyl group, a benzotriazolyl group, a carbazolyl group, or a phenothiazinyl group.

[0058] (Method for producing the HCA derivative of the present invention) The HCA derivative of the present invention (the compound of formula (1) or its salt) can be synthesized by synthesizing a compound represented by general formula (2) through a three-component condensation reaction of HCA, aldehydes, and primary amines, and then reacting the compound with cyanuric chloride and amines.

[0059] As an example of a method for producing the compound of formula (1) or a salt thereof, a representative production method will be described below, but the production method is not limited to these. Unless a specific production method is described, the starting compound can be a commercially available compound that is easily obtained and used, or can be produced according to a method known per se or a method similar thereto.

[0060] First, a compound represented by general formula (2) is obtained by a three-component condensation reaction of HCA, an aldehyde represented by general formula (3), and a primary amine represented by general formula (4) (Step 1). The reaction temperature in this step is 60 to 180°C, and the reaction time is 1 to 24 hours.

[0061]

[0062] (The symbols in the formula have the same meanings as defined above.)

[0063] Next, the compound represented by general formula (2) is reacted with cyanuric chloride in the presence of a base to obtain a compound represented by general formula (5) (Step 2). The reaction in Step 2 is carried out in the presence of an organic or inorganic base. Examples of organic bases include trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, pyridine, 1,8-diazabicyclo[5.5.0]undec-7-ene, and compound (2). Examples of inorganic bases include sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, and potassium tert-butoxide. The reaction temperature in this step is 0 to 120°C, and the reaction time is 1 to 24 hours.

[0064]

[0065] (The symbols in the formula have the same meanings as defined above.)

[0066] Next, a compound represented by general formula (5) is reacted with an amine represented by general formula (6) in the presence of a base to obtain a compound represented by general formula (7) (Step 3). The reaction in Step 3 is carried out in the presence of an organic or inorganic base. Examples of organic bases include trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, pyridine, 1,8-diazabicyclo[5.5.0]undecane-7-ene, and compound (6). Examples of inorganic bases include sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, and potassium tert-butoxide. The reaction temperature in this step is 0 to 120°C, and the reaction time is 1 to 24 hours.

[0067]

[0068] (The symbols in the formula have the same meanings as defined above.)

[0069] Finally, the compound represented by general formula (7) is reacted with an amine represented by general formula (8) in the presence of a base to obtain the HCA derivative represented by general formula (1) (Step 4). The reaction in Step 4 is carried out in the presence of an organic or inorganic base. Examples of organic bases include trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, pyridine, 1,8-diazabicyclo[5.5.0]undecane-7-ene, and compound (8). Examples of inorganic bases include sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, and potassium tert-butoxide. The reaction temperature in this step is 0 to 120°C, and the reaction time is 1 to 24 hours.

[0070]

[0071] (The symbols in the formula have the same meanings as defined above.)

[0072] In each step, the intermediate compound produced may be isolated and purified by a method such as column chromatography, recrystallization, or distillation, or may be used in the next step without isolation.

[0073] (Flame Retardant of the Present Invention) The flame retardant of the present invention is characterized by containing the HCA derivative (the compound of formula (1) or a salt thereof).

[0074] The flame retardant of the present invention may be the HCA derivative (the compound of formula (1) or a salt thereof) used alone, or may be used in combination with other flame retardants as required.

[0075] Examples of other flame retardants include metal hydroxides such as aluminum hydroxide and magnesium hydroxide; HCA and HCA derivatives such as HCA, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ), and 10-[2'-(1',4'-dihydroxynaphthyl)]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA-NQ); phosphate esters such as triphenyl phosphate and tricresyl phosphate; condensed phosphate esters such as bisphenol A bis(diphenyl)phosphate and resorcinol bis(diphenyl)phosphate; phosphazene derivatives; and silicone-based flame retardants.

[0076] The flame retardant of the present invention may be either an additive flame retardant or a reactive flame retardant. Here, the additive flame retardant means a flame retardant that is mixed as an additive with a resin to form a resin composition, while the reactive flame retardant means a flame retardant that exhibits flame retardancy by being incorporated into the resin through polymerization with a monomer component that constitutes the resin.

