Maleimide compound, maleamic acid compound, curable composition, cured product, electronic device, method for producing maleimide compound and method for producing maleamic acid compound

Abstract

Provided is a maleimide compound having a partial structure represented by -CH(CF3)-. Also provided is a maleamic acid compound having a partial structure represented by -CH(CF3)-. Also provided is a curable compound comprising the maleimide compound or the maleamic acid compound. Also provided is a cured product of the curable compound. Also provided is an electronic device that is provided with the cured product.

Description

Maleimide compound, maleamic acid compound, curable composition, cured product, electronic device, method for producing maleimide compound, and method for producing maleamic acid compound

[0001] The present disclosure relates to a maleimide compound, a maleamic acid compound, a curable composition, a cured product, an electronic device, a method for producing a maleimide compound, and a method for producing a maleamic acid compound.

[0002] In recent years, electronic devices have become smaller, lighter, and more powerful, which has led to a demand for materials with excellent heat resistance. The development of materials with excellent heat resistance is particularly desirable in fields such as printed circuit boards, semiconductor encapsulants, adhesives, and optical materials. The fifth-generation communication system "5G," currently under development, will further increase capacity and speed, creating a growing need for materials with low dielectric constants and low dielectric loss tangents.

[0003] Against this background, the use of maleimide compounds has been investigated as materials with excellent heat resistance and electrical properties. Examples of maleimide compounds that are readily available on the market include 4,4'-diphenylmethane bismaleimide. It is known that the use of curable compositions containing maleimide compounds enables the formation of cured products with excellent heat resistance.

[0004] For example, Patent Document 1 discloses a 1,1,1,3,3,3-hexafluoro-2,2-propanediyl group (hereinafter referred to as "-C(CF ３ ) ２ According to the description in Patent Document 1, a cured product formed using this compound has high heat resistance and excellent electrical properties. However, the raw material -C(CF ３ ) ２ Amine compounds having a - group generally have problems such as high cost.

[0005] Japanese Patent Application Publication No. 2-51529

[0006] According to the findings of the present inventors, conventional maleimide compounds have the problem of low solubility in solvents, and cured products formed using conventional maleimide compounds have room for improvement, for example, in terms of heat resistance.

[0007] An object of the present invention is to provide a maleimide compound which can give a cured product having excellent solvent solubility and heat resistance.

[0008] The present inventors have conducted extensive research to achieve the above object. As a result, they have found that -CH(CF ３ The researchers have succeeded in synthesizing a maleimide compound having a methyl group. They have also discovered that this compound has excellent solvent solubility, and that the cured product of a curable composition containing this compound has excellent heat resistance, making it suitable as a material for manufacturing electronic devices.

[0009] The present invention is as follows.

[0010] 1. -CH(CF ３ 2. A maleimide compound according to 1. above, which is a maleimide compound represented by the following general formula (1): In general formula (1), R １ When a plurality of n's are present, each independently represents a monovalent substituent, and two n's each independently represent an integer of 0 to 4. 3. The maleimide compound according to 2., which is represented by the following general formula (2): In general formula (2), R １ and n are defined as R in general formula (1). １ 4. The maleimide compound according to any one of 1. to 3., which is represented by the following formula (3): 5. The maleimide compound according to any one of 1. to 3., which is represented by the following formula (4): 6. The maleimide compound according to any one of 1. to 3., which is represented by the following formula (5): 7. -CH(CF ３8. A maleamic acid compound according to item 7, which is a maleamic acid compound represented by the following general formula (2-1): In general formula (2-1), R １ When a plurality of n's are present, each independently represents a monovalent substituent, and two n's each independently represent an integer of 0 to 4. 9. The maleamic acid compound according to 8., which is represented by the following general formula (2-2): In general formula (2-2), R １ and n are defined as R １ and n are synonymous with each other. 10. The maleamic acid compound according to any one of 7. to 9., which is represented by the following formula (2-3): 11. The maleamic acid compound according to any one of 7. to 9., which is represented by the following formula (2-4): 12. The maleamic acid compound according to any one of 7. to 9., which is represented by the following formula (2-5): 13. A curable composition comprising the maleimide compound or maleamic acid compound according to any one of 1. to 12. 14. A cured product of the curable composition according to 13. 15. An electronic device comprising the cured product according to 14. 16. A method for producing the maleimide compound according to any one of 1. to 6., comprising a step of reacting an aromatic amine compound represented by the following general formula (1a) with maleic acid or a maleic acid derivative: In general formula (1a), R １ When a plurality of n's are present, each independently represents a monovalent substituent, and two n's each independently represent an integer of 0 to 4. 17. A method for producing a maleamic acid compound according to any one of 7. to 12., comprising a step of reacting an aromatic amine compound represented by the following general formula (1a) with maleic acid or a maleic acid derivative: In general formula (1a), R１ When a plurality of n's are present, each independently represents a monovalent substituent, and two n's each independently represent an integer of 0 to 4. 18. A method for producing a maleimide compound according to any one of 1. to 6., comprising a step of subjecting a maleamic acid compound represented by the following general formula (2-1) to a dehydration ring-closure reaction: In general formula (2-1), R １ When a plurality of n's are present, each independently represents a monovalent substituent, and two n's each independently represent an integer of 0 to 4.

[0011] The maleimide compound of the present invention has excellent solvent solubility. Furthermore, by using the maleimide compound of the present invention, a cured product having excellent heat resistance can be obtained.

[0012] The following describes embodiments of the present invention. The present invention is not limited to the following embodiments, and can be practiced after appropriate modifications based on the ordinary knowledge of those skilled in the art, within the scope of the disclosed subject matter.

[0013] In this specification, unless otherwise specified, the expression "X to Y" in the description of a numerical range means at least X and at most Y. For example, "1 to 5% by mass" means "at least 1% by mass and at most 5% by mass."

[0014] In the description of groups (atomic groups) in this specification, when a notation does not specify whether it is substituted or unsubstituted, it encompasses both those that have no substituents and those that have a substituent. For example, "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). In this specification, the notation "(meth)allyl" represents a concept that encompasses both allyl and methallyl. In chemical formulas in this specification, the notation "Me" represents a methyl group (CH ３ The term "electronic device" as used herein is used to encompass elements, devices, final products, etc. to which electronic engineering technology is applied, such as semiconductor chips, semiconductor elements, printed wiring boards, electric circuit display devices, information and communication terminals, light-emitting diodes, physical batteries, and chemical batteries.

[0015] In this specification, an amic acid means a compound having both an amide bond and a carboxy group in one molecule, but not corresponding to the following maleamic acid. Also, in this specification, maleamic acid means a compound having an amide group derived from maleic acid or its derivative, a cis-type carbon-carbon double bond structure, and a carboxy group in one molecule.

[0016] <Maleimide compound> The maleimide compound of this embodiment has a partial structure represented by -CH(CF ３ ).

[0017] The maleimide compound of this embodiment has good solvent solubility. Why it has good solubility is not necessarily clear, but it is presumed that the "asymmetry" of the partial structure represented by -CH(CF ３ ) is related to the appropriate suppression of the crystallinity of the compound.

[0018] Also, the cured product of the curable composition containing the maleimide compound of this embodiment is excellent in heat resistance. Generally, a methylene group (especially a methylene group connecting two aromatic rings) is easily oxidized. In particular, since a methylene group is easily oxidized at high temperatures, the heat resistance of conventional maleimides containing a methylene group tends to be poor. In contrast, the partial structure represented by -CH(CF ３ ) possessed by the maleimide compound of this embodiment is considered to be difficult to oxidize even at high temperatures. Therefore, it is presumed that the cured product of the curable composition containing the maleimide compound of this embodiment is excellent in heat resistance. Also, although the details are unclear, the cured product formed from the curable composition containing the maleimide compound of this embodiment probably has a tendency for the glass transition temperature to be relatively high due to the appropriate rigidity of the partial structure represented by -CH(CF ３ ). A high glass transition temperature of the cured product usually means that the cured product is difficult to undergo thermal motion. That is, in addition to the above-mentioned "difficult to oxidize", the point of "difficult to undergo thermal motion and having a high glass transition temperature" is also presumed to be one of the reasons why the cured product of the curable composition containing the maleimide compound of this embodiment is excellent in heat resistance.

[0019] Additionally, the cured product of the curable composition containing the maleimide compound of this embodiment tends to have a low dielectric constant. This is because the CF contained in the maleimide compound of this embodiment ３ This is presumably because the polarizability of the C—F bond in the group is small. The low dielectric constant means that the curable composition containing the maleimide compound of this embodiment can be suitably applied to the production of insulating members.

[0020] The maleimide compound of this embodiment will be further described below.

[0021] The maleimide compound of this embodiment is typically a bismaleimide compound. The maleimide compound of this embodiment preferably has a structure represented by general formula (1).

[0022]

[0023] In general formula (1), R １ When a plurality of n's are present, each independently represents a monovalent substituent, and two n's each independently represent an integer of 0 to 4.

[0024] When n is 2 or more, a plurality of R １ may be the same or different, and two or more R １ may be linked to form a saturated or unsaturated, monocyclic or polycyclic ring group having 3 to 10 carbon atoms.

[0025] R １ The monovalent substituent is not limited, and examples thereof include an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, an aryloxy group, an amino group, a cyano group, a nitro group, a silyl group, a hydroxyl group, and a halogen atom.

