Composition and polymer

Abstract

[Problem] To provide a composition that suppresses coloring during storage. [Solution] Provided is a composition containing at least: a diamine compound (A) that is represented by formula (1); a solvent (B-1) that is represented by CaHbNcOd; a solvent (B-2) that is represented by CeHf; and a compound (C) that is represented by CgHhOi and that has a molecular weight of 300 or less in a solid state at 23°C under atmospheric pressure, wherein the total amount of the solvents in 100 parts by weight of the composition is 1-20,000 ppm. (In the chemical formulae of the solvent (B-1), the solvent (B-2), and the compound (C), a, b, e, f, g, h, and i each represent a natural number of 1 or greater, and c and d each represent an integer of 0 or greater. However, either c or d represents an integer of 1 or greater.) (In formula (1), R1 represents a 3-6 valent organic group having 2-33 carbon atoms, and R2 and R3 each independently represent hydrogen or a monovalent amino group having 3-13 carbon atoms. j represents an integer from 1 to 4.)

Description

Composition, Polymer

[0001] The present invention relates to a composition and a polymer obtained by reacting the same.

[0002] Diamine compounds are important as raw materials for heat-resistant polymers such as polyimides and polyamides. As conventional diamine compounds, diamine compounds having a residue derived from bis(amino-hydroxyphenyl)hexafluoropropane) and a phenolic hydroxyl group are used (Patent Document 1).

[0003] Japanese Unexamined Patent Publication No. 11-199557

[0004] The diamine compound described in Patent Document 1 has a problem of coloring during storage. Suppression of coloring of the diamine compound is important for suppressing coloring of the produced polymer.

[0005] Accordingly, an object of the present invention is to provide a composition in which coloring during storage is suppressed.

[0006] As a result of intensive studies, the present inventors have found that the use of a diamine compound, a solvent type composed of a specific element, and a solid-state compound composed of a specific element can suppress coloring of the composition during storage, and thus completed the present invention.

[0007] That is, in order to achieve the above object, the present invention mainly adopts the following constitution. [1] At least the diamine compound (A) represented by formula (1), C ａ H ｂ N ｃ O ｄ solvent (B-1) represented by, C ｅ H ｆ solvent (B-2) represented by and C ｇ H ｈ O ｉA composition comprising a compound (C) having a molecular weight of 300 or less and being in a solid state at 23°C under atmospheric pressure represented by , wherein the total amount of solvents contained in 100 parts by weight of the composition is 1 ppm or more and 20000 ppm or less. (In the chemical formulas of the solvent (B-1), the solvent (B-2), and the compound (C), a, b, e, f, g, h and i represent natural numbers of 1 or more, and c and d represent integers of 0 or more, provided that either c or d represents 1 or more.)

[0008]

[0009] (In formula (1), R １ represents a trivalent to hexavalent organic group having 2 to 33 carbon atoms, and R ２ and R ３(Each represents hydrogen or a monovalent amino group having 3 to 13 carbon atoms. j represents an integer from 1 to 4.) [2] The composition according to [1], wherein the solvent (B-1) comprises any of those selected from the group consisting of methanol, ethanol, isopropyl alcohol, tetrahydrofuran, methyl ethyl ketone, butyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetonitrile, and 3-methoxy-N,N-dimethylpropanamide. [3] The composition according to [1] or [2], wherein the content of the solvent (B-1) in 100 parts by weight of the composition is 500 to 10000 ppm. [4] The composition according to any one of [1] to [3], wherein the solvent (B-2) comprises any of those selected from the group consisting of hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene. [5] The composition according to any one of [1] to [4], wherein the content of the solvent (B-2) in 100 parts by weight of the composition is 10 to 3000 ppm. [6] The composition according to any one of [1] to [5], wherein the compound (C) comprises any selected from the group consisting of ditertically butylhydroxytoluene, 4-tertically butylcatechol, tertically butylhydroquinone, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, 2,4-ditertically butylphenol, and 6-tertically butyl-2,4-xylenol. [7] The composition according to any one of [1] to [6], wherein the content of the compound (C) in 100 parts by weight of the composition is 10 to 3000 ppm. [8] The composition according to any one of [1] to [7], wherein when the total content of solvent (B-1), solvent (B-2), and compound (C) in the composition is 100 parts by weight, the content of compound (C) is 1 to 50 parts by weight. [9] The composition according to any one of [1] to [8], wherein the compound represented by formula (1) is the compound represented by formula (2).