[0077] (Flame-retardant resin composition of the present invention and molded article thereof) The flame-retardant resin composition of the present invention is characterized by containing a flame retardant containing the HCA derivative (a compound of formula (1) or a salt thereof) and at least one resin such as a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin and the thermosetting resin include the resins described above. These resins may be used alone or in combination of two or more. The resin may also be alloyed.

[0078] The resin used in the present invention can be used regardless of the molecular weight, degree of polymerization, density, softening point, proportion of solvent-insoluble matter, degree of stereoregularity, presence or absence of catalyst residue, types and blending ratios of raw material monomers, type of polymerization catalyst (for example, Ziegler catalyst, metallocene catalyst, etc.), etc.

[0079] The mixing ratio (parts by mass) of the HCA derivative (the compound of formula (1) or a salt thereof) in the flame-retardant resin composition of the present invention is not particularly limited, but when used as an additive flame retardant, the flame retardant is used in an amount of 0.1 to 400 parts by mass, preferably 1 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the resin. When used as a reactive flame retardant, the ratio of the compound of formula (1) or a salt thereof to the total weight of the flame-retardant resin composition can be appropriately determined depending on the purpose.

[0080] The flame-retardant resin composition of the present invention may contain, as needed, a phenolic antioxidant, a phosphite antioxidant, a thioether antioxidant, other antioxidants, a nucleating agent, an ultraviolet absorber, a light stabilizer, a plasticizer, a filler, a fatty acid metal salt, an antistatic agent, a pigment, a dye, etc. These components may be blended in advance with the flame-retardant resin composition of the present invention, or may be blended with the resin.

[0081] The flame-retardant resin composition of the present invention can be molded to obtain molded articles with excellent flame retardancy. The molding method is not particularly limited, and examples thereof include extrusion, calendaring, injection molding, rolling, compression molding, and blow molding, and molded articles of various shapes such as resin plates, sheets, films, and irregular shapes can be produced.

[0082] The flame-retardant resin composition of the present invention and a molded article thereof can be used in a wide range of industrial fields, such as electricity, electronics, and communications, electronics and engineering, agriculture, forestry, and fisheries, mining, construction, food, textiles, clothing, medicine, coal, petroleum, rubber, leather, automobiles, precision instruments, wood, building materials, civil engineering, furniture, printing, and musical instruments. More specifically, the material is used for office supplies such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic organizers, cards, holders, and stationery; home appliances such as office automation equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game consoles, irons, and kotatsu tables; audio-visual equipment such as TVs, VTRs, video cameras, radio cassette players, tape recorders, minidiscs, CD players, speakers, and liquid crystal displays; electrical and electronic components and communication devices such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers, deflection yokes, distribution boards, and clocks; housings (frames, enclosures, covers, exteriors) and parts for office automation equipment; and interior and exterior components for automobiles. Among these, the material is particularly suitable for electronic components such as electric wires and automobile components such as interior and exterior components for automobiles.

[0083] Furthermore, the flame-retardant resin composition of the present invention and its molded article can be used in a wide variety of applications, including seats (padding, upholstery, etc.), belts, ceiling coverings, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulating materials, hand straps, hand strap bands, wire covering materials, electrical insulating materials, paints, coating materials, covering materials, flooring materials, corner walls, carpets, wallpaper, wall covering materials, exterior materials, interior materials, roofing materials, deck materials, wall materials, and pillar materials. It is used for a variety of purposes, including floor boards, fence materials, frames and moldings, window and door profiles, shingles, paneling, terraces, balconies, soundproofing boards, heat insulation boards, window materials, automobiles, hybrid cars, electric cars, vehicles, ships, aircraft, buildings, housing and construction materials, civil engineering materials, clothing, curtains, sheets, plywood, synthetic fiber boards, carpets, entrance mats, sheets, buckets, hoses, containers, glasses, bags, cases, goggles, skis, rackets, tents, musical instruments and other daily necessities, sporting goods, etc.

[0084] The present invention will be described in more detail below with reference to specific examples and test examples, but the present invention is not limited to the examples and test examples shown below.

[0085] (Refractive index nD) A sample was dissolved in 1-bromonaphthalene, and the refractive index of the solution was measured at a temperature of 25°C and a wavelength of 589 nm using a refractometer (ATAGO DR-M2 Abbe refractometer). The refractive index of the solution was used to roughly calculate the refractive index of the compound.