[0026] The alkyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Among these, n-butyl, s-butyl, isobutyl, t-butyl, n-propyl, i-propyl, ethyl and methyl groups are preferred, with ethyl and methyl groups being particularly preferred.

[0027] The alkoxy group is preferably a linear or branched alkoxy group having 1 to 6 carbon atoms. Among these, n-butoxy, s-butoxy, isobutoxy, t-butoxy, n-propoxy, i-propoxy, ethoxy, and methoxy groups are preferred, with ethoxy and methoxy groups being particularly preferred.

[0028] The alkenyl group is preferably a straight-chain or branched alkenyl group having 2 to 10 carbon atoms. Of these, vinyl, allyl, and 1-butenyl groups are preferred, with vinyl being particularly preferred.

[0029] The alkynyl group is preferably a straight-chain or branched alkynyl group having 2 to 10 carbon atoms. Among these, an ethynyl group and a propargyl group are preferred, and an ethynyl group is particularly preferred.

[0030] The aryl group preferably has 6 to 12 carbon atoms. Among these, a phenyl group and a naphthyl group are preferred, and a phenyl group is particularly preferred.

[0031] The aryloxy group preferably has 6 to 12 carbon atoms. Among these, a phenoxy group and a naphthoxy group are preferred, and a phenoxy group is particularly preferred.

[0032] The silyl group is preferably a trimethylsilyl group, a triethylsilyl group, a trimethoxysilyl group or a triethoxysilyl group, and particularly preferably a trimethylsilyl group.

[0033] Examples of halogen atoms include fluorine atom (F), chlorine atom (Cl), bromine atom (Br) and iodine atom (I). F is particularly preferred.

[0034] The above-mentioned alkyl group, alkoxy group, alkenyl group, alkynyl group, aryl group, and aryloxy group may further have a substituent. That is, any carbon of these groups may be substituted with any number and any combination of, for example, a halogen atom, an alkoxy group, an alkoxycarbonyl group, a carboxyl group protector, an amino group protector, and a hydroxyl group protector. The protecting groups for the carboxyl group, the amino group, and the hydroxyl group are the protecting groups described in Protective Groups in Organic Synthesis, Third Edition, 1999, John Wiley & Sons, Inc., etc.

[0035] Specific examples of the maleimide compound represented by general formula (1) are listed below.

[0036]

[0037]

[0038]

[0039] In the structure represented by the general formula (1), —CH(CF ３ In other words, the maleimide compound of the present embodiment is preferably represented by the following general formula (2):

[0040]

[0041] In general formula (2), R １ and n are defined as R in general formula (1). １ and n.

[0042] In terms of production costs and ease of procurement of raw materials, n is preferably 0. That is, in terms of production costs and ease of procurement of raw materials, a maleimide compound represented by the following formula (3) is preferred.

[0043]

[0044] On the other hand, R １By appropriately selecting R and n, various properties such as heat resistance and electrical properties can be adjusted. From the viewpoint of the balance of various properties, n is, for example, 1 or 2, and R １ is preferably a methyl group. Preferred examples of maleimide compounds in which n is 1 or 2 are shown in the following formulas (4) and (5).

[0045]

[0046] <Maleamic Acid Compound> The maleamic acid compound of the present embodiment is —CH(CF ３ )-.

[0047] The maleamic acid compound of the present embodiment is preferably a bismaleamic acid compound, and more preferably represented by the following general formula (2-1).

[0048]

[0049] In general formula (2-1), R １ and n are defined as R in general formula (1). １ and n are the same as those in the preferred embodiments. When n is 2 or more, R １ may be the same or different, and two or more R １ may be linked to form a saturated or unsaturated, monocyclic or polycyclic ring group having 3 to 10 carbon atoms.

[0050] Specific examples of the maleamic acid compound represented by formula (2-1) are listed below.

[0051]

[0052]

[0053]

[0054] In the structure represented by the general formula (2-1), —CH(CF ３ In other words, a maleamic acid compound that is preferable from the viewpoint of production cost and ease of raw material procurement is represented by the following general formula (2-2):

[0055]

[0056] In general formula (2-2), R １ and n are defined as R １ and n.

[0057] From the viewpoint of production cost and ease of procurement of raw materials, n is preferably 0. That is, a maleamic acid compound that is preferable from the viewpoint of production cost and ease of procurement of raw materials is represented by the following formula (2-3).

[0058]

[0059] On the other hand, R １ By changing R and n, various properties such as heat resistance and electrical properties can be adjusted. From the viewpoint of the balance of various properties, n is, for example, 1 or 2, and R １ is preferably a methyl group. Suitable maleamic acid compounds in which n is 1 or 2 are exemplified by the following formulae (2-4) and (2-5).

[0060]

[0061] <Methods for Producing Various Compounds> (Method for Producing Maleimide Compound [Part 1]) The method for producing the maleimide compound of the present embodiment is not particularly limited. For example, the maleimide compound can be produced by reacting an amine compound with maleic acid or a maleic acid derivative in the presence of a solvent, an acid catalyst, and / or a dehydrating agent.

[0062] Examples of maleic acid or maleic acid derivatives include maleic acid, ester compounds such as dimethyl maleate and diethyl maleate, and maleic anhydride. Of these, maleic anhydride is preferred. The maleic acid derivative is usually used in an amount of 1 to 3 mol, preferably 1 to 2 mol, per mol of amino groups in the aromatic amine compound.

[0063] Examples of solvents used in the reaction include aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, halogen-based solvents such as methylene chloride and 1,2-dichloroethane, ethers such as tetrahydrofuran and tert-butyl methyl ether, esters such as ethyl acetate and n-butyl acetate, amides such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone, nitriles such as acetonitrile and propionitrile, and dimethyl sulfoxide. Among these, aromatic hydrocarbons such as toluene and xylene, halogen-based solvents such as methylene chloride and 1,2-dichloroethane, amides such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone, nitriles such as acetonitrile and propionitrile, and dimethyl sulfoxide are preferred. These reaction solvents can be used alone or in combination. The amount of the reaction solvent used may be 0.05 L (liter) or more per 1 mol of the amine compound, preferably 0.1 to 20 L, and particularly preferably 0.15 to 10 L.

[0064] A step of removing water generated during the reaction from the system may be carried out. The procedure for removing the water generated from the reaction solution is not particularly limited. For example, the water can be removed by azeotropically distilling the generated water with the solvent system in the reaction solution. The generated water can be removed from the reaction system using, for example, a pressure-equalizing dropping funnel equipped with a stopcock, a Dimroth condenser, a Dean-Stark apparatus, or the like.

[0065] The acid catalyst used in the reaction is not particularly limited. Examples include p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, polyphosphoric acid, sulfuric acid, ammonium hydrogen sulfate, and hydrofluoric acid. Among these, p-toluenesulfonic acid and trifluoromethanesulfonic acid are preferred. The amount of the acid catalyst used is usually 0.001 to 1 mol, and preferably 0.01 to 0.3 mol, per 1 mol of amino groups in the amine compound.

[0066] Dehydrating agents that can be used in the reaction include those typically used as dehydrating agents. Examples include acid anhydrides such as acetic anhydride, carbodiimide compounds such as dicyclohexylcarbodiimide, and hexamethyldisilazane. These dehydrating agents can also be used in combination with appropriate additives such as sodium acetate, N-hydroxysuccinimide, and zinc bromide. Among these, acid anhydrides such as acetic anhydride are preferred. The amount of dehydrating agent used is typically 1 to 3 mol, and preferably 1 to 2 mol, per mol of amino groups in the aromatic amine compound represented by general formula (3).

[0067] The reaction temperature is, for example, -80 to +200°C, preferably -40 to +180°C, and more preferably -20 to +150°C.

[0068] The reaction time is preferably within 240 hours. The reaction rate varies depending on the raw material substrate and reaction conditions. Therefore, it is preferable to follow the progress of the reaction by analytical means such as gas chromatography, liquid chromatography, gel permeation chromatography, or nuclear magnetic resonance, and to determine the end point as the time when the decrease in the raw material substrate is no longer observed.

[0069] For post-treatment after the reaction, general operations in organic synthesis can be adopted. For example, the crude product obtained by the reaction can be purified to a higher purity by treating it with activated carbon, recrystallizing it, or the like, as necessary.

[0070] The raw material amine compound is preferably an aromatic amine compound, and particularly preferably an aromatic amine compound represented by the following general formula (1a):

[0071]

[0072] In general formula (1a), R １ The definition and specific examples of n are as follows: １ and n.

[0073] Specific examples of the compound represented by formula (1a) are shown below.

[0074]

[0075]

[0076] (Method for Producing Aromatic Amine Compound) An amine compound usable as a raw material in the above-mentioned method for producing a maleimide compound [part 1], particularly an aromatic amine compound represented by general formula (1a), can be produced, for example, by reacting trifluoroacetaldehyde (fluoral) or an equivalent thereof with an aniline compound in the presence of an acid catalyst.

[0077] As for fluoral, its equivalents include commercially available hydrates and hemiacetals of fluoral (manufactured by Tokyo Chemical Industry Co., Ltd.) Incidentally, fluoral hydrates and hemiacetals can be prepared by the methods described in Japanese Patent Laid-Open No. 5-97757 and other publications.