[0010]

[0011] (In formula (2), R ２ and R ３each independently represents hydrogen or a monovalent amino group having 3 to 13 carbon atoms. R ４ represents an ether group, a thioether group, a sulfonyl group, or a divalent organic group having 1 to 13 carbon atoms, and R ５ and R ６ each independently represents hydrogen or an organic group having 1 to 2 carbon atoms. k and l each independently represent a natural number of 1 or 2. m and n each independently represent an integer of 0 to 2.)

[10] The composition according to any one of [1] to [9], wherein the compound represented by the formula (1) is a compound represented by the formula (3).

[0012]

[0013] (In formula (3), R ４ represents an ether group, a thioether group, a sulfonyl group, or a divalent organic group having 1 to 13 carbon atoms, and R ５ and R ６ each independently represents hydrogen or an organic group having 1 to 2 carbon atoms. R ７ and R ８ represents a divalent organic group having 2 to 12 carbon atoms. k and l each independently represent a natural number of 1 or 2. m and n each independently represent an integer of 0 to 2.)

[11] A polymer obtained by reacting the composition according to any one of [1] to

[10] with an acid anhydride.

[0014] In each of the above items and in the description of the present application, "ppm" is an abbreviation for "×10 －６ parts by weight".

[0015] According to the present invention, a composition with suppressed coloration during storage can be provided.

[0016] Embodiments of the present invention will be described in detail.

[0017] The composition of the present invention comprises at least a diamine compound (A) represented by formula (1), C ａ H ｂ N ｃ O ｄ a solvent (B-1) represented by C ｅ H ｆ a solvent (B-2) represented by and C ｇ H ｈ Oｉ A composition containing a compound (C) having a molecular weight of 300 or less in a solid state at atmospheric pressure and 23°C, wherein the total amount of solvent contained in 100 parts by weight of the composition is 1 ppm or more and 20,000 ppm or less. (In the chemical formulas of solvent (B-1), solvent (B-2), and compound (C), a, b, e, f, g, h, and i represent natural numbers of 1 or more, and c and d represent integers of 0 or more. However, either c or d represents 1 or more.)

[0018]

[0019] (In formula (1), R １ R represents an organic group with 2 to 33 carbon atoms and 3 to 6 valents, ２ and R ３ Each of these independently represents hydrogen or a monovalent amino group having 3 to 13 carbon atoms. j represents an integer from 1 to 4.) <Diamine compound (A) represented by formula (1)> The composition of the present invention contains the diamine compound (A) represented by formula (1).

[0020] From the viewpoint of further suppressing discoloration during storage, the compound represented by formula (1) is preferably the compound represented by formula (2), and more preferably the compound represented by formula (3).

[0021]

[0022] (In formula (2), R ２ and R ３ Each of these independently represents either hydrogen or a monovalent amino group having 3 to 13 carbon atoms. ４ R represents an ether group, a thioether group, a sulfonyl group, or a divalent organic group having 1 to 13 carbon atoms. ５ and R ６ Each of the following independently represents hydrogen or an organic group with 1 to 2 carbon atoms. k and l independently represent natural numbers 1 or 2. m and n independently represent integers from 0 to 2.