[0086] Example 1: Synthesis of compound of formula (9)

[0087]

[0088] A four-neck flask was charged with 10.6 g of benzaldehyde, 6.1 g of 2-aminoethanol, and 109.6 g of toluene, and the mixture was heated to 120°C and refluxed for 1 hour. The mixture was then cooled to 90°C, 21.6 g of HCA was added, and stirring was continued for 2 hours to complete the reaction. After cooling to room temperature, filtration, washing, and drying were performed to obtain 23.9 g of a white powder. 18.7 g of the resulting white powder, 4.6 g of cyanuric chloride, and 77.0 g of toluene were charged, and the mixture was heated to 80°C over 1 hour. Stirring was continued for 1 hour to complete the reaction, and the precipitate was filtered off while maintaining the temperature. The filtrate was charged to a four-neck flask, and 9.5 g of aniline was added dropwise over 1 hour while maintaining the temperature at 80°C. After stirring for 4 hours, the mixture was cooled to room temperature. The reaction mixture was filtered, washed, and dried to obtain 17.1 g of a pale yellow powder. The resulting pale yellow powder was crystallized using 2-propanol solvent, filtered, washed, and dried to obtain the title compound as a white powder. The refractive index was 1.69. The IR chart is shown in Figure 1.

[0089] Example 2: Synthesis of compound of formula (10)

[0090]

[0091] A four-neck flask was charged with 10.6 g of benzaldehyde, 10.7 g of benzylamine, and 167.8 g of toluene, and the mixture was heated to 120°C and refluxed for 1 hour. The mixture was then cooled to 90°C, 24.8 g of HCA was added, and stirring was continued for 2 hours. After cooling to 60°C, 17.9 g of N,N-diethylaniline was added, followed by 18.4 g of cyanuric chloride, which was added in portions over 2 hours. Stirring was continued for 6 hours to complete the reaction. After cooling to room temperature, the precipitate was filtered off. 32.8 g of N,N-diethylaniline was added to the filtrate. The mixture was then heated to 60°C, and 10.3 g of aniline was added dropwise. The mixture was then heated to 80°C, and 10.3 g of aniline was added dropwise. After stirring at 80°C for 4 hours, 200.0 g of hexane was added, and the mixture was cooled to room temperature. The precipitate was then filtered off. The precipitate was washed with purified water and then dried to obtain 60.3 g of a white powder. The obtained white powder was crystallized using toluene, filtered, washed, and dried to obtain the title compound as a white powder. The refractive index was 1.68. The IR chart is shown in Figure 2.

[0092] Example 3: Synthesis of compound of formula (11)

[0093]

[0094] A four-neck flask was charged with 11.1 g of benzaldehyde, 10.7 g of benzylamine, and 167.8 g of toluene. The mixture was heated to 120°C and refluxed for 1 hour, then cooled to 90°C. 24.8 g of HCA was added and stirring was continued for 2 hours. After cooling the reaction solution to room temperature, 9.2 g of cyanuric chloride was added to the reaction solution. The temperature was raised to 60°C and stirring was continued at that temperature for 6 hours to complete the reaction. After cooling the reaction solution to room temperature, the precipitate was filtered off. The filtrate was concentrated, and the residue was mixed with 170.0 g of hexane. The mixture was then filtered, washed, and dried to obtain 17.8 g of a white powder. The resulting white powder was dispersed in 35.1 g of methanol, stirred for 1 hour, and then filtered, washed, and dried to obtain 9.3 g of a white powder. 0.28 g of the obtained white powder and 1.5 g of toluene were charged and heated to 60°C, after which 0.14 g of 2-aminoethanol was added and the temperature was raised to 80°C to complete the reaction. Subsequently, 2.0 g of hexane was added and mixed well, followed by filtration, washing, and drying to obtain 0.18 g of the title compound as a white powder. The refractive index was 1.66. The IR chart is shown in Figure 3.

[0095] Example 4: Synthesis of compound of formula (12)

[0096]

[0097] A four-neck flask was charged with 32.8 g of 1-naphthaldehyde, 21.4 g of benzylamine, and 46.2 g of toluene, and the mixture was heated to 130°C and refluxed for 1 hour. The mixture was then cooled to 90°C, and 49.7 g of HCA was added and stirred for 2 hours. After cooling to 60°C, 32.8 g of N,N-diethylaniline was added, followed by 36.9 g of cyanuric chloride, which was added in portions over 30 minutes. The reaction was then completed by stirring at the same temperature for 6 hours. 200 g of methanol was added to the reaction mixture, and the mixture was slowly cooled to cause crystallization. The precipitate was then filtered, washed, and dried, yielding 86.6 g of the compound of formula (12A) as a white powder.