[0078] Generally, fluoral is often used as a hydrate or hemiacetal. When fluoral is used under anhydrous conditions, anhydrous fluoral can be prepared by dehydrating the hydrate or hemiacetal of fluoral. Meanwhile, as described in Japanese Patent Laid-Open Publication No. 3-184933, inexpensive chloral can be converted to fluoral almost quantitatively by catalytic gas-phase fluorination, and this method can also be used to prepare anhydrous fluoral. Anhydrous fluoral is generally a highly self-reactive compound that is difficult to handle. However, when anhydrous fluoral is mixed with hydrogen fluoride, 1,2,2,2-tetrafluoroethanol, an adduct of fluoral and hydrogen fluoride, is produced and stabilized. It is believed that this 1,2,2,2-tetrafluoroethanol is in equilibrium with fluoral. When excess hydrogen fluoride is present in the system, the equilibrium shifts towards 1,2,2,2-tetrafluoroethanol, which is further stabilized and can be easily handled as a fluoral / hydrogen fluoride mixture.

[0079] When fluoral is used as a mixture with hydrogen fluoride, the amount of hydrogen fluoride added is usually 0.1 to 100 mol, preferably 1 to 75 mol, and more preferably 2 to 50 mol, per mol of prepared fluoral. Adding less than 0.1 mol of hydrogen fluoride is undesirable because it does not provide a sufficient stabilizing effect. Adding 100 mol or more of hydrogen fluoride can be expected to achieve a similar stabilizing effect, but is undesirable from the standpoints of productivity and economy. As mentioned above, fluoral / hydrogen fluoride mixtures may contain excess hydrogen fluoride. However, because hydrogen fluoride itself functions as an acidic substance, it can effectively act as an acid catalyst or dehydrating agent and can also be used as an additive to promote the reaction. Therefore, it can be said that there is an advantage to handling the fluoral / hydrogen fluoride mixture as a raw material.

[0080] As the aniline compound, a compound represented by the following general formula (AN) can be used.

[0081]

[0082] In the general formula (AN), R １ and n are defined as R in general formula (1). １ and n have the same meaning. Specific examples are also the same. Furthermore, when the number of n in general formula (AN) is 2 or more, a plurality of R １ may be the same or different, and two or more R １ may be linked to form a saturated or unsaturated, monocyclic or polycyclic ring group having 3 to 10 carbon atoms.

[0083] The amount of aniline used is typically 0.8 mol or more per mol of fluoral, and it is preferable to use 0.9 to 1.8 mol since the reaction proceeds smoothly, and 1.0 to 1.5 mol is particularly preferable.

[0084] A solvent can be used for the reaction. Examples of solvents include aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, halogen-based solvents such as methylene chloride and 1,2-dichloroethane, ethers such as tetrahydrofuran and tert-butyl methyl ether, esters such as ethyl acetate and n-butyl acetate, amides such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone, nitriles such as acetonitrile and propionitrile, and dimethyl sulfoxide. Among these, halogen-based solvents such as methylene chloride and 1,2-dichloroethane, amides such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone, and nitriles such as acetonitrile and propionitrile are preferred. These reaction solvents can be used alone or in combination. The amount of the reaction solvent used may be 0.05 L (liter) or more per 1 mol of the aniline represented by the general formula (AN), preferably 0.1 to 20 L, particularly preferably 0.15 to 10 L. Incidentally, the reaction can also be carried out without using a solvent. Carrying out the reaction without a solvent has the advantage that the purification procedure after the reaction is simplified and a highly pure target product can be obtained with only a simple purification procedure.

[0085] Either a Lewis acid or a Brønsted acid can be used as the acid catalyst. Alternatively, a Lewis acid and a Brønsted acid can be used in combination. Usable Lewis acids include metal halides containing at least one metal selected from the group consisting of boron (III: oxidation number; the same applies hereinafter), tin (II), tin (IV), titanium (IV), zinc (II), aluminum (III), antimony (III), and antimony (V). The metal halides used are preferably halides of metals with the highest possible valence. Among these metal halides, boron (III) trifluoride, aluminum (III) trichloride, zinc (II) dichloride, titanium (IV) tetrachloride, tin (IV) tetrachloride, and antimony (V) pentachloride are particularly preferred. These may be used alone or in combination. To ensure that the Lewis acid functions satisfactorily, the amount used is preferably 0.001 mol or more, more preferably 0.01 to 2.0 mol, per 1 mol of fluoral.

[0086] The Brønsted acid used in the reaction can be an inorganic acid or an organic acid. Specific examples of inorganic acids include phosphoric acid, hydrogen fluoride, hydrogen chloride, hydrogen bromide, concentrated nitric acid, concentrated sulfuric acid, fuming nitric acid, and fuming sulfuric acid. Specific examples of organic acids include formic acid, acetic acid, oxalic acid, benzoic acid, methanesulfonic acid, benzenesulfonic acid, paratoluenesulfonic acid, and trifluoromethanesulfonic acid. A single Brønsted acid may be used, or two or more types may be used in combination. To ensure that the Brønsted acid functions sufficiently, the amount used is preferably 0.001 mol or more, more preferably 0.01 to 2.0 mol, per mol of fluoral. As mentioned above, the fluoral / hydrogen fluoride mixture contains hydrogen fluoride, and the hydrogen fluoride contained therein can also be used as a Brønsted acid. In this case, the amount of hydrogen fluoride used may be any amount that is favorable for stabilizing fluoral.

[0087] The reaction temperature may be in the range of -20 to +200°C, preferably -10 to +180°C, and more preferably 0 to +160°C.

[0088] The reaction pressure may be in the range of atmospheric pressure to 4.0 MPa (absolute pressure, the same applies hereinafter), and is usually preferably atmospheric pressure to 2.0 MPa, and more preferably atmospheric pressure to 1.5 MPa. Usable reaction vessels include metal vessels such as stainless steel, Monel™, Hastelloy™, and nickel, and vessels lined with tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, propylene resin, polyethylene resin, and the like, which are capable of carrying out the reaction sufficiently under normal pressure or pressure.

[0089] The reaction time may be within a range of 240 hours. Since the reaction rate varies depending on the raw material substrates and reaction conditions, it is preferable to follow the progress of the reaction by analytical means such as gas chromatography, liquid chromatography, gel permeation chromatography, or nuclear magnetic resonance, and to determine the end point as the time when the decrease in the raw material substrates is no longer observed.

[0090] Post-reaction workup can be performed by a conventional purification procedure on the reaction-terminated solution, for example, by pouring the reaction-terminated solution into water or an aqueous solution of an inorganic base of an alkali metal (e.g., sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, etc.) and extracting with an organic solvent (e.g., ethyl acetate, toluene, methyl isobutyl ketone, diisopropyl ether, methylene chloride, chloroform, etc.). In this way, the aromatic amine compound represented by the general formula (1a) can be easily obtained as a simple substance. The target product can be further purified to a higher chemical purity by activated carbon treatment, distillation, recrystallization, column chromatography, etc., as necessary.

[0091] (Method for Producing Maleimide Compound [Part 2]) The maleimide compound of this embodiment can also be produced by dehydrating and cyclizing the maleamic acid compound of this embodiment. For example, the maleimide compound of general formula (1) can be produced by heating the maleamic acid compound of general formula (2-1) in the presence of a solvent, an acid catalyst, and / or a dehydrating agent.

[0092] The acid catalyst that can be used in the reaction is not particularly limited. Examples include p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, polyphosphoric acid, sulfuric acid, ammonium hydrogen sulfate, and hydrofluoric acid. Among these, p-toluenesulfonic acid and trifluoromethanesulfonic acid are preferred. When an acid catalyst is used, the amount used is, for example, 0.001 to 1 mol, preferably 0.01 to 0.3 mol, per 1 mol of amic acid groups in the maleamic acid compound represented by general formula (2-1).

[0093] Examples of dehydrating agents that can be used in the reaction include those that are typically used as dehydrating agents. Examples include acid anhydrides such as acetic anhydride, carbodiimide compounds such as dicyclohexylcarbodiimide, and hexamethyldisilazane. These dehydrating agents can also be used in combination with appropriate additives such as N-hydroxysuccinimide and zinc bromide. Among these, acid anhydrides such as acetic anhydride are preferred. The amount of dehydrating agent used is typically 1 to 3 mol, and preferably 1 to 2 mol, per mol of amic acid groups in the maleamic acid compound represented by general formula (2-1).

[0094] Examples of solvents that can be used in the reaction include aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, halogen-containing solvents such as methylene chloride and 1,2-dichloroethane, ethers such as tetrahydrofuran and tert-butyl methyl ether, esters such as ethyl acetate and n-butyl acetate, amides such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone, nitriles such as acetonitrile and propionitrile, and dimethyl sulfoxide. Among these, aromatic hydrocarbons such as toluene and xylene, halogen-containing solvents such as methylene chloride and 1,2-dichloroethane, amides such as N,N-dimethylformamide, 1-methyl-2-pyrrolidone, N,N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone, nitriles such as acetonitrile and propionitrile, and dimethyl sulfoxide are preferred. The reaction solvents can be used alone or in combination. The amount of the reaction solvent used may be 0.05 L (liters) or more per mol of the maleamic acid compound represented by formula (2), preferably 0.1 to 20 L, and particularly preferably 0.15 to 10 L.

