Method for producing imide compounds

Abstract

The present invention provides a method for producing imide compounds in which the imidation reaction proceeds sufficiently even at low temperatures. [Solution] A method for producing an imide compound is provided, which includes the step of imidizing a compound having a substructure represented by formula (1) at a low temperature. TIFF2026141771000029.tif47170 (In formula (1), R 1 * represents a divalent to tetravalent organic group with 2 to 50 carbon atoms. n1 represents an integer between 0 and 2. * represents a bond point with the remainder of the compound.

Description

[Technical Field]

[0001] This invention relates to a method for producing imide compounds. More specifically, it relates to a method for producing imide compounds in which imidation proceeds at low temperatures. [Background technology]

[0002] Due to its excellent heat resistance, insulating properties, and mechanical properties, polyimide is used as an insulating film and planarization film in semiconductor and display devices. A common method for forming polyimide films involves coating a substrate with a solution of polyamic acid or its derivatives as a precursor, and then applying heat treatment at over 300°C to form the polyimide. In recent years, however, a method has been adopted in which a solution using solvent-soluble polyimide is coated onto a substrate to lower the heat treatment temperature to room temperature to 250°C.

[0003] In the production of the above-mentioned solvent-soluble polyimides, a common method is to react the starting material, a diamine, with an acidic dianhydride in a solvent to obtain a polyamic acid solution, and then raise the temperature of this solution to 180°C or higher to dehydrate and cyclize it, thereby promoting imidation. Techniques to lower the temperature of the imidation reaction include processing in the presence of a dehydrating agent such as dicyclohexylcarbodiimide or an acid catalyst (see, for example, Patent Documents 1 and 2), processing in the presence of an organic carboxylic acid anhydride and a base catalyst such as a trialkylamine or pyridine (see, for example, Patent Document 3), and processing in the presence of a basic compound with a pKa greater than 8 (see, for example, Patent Document 4). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 5-310933 [Patent Document 2] Japanese Patent Application Publication No. 6-192420 [Patent Document 3] Japanese Patent Application Publication No. 59-199720 [Patent Document 4] Japanese Unexamined Patent Application Publication No. 2006-28417 Summary of the Invention Problem to be Solved by the Invention

[0005] However, when dicyclohexylcarbodiimide is used, it is difficult to completely convert polyisoimide generated as an intermediate in the imidization reaction into polyimide, and dicyclohexylurea, which is a by-product after dehydration, precipitates, resulting in low purity of the obtained polyimide, which makes practical application difficult. In addition, even when using an acid catalyst, a combination of an organic carboxylic acid anhydride and a base catalyst, or a basic compound having a pKa of more than 8, a temperature of 100°C or higher is required for the imidization reaction to allow the imidization to proceed by 90% or more. Therefore, there have been problems in producing polyimide at a lower temperature of less than 100°C.

[0006] An object of the present invention is to provide a method for producing an imide compound in which the imidization reaction sufficiently proceeds even at low temperatures. Means for Solving the Problem

[0007] In order to solve the above problems, the present invention has the following configuration.

[0008] <1> (a) a compound having a partial structure represented by formula (1) (hereinafter referred to as compound (a)), (b) a compound represented by formula (2) (hereinafter referred to as compound (b)), and (c) at least one selected from the group consisting of a compound represented by formula (3) and a resin having a structure represented by formula (4) in a side chain (hereinafter, these compounds or resins are referred to as compound (c)), A method for producing an imide compound, comprising a step of mixing the foregoing components and imidizing the compound (a).

[0009]

Chemical Formula

[0010] (in formula (1), R1 * represents a divalent to tetravalent organic group with 2 to 50 carbon atoms. n1 represents an integer between 0 and 2. * represents a bond point with the remainder of compound (a).

[0011] [ka]

[0012] (In formula (2), R 2 and R 3 Each of these independently represents a hydrocarbon group with 1 to 20 carbon atoms.

[0013] [ka]

[0014] (In formula (3), R 4 and R 5 Each of these independently represents a hydrocarbon group with 1 to 20 carbon atoms, and R 6 (where n² represents a hydrocarbon group with 1 to 6 carbon atoms, and n² represents an integer from 0 to 4.)

[0015] [ka]

[0016] (In formula (4), R 7 R represents a hydrocarbon group with 1 to 20 carbon atoms. 8 (where n3 represents a hydrocarbon group with 1 to 6 carbon atoms, and n3 represents an integer from 0 to 4. * represents a bonding point with the resin.)

[0017] <2> A powder, fiber, or film containing compound (a) is immersed in a solution or dispersion containing compound (b) and compound (c). <1> A method for producing the imide compound described above.

[0018] <3> A powder, fiber, or film containing compound (a) is sprayed with a solution or dispersion containing compound (b) and compound (c). <1> A method for producing the imide compound described above.

[0019] <4> The (b) compound is at least one selected from the compounds represented below. <1> ~ <3> A method for producing an imide compound as described in any of the following.

[0020] [ka]

[0021] <5> The imide compound is a polyimide, polyamideimide, or bismaleimide. <1> ~ <4> A method for producing an imide compound as described in any of the following.

[0022] <6> The process includes mixing compound (a) and an organic base compound different from compound (c) with compound (b) and compound (c) to imide compound (a), <1> ~ <5> A method for producing an imide compound as described in any of the following. [Effects of the Invention]

[0023] According to the present invention, it is possible to provide a method for producing polyimide in which more than 90% of the imidation proceeds even at low temperatures, for example, 25°C to 40°C. Furthermore, the present invention can be applied not only to the production of polyimide but also to the production of other imide compounds. [Modes for carrying out the invention]

[0024] The method for producing an imide compound according to an embodiment of the present invention is: (a) A compound having a substructure represented by formula (1) (hereinafter referred to as compound (a)), (b) A compound represented by formula (2) (hereinafter referred to as compound (b)), (c) A compound represented by formula (3) and at least one selected from resins having a structure represented by formula (4) in their side chains (hereinafter, these compounds or resins are referred to as (c) compounds), The method for producing an imide compound includes the step of mixing (a) a compound to imide it.