[0023]

[0024] (In formula (3), R ４R represents an ether group, a thioether group, a sulfonyl group, or a divalent organic group having 1 to 13 carbon atoms. ５ and R ６ Each of these independently represents either hydrogen or an organic group having 1 to 2 carbon atoms. ７ and R ８ R represents a divalent organic group having 2 to 12 carbon atoms. k and l each independently represent a natural number of 1 or 2. m and n each independently represent an integer from 0 to 2.) In formulas (2) and (3) above, R ４ is, -SO ２ -ien-CH ２ -, -CH(CH ３ )-,-C(CH ３ ) ２ -, -C (CF ３ ) ２ -, -C(CH ３ ) [CH ２ CH (CH ３ ) ２ It is preferable that the group is a divalent group represented by formulas (4) to (6). ５ and R ６ It is preferable that it be hydrogen or a methyl group.

[0025]

[0026] (* in formulas (4) to (6) indicates a bonding site.) Specifically, as the diamine compound (A) represented by formula (1), for example, the following compounds can be used.

[0027]

[0028] In the present invention, the content of diamine compound (A) is preferably 98.00 parts by weight or more per 100 parts by weight of the composition, from the viewpoint of suppressing discoloration during storage. From the same viewpoint, it is also preferable that the content is 99.99 parts by weight or less.

[0029] The diamine compound (A) represented by formula (1) in the present invention is synthesized by known methods. For example, a method in which a bisphenol compound is nitrated and then a dinitro compound is reduced, or a method in which a hydroxydiamino compound is reacted with a nitrocarboxylic acid or nitrocarboxylic acid chloride and then the resulting dinitro compound is reduced.

[0030] <Solvent (B-1)> The composition of the present invention is C ａ H ｂ N ｃ O ｄ The composition contains a solvent (B-1) represented by [formula]. Here, a solvent in this invention is defined as a compound that is in a liquid state at atmospheric pressure and 23°C. By containing solvent (B-1), the composition of this invention can suppress discoloration during storage. Here, a and b are natural numbers of 1 or more, and c and d are integers of 0 or more. However, either c or d is 1 or more.

[0031] Specifically, the solvent (B-1) includes methanol, ethanol, isopropyl alcohol, butanol, 2-ethylhexanol, 2-methyl-2-butanol, isopentyl alcohol, octanol, pentanol, propylene glycol, dibutyl ether, diethylene glycol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, dipropyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, butyl methyl ether, diisopropyl ether, and triethylene glycol dimethyl ether. Examples include acetone, acetylacetone, methyl ethyl ketone, butyl acetate, diethyl carbonate, ethyl acetate, ethyl benzoate, ethyl formate, ethyl acetoacetate, ethyl propionate, methyl acetate, isopentyl acetate, pentyl acetate, propyl acetate, dimethyl carbonate, cyclohexanone, propylene carbonate, butyl butyrate, ethylmethyl carbonate, methyl isobutyl ketone, acetonitrile, propionitrile, benzonitrile, benzaldehyde, dimethylacetamide, diethylacetamide, diethylformamide, formamide, N-methylpyrrolidone, N-butylpyrrolidone, 2-pyrrolidone, gamma-butyrolactone, methylformamide, dimethylformamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamideaniline, nitrobenzene, pyridine, triethylamine, acetic acid, acetic anhydride, formic acid, propionic acid, and butyric acid. Two or more of these may be included. The solvent (B-1) preferably contains any of the following selected from the group consisting of methanol, ethanol, isopropyl alcohol, tetrahydrofuran, methyl ethyl ketone, butyl acetate, ethyl acetate, acetonitrile, dimethylacetamide, N-methylpyrrolidone, dimethylformamide, and 3-methoxy-N,N-dimethylpropanamide.

[0032] In the present invention, the content of solvent (B-1) is preferably 500 ppm or more, and more preferably 1000 ppm or more, per 100 parts by weight of the composition, from the viewpoint of suppressing discoloration during storage. Furthermore, from the same viewpoint, it is preferably 10000 ppm or less, and more preferably 5000 ppm or less.

[0033] Solvent (B-1) can be easily obtained by purchasing reagents or commonly available industrial products.

[0034] <Solvent (B-2)> The composition of the present invention, C ｅ H ｆ The composition contains solvent (B-2) represented by [formula]. By containing solvent (B-2), the composition of the present invention can suppress discoloration during storage. Here, e and f represent natural numbers of 1 or more.