[0095] A step of removing water generated during the reaction from the system may be carried out. The procedure for removing the water generated from the reaction solution is not particularly limited. For example, the water can be removed by azeotropically distilling the generated water with the solvent system in the reaction solution. The generated water can be removed from the reaction system using, for example, a pressure-equalizing dropping funnel equipped with a stopcock, a Dimroth condenser, a Dean-Stark apparatus, or the like.

[0096] The reaction temperature is usually from -20 to +180°C, preferably from 0 to +150°C, and more preferably from +20 to +120°C.

[0097] The reaction time may be within a range of 240 hours. Since the reaction rate varies depending on the raw material substrate, catalyst, and reaction conditions, it is preferable to follow the progress of the reaction by analytical means such as gas chromatography, liquid chromatography, gel permeation chromatography, or nuclear magnetic resonance, and to determine the end point as the time when almost no decrease in the raw material substrate is observed.

[0098] For post-treatment after the reaction, general procedures in organic synthesis can be adopted. For example, the crude product obtained from Reaction 2 can be purified to a higher purity by treating it with activated carbon, recrystallizing, etc., as necessary.

[0099] (Method for Producing Maleamic Acid Compound) In the above-mentioned method for producing a maleimide compound [part 2], a maleamic acid compound usable as a raw material, particularly a maleamic acid compound represented by the above-mentioned general formula (2-1), can be produced, for example, by reacting an aromatic amine compound represented by the above-mentioned general formula (1a) with a maleic acid derivative in the presence of a solvent.

[0100] Examples of the maleic acid derivative include maleic acid and maleic anhydride. Among these, maleic anhydride is preferred. The maleic acid derivative is usually used in an amount of 1 to 3 mol, preferably 1 to 2 mol, per mol of amino groups in the aromatic amine compound represented by general formula (1a).

[0101] Examples of solvents that can be used in the reaction include the same solvents as those used in the production of maleimide compounds. The preferred solvents are also the same. The reaction solvents can be used alone or in combination. The amount of reaction solvent used should be 0.05 L (liters) or more per mol of the aromatic amine compound represented by general formula (1a), preferably 0.1 to 20 L, and particularly preferably 0.15 to 10 L.

[0102] The reaction temperature may be in the range of -80 to +120°C, preferably -40 to +100°C, and particularly preferably -20 to +80°C. The reaction time may be within a range of 240 hours. Since the reaction rate varies depending on the raw material substrates and reaction conditions, it is preferable to follow the progress of the reaction by analytical means such as gas chromatography, liquid chromatography, gel permeation chromatography, and nuclear magnetic resonance, and to define the time point at which almost no decrease in the raw material substrates is observed as the end point.

[0103] For post-treatment after the reaction, general procedures in organic synthesis can be adopted. For example, the crude product obtained from Reaction 2 can be purified to a higher purity by treating it with activated carbon, recrystallizing, etc., as necessary.

[0104] <Curable Composition> The curable composition of the present embodiment contains at least one of the maleimide compound and the maleamic acid compound described above. Hereinafter, components that the curable composition of the present embodiment can preferably contain, other than the maleimide compound and the maleamic acid compound, will be described.

[0105] (Curing Agent) The curable composition of this embodiment preferably contains a compound capable of crosslinking with at least one of the maleimide compound and the maleamic acid compound, i.e., a curing agent. The curing agent is not particularly limited. Specific examples include compounds having a crosslinkable functional group (or structure) such as an amino group, a cyanate group, a phenolic hydroxy group, an alcoholic hydroxy group, a (meth)allyl group, a (meth)acryloyl group, a vinyl group, or a conjugated diene group. The curing agent preferably has multiple crosslinkable functional groups (or structures) in one molecule, more preferably 2 to 6, and even more preferably 2 to 4. When a curing agent is used, only one curing agent may be used, or two or more curing agents may be used in combination.

[0106] An amine compound and a maleimide compound can react to form a covalent bond. Therefore, an amine compound, specifically an aromatic amine compound, particularly an aromatic amine compound represented by the above-mentioned general formula (1a), can be used as the curing agent. In this case, an amine compound other than the aromatic amine compound represented by the general formula (1a) or a maleimide compound other than the maleimide compound of the embodiment may be used in combination.

[0107] In addition to the above, examples of amine compounds that can be used as curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N-aminoethylpiperazine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, bis(4-amino-3-methylcyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, isophoronediamine, bis(4-aminocyclohexyl)methane, 1,3-bis(aminomethyl)cyclohexane, m-xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, polyoxypropylenediamine, polyoxypropylenetriamine, and aniline-formalin resin. Of course, usable amines are not limited to these. These may be used alone or in combination of two or more.

[0108] Examples of compounds having a cyanate group that can be used as a curing agent include known cyanate ester compounds. More specifically, examples include cyanate esters obtained by reacting polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and polycondensates of bisphenols and various aldehydes with cyanogen halides. Of course, the compounds having a cyanate group are not limited to these.

[0109] Examples of phenols (compounds having a phenolic hydroxy group) that can be used as curing agents include phenol, alkyl-substituted phenols, aromatic-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, and dihydroxynaphthalene. Furthermore, as a type of phenol, a bisphenol compound can also be used as a curing agent. Specific examples include bisphenol A, bisphenol F, bisphenol S, biphenol, and bisphenol AD. Furthermore, as a type of phenol, a phenolic resin can also be used. Specific examples of phenolic resins include bisphenols, polycondensates of phenols and various aldehydes, polymers of phenols and diene compounds, polycondensates of phenols and ketones, polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-tetramethylbenzenedimethanol, biphenyldimethanol, α,α,α',α'-tetramethylbiphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, and modified products thereof. Of course, usable phenolic resins are not limited to these.

[0110] Examples of diene compounds that can be used as curing agents include dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, and isoprene.

[0111] Examples of compounds having a (meth)allyl group that can be used as a curing agent include 4,4'-bisphenol A diallyl ether, 4,4'-bisphenol F di(meth)allyl ether, tri(meth)allyl isocyanurate, 2,2-di(4-acetyloxy-3-(meth)allylphenyl)propane, di(4-acetyloxy-3-(meth)allylphenyl)methane, di(4-acetyloxy-3-(meth)allylphenyl)sulfone, 2,2-di(4-benzoyloxy-3-(meth)allylphenyl)propane, di(4-benzoyloxy-3-(meth)allylphenyl)methane, di(4-benzoyloxy-3-(meth)allylphenyl)sulfone, 2,2-di(4-toluoyloxy-3-(meth)allylphenyl)propane, di(4-toluoyloxy-3-(meth)allyl phenyl)methane, di(4-toluoyloxy-3-(meth)allylphenyl)sulfone, 2,2-di(4-propionyloxy-3-(meth)allylphenyl)propane, di(4-propionyloxy-3-(meth)allylphenyl)methane, di(4-propionyloxy-3-(meth)allylphenyl)sulfone, 2,2-di(4-butyryloxy-3-(meth)allylphenyl)propane, 2,2-di(4-isobutyryloxy-3-(meth)allylphenyl)propane, allyl chloride, allyl alcohol, allyl ethyl ether, allyl-2-hydroxyethyl ether, (meth)allyl glycidyl ether, diallyl phthalate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, triallyl isocyanurate, and the like.

[0112] When a curing agent is used, the amount thereof is usually preferably set so that the number of moles N of all maleimide structures in the composition is approximately equal to the number of moles n of crosslinkable functional groups in the curing agent, where n / N is, for example, 0.5 to 2, preferably 0.7 to 1.3.

[0113] (Concomitant Maleimide Compound) The curable composition of the present embodiment may contain a conventional maleimide compound in addition to the maleimide compound and maleamic acid compound described above. Specific examples of such a "concomitant maleimide compound" include compounds having one maleimide group per molecule, such as N-phenylmaleimide, N-ethylmaleimide, and N-cyclohexylmaleimide, and compounds having two or more maleimide groups per molecule, such as 4,4'-diphenylmethane dimaleimide, N,N'-1,3-phenylene dimaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, and polyphenylmethane maleimide.

[0114] When a combined maleimide compound is used, it may be used alone or in combination of two or more. When a combined maleimide compound is used, the amount thereof is preferably 500 parts by mass or less, more preferably 200 parts by mass or less, and is usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, based on 100 parts by mass of the total amount of the maleimide compound and the maleamic acid compound.

[0115] (Epoxy Resin) The curable composition of this embodiment may further contain an epoxy resin. Any known epoxy resin can be used as the epoxy resin. Specific examples include glycidyl ether-based epoxy resins, alicyclic epoxy resins such as 4-vinyl-1-cyclohexene diepoxide and 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, glycidyl amine-based epoxy resins such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol, and glycidyl ester-based epoxy resins.

[0116] When an epoxy resin is used, it may be used alone or in combination of two or more kinds. When the curable composition of the present embodiment contains an epoxy resin, the amount thereof is preferably 10 to 1000 parts by mass, more preferably 20 to 400 parts by mass, relative to 100 parts by mass of the maleimide resin.

[0117] (Curing Accelerator) The curable composition of the present embodiment may contain a curing catalyst (curing accelerator). Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole; triethylamine; triethylenediamine; 2-( dimethylaminomethyl)phenol, 1,8-diaza-bicyclo(5,4,0)undecene-7, tris(dimethylaminomethyl)phenol, amines such as benzyldimethylamine, phosphines such as triphenylphosphine, tributylphosphine, trioctylphosphine, organic metal salts such as tin octoate, zinc octoate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, tin oleate, metal chlorides such as zinc chloride, aluminum chloride, tin chloride, organic peroxides such as di-tert-butyl peroxide, dicumyl peroxide, azo compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, Lewis acids such as boron trifluoride, and salts such as sodium carbonate and lithium chloride.