[0025] [Chemical Formula]

[0026] In formula (1), R 1 represents a divalent to tetravalent organic group having 2 to 50 carbon atoms. n1 represents an integer of 0 to 2. * represents a bonding site to the remainder of the compound (a).

[0027] [Chemical Formula]

[0028] In formula (2), R 2 and R 3 each independently represent a hydrocarbon group having 1 to 20 carbon atoms.

[0029] [Chemical Formula]

[0030] In formula (3), R 4 and R 5 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, R 6 represents a hydrocarbon group having 1 to 6 carbon atoms, and n2 represents an integer of 0 to 4.

[0031] [Chemical Formula]

[0032] In formula (4), R 7 represents a hydrocarbon group having 1 to 20 carbon atoms, R 8 represents a hydrocarbon group having 1 to 6 carbon atoms, n3 represents an integer of 0 to 4, and * represents a bonding site to a resin.

[0033] The imidization reaction refers to a reaction in which a precursor structure of imide undergoes ring closure by heat, light or a chemical reaction to form an imide structure. In the case of the structure represented by formula (1), it is a reaction that undergoes ring closure to be converted into the structure represented by formula (5). The conversion rate obtained in this case is hereinafter referred to as the imidization rate.

[0034] [ka]

[0035] In formula (5), R 1 n1 represents the same structure as in formula (1). * represents the bond site with the remainder of the imide compound.

[0036] <(a) Compound> In formula (1), R 1 The symbol represents a divalent to tetravalent organic group having 2 to 50 carbon atoms. Preferred specific examples of divalent to tetravalent organic groups having 2 to 50 carbon atoms include organic groups having 6 to 50 carbon atoms that contain an aromatic ring, organic groups having 6 to 50 carbon atoms that contain an alicyclic structure, or organic groups having 1 to 50 carbon atoms that contain a linear or branched alkyl group.

[0037] From the perspective of accelerating the progress of the imidation reaction, R 1 In the structure, the carbon atom bonded to the amide bond and the carbon atom bonded to the carboxyl group are preferably adjacent to each other, or with one or two carbon atoms in between, and more preferably adjacent.

[0038] In equation (1), n1 represents an integer between 0 and 2. When n1=0, the structure of equation (1) can take the form of, for example, the terminal structure of a low molecular weight compound or polymer, or a structure bonded to the side chain of a polymer. When n1=1 or 2, the structure of equation (1) can take the form of, for example, a structure included in the repeating structural unit of a polymer.

[0039] The imide compound produced by the manufacturing method of the present invention is preferably a polyimide, polyamideimide, or bismaleimide. Preferred (a) compounds in this case include compounds having a structural unit represented by formula (6) or formula (7), and compounds represented by formula (8).

[0040] [ka]

[0041] Formula (6) represents the structural unit of a polyimide precursor. In formula (6), X1 represents a tetravalent organic group having 4 to 50 carbon atoms, and Y1 represents a divalent organic group having 2 to 50 carbon atoms.

[0042] [ka]

[0043] Formula (7) represents the structural unit of a polyamide-imide precursor. In formula (7), X2 represents a trivalent organic group having 3 to 50 carbon atoms, and Y2 represents a divalent organic group having 2 to 50 carbon atoms.

[0044] [ka]

[0045] Formula (8) represents the bismaleimide structure. In formula (8), Y3 represents a divalent organic group having 2 to 50 carbon atoms.

[0046] In formula (6), X1 represents a tetravalent organic group having 4 to 50 carbon atoms. Specific examples of preferred X1 include tetracarboxylic acid residues, and preferred tetracarboxylic acids in this case include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-di Examples include, but are not limited to, carboxyphenyl)methane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1.]heptanetetracarboxylic acid, bicyclo[3.3.1.]tetracarboxylic acid, bicyclo[3.1.1.]hepto-2-enetetracarboxylic acid, bicyclo[2.2.2.]octanetetracarboxylic acid, and adamatanetetracarboxylic acid. These tetracarboxylic acids can be used individually or in combination of two or more.

[0047] In formula (6), Y1 represents a divalent organic group having 2 to 50 carbon atoms. Specific examples of preferred Y1 include diamine residues, and preferred diamines in this case include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, and 1,4-bis( 4-aminophenoxy)benzene, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy C)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl , 2,4-diaminophenol, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)fluorene, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, 2,Examples of aromatic diamines include, but are not limited to, 4-diaminothiophenol, bis(3-amino-4-mercapto)biphenyl, bis(3-amino-4-mercaptophenyl)methane, bis(3-amino-4-mercaptophenyl)ether, bis(3-amino-4-mercaptophenyl)propane, bis(3-amino-4-mercaptophenyl)fluorene, bis(3-amino-4-mercaptophenyl)hexafluoropropane, and bis(3-amino-4-mercaptophenyl)sulfone; diamines in which some of the hydrogen atoms of the aromatic ring of the above aromatic diamines are substituted with alkyl or halogen atoms; diamines in which the aromatic ring of the above aromatic diamines is hydrogenated, such as cyclohexyldiamine and methylenebiscyclohexylamine; and siloxanediamines listed below. These diamines can be used individually or in combination of two or more.

[0048] [ka]

[0049] R 9 ~R 12 R represents a hydrocarbon group with 1 to 6 carbon atoms, and may be the same or different. 9 ~R 12 Preferred specific examples include, but are not limited to, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, amyl group, hexyl group, cyclohexyl group, cyclopentyl group, and 1,1-dimethylbutyl group. m represents an integer from 1 to 30. The range of m is preferably from 1 to 20, and more preferably from 1 to 10.