[0098]

[0099] A four-neck flask was charged with 30.5 g of the compound of formula (12A), 19.6 g of aniline, and 54.2 g of methanol, and the mixture was heated to 60°C and stirred for 2 hours. The mixture was then slowly cooled to allow crystallization, and the precipitate was filtered, washed, and dried to obtain 34.5 g of the title compound as a white powder. The refractive index was 1.70. The IR chart is shown in Figure 4.

[0100] Example 5: Synthesis of compound of formula (13)

[0101]

[0102] A four-neck flask was charged with 61.2 g of the compound of formula (12A) and 100.9 g of methanol, and 30.7 g of 2-aminoethanol was added dropwise over 1 hour while maintaining the temperature at 50 to 60°C. The temperature was then raised to 70°C and the mixture was stirred for 8 hours. The mixture was then slowly cooled to cause crystallization, and the precipitate was then filtered, washed, and dried to obtain 58.8 g of the title compound as a white powder. The refractive index was 1.68. The IR chart is shown in Figure 5.

[0103] Example 6: Synthesis of compound of formula (14)

[0104]

[0105] A four-neck flask was charged with 30.5 g of the compound of formula (12A) and 81.1 g of toluene, and the temperature was raised to 60°C. While maintaining the same temperature, 34.3 g of 2-anilinoethanol was added dropwise over 1 hour. The reaction mixture was then heated to 70°C and stirred for 12 hours. After cooling to room temperature, unreacted 2-anilinoethanol was removed by washing with water, and the mixture was mixed with hexane, followed by filtration, washing, and drying to obtain 29.4 g of a crude product as a white powder. The resulting crude product was crystallized using isopropyl acetate, followed by filtration, washing, and drying to obtain the title compound as a white powder. The refractive index was 1.67. The IR chart is shown in Figure 6.

[0106] Example 7: Synthesis of compound of formula (15)

[0107]

[0108] A test tube was charged with 0.30 g of the compound of formula (12A), 0.49 g of dibenzylamine, and 1.4 g of methanol, and the mixture was heated to 65°C and stirred for 14 hours. After cooling to room temperature, the precipitate was filtered off, washed with water, filtered, washed, and dried to obtain 0.33 g of the title compound as a white powder. The refractive index was 1.67. The IR chart is shown in Figure 7.

[0109] Example 8: Synthesis of compound of formula (16)

[0110]

[0111] A test tube was charged with 0.30 g of the compound of formula (12A), 0.30 g of benzimidazole, and 1.3 g of toluene, and the mixture was heated to 60°C and stirred for 1 hour, followed by stirring at 80°C for 9 hours. After the reaction solution was cooled to room temperature, the precipitate was filtered off, washed with water, filtered, washed, and dried to obtain 0.25 g of the title compound as a white powder. The IR chart is shown in Figure 8.

[0112] Example 9: Synthesis of compound of formula (17)

[0113]

[0114] The title compound was obtained as a white powder by the same procedure as in Example 7, except that dibenzylamine used in Example 7 was replaced with 3-aminophenol. The IR chart is shown in FIG.

[0115] Example 10: Synthesis of compound of formula (18)

[0116]

[0117] A four-neck flask was charged with 23.6 g of cyclohexanecarboxaldehyde, 21.4 g of benzylamine, and 226.2 g of toluene. The mixture was heated to 120°C and refluxed for 1 hour, then cooled to 90°C. 49.7 g of HCA was added and stirring was continued for 2 hours. After cooling the reaction mixture to 60°C, 32.8 g of N,N-diethylaniline was added, followed by 36.9 g of cyanuric chloride, which was added in portions over 1.5 hours. Stirring was continued at the same temperature for 4 hours to complete the reaction. After cooling the reaction solution to room temperature, the precipitate was filtered off. This precipitate was dispersed in 260 g of methanol, stirred for 1 hour, filtered, washed, and dried to obtain 45.0 g of a white powder. 0.57 g of the resulting white powder, 0.31 g of 2-aminoethanol, and 1.8 g of methanol were charged into a test tube, heated to 60°C, and stirring was continued for 7 hours. After cooling to room temperature, the reaction mixture was mixed with 27.0 g of purified water, filtered, washed, and dried to obtain 0.51 g of the title compound as a white powder. The refractive index was 1.64. The IR chart is shown in Figure 10.