[0118] When a curing accelerator is used, it may be used alone or two or more curing accelerators with different chemical structures may be used. When a curing accelerator is used, the amount thereof is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total amount of the curing composition.

[0119] (Other Components) Depending on the intended use, the curable composition of the present embodiment may contain components such as fillers, flame retardants, colorants, plasticizers, solvents, leveling agents, release agents, molecular weight modifiers, epoxy resin curing agents, polybutadiene and modified products thereof, modified acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesins, silicone gels, and silicone oils. Preferred fillers include inorganic fillers such as silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, mica, and glass powder. Flame retardants include antimony trioxide, bromine compounds, and phosphorus compounds. Colorants include various organic and inorganic pigments such as carbon black, phthalocyanine blue, and phthalocyanine green.

[0120] (Solvent) The curable composition of this embodiment may contain a solvent. In other words, the curable composition of this embodiment may be one in which each component, such as the maleimide compound, is dissolved or dispersed in a solvent. The solvent is typically an organic solvent. Specific examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, and amyl acetate; ethers such as ethylene glycol monomethyl ether; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; alcohols such as methanol and ethanol; and hydrocarbons such as toluene and xylene.

[0121] When a solvent is used, only one solvent may be used, or two or more solvents may be used. When a solvent is used, it is used in such a range that the concentration of non-volatile components in the composition becomes generally 10 to 80% by mass, preferably 20 to 7% by mass.

[0122] (Method for Producing Composition) The curable composition of the present embodiment can be prepared by a general method such as melt mixing, powder mixing, or solution mixing.

[0123] <Cured Product and Electronic Device> A cured product can be obtained by curing the curable composition of this embodiment. Curing can be carried out by one or both of light and heat. Specifically, the curable composition is typically heated at 30 to 250°C for 0.1 to 4 hours. This allows a cured product to be obtained. To improve curing performance, "post-curing" may be carried out at 70 to 250°C for 0.1 to 10 hours.

[0124] The cured product may be in the form of a molded product, laminate, cast product, film, or the like. As one example, a cured product that is a molded product can be obtained by molding the curable composition by casting, transfer molding, injection molding, or the like, and then heating at 30 to 250°C for 0.1 to 4 hours. As another example, a curable material for lamination can be produced by applying and / or impregnating a substrate (preferably a fiber substrate) such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, or paper with the curable composition.

[0125] The curable composition of this embodiment is preferably used, for example, as a sealing material for electronic components. Furthermore, the above-mentioned curable lamination material can be suitably used in the production of printed wiring boards such as multilayer electrical laminates, build-up laminates, and flexible laminates. In short, the curable composition of this embodiment is preferably used in the production of electronic devices.

[0126] As described above, the cured product of the curable composition containing the maleimide compound represented by general formula (1) has excellent heat resistance.

[0127] In addition to heat resistance, -CH(CF ３ Due to the presence of the )- structure, the cured product tends to have a low dielectric constant. In this respect, the maleimide compound, maleamic acid compound, curable composition, and cured product thereof of this embodiment are considered to be useful for manufacturing electronic devices.

[0128] <Laminated Plate Material> As briefly mentioned above, a laminated plate material can be cited as a specific application example of the curable composition of this embodiment. That is, a laminated plate material comprising the curable composition of this embodiment or a cured product of the curable composition of this embodiment can be cited as a preferred application. More specifically, the laminated plate material comprises (i) a layer containing the curable composition of this embodiment or a cured product of the curable composition of this embodiment, and (ii) a conductive metal layer. A more specific example of the laminated plate material is one in which (i) a layer containing the curable composition of this embodiment or a cured product of the curable composition of this embodiment and (ii) a conductive metal layer are alternately stacked.

[0129] As briefly mentioned above, another example of a specific application of the curable composition of the present embodiment is an electronic component encapsulant containing the curable composition of the present embodiment or a cured product of the curable composition of the present embodiment. More specifically, examples of the electronic component encapsulant include those obtained by blending the curable composition of the present embodiment and / or a cured product of the curable composition of the present embodiment with various curing agents, fillers, pigments, etc. according to various uses and desired properties, and then mixing and pulverizing or processing into a suitable shape.

[0130] <Summary of Applications> The maleimide compound of this embodiment can be used to prepare a thermosetting composition. A cured product of the curable composition of this embodiment has excellent heat resistance and electrical properties. Therefore, the curable composition of this embodiment can be suitably used as a varnish that can be applied to various substrates, a prepreg impregnated with the varnish, a printed circuit board, a sealant for electronic components, a dielectric material, an insulating material, a heat-resistant material, a laminating material, a structural material, a pressure-sensitive adhesive, an adhesive, and the like in fields such as the electrical and electronics industry and the aerospace industry.

[0131] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

[0132] The present invention will be described in detail below with reference to examples. The present invention is not limited to the description of these examples. In the following, the "%" in the composition analysis value represents the "area %" of the composition obtained by measuring the raw material or product by gas chromatography (hereinafter referred to as GC; unless otherwise specified, the detector is FID) or liquid chromatography (hereinafter referred to as LC; unless otherwise specified, the detector is UV).

[0133] <Synthesis of Fluoral> [Preparation Example 1] (Preparation of catalyst) 896 g of special grade CrCl ３ ・6H ２ O was dissolved in pure water to a total volume of 3.0 L. 400 g of granular alumina was immersed in this solution and allowed to stand overnight. The solution was then filtered to remove the alumina, which was then dried overnight at 100°C in a hot air circulation oven. Chromium-supported alumina was thus obtained. The resulting chromium-supported alumina was packed into a cylindrical SUS316L reactor tube (4.2 cm in diameter and 60 cm in length) equipped with an electric furnace, and the temperature was raised to 300°C while nitrogen gas was flowing at a flow rate of approximately 20 mL / min. When water outflow was no longer observed, hydrogen fluoride was entrained in the nitrogen gas, and its concentration was gradually increased. When the hot spot caused by fluorination of the packed chromium-supported alumina reached the outlet end of the reactor tube, the reactor temperature was raised to 350°C and maintained at that state for 5 hours. A catalyst was thus prepared.

[0134] (Synthesis of Fluoral)

[0135]

[0136] A gas-phase reactor (SUS316L, diameter 2.5 cm, length 40 cm) consisting of a cylindrical reaction tube equipped with an electric furnace was filled with 125 mL of the catalyst prepared in the above Catalyst Preparation Example. While flowing air at a flow rate of approximately 100 mL / min, the temperature of the reaction tube was raised to 280°C, and hydrogen fluoride was introduced at a rate of approximately 0.32 g / min over 1 hour. Next, the feedstock chloral was started to be supplied to the reaction tube at a rate of approximately 0.38 g / min (contact time 15 seconds). One hour after the start of the reaction, the reaction stabilized, and the gas flowing out of the reactor was collected over 18 hours in a SUS304 cylinder equipped with an inlet tube cooled with a refrigerant at -15°C.

[0137] The hydrogen fluoride content, hydrogen chloride content, and organic matter content of the 484.8 g of fluoral-containing collected solution obtained here were calculated by titration. The calculation results showed that the hydrogen fluoride content was 40 mass %, the hydrogen chloride content was 11 mass %, and the organic matter content was 49 mass %, and the organic matter recovery rate was 88% (based on the number of moles of chloral in the feedstock). In addition, a portion of the recovered organic matter was collected in a resin NMR tube, １９ The degree of fluorination was confirmed by F-NMR, and as a result, it was confirmed that almost no low-order fluorinated products were detected, and that fluorination had progressed quantitatively.

[0138] Next, 150 g of the collected fluoral-containing mixture (hydrogen fluoride: 40% by mass, hydrogen chloride: 11% by mass, organic matter: 49% by mass) was charged into a 500 mL SUS reactor equipped with a condenser through which a -15°C refrigerant was passed, a thermometer, and a stirrer, and the reactor was heated to 25°C. While refluxing the hydrogen fluoride through the condenser under normal pressure, hydrogen chloride that slipped through the top column of the condenser was absorbed into water and removed. Refluxing was continued for 5 hours to obtain a fluoral-containing mixture for use in the synthesis of the aromatic amine compound described below.

[0139] The hydrogen fluoride content, hydrogen chloride content, and organic matter content of the fluoral-containing mixture were calculated by titration. The calculated results were hydrogen fluoride: 35.9% by mass, hydrogen chloride: 0.1% by mass, and organic matter: 64% by mass. A portion of the mixture was collected in a resin NMR tube, and １９ F-NMR spectra were measured. From the integral ratio of the measured spectra, it was confirmed that the fluoral in the anhydrous hydrogen fluoride had been converted to 1,2,2,2-tetrafluoroethanol (chemical formula hereinafter), which is a fluoral / hydrogen fluoride composition. On the other hand, when the water used to absorb the hydrogen chloride was subjected to titration, it was found to contain some hydrogen fluoride due to entrainment, but almost no organic matter.