[0050] In formula (7), X2 represents a trivalent organic group having 3 to 50 carbon atoms. Preferred specific examples of X2 include tricarboxylic acid residues, and preferred tricarboxylic acids include, but are not limited to, aromatic tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid, tricarboxylic acids in which some of the hydrogen atoms of the aromatic ring of the above aromatic tricarboxylic acid are substituted with alkyl groups or halogen atoms, and tricarboxylic acids in which the aromatic ring of the above aromatic tricarboxylic acid is hydrogenated. These tricarboxylic acids can be used individually or in combination of two or more.

[0051] In formula (7), Y2 represents a divalent organic group having 2 to 50 carbon atoms. A specific example of a preferred Y2 is the same as Y1 in formula (6).

[0052] In formula (8), Y3 represents a divalent organic group having 2 to 50 carbon atoms. A specific example of a preferred Y3 is the same as Y1 in formula (6).

[0053] If the imide compound is a polyimide or polyamideimide, (a) the polymer ends of the compound can also be encapsulated with an end-capturing agent. In particular, when a thermally crosslinkable compound is used as the end-capturing agent, there is a concern that the polymer may precipitate due to the crosslinking reaction if the imidation reaction is carried out at high temperatures, so the manufacturing method of the present invention, which allows imidation at low temperatures, is more preferably applied.

[0054] As end-capturing agents, monoamines, monocarboxylic acid derivatives such as acid chlorides, and acid anhydrides can be used.

[0055] Examples of monoamines include aniline, naphthylamine, aminopyridine, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene Talen, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. are preferably used. Furthermore, as thermally crosslinkable monoamines, 4-ethynylaniline, 3-ethynylaniline, 4-aminostyrene, etc. are preferably used. These monoamines can be used individually or in combination of two or more.

[0056] Examples of monocarboxylic acid derivatives and acid anhydrides include acid anhydrides such as phthalic anhydride, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic acid anhydride, as well as 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, and 4-carboxy Preferably used are monocarboxylic acids such as benzenesulfonic acid, mono-acid chloride compounds in which the carboxyl groups of these are acid-chlorinated, mono-acid chloride compounds in which only the monocarboxyl groups of dicarboxylic acids such as terephthalic acid, phthalic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene are acid-chlorinated, and active ester compounds obtained by the reaction of mono-acid chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide. Furthermore, preferably used as thermally crosslinkable monocarboxylic acid derivatives and acid anhydrides are maleic anhydride, nadic acid, methacrylic anhydride, acrylic anhydride, 4-ethynylphthalic anhydride, 3-ethynylphthalic anhydride, methacrylate chloride, acrylate chloride, and 4-vinylbenzoic acid chloride. These can be used individually or in combination of two or more.

[0057] When using the above-mentioned end-capturing agents such as monoamines, monocarboxylic acid derivatives, and acid anhydrides, the amount added is preferably 1 to 40 mol% per 100 mol% of acid dianhydride in the case of monoamines, and preferably 1 to 40 mol% per 100 mol% of diamine in the case of monocarboxylic acid derivatives and acid anhydrides.

[0058] The present invention provides a method for producing an imide compound, which involves mixing compound (a), compound (b), and compound (c) to carry out an imidation reaction. The mixing method and order are not particularly limited. For example, if compound (b) and compound (c) are added to a solution of compound (a), either compound can be added first, or compound (b) and compound (c) can be added simultaneously.

[0059] Furthermore, the method for producing the imidide of the present invention includes not only a form in which compound (a), compound (b), and compound (c) are directly mixed, but also a form in which they are indirectly mixed. Examples of indirect mixing include, for example, mixing compound (a) with a complex compound represented by the following formula (9) which has been formed by mixing compound (b) and compound (c) in advance, or mixing compound (a) with a complex compound represented by the following formula (9) which has been formed by mixing compound (b) and compound (c).

[0060] [ka]

[0061] In formula (9), R 2 ~R 6 , and n2 represents the same structure as equations (2) and (3).

[0062] In other words, the method for producing the imide compound of the present invention involves mixing the above-mentioned compound (a), compound (b), and compound (c), (1) Step 1 involves mixing compound (b) and compound (c), (2) A method for producing an imide compound may also be a method comprising step 2 of mixing the mixture from step 1 with (a) the compound.

[0063] Furthermore, the method for producing the imide compound of the present invention may also include a step of imidizing compound (a) in the presence of a mixture of compound (b) and compound (c), or a complex compound represented by the following formula (9).

[0064] Furthermore, compounds (a), (b), and (c) may be added in their entirety at once, or they may be added in several portions.

[0065] The imidation reaction is thought to proceed via salt formation between the carboxyl group of compound (a) and compound (c), and complex formation between compound (b) and compound (c).

[0066] Furthermore, methods such as immersing a powder, fiber, or film containing compound (a) in a solution or dispersion containing compound (b) and compound (c), or spraying a solution or dispersion containing compound (b) and compound (c) onto a powder, fiber, or film containing compound (a) can also be preferably used.

[0067] This method allows for the easy production of powders, fibers, and films containing imide compounds such as polyimide and bismaleimide.

[0068] The temperature for the imidation reaction is preferably 0°C or higher and less than 100°C, and more preferably 0°C or higher and 40°C or lower. In particular, if the imide compound has a thermally crosslinkable functional group, if the reaction temperature is high, insolubilization of the resin due to intermolecular crosslinking may occur during the imidation reaction, so it is more preferable to carry out the reaction within the above temperature range.

[0069] The imidation reaction time is preferably 5 minutes to 12 hours. The reaction time can be adjusted as appropriate depending on the amount of compound (c) added.

[0070] (a) When the compound is a compound having a structural unit represented by formula (6) or formula (7), or when it is a compound represented by (8), it is preferable to carry out imidation by the method listed below as an example, but is not limited to these.