[0118] Example 11: Synthesis of compound of formula (19)

[0119]

[0120] A four-neck flask was charged with 25.7 g of 4-hydroxybenzaldehyde, 23.6 g of benzylamine, and 230.2 g of toluene, and the mixture was heated to 120°C and refluxed for 1 hour. The mixture was then cooled to 90°C, 49.7 g of HCA was added, and stirring was continued for 2 hours. After cooling to room temperature, filtration, washing, and drying were performed to obtain 71.2 g of a white powder. 34.2 g of the obtained white powder, 23.9 g of N,N-diethylaniline, 14.8 g of cyanuric chloride, and 115.1 g of tetrahydrofuran were charged to a four-neck flask, and the mixture was heated to 30°C and stirring was continued for 4 hours. Subsequently, 52.4 g of 3-aminophenol was added, and the mixture was heated to 60°C and stirring was continued for 6 hours. After cooling to room temperature, the mixture was mixed with 1000 g of ethyl acetate, and the precipitate was filtered off. The obtained filtrate was washed with water to remove unreacted 3-aminophenol, concentrated using an evaporator, mixed with 190 g of toluene, stirred for 1 hour, filtered, washed, and dried to obtain 9.2 g of the title compound as a pale ochre powder.

[0121] Test Example 1: (Sample Preparation) A compound of formula (12) (20 parts by mass) was added to NORYL (registered trademark) SA90 resin (80 parts by mass) manufactured by SABIC and kneaded to prepare a resin composition of Example 12. A known flame-retardant compound, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name: HCA-HQ; manufactured by Sanko Co., Ltd.) (9 parts by mass) was added to NORYL (registered trademark) SA90 resin (91 parts by mass) manufactured by SABIC and kneaded to prepare a resin composition of Comparative Example 2. A resin composition of NORYL (registered trademark) SA90 resin (100 parts by mass) manufactured by SABIC was used as Comparative Example 1.

[0122] These resin compositions were subjected to thermogravimetric analysis under a nitrogen gas flow using a Shimadzu TGA-60. The target temperature was set to 450°C, and the temperature was increased at a rate of 90°C / min. After holding for 10 minutes, the residue rate of each sample was measured. In addition, each sample was ignited and burned with a gas burner to evaluate its flammability. The results are shown in Table 1.

[0123]

[0124] According to the results in Table 1, the residual rate of the resin composition in thermogravimetric analysis was higher when the compound of formula (12) was mixed (Example 12) than when SA90 was used alone (Comparative Example 1). This is presumed to be due to the fact that the compound of formula (12) promoted the formation of a charred layer, indicating that the compound of formula (12) functions as a flame retardant. Furthermore, the effect of adding the compound of formula (12) was confirmed in a combustion test.

[0125] Test Example 2: (Sample Preparation) A compound of formula (12) (20 parts by mass) was added to polystyrene resin (80 parts by mass, hereinafter abbreviated as "PS") purchased from Fujifilm Wako Pure Chemical Industries, Ltd., and the mixture was kneaded to prepare a resin composition of Example 13. HCA-HQ (manufactured by Sanko Co., Ltd.) (9 parts by mass) was added to PS (91 parts by mass), and the mixture was kneaded to prepare a resin composition of Comparative Example 4. A resin composition containing PS (100 parts by mass) was used as Comparative Example 3.

[0126] These resin compositions were subjected to thermogravimetric analysis under a nitrogen gas flow using a Shimadzu TGA-60. The target temperature was set to 450°C, and the temperature was increased at a rate of 90°C / min. After holding for 10 minutes, the residue rate of each sample was measured. In addition, each sample was ignited and burned with a gas burner to evaluate its flammability. The results are shown in Table 2.

[0127]

[0128] According to the results in Table 2, the residual rate of the resin composition in thermogravimetric analysis was higher when the compound of formula (12) was mixed (Example 13) than when PS was used alone (Comparative Example 3). This is presumed to be due to the fact that the compound of formula (12) promoted the formation of a char layer, indicating that the compound of formula (12) functions as a flame retardant. Furthermore, the effect of adding the compound of formula (12) was confirmed in a combustion test.