[0140]

[0141] 1,2,2,2-Tetrafluoroethanol: １９F-NMR (400MHz, CFCl ３ ) δ (ppm): -85.8 (3F, s), -137.8 (1F, d, J = 54.9 Hz). Hydrogen fluoride: １９ F-NMR (400MHz, CFCl ３ ) δ (ppm): -193.4 (1F, s)

[0142] <Synthesis of Aromatic Amine Compound> [Synthesis Example 1] In a 1 L stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 176 g (fluoral: 1.15 mol, hydrogen fluoride: 3.17 mol) of the fluoral-containing mixture obtained in Preparation Example 1 (hydrogen fluoride: 35.9 wt%, hydrogen chloride: 0.1 wt%, organic matter: 64 wt%), 213 g (10.63 mol) of hydrogen fluoride, and 321 g (3.45 mmol) of aniline were placed. The reaction vessel was heated in a 90 ° C. oil bath and reacted for 7 hours at an absolute pressure of 0.15 MPa. Thereafter, the reaction solution was poured into a mixture of 600 g of ice water and 1080 g of toluene, and neutralized by dropwise addition of 1250 g of 48% aqueous potassium hydroxide solution. The organic layer recovered by liquid separation was further washed with 750 g of 18% aqueous potassium hydroxide solution and then with 600 g of water. The organic layer was then heated to 80°C, and 410 g of n-heptane was added dropwise to perform recrystallization. The precipitated solid was filtered off to obtain 189 g of the target product, 1,1,1-trifluoro-2,2-bis(4-aminophenyl)ethane (chemical formula below), in a yield of 63% and a purity of 99.6% (GC).

[0143]

[0144] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 3.42 (4H, s), 4.45 (1H, q, J = 10.1Hz), 6.62 (4H, d, J = 8.3Hz), 7.12 (4H, d, J = 8.3Hz). １９ F-NMR (400MHz, CDCl ３ , CFCl ３ ) δ (ppm): -66.9 (3F, d, J = 11.5 Hz).

[0145] ​Synthesis Example 2 Into a 1 L stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 169 g (fluoral: 1.10 mol, hydrogen fluoride: 3.04 mol) of the fluoral-containing mixture obtained in Preparation Example 1 (hydrogen fluoride: 35.9 wt%, hydrogen chloride: 0.1 wt%, organic matter: 64 wt%), 203 g (10.15 mol) of hydrogen fluoride, and 353 g (3.30 mmol) of o-toluidine were placed. The reaction vessel was heated in a 90°C oil bath and reacted for 7 hours at an absolute pressure of 0.15 MPa. Thereafter, the reaction solution was poured into a mixture of 600 g of ice water and 1080 g of toluene, and neutralized by the dropwise addition of 1250 g of 48% aqueous potassium hydroxide solution. The organic layer recovered by liquid separation was further washed with 750 g of 18% aqueous potassium hydroxide solution and then with 600 g of water. The organic layer was then heated to 80°C, and 410 g of n-heptane was added dropwise to perform recrystallization. The precipitated solid was filtered off to obtain 252 g of the target product, 1,1,1-trifluoro-2,2-bis(3-methyl-4-aminophenyl)ethane (chemical formula below), in a yield of 86% and a purity of 99.4% (GC).

[0146]

[0147] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 2.13 (6H, s), 3.14 (4H, s), 4.41 (1H, q, J = 10.4Hz), 6.62 (2H, d, J = 10.4Hz), 7.01 (2H, s), 7.02 (2H, d, J = 8.3Hz). １９ F-NMR (400MHz, CDCl ３ , CFCl ３ ) δ (ppm): -66.7 (3F, d, J = 11.5 Hz).

[0148] ​Synthesis Example 3 Into a 1 L stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, 169 g (fluoral: 1.10 mol, hydrogen fluoride: 3.04 mol) of the fluoral-containing mixture obtained in Preparation Example 1 (hydrogen fluoride: 35.9 wt%, hydrogen chloride: 0.1 wt%, organic matter: 64 wt%), 203 g (10.15 mol) of hydrogen fluoride, and 267 g (2.20 mmol) of 2,6-xylidine were placed. The reaction vessel was heated in an oil bath at 130°C, and the reaction was carried out for 7 hours at an absolute pressure of 0.35 MPa. Thereafter, the reaction solution was poured into a mixture of 700 g of ice water and 1130 g of toluene, and neutralized by the dropwise addition of 1312 g of 48% aqueous potassium hydroxide solution. The organic layer recovered by the liquid separation operation was further washed with 939 g of 12% aqueous potassium hydroxide solution and then with 700 g of water. From the obtained organic layer, 496 g of toluene was distilled off using an evaporator under conditions of 20 kPa and a water bath of 70°C, and then the organic layer was heated to 80°C and recrystallized by adding 319 g of n-heptane dropwise. The precipitated solid was filtered off to obtain 308 g of the target product, 1,1,1-trifluoro-2,2-bis(3,5-dimethyl-4-aminophenyl)ethane (chemical formula hereinafter), in a yield of 87% and a purity of 99.6% (GC).

[0149]

[0150] １ H-NMR (400MHz, CDCl ３ ) δ (ppm): 2.15 (12H, s), 3.55 (4H, s), 4.36 (1H, q, J=10.4Hz), 6.93 (4H, s). １９ F-NMR (400MHz, CDCl ３ , CFCl ３ ) δ (ppm): -66.6 (3F, d, J = 8.6Hz).

[0151] ​<Synthesis of Maleimide Compound> [Synthesis Example 2-1] 32.7 g (123 mmol) of 1,1,1-trifluoro-2,2-bis(4-aminophenyl)ethane obtained in Synthesis Example 1 was placed in a 500 mL four-neck flask equipped with a thermometer, a Dimroth condenser, a dropping funnel, and a stirrer, and dissolved in 190 g of acetone. 24.7 g (252 mmol) of maleic anhydride was added thereto, and the mixture was stirred at room temperature for 30 minutes. Subsequently, 20.4 g (246 mmol) of sodium acetate and 30.2 g (295 mmol) of acetic anhydride were added, and the mixture was heated in a 60°C oil bath and reacted for 8 hours. After completion of the reaction, 60 g of water was added dropwise to the reaction solution to perform recrystallization. The precipitated solid was filtered off to obtain 38.3 g of the target product, 1,1,1-trifluoro-2,2-bis(4-aminophenyl)ethane bismaleimide (chemical formula below), with a yield of 73% and a purity of 94% (LC). The melting point of the obtained crystals was 185-188°C.

[0152]

[0153] １ H-NMR (400MHz, CD ３ CN) δ (ppm): 5.09 (1H, q, J = 10.3Hz), 6.90 (4H, s), 7.37 (4H, d, J = 8.5Hz), 7.56 (4H, d, J = 8.2Hz). １９ F-NMR (400MHz, CD ３ CN, CFCl ３ ) δ (ppm): -66.5 (3F, d, J = 11.6 Hz).

[0154] ​Synthesis Example 2-2: 10.0 g (34.0 mmol) of 1,1,1-trifluoro-2,2-bis(3-methyl-4-aminophenyl)ethane obtained in Synthesis Example 2 was placed in a 200 mL four-neck flask equipped with a thermometer, a Dimroth condenser, a dropping funnel, and a stirrer, and dissolved in 32 g of acetonitrile. 7.3 g (74.8 mmol) of maleic anhydride was added thereto, and the mixture was stirred at room temperature for 50 minutes. Subsequently, 2.8 g (27.2 mmol) of sodium acetate and 11.2 g (136.1 mmol) of acetic anhydride were added, and the mixture was heated in a 70°C oil bath and allowed to react for 5 hours. After completion of the reaction, 30 g of water was added dropwise to the reaction solution to perform recrystallization. The precipitated solid was filtered off to obtain 11.2 g of the target product, 1,1,1-trifluoro-2,2-bis(3-methyl-4-aminophenyl)ethane bismaleimide (chemical formula below), in a yield of 72% and a purity of 88% (LC). The melting point of the obtained crystals was 202-203°C.

[0155]

[0156] １ H-NMR (400MHz, CD ３ CN) δ (ppm): 2.12 (6H, s), 5.05 (1H, q, J = 10.1Hz), 6.92 (4H, s), 7.20 (2H, d, J = 8.0Hz), 7.41 (2H, dd, J = 8.1, 1.6Hz), 7.46 (2H, d, J=1.6Hz). １９ F-NMR (400MHz, CD ３ CN, CFCl ３ ) δ (ppm): -65.5 (3F, d, J = 8.7 Hz).

[0157] ​Synthesis Example 2-3: 8.92 g (27.7 mmol) of 1,1,1-trifluoro-2,2-bis(3,5-dimethyl-4-aminophenyl)ethane obtained in Synthesis Example 3 was placed in a 200 mL four-neck flask equipped with a thermometer, a Dimroth condenser, a dropping funnel, and a stirrer, and 44 g of acetone was added to dissolve the ethane. 6.0 g (60.9 mmol) of maleic anhydride was added, and the mixture was heated in a 50°C oil bath and allowed to react for 1 hour. Subsequently, 0.12 g (1.4 mmol) of sodium acetate and 7.1 g (69.5 mmol) of acetic anhydride were added, and the mixture was heated in a 70°C oil bath and allowed to react for 24 hours. After completion of the reaction, 55 g of water was added dropwise to the reaction solution to perform recrystallization. The precipitated solid was filtered off to obtain 8.4 g of the target product, 1,1,1-trifluoro-2,2-bis(3,5-dimethyl-4-aminophenyl)ethane bismaleimide (chemical formula below), in a yield of 63% and with a purity of 93% (LC). The melting point of the obtained crystals was 264-268°C.