[0071] (a) When the compound is a compound having a structural unit represented by formula (6), the imidation reaction according to the present invention is a reaction that converts a polyimide precursor into a polyimide. The polymerization method in this case is generally to dissolve the diamine in a solvent and add a tetracarboxylic dianhydride to carry out the reaction. The reaction temperature is preferably 0°C to 80°C. The reaction time is generally 1 minute to 100 hours, and preferably 2 hours to 24 hours. When using an end-capturing agent, after the polymerization of the diamine and acid dianhydride is complete, a predetermined amount of monoamine, monocarboxylic acid derivative, or acid anhydride is added and the reaction is carried out further at 0°C to 80°C for 2 hours to 24 hours. During the reaction, it is preferable to prevent moisture from entering the system by flowing nitrogen.

[0072] Subsequently, compounds (b) and (c) are added to the polymer, and the imidation reaction is carried out. After the imidation reaction, the polymerization solution may be used as is, or the polymerization solution may be added to water or alcohol to remove t-butanol and compound (c), the polymer may be precipitated, filtered, and the polymer obtained. After imidation, a polyimide having structural units represented by formula (10) is obtained.

[0073] [ka]

[0074] In equation (10), X1 and Y1 represent the same structures as those in equation (6).

[0075] (a) When the compound is a compound having a structural unit represented by formula (7), the imidation reaction according to the present invention is a reaction that converts a polyamide-imide precursor into a polyamide-imide. The polymerization method in this case is generally to dissolve the diamine in a solvent and add the tricarboxylic acid derivative to proceed with the reaction. The reaction temperature is preferably -20°C to 40°C. The reaction time is generally 1 minute to 100 hours, and preferably 2 hours to 24 hours. When using an end-capturing agent, after the polymerization of the diamine and the tricarboxylic acid derivative is complete, a predetermined amount of monoamine, monocarboxylic acid derivative, or acid anhydride is added and the reaction is further carried out at -20°C to 40°C for 2 hours to 24 hours. During the reaction, it is preferable to prevent moisture from entering the system by flowing nitrogen through it.

[0076] Subsequently, compounds (b) and (c) are added to the polymer, and the imidation reaction is carried out. After the imidation reaction, the polymerization solution may be used as is, or the polymerization solution may be added to water or alcohol to remove t-butanol, compound (c), hydrogen chloride, etc., and the polymer may be precipitated, filtered, and the polymer obtained. After imidation, a polyamide-imide having structural units represented by formula (11) is obtained.

[0077] [ka]

[0078] In equation (11), X2 and Y2 represent the same structure as in equation (7).

[0079] (a) When the compound is the compound represented by formula (8), the imidation reaction according to the present invention is a reaction that converts a bismaleimide precursor into bismaleimide. The method for synthesizing bismaleimide in this case is generally to dissolve the diamine in a solvent and add maleic anhydride to carry out the reaction. The reaction temperature is preferably 0°C to 80°C. The reaction time is generally 1 minute to 100 hours, and preferably 2 hours to 24 hours. During the reaction, it is preferable to prevent water from entering the system by flowing nitrogen through it.

[0080] Subsequently, compounds (b) and (c) are added to the polymer, and the imidation reaction is carried out. After the imidation reaction, the polymerization solution may be used as is, or the polymerization solution may be added to water or alcohol to remove t-butanol and compound (c), the polymer may be precipitated, filtered, and bismaleimide may be obtained. After imidation, the bismaleimide has the structure represented by formula (12).

[0081] [ka]

[0082] In equation (12), Y3 represents the same structure as in equation (8).

[0083] When obtaining bismaleimide from a bismaleimide precursor, there is a concern that polymer precipitation may occur due to the polymerization reaction of bismaleimide if the imidation reaction is carried out at high temperatures. Therefore, the production method of the present invention, which allows imidation at low temperatures, is more preferably applied.

[0084] The present invention may also be a method for producing an imide compound, which includes the step of mixing compound (b) and compound (c) with a mixture of compound (a) and an organic base compound different from compound (c) (hereinafter referred to as the (a') mixture) to imide compound (a).

[0085] In other words, the method for producing the imide compound of the present invention involves mixing the above-mentioned compound (a), compound (b), and compound (c), (1) Step 1' involves mixing compound (a) with an organic base compound different from compound (c), (2) A method for producing an imide compound may also be a method comprising step 2' of mixing the mixture from step 1' with compound (b) and compound (c).

[0086] Organic base compounds refer to organic compounds used as bases, and more specifically, those that accept a proton on a nitrogen atom to become a cation. More specifically, examples include amine compounds with 1 to 30 carbon atoms containing a nitrogen atom, and heterocyclic compounds with 1 to 30 carbon atoms containing a nitrogen atom.

[0087] Preferred specific examples of amine compounds having 1 to 30 carbon atoms and containing a nitrogen atom include, but are not limited to, ammonia, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triethanolamine, diethanolamine, ethanolamine, triisopropanolamine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1-methylpiperidine, pyrrolidine, 1-methylpyrrolidine, N,N-dimethylaniline, aniline, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2]octane, and 1,5-diazabicyclo[4.3.0]-5-nonene. From the viewpoint of improving the imidization rate, it is more preferable that the compound be an aliphatic amine, even more preferable that it be an aliphatic secondary or tertiary amine, and most preferable that it be an aliphatic tertiary amine.

[0088] Preferred examples of heterocyclic compounds having 1 to 30 carbon atoms and containing a nitrogen atom include, but are not limited to, pyridine, imidazole, 1-methylimidazole, and quinoline. From the viewpoint of improving the imidation rate, imidazole and 1-methylimidazole are more preferred.

[0089] In this case, mixture (a') contains a salt of the carboxyl group of compound (a) and an organic base compound.

[0090] The amount of organic base compound added is preferably 0.005 to 5 moles per mole of carboxyl group. From the viewpoint of improving the imidization rate, the above amount is more preferably 0.01 to 3 moles, and even more preferably 0.1 to 2 moles.