[0129] Test Example 3: A varnish is prepared by uniformly mixing an epoxy resin, a compound of formula (17), triphenylphosphine, dicyandiamide, a polymerization catalyst such as 2-methyl-4-imidazole, aluminum hydroxide, silica powder, and an organic solvent. The varnish is impregnated into a glass cloth and heated to produce a prepreg. This prepreg is then layered, and copper foil is placed on both sides of the prepreg and hot-pressed to obtain a laminate with sufficient flame retardancy.

[0130] Test Example 4: A polyamide resin having sufficient flame retardancy can be obtained by melt-kneading a polyamide resin, a compound of formula (12), and glass fibers.

[0131] Test Example 5: Dimethyl terephthalate, ethylene glycol, and the compound of formula (13) are mixed, and a polymerization catalyst is added to carry out a polymerization reaction, thereby obtaining a polyester resin having sufficient flame retardancy.

[0132] According to the present invention, the novel HCA derivative of the present invention has excellent thermal stability and is expected to be used as a flame retardant exhibiting high flame retardancy due to the synergistic effect of phosphorus and nitrogen. In addition, the novel HCA derivative of the present invention has 0 to 4 reactive functional groups, and can be polymerized with a resin monomer or added to a resin composition containing one or more thermoplastic resins, thermosetting resins, etc. to obtain a flame-retardant resin composition.

[0133] This application is based on Japanese Patent Application No. 2023-130622 filed on August 10, 2023 in Japan, the contents of which are incorporated in their entirety herein.

Claims

1. The following general formula (1): (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , and R ６ each independently represents a hydrogen atom; an alkyl group which may be substituted by one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group which may be substituted; ３ and R ５ , and / or R ４ and R ６ each independently bonds to each other to form a ring group together with the nitrogen atom to which they are bonded, or a salt thereof.

2. In the general formula (1), R １ is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ２ is a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ３ is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ４ is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; ５ is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; and ６ is a hydrogen atom; a linear, branched or alicyclic alkyl group having 1 to 10 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, an aryl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or an aryl group having 6 to 12 carbon atoms which may be substituted with one or more substituents selected from the group consisting of a halogen atom, an alkyl group, a vinyl group, an allyl group, a hydroxy group, an alkoxy group, a carboxy group, a nitro group, a cyano group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfanyl group; or ３ and R ５ , and / or R ４ and R ６ are each independently bonded to each other to form a ring group with the nitrogen atom to which they are attached.

3. In the general formula (1), R １ is a phenyl group, a tolyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a vanillyl group, a nitrophenyl group, a carboxyphenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl group, or a cyclohexyl group; R ２ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a phenyl group, a tolyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group; R ３ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group; R ４ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group; R ５ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group, and R ６ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an adamantyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a phenyl group, a tolyl group, a benzyl group, a vinylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a nitrophenyl group, a chlorophenyl group, a bromophenyl group, a 1-naphthyl group, a 2-naphthyl group, or a biphenyl group, or R ３ and R ５ , and / or R ４ and R ６ are each independently bonded to one another to form, together with the nitrogen atom to which they are bonded, a pyrrolyl group, an indolinyl group, an imidazolyl group, a benzimidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a carbazolyl group, a piperidyl group, a morpholinyl group, or a phenothiazinyl group.

4. In the general formula (1), R １ is a phenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a cyclohexyl group; R ２ is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a hydroxymethyl group, or a 2-hydroxyethyl group; R ３ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group; R ４ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a carboxyphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group; R ５ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, and R ６ is a hydrogen atom, a phenyl group, a benzyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 4-hydroxy-3-methoxyphenyl group, a 2-hydroxyethyl group, or a 3-hydroxypropyl group, or R ３ and R ５ , and / or R ４ and R ６ are each independently bonded to one another to form, together with the nitrogen atom to which they are attached, a benzimidazolyl group, a benzotriazolyl group, a carbazolyl group, or a phenothiazinyl group.

5. A flame-retardant resin composition comprising the flame retardant and a resin according to any one of claims 1 to 4.

6. The flame-retardant resin composition according to claim 5, wherein the resin is a thermoplastic resin or a thermosetting resin.

7. The flame-retardant resin composition according to claim 5, which contains 0.1 to 400 parts by mass of a flame retardant per 100 parts by mass of the resin.

8. A molded article made from the flame-retardant resin composition according to claim 5.