[0158]

[0159] １ H-NMR (400MHz, CD ３ CN) δ (ppm): 2.07 (12H, s), 4.88 (1H, q, J=10.1Hz), 6.95 (4H, s), 7.30 (4H, s). １９ F-NMR (400MHz, CD ３ CN, CFCl ３ ) δ (ppm): -66.2 (3F, d, J = 8.7 Hz).

[0160] Synthesis Example 3-1: 10.1 g (37.9 mmol) of 1,1,1-trifluoro-2,2-bis(4-aminophenyl)ethane was placed in a 100 mL three-neck flask equipped with a thermometer and a stirrer, and 32 g of acetonitrile was added to dissolve the mixture. 8.2 g (83.6 mmol) of maleic anhydride was added, and the mixture was stirred at room temperature for 30 minutes. After stirring was completed, the precipitated crystals were filtered off, yielding 16.8 g (36.3 mmol) of a maleamic acid compound represented by the following formula as white crystals (yield: 96%). The crude product obtained was used directly in the next reaction without purification.

[0161] ​

[0162] １ H-NMR (400MHz, CD ３ CN) δ (ppm): 4.96 (1H, q, J = 10.3Hz), 6.35 (2H, dd, J = 12.9, 2.8Hz), 6.51 (2H, dd, J = 1 2.9, 2.8Hz), 7.45 (4H, dd, J = 8.5, 2.5Hz), 7.65 (4H, dd, J = 8.5, 2.5Hz), 9.37 (2H, s). １９ F-NMR (400MHz, CD ３ CN, CFCl ３ ) δ (ppm): -66.8 (3F, d, J = 8.7Hz).

[0163] In a 100 mL four-neck flask equipped with a thermometer, Dimroth condenser, dropping funnel, and stirrer, 10.0 g (21.6 mmol) of the maleamic acid obtained above was placed and dissolved in 28 g of acetonitrile. Subsequently, 3.6 g (43.9 mmol) of sodium acetate and 5.3 g (51.9 mmol) of acetic anhydride were added, and the mixture was heated in a 60°C oil bath and allowed to react for 8 hours. After completion of the reaction, 10 g of water was added dropwise to the reaction solution to cause recrystallization. The precipitated solid was filtered off, yielding 7.2 g of the target product, 1,1,1-trifluoro-2,2-bis(4-aminophenyl)ethane bismaleimide, with a yield of 78% and a purity of 95% (LC). (For the chemical formula of the target product, see Synthesis Example 2-1.)

[0164] Synthesis Example 3-2: 10.0 g (33.9 mmol) of 1,1,1-trifluoro-2,2-bis(3-methyl-4-aminophenyl)ethane obtained in Synthesis Example 2 was placed in a 100 mL three-neck flask equipped with a thermometer and a stirrer, and dissolved in 45 g of acetonitrile. 7.3 g (74.6 mmol) of maleic anhydride was added thereto, and the mixture was stirred at room temperature for 30 minutes. After stirring was completed, the reaction solution was concentrated using an evaporator, yielding 15.9 g (32.4 mmol) of a maleamic acid compound represented by the following formula as a white amorphous substance (yield: 96%). The obtained crude product was used directly in the next reaction without purification.

[0165]

[0166] ​​１ H-NMR (400MHz, CD ３ CN) δ (ppm): 2.25 (6H, s), 4.89 (1H, q, J = 10.2Hz), 6.36 (2H, d, J = 12.7Hz), 6.62 (2H, d , J=12.7Hz), 7.32 (2H, d, J=8.7Hz), 7.34 (2H, s), 7.50 (2H, d, J=8.2Hz), 9.00 (2H, s). １９ F-NMR (400MHz, CD ３ CN, CFCl ３ ) δ (ppm): -65.5 (3F, d, J = 11.6 Hz).

[0167] In a 100 mL four-neck flask equipped with a thermometer, Dimroth condenser, dropping funnel, and stirrer, 10.3 g (21.0 mmol) of the maleamic acid obtained above was placed and dissolved in 28 g of acetonitrile. Subsequently, 3.5 g (42.7 mmol) of sodium acetate and 5.1 g (50.0 mmol) of acetic anhydride were added, and the mixture was heated in a 70°C oil bath and allowed to react for 5 hours. After completion of the reaction, 30 g of water was added dropwise to the reaction solution to cause recrystallization. The precipitated solid was filtered off, yielding 7.6 g of the target product, 1,1,1-trifluoro-2,2-bis(3-methyl-4-aminophenyl)ethane bismaleimide, in an 80% yield and 91% purity (LC). (For the chemical formula of the target product, see Synthesis Example 2-2.)

[0168] Synthesis Example 3-3: 14.0 g (43.4 mmol) of 1,1,1-trifluoro-2,2-bis(3,5-dimethyl-4-aminophenyl)ethane obtained in Synthesis Example 3 was placed in a 100 mL three-neck flask equipped with a thermometer and a stirrer, and 57 g of acetonitrile was added to dissolve the mixture. 9.4 g (95.8 mmol) of maleic anhydride was then added, and the mixture was heated in a 50°C oil bath to allow the reaction to proceed for 1 hour. After completion of the reaction, the reaction solution was concentrated using an evaporator, yielding 22.5 g (43.3 mmol) of a maleamic acid compound represented by the following formula as a white solid (yield: 99%). The crude product obtained was used directly in the next reaction without purification.

[0169]

[0170] １ ​H-NMR (400MHz, CD ３ CN) δ (ppm): 2.20 (12H, s), 4.81 (1H, q, J = 10.4Hz), 6.39 (2H, d, J = 12.8Hz), 6.65 (2H, d, J = 12.8Hz), 7.24 (4H, s), 9.01 (2H, s). １９ F-NMR (400MHz, CD ３ CN, CFCl ３ ) δ (ppm): -65.5 (3F, d, J = 11.6 Hz).

[0171] A 100 mL four-neck flask equipped with a thermometer, Dimroth condenser, dropping funnel, and stirrer was charged with 10.8 g (20.8 mmol) of the maleamic acid obtained above, and 28 g of acetonitrile was added to dissolve it. Subsequently, 3.5 g (42.7 mmol) of sodium acetate and 5.3 g (51.9 mmol) of acetic anhydride were added, and the mixture was heated in a 70°C oil bath and allowed to react for 24 hours. After completion of the reaction, 30 g of water was added dropwise to the reaction solution to cause recrystallization. The precipitated solid was filtered off, yielding 7.1 g of the target product, 1,1,1-trifluoro-2,2-bis(3,5-dimethyl-4-aminophenyl)ethane bismaleimide, with a yield of 71% and a purity of 95% (LC). (See Synthesis Example 2-3 for the chemical formula of the target product.)

[0172] <Evaluation: Solvent Solubility of Maleimide Compound> The maleimide compounds obtained in Synthesis Examples 2-1 to 2-3 and a known maleimide compound, 4,4'-diphenylmethane bismaleimide (BMI-1000 manufactured by Daiwa Kasei), were evaluated for solubility in solvents. Specifically, the maleimide compound was added to dimethylformamide in an amount such that the solid content was 30% by mass, and the mixture was allowed to stand at 25°C or 50°C for 3 hours without stirring, after which the state was observed. The evaluation was performed by visually observing the appearance of the solvent and expressed on the following three-point scale. The results are shown in Table 1. A: Completely dissolved, no turbidity observed. B: Turbidity observed, but no undissolved solid matter was confirmed. C: Undissolved solid matter has sunk to the bottom.

[0173]

[0174] The maleimide compounds obtained in Synthesis Examples 2-1 to 2-3 were —CH(CF３ It showed higher solubility in solvents than BMI-1000 which does not contain the )-structure.

[0175] <Preparation of cured products and evaluation of heat resistance> First, a maleimide compound and a curing agent (both in powder form) were mixed in the compositions shown in the table below to prepare curable compositions of "Composition 1" and "Composition 2." Diaminodiphenylmethane purchased from Tokyo Chemical Industry Co., Ltd. was used as the curing agent.

[0176]

[0177] Example 1 The curable composition of Composition 1 was heated to 130°C on a hot plate while stirring for about 10 minutes to dissolve the composition, yielding a melt. The melt was transferred to a vacuum oven and degassed at 130°C under reduced pressure for about 5 minutes. The melt was then returned to normal pressure and poured into a mold made of silicone resin, where it was heated at 150°C for 1.5 hours, then at 175°C for 1.5 hours, and then at 200°C for 1.5 hours. The mixture was then naturally cooled, removed from the mold, and post-cured in an oven at 230°C for 4 hours. This yielded a cured product for evaluation.

[0178] Comparative Example 1 A cured product was obtained in the same manner as in Example 1, except that the composition of composition 2 was used instead of composition 1.

[0179] The cured products were evaluated for glass transition temperature, weight loss temperature, dielectric constant, and dielectric loss tangent using the following specific evaluation methods.

[0180] Glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC7000 manufactured by Hitachi High-Tech Science Corp.) under the conditions of a temperature rise rate of 5°C / min and a nitrogen atmosphere.