[0091] The mixing method and mixing order when carrying out the imidation reaction by mixing (a'), compound (b), and compound (c) are not particularly limited, and can be carried out in the same way as when carrying out the imidation reaction by mixing (a), compound (b), and compound (c).

[0092] (a) Solvents used for the synthesis of the compound and / or the imidation reaction of the compound (a) include aprotic solvents such as N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutylamide, dimethyl sulfoxide, γ-butyrolactone, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and diethylene glycol dimethyl ether. Examples of acetates include, but are not limited to, ethers such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; ketones such as acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and 2-heptanone; alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol; and aromatic hydrocarbons such as toluene and xylene.

[0093] <(b) Compound> In formula (2), R 2 and R 3Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms. Preferred specific examples of hydrocarbon groups having 1 to 20 carbon atoms include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, amyl, hexyl, cyclohexyl, cyclopentyl, and 1,1-dimethylbutyl groups.

[0094] From the viewpoint of improving the imidization rate, it is more preferable that compound (b) is selected from at least one of the compounds represented below.

[0095] [ka]

[0096] (b) The amount of compound to be added is preferably 0.9 to 5 moles per mole of the functional group to be imidized (e.g., carboxyl group). From the viewpoint of improving the imidization rate, the above amount is more preferably 1 to 3 moles, and even more preferably 1 to 2 moles.

[0097] <(c) Compound> In formula (3), R 4 and R 5 Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms. Preferred specific examples of hydrocarbon groups having 1 to 20 carbon atoms include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, amyl, hexyl, cyclohexyl, cyclopentyl, and 1,1-dimethylbutyl groups.

[0098] From the perspective of improving the imidization rate, R 4 and R 5 Each of these is preferably independently a methyl group, an ethyl group, a propyl group, or an isopropyl group.

[0099] In formula (3), R 6The symbol represents a hydrocarbon group having 1 to 6 carbon atoms. Preferred examples of hydrocarbon groups having 1 to 6 carbon atoms include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, amyl, hexyl, cyclohexyl, cyclopentyl, and 1,1-dimethylbutyl groups.

[0100] From the perspective of improving the imidization rate, R 6 The group is preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group.

[0101] In equation (3), n² represents an integer between 0 and 4. From the viewpoint of improving the imidization rate, n² is preferably between 0 and 1, and more preferably 0.

[0102] The following compounds are examples of preferred specific examples of compounds represented by formula (3).

[0103] [ka]

[0104] In formula (4), R 7 R represents a hydrocarbon group having 1 to 20 carbon atoms. A preferred specific example of a hydrocarbon group having 1 to 20 carbon atoms is R 4 and R 5 The same things can be listed.

[0105] In formula (4), R 8 R represents a hydrocarbon group having 1 to 6 carbon atoms. A preferred specific example of a hydrocarbon group having 1 to 6 carbon atoms is R 6 The same things can be listed.

[0106] In equation (4), n3 represents an integer between 0 and 4. From the viewpoint of improving the imidization rate, n3 is preferably between 0 and 1, and more preferably 0.

[0107] In formula (4), * represents a bonding point with the resin. The bonding to the resin can be selected as appropriate depending on the resin to be bonded, and may include single bonds, bonds via hydrocarbon groups such as saturated hydrocarbon groups and unsaturated hydrocarbon groups, or bonds via organic groups containing oxygen and nitrogen such as ester groups, amide groups, sulfonyl groups, and oxyester groups. Preferred resins include vinyl resins, acrylic resins, thermoset epoxy resins, polysiloxane resins, and phenolic resins.

[0108] After the imidation reaction is complete, compound (c) can be easily removed from the polymerization solution by filtration or the like, and from the viewpoint of simplifying the purification process of the imide compound after the reaction, it is preferable that compound (c) is a resin having a structure represented by formula (4) in its side chain, and it is more preferable that the resin contains a crosslinked structure. For example, in the case of polyimide, since compound (c) can be removed from the polymerization solution, it is possible to omit steps such as adding the polymerized solution to water or the like to precipitate the polymer.

[0109] Examples of resins having a crosslinked structure include epoxy resins after thermosetting, styrene-divinylbenzene copolymers, oxyethylene diacrylate-methyl acrylate copolymers, and resins polymerized by mixing polyfunctional monomers that form a network structure.

[0110] The most preferred specific example of formula (3) is a polymer supported with 4-dimethylaminopyridine (CAS number: 82942-26-5).

[0111] (c) The amount of compound to be added is preferably 0.05 to 5 moles per mole of the functional group to be imidized (e.g., carboxyl group). From the viewpoint of improving the imidization rate, the above amount is more preferably 1 to 3 moles, and even more preferably 1 to 2 moles. [Examples]

[0112] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The imidization rate in each example and comparative example was evaluated by the following method.

[0113] (1) Evaluation of the imidization rate Solutions A to I were applied to a 4-inch silicon wafer by spin coating using a spinner (Mikasa Corporation: MS-A150), and dried on a 60°C hot plate for 5 minutes to obtain a film with a thickness of 3 μm. At this time, the film thickness was measured using an optical interferometry film thickness analyzer (SCREEN Holdings Corporation: Lambda Ace STM-602). The infrared absorption spectrum of this film was measured using an FT-720 (Horiba, Ltd.). Next, the wafer after measurement was heat-treated on a 300°C hot plate for 5 minutes, and the infrared absorption spectrum of the film after heat treatment was measured. 1780 cm² before heat treatment at 300°C -1 The peak intensity in the vicinity was measured at T1, 1780 cm² after heat treatment at 300°C. -1 The imidization rate was calculated from the value of T1 / T2 × 100, with the peak intensity in the vicinity being defined as T2. A rate of 90% or higher was considered acceptable, while a rate below 90% was considered unacceptable.