[0181] ・5% weight loss temperature (Td ５ ), 20% weight loss temperature (Td ２０ ) and 30% weight loss temperature (Td ３０ The measurement was carried out using a thermogravimetric differential thermal analyzer (STA7200 manufactured by Hitachi High-Tech Science Corporation) under the conditions of a nitrogen atmosphere and a temperature rise rate of 10°C / min.

[0182] Relative permittivity and dielectric loss tangent: Measurements were taken using a network analyzer "P5007A" manufactured by Keysight Technologies under conditions of 23°C, humidity 50%, and a frequency of 10 GHz.

[0183] The evaluation results are shown in the table below.

[0184]

[0185] The glass transition temperature of the cured product of Example 1 was 214°C, and the glass transition temperature of the cured product of Comparative Example 1 was 181°C. In other words, the glass transition temperature of the cured product of Example 1 was higher than that of Comparative Example 1. A high glass transition temperature of a cured product usually means that the cured product is less susceptible to thermal movement. In other words, it can be said that the cured product of Example 1 has better heat resistance than the cured product of Comparative Example 1. Although the details are unknown, it is believed that the -CH(CF ３ The partial structure represented by )- is moderately rigid, which may be why the glass transition temperature is high.

[0186] Furthermore, the 5% weight loss temperature of the cured product of Example 1 was equivalent to that of Comparative Example 1, but the 20% and 30% weight loss temperatures of Example 1 were superior to those of Comparative Example 1. In other words, the cured product of Example 1 is less susceptible to thermal decomposition and has superior heat resistance compared to the cured product of Comparative Example 1. This is because the cured product of Example 1 is -CH(CF ３ )-structure, oxidation of the methylene group is suppressed, and stability at high temperatures is improved.

[0187] Furthermore, the relative dielectric constant of the cured product of Example 1 was smaller than that of the cured product of Comparative Example 1, and the dielectric loss tangent of the cured product of Example 1 was comparable to that of the cured product of Comparative Example 1. In other words, it can be seen that the cured product of Example 1 has electrical properties that are equal to or superior to those of conventional products. Such good electrical properties are due to the CF ３ This is thought to be related to the small polarizability of the C—F bond of the group.

[0188] <Preparation of cured products and evaluation of heat resistance (additional)> A maleimide compound, curing agent, curing accelerator, and cyclohexanone were mixed in the ratios shown in the table below to prepare compositions 3 to 6. Diaminodiphenylmethane purchased from Tokyo Chemical Industry Co., Ltd. was used as the curing agent. 1,8-diazabicyclo[5.4.0]-7-undecene was used as the curing accelerator.

[0189]

[0190] [Example 2] A uniform varnish-like composition (varnish) was obtained by stirring the composition of Composition 3 for about 15 minutes while warming it in a water bath at 85°C. After cooling the obtained varnish to room temperature, it was applied to a PET film using a bar coater to a thickness of about 20 μm and dried on a hot plate at 120°C for 10 minutes. The obtained coating film was peeled off from the PET film and crushed in a mortar to obtain powder. This powder was placed in a mold for tableting and crushed at 180°C and 80 kg / cm. ２ After molding, the composition was removed from the mold and post-cured at 200°C for 8 hours, thereby obtaining a cured product for evaluation.

[0191] Example 3 A cured product was obtained in the same manner as in Example 2, except that composition 4 was used instead of composition 3.

[0192] Example 4 A cured product was obtained in the same manner as in Example 2, except that the composition of composition 5 was used instead of composition 3.

[0193] Comparative Example 2 The composition of composition 6 was stirred for about 1 hour while being heated in a water bath at 75° C. However, a uniform varnish could not be obtained.

[0194] The cured products for evaluation were evaluated for glass transition temperature and 5% weight loss temperature. The evaluation results are shown in the table below.

[0195]

[0196] In Examples 2 to 4, it was possible to prepare a uniform varnish-like composition and to prepare a cured product using the varnish, but it was not possible to obtain a uniform varnish in Comparative Example 2. The maleimide compounds obtained in Synthesis Examples 2-1 to 2-3 were -CH(CF ３ It is understood that this has higher solubility in solvents than BMI-1000 which does not contain the )-structure and is therefore suitable for producing a varnish.

[0197] <Preparation and Evaluation of Cured Material Containing Modified Polyphenylene Ether> A maleimide compound, a modified polyphenylene ether having a terminal polymerizable unsaturated double bond (SA9000 manufactured by SABIC), a polymerization initiator, and cyclohexanone were mixed in the compositions shown in the table below, and the resulting compositions were designated "Composition 7" and "Composition 8." Dicumyl peroxide purchased from Tokyo Chemical Industry Co., Ltd. was used as the polymerization initiator.

[0198]

[0199] Example 5 A uniform varnish-like composition (varnish) was obtained by stirring the composition of Composition 7 for about 15 minutes while warming it in a 75°C water bath. The obtained varnish was cooled to room temperature, then coated onto copper foil (thickness 12 μm) using a bar coater so that the dried thickness would be about 20 μm, and then dried on a hot plate at 120°C for 10 minutes. The obtained copper foil-attached sheet was post-cured in an oven at 175°C for 1 hour and then at 215°C for 4 hours. The copper foil was then removed by etching and washed with ultrapure water to obtain a sheet. The sheet was dried at 60°C for 24 hours and returned to room temperature. The 5% weight loss temperature (Td ５ ) was evaluated using a thermogravimetric differential thermal analyzer under conditions of a nitrogen atmosphere and a heating rate of 10°C / min, as described above. ５ The temperature was 353°C.

[0200] Comparative Example 3 The composition of Composition 8 was stirred for about 1 hour while being heated in a water bath at 75° C. However, a uniform varnish could not be obtained, and it was impossible to prepare a sheet for evaluation.

[0201] From Example 5 and Comparative Example 3, it was found that the maleimide compound obtained in Synthesis Example 2-1 was —CH(CF ３It can be seen that, compared with BMI-1000 which does not contain a )-structure, even a composition containing a modified polyphenylene ether having a terminal polymerizable unsaturated double bond has excellent solvent solubility and compatibility, and is suitable for curing by radical polymerization.

[0202] This application claims priority based on Japanese Patent Application No. 2022-051515, filed March 28, 2022, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. -CH(CF ３ )-,

2. The maleimide compound according to claim 1, A maleimide compound represented by the following general formula (1): 【Chemistry 1】 In general formula (1), R １ When a plurality of groups are present, each independently represents a monovalent substituent, The two n's each independently represent an integer of 0 to 4.

3. The maleimide compound according to claim 2, A maleimide compound represented by the following general formula (2): 【Chemistry 2】 In general formula (2), R １ and n are defined as R in general formula (1). １ and n.

4. The maleimide compound according to any one of claims 1 to 3, A maleimide compound represented by the following formula (3): 【Chemistry 3】

5. The maleimide compound according to any one of claims 1 to 3, A maleimide compound represented by the following formula (4): 【Chemistry 4】

6. The maleimide compound according to any one of claims 1 to 3, A maleimide compound represented by the following formula (5): 【Chemistry 5】

7. -CH(CF ３ )-, a maleamic acid compound having a partial structure represented by the formula:

8. 8. The maleamic acid compound according to claim 7, A maleamic acid compound represented by the following general formula (2-1): 【Chemistry 6】 In general formula (2-1), R １ When a plurality of groups are present, each independently represents a monovalent substituent, The two n's each independently represent an integer of 0 to 4.

9. 9. The maleamic acid compound according to claim 8, A maleamic acid compound represented by the following general formula (2-2): 【Chemistry 7】 In general formula (2-2), R １ and n are defined as R １ and n.

10. The maleamic acid compound according to any one of claims 7 to 9, A maleamic acid compound represented by the following formula (2-3): 【Chemistry 8】

11. The maleamic acid compound according to any one of claims 7 to 9, A maleamic acid compound represented by the following formula (2-4): 【Chemistry 9】

12. The maleamic acid compound according to any one of claims 7 to 9, A maleamic acid compound represented by the following formula (2-5): 【Chemistry 10】

13. A curable composition comprising the maleimide compound according to any one of claims 1 to 3 or the maleamic acid compound according to any one of claims 7 to 9.

14. A cured product of the curable composition according to claim 13.

15. An electronic device comprising the cured product according to claim 14.

16. A method for producing the maleimide compound according to any one of claims 1 to 3, comprising the steps of: A method for producing a maleimide compound, comprising a step of reacting an aromatic amine compound represented by the following general formula (1a) with maleic acid or a maleic acid derivative: 【Chemistry 11】 In general formula (1a), R １ When a plurality of groups are present, each independently represents a monovalent substituent, The two n's each independently represent an integer of 0 to 4.

17. A method for producing the maleamic acid compound according to any one of claims 7 to 9, comprising the steps of: A method for producing a maleamic acid compound, comprising a step of reacting an aromatic amine compound represented by the following general formula (1a) with maleic acid or a maleic acid derivative: 【Chemistry 12】 In general formula (1a), R １ When a plurality of groups are present, each independently represents a monovalent substituent, The two n's each independently represent an integer of 0 to 4.

18. A method for producing the maleimide compound according to any one of claims 1 to 3, comprising the steps of: A method for producing a maleimide compound, comprising a step of subjecting a maleamic acid compound represented by the following general formula (2-1) to a dehydration ring-closing reaction: 【Chemistry 13】 In general formula (2-1), R １ When a plurality of groups are present, each independently represents a monovalent substituent, The two n's each independently represent an integer of 0 to 4.

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