[0114] Example 1 Under a stream of dry nitrogen, 9.93 g (0.04 mol) of 3,3'-diaminodiphenylsulfone (DDS) and 16.9 g (0.06 mol) of 4,4'-methylenebis(2-ethyl-6-methylaniline) (MEDX) were dissolved in 132 g of N-methyl-2-pyrrolidone (NMP) at room temperature. To this, 10.8 g (0.0495 mol) of pyromellitic anhydride (PMDA) and 16.0 g (0.0495 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) were added along with 20.0 g of NMP, and the mixture was reacted at room temperature for 8 hours. Subsequently, 0.384 g (0.002 mol) of trimellitic anhydride (TMA) was added along with 10.0 g of NMP, and the mixture was reacted further at room temperature for 4 hours to obtain (a) a polyimide precursor solution.

[0115] To this polyimide precursor solution, 24.4 g (0.2 mol) of compound (c), 4-dimethylaminopyridine (DMAP), was added along with 50.0 g of NMP to dissolve the DMAP. Then, 43.7 g (0.2 mol) of compound (b), di-t-butyl dicarbonate (DTBC), was added, and the imidation reaction was carried out at room temperature for 4 hours to obtain solution A. When solution A was evaluated according to (1), the imidation rate was 98%.

[0116] Example 2 Solution A was added to 3 L of pure water to precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 12 hours to obtain polyimide powder. 10.0 g of this powder was dissolved in 30.0 g of NMP to obtain solution B. When solution B was evaluated according to (1), the imidization rate was 98%.

[0117] Comparative Example 1 Under a stream of dry nitrogen, 9.93 g (0.04 mol) of DDS and 16.9 g (0.06 mol) of MEDX were dissolved in 132 g of NMP at room temperature. To this, 10.8 g (0.0495 mol) of PMDA and 16.0 g (0.0495 mol) of BTDA were added together with 20.0 g of NMP, and the mixture was reacted at room temperature for 8 hours. Subsequently, 0.384 g (0.002 mol) of TMA was added together with 10.0 g of NMP, and the mixture was reacted at room temperature for a further 4 hours to obtain (a) a polyimide precursor solution.

[0118] This polyimide precursor solution was added to 3 L of pure water without imidization to precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 12 hours to obtain polyimide powder. 10.0 g of this powder was dissolved in 30.0 g of NMP to obtain solution C. When solution C was evaluated according to (1), the imidization rate was found to be 8%.

[0119] Comparative Example 2 Under a stream of dry nitrogen, 9.93 g (0.04 mol) of DDS and 16.9 g (0.06 mol) of MEDX were dissolved in 132 g of NMP at room temperature. To this, 10.8 g (0.0495 mol) of PMDA and 16.0 g (0.0495 mol) of BTDA were added together with 20.0 g of NMP, and the mixture was reacted at room temperature for 8 hours. Subsequently, 0.384 g (0.002 mol) of TMA was added together with 10.0 g of NMP, and the mixture was reacted at room temperature for a further 4 hours to obtain (a) a polyimide precursor solution.

[0120] To this polyimide precursor solution, 20.4 g (0.2 mol) of acetic anhydride and 15.8 g (0.2 mol) of pyridine were added along with 10.0 g of NMP, and the imidation reaction was carried out at room temperature for 4 hours.

[0121] This solution was added to 3 L of pure water to precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 12 hours to obtain polyimide powder. 10.0 g of this powder was dissolved in 30.0 g of NMP to obtain solution D. When solution D was evaluated according to (1), the imidization rate was 64%.

[0122] Example 3 Under a stream of dry nitrogen, 9.93 g (0.04 mol) of DDS and 16.9 g (0.06 mol) of MEDX were dissolved in 132 g of NMP at room temperature. 9.82 g (0.045 mol) of PMDA and 14.5 g (0.045 mol) of BTDA were added along with 20.0 g of NMP, and the mixture was reacted at room temperature for 8 hours. Subsequently, 3.44 g (0.02 mol) of 4-ethynylphthalic anhydride was added along with 10.0 g of NMP, and the mixture was reacted further at room temperature for 4 hours to obtain (a) a polyimide precursor solution.

[0123] To this polyimide precursor solution, 24.4 g (0.2 mol) of compound (c) DMAP and 43.7 g (0.2 mol) of compound (b) DTBC were dissolved in 50.0 g of NMP, and the imidization reaction was carried out at room temperature for 4 hours.

[0124] This solution was added to 3 L of pure water to precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 12 hours to obtain polyimide powder. 10.0 g of this powder was dissolved in 30.0 g of NMP to obtain solution E. When solution E was evaluated according to (1), the imidization rate was 99%.

[0125] Comparative Example 3 Under a stream of dry nitrogen, 9.93 g (0.04 mol) of DDS and 16.9 g (0.06 mol) of MEDX were dissolved in 132 g of NMP at room temperature. 9.82 g (0.045 mol) of PMDA and 14.5 g (0.045 mol) of BTDA were added along with 20.0 g of NMP, and the mixture was reacted at room temperature for 8 hours. Subsequently, 3.44 g (0.02 mol) of 4-ethynylphthalic anhydride was added along with 10.0 g of NMP, and the temperature was raised to 200°C. During the reaction, the polymer gradually precipitated and finally gelled.

[0126] A comparison of Example 3 and Comparative Example 3 reveals that when a thermally crosslinkable compound such as 4-ethynylphthalic anhydride is used as the end-capturing agent, polymer precipitation occurs due to the crosslinking reaction when the imidation reaction is performed at high temperatures. Therefore, the manufacturing method of the present invention, which allows imidation at low temperatures, is more preferably applicable.

[0127] Example 4 Under a stream of dry nitrogen, 34.8 g (0.095 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were dissolved in 169 g of 3-methoxy-N,N-dimethylpropanamide (MPA) at room temperature. To this, 27.9 g (0.09 mol) of 4,4'-oxydiphthalic anhydride was added along with 20.0 g of MPA, and the mixture was reacted at room temperature for 8 hours. Subsequently, 2.34 g (0.02 mol) of 4-ethynylaniline was added along with 10.0 g of MPA, and the mixture was reacted at room temperature for a further 4 hours to obtain compound (a), a polyimide precursor solution.

[0128] To this polyimide precursor solution, 48.9 g (0.4 mol) of compound (c) DMAP was added along with 100 g of MPA to dissolve the DMAP. Then, 87.3 g (0.4 mol) of compound (b) DTBC was added, and the imidation reaction was carried out at room temperature for 4 hours.

[0129] This solution was added to 3 L of pure water to precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 12 hours to obtain polyimide powder. 10.0 g of this powder was dissolved in 30.0 g of MPA to obtain solution F. When solution F was evaluated according to (1), the imidization rate was 97%.

[0130] Example 5 Under a stream of dry nitrogen, 24.8 g (0.1 mol) of DDS was dissolved in 123 g of NMP at room temperature. 19.6 g (0.2 mol) of maleic anhydride was added to this mixture along with 10.0 g of NMP, and the mixture was reacted at room temperature for 8 hours to obtain (a) a bismaleimide precursor solution.

[0131] To this bismaleimide precursor solution, 24.4 g (0.2 mol) of compound (c), DMAP, was added along with 50.0 g of NMP to dissolve the DMAP. Then, 43.7 g (0.2 mol) of compound (b), DTBC, was added and the mixture was reacted at room temperature for 4 hours.

[0132] This solution was added to 3 L of pure water to precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 12 hours to obtain bismaleimide powder. 10.0 g of this powder was dissolved in 30.0 g of NMP to obtain solution G. When solution G was evaluated according to (1), the imidization rate was 100%.

[0133] Comparative Example 4 Under a stream of dry nitrogen, 24.8 g (0.1 mol) of DDS was dissolved in 123 g of NMP at room temperature. 19.6 g (0.2 mol) of maleic anhydride was added to this mixture along with 10.0 g of NMP, and the temperature was raised to 200°C. During the reaction, bismaleimide polymerized and gradually precipitated, eventually forming a gel.

[0134] A comparison of Example 5 and Comparative Example 4 shows that when obtaining bismaleimide from a bismaleimide precursor, the imidation reaction is carried out at high temperatures, resulting in the precipitation of a polymer due to the polymerization reaction of bismaleimide. Therefore, the manufacturing method of the present invention, which allows imidation at low temperatures, is more preferably applicable.

[0135] Example 6 Under a stream of dry nitrogen, 86.0 g (0.1 mol) of KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd., long-chain silicone diamine) was dissolved in 200 g of cyclohexanone at room temperature. 27.9 g (0.09 mol) of 4,4'-oxydiphthalic anhydride was added to this mixture along with 20.0 g of cyclohexanone, and the mixture was reacted at room temperature for 8 hours. Subsequently, 2.38 g (0.02 mol) of 4-aminostyrene was added along with 10.0 g of cyclohexanone, and the mixture was reacted further at room temperature for 4 hours to obtain compound (a), a polyimide precursor solution.

[0136] To this polyimide precursor solution, 24.4 g (0.2 mol) of compound (c), DMAP, was added together with 50.0 g of cyclohexanone to dissolve the DMAP. Then, 43.7 g (0.2 mol) of compound (b), DTBC, was added and the reaction was allowed to proceed at room temperature for 4 hours to obtain solution H. When solution H was evaluated according to (1), the imidization rate was 99%.

[0137] Example 7 Under a stream of dry nitrogen, 19.8 g (0.1 mol) of 4,4'-diaminodiphenylmethane was dissolved in 4 g of NMP at room temperature. 19.0 g (0.09 mol) of trimellitic anhydride chloride was added along with 20.0 g of NMP, and the mixture was reacted at room temperature for 8 hours. Then, 2.38 g (0.02 mol) of 4-aminostyrene was added along with 10.0 g of NMP, and the mixture was reacted at room temperature for a further 4 hours to obtain (a) a polyamide-imide precursor solution.

[0138] To this polyamide-imide precursor solution, 24.4 g (0.2 mol) of compound (c) DMAP was added along with 50.0 g of NMP to dissolve the DMAP. Then, 43.7 g (0.2 mol) of compound (b) DTBC was added and the mixture was reacted at room temperature for 4 hours.

[0139] This solution was added to 3 L of pure water to precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 12 hours to obtain polyamide-imide powder. 10.0 g of this powder was dissolved in 30.0 g of NMP to obtain solution I. When solution I was evaluated according to (1), the imidization rate was 99%.

[0140] Example 8 Under a stream of dry nitrogen, 86.0 g (0.1 mol) of KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd., long-chain silicone diamine) was dissolved in 200 g of cyclohexanone at room temperature. 27.9 g (0.09 mol) of 4,4'-oxydiphthalic anhydride was added to this mixture along with 20.0 g of cyclohexanone, and the mixture was reacted at room temperature for 8 hours. Subsequently, 2.38 g (0.02 mol) of 4-aminostyrene was added along with 10.0 g of cyclohexanone, and the mixture was reacted further at room temperature for 4 hours to obtain compound (a), a polyimide precursor solution.

[0141] To this polyimide precursor solution, 60.0 g (0.18 mol in terms of DMAP) of cross-linked polystyrene (cross-linked with 2% divinylbenzene) with approximately 3.0 mmol / g of DMAP supported, and 50.0 g of cyclohexanone were added and thoroughly dispersed. Then, 43.7 g (0.2 mol) of compound (b), DTBC, was added and the reaction was carried out at room temperature for 4 hours. After the reaction, the cross-linked polystyrene with DMAP supported was filtered off to obtain solution J. When solution J was evaluated according to (1), the imidization rate was 98%.

[0142] Example 9 Under a stream of dry nitrogen, 9.93 g (0.04 mol) of 3,3'-diaminodiphenylsulfone (DDS) and 16.9 g (0.06 mol) of 4,4'-methylenebis(2-ethyl-6-methylaniline) (MEDX) were dissolved in 132 g of N-methyl-2-pyrrolidone (NMP) at room temperature. To this, 10.8 g (0.0495 mol) of pyromellitic anhydride (PMDA) and 16.0 g (0.0495 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) were added along with 20.0 g of NMP, and the mixture was reacted at room temperature for 8 hours. Subsequently, 0.384 g (0.002 mol) of trimellitic anhydride (TMA) was added along with 10.0 g of NMP, and the mixture was reacted further at room temperature for 4 hours to obtain (a) a polyimide precursor solution.

[0143] To this polyimide precursor solution, 16.4 g (0.2 mol) of 1-methylimidazole was added along with 50.0 g of NMP and stirred at room temperature for 1 hour. Then, 24.4 g (0.2 mol) of compound (c), 4-dimethylaminopyridine (DMAP), was added along with 50.0 g of NMP to dissolve the DMAP. To this, 43.7 g (0.2 mol) of compound (b), di-t-butyl dicarbonate (DTBC), was added and the imidation reaction was carried out at room temperature for 4 hours. The reaction solution was added to 3 L of pure water to precipitate. This precipitate was collected by filtration, washed three times with pure water, and then dried in a vacuum dryer at 50°C for 12 hours to obtain polyimide powder. 10.0 g of this powder was dissolved in 30.0 g of NMP to obtain solution K. When solution K was evaluated according to (1), the imidation rate was 99%.

[0144] Example 10 Under a stream of dry nitrogen, 9.93 g (0.04 mol) of DDS and 16.9 g (0.06 mol) of MEDX were dissolved in 132 g of NMP at room temperature. 9.82 g (0.045 mol) of PMDA and 14.5 g (0.045 mol) of BTDA were added along with 20.0 g of NMP, and the mixture was reacted at room temperature for 8 hours. Subsequently, 3.44 g (0.02 mol) of 4-ethynylphthalic anhydride was added along with 10.0 g of NMP, and the mixture was reacted further at room temperature for 4 hours to obtain (a) a polyimide precursor solution.

[0145] This polyimide precursor solution was applied to a 4-inch silicon wafer by spin coating using a spinner (Mikasa Corporation: MS-A150), and dried on a 60°C hot plate for 5 minutes to obtain a film with a thickness of 3 μm. Next, the substrate with this film was immersed at room temperature for 4 hours in a solution prepared by dissolving compound (c) DMAP 24.4 g (0.2 mol) and compound (b) DTBC 43.7 g (0.2 mol) in 50.0 g of NMP. After 4 hours, the substrate was washed with water and air-dried, and evaluation (1) was performed, showing an imidization rate of 98%.

[0146] Example 11 The procedure was the same as in Example 9 until a 3 μm thick film was obtained by drying on a 60°C hot plate for 5 minutes. Then, a solution of (c) compound DMAP 24.4 g (0.2 mol) and (b) compound DTBC 43.7 g (0.2 mol) dissolved in 50.0 g of NMP was sprayed onto the film-coated substrate at room temperature for 2 minutes, and left to stand at room temperature for 4 hours. After 4 hours, the substrate was washed with water, air-dried, and evaluated according to (1), showing an imidization rate of 97%.

[0147] Table 1 summarizes the compound (a) in each example and comparative example, and Tables 2 and 3 summarize the imidation process and its results, respectively.

[0148] [Table 1]

[0149] [Table 2]

[0150] [Table 3]

Claims

1. (a) A compound having a substructure represented by formula (1) (hereinafter referred to as compound (a)), (b) A compound represented by formula (2) (hereinafter referred to as compound (b)), (c) At least one selected from the compounds represented by formula (3) and resins having a structure represented by formula (4) in their side chains (hereinafter, these compounds or resins are referred to as (c) compounds), A method for producing an imide compound, comprising the step of mixing (a) a compound and imidizing the compound. 【Chemistry 1】 (In formula (1), R １ n represents a divalent to tetravalent organic group with 2 to 50 carbon atoms. １ The integers 0 to 2 are represented. * represents the bond point with the remainder of compound (a). 【Chemistry 2】 (In formula (2), R ２ and R ３ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms. 【Transformation 3】 (In formula (3), R ４ and R ５ Each of these independently represents a hydrocarbon group having 1 to 20 carbon atoms, R ６ represents a hydrocarbon group with 1 to 6 carbon atoms, n ２ (This represents an integer between 0 and 4.) 【Chemistry 4】 (In formula (4), R ７ represents a hydrocarbon group having 1 to 20 carbon atoms, R ８ represents a hydrocarbon group having 1 to 6 carbon atoms, n ３ represents an integer of 0 to 4. * represents a bonding site to the resin.)

2. A method for producing an imide compound according to claim 1, comprising immersing a powder, fiber, or film containing compound (a) in a solution or dispersion containing compound (b) and compound (c).

3. A method for producing an imide compound according to claim 1, comprising spraying a solution or dispersion containing the (b) compound and the (c) compound onto a powder, fiber, or film containing the (a) compound.

4. A method for producing an imide compound according to any one of claims 1 to 3, wherein the (b) compound is selected from at least one of the compounds represented below. 【Transformation 5】

5. A method for producing an imide compound according to any one of claims 1 to 3, wherein the imide compound is a polyimide, a polyamideimide, or a bismaleimide.

6. A method for producing an imide compound according to any one of claims 1 to 3, comprising the step of mixing compound (b) and compound (c) with a mixture of compound (a) and an organic base compound different from compound (c) to imide compound (a).

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