[0035] Examples of solvents (B-2) include pentane, hexane, heptane, octane, nonane, decane, 2,2,4-trimethylpentane, cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, decahydronaphthalene, benzene, toluene, xylene, ethylbenzene, mesitylene, and tetralin. Two or more of these may be included. Preferably, solvent (B-2) contains any of the following selected from the group consisting of hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene.

[0036] In the present invention, the solvent (B-2) content is preferably 10 ppm or more, and more preferably 30 ppm or more, per 100 parts by weight of the composition, from the viewpoint of suppressing discoloration during storage. Furthermore, from the same viewpoint, it is preferably 3000 ppm or less, and more preferably 1000 ppm or less.

[0037] Solvent (B-2) can be easily obtained by purchasing reagents or commercially available industrial products.

[0038] <Compound (C)> The composition of the present invention is C ｇ H ｈ O ｉThe composition contains compound (C), which is in a solid state at atmospheric pressure and 23°C and has a molecular weight of 300 or less. By containing compound (C), the composition of the present invention can suppress discoloration during storage. Here, g, h, and i are natural numbers of 1 or more.

[0039] Specifically, compound (C) includes ditertically butylhydroxytoluene, 4-tertically butylcatechol, tertically butylhydroquinone, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, 2,4-ditertically butylphenol, 6-tertically butyl-2,4-xylenol, 2-tertically butyl-1,4-benzoquinone, 2,6-ditertically butylphenol, 2,6-ditertically butyl paracresol, and 2,6-ditertically butyl-4-methoxy Examples include phenol, 3,6-dihydroxybenzonorbornene, 2,5-ditteretherlybutylhydroquinone, 2,6-ditteretherlybutyl-4-ethylphenol, 3-(3,5-ditteretherlybutyl-4-hydroxyphenyl)propionic acid, methyl 3-(3,5-ditteretherlybutyl-4-hydroxyphenyl)propionate, 4,6-ditteretherlybutylresorcinol, 4-(hexyloxy)-2,3,6-trimethylphenol, and 2,5-ditteretherlyamylhydroquinone. Two or more of these may be included. Compound (C) preferably contains any of the following selected from the group consisting of diitteretherlybutylhydroxytoluene, 4-tertitterlybutylcatechol, tertitterlybutylhydroquinone, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, 2,4-ditteretherlybutylphenol, and 6-tertitterlybutyl-2,4-xylenol.

[0040] In the present invention, the content of compound (C) is preferably 10 ppm or more, more preferably 50 ppm or more, and even more preferably 100 ppm or more, per 100 parts by weight of the composition, from the viewpoint of suppressing discoloration during storage. Also from the same viewpoint, it is preferably 3000 ppm or less, more preferably 1500 ppm or less, and even more preferably 1000 ppm or less.

[0041] In the present invention, from the viewpoint of suppressing discoloration during storage, when the total content of solvent (B-1), solvent (B-2), and compound (C) is 100 parts by weight, the content of compound (C) is preferably 1 part by weight or more, and more preferably 10 parts by weight or more. Also from the same viewpoint, it is preferably 50 parts by weight or less, and more preferably 40 parts by weight or less.

[0042] <Composition> The composition of the present invention contains a total amount of solvents of 1 ppm to 20,000 ppm per 100 parts by weight of the composition. By setting the total amount of solvents to 1 ppm to 20,000 ppm, discoloration during storage can be suppressed. The total amount of solvents refers to the total amount of all solvents contained in the composition, including solvent (B-1) and solvent (B-2).

[0043] <Method for producing polymers> The composition of the present invention can be used as a monomer when polymerizing polymers. The polymer is not particularly limited as long as it uses the composition of the present invention containing a diamine compound as a monomer, and can be used as a monomer for example, polyimides, polybenzoxazoles, their precursors, or copolymers thereof.

[0044] The polymer obtained by reacting the above composition with an acid anhydride can be used as a polyimide or polyimide precursor, and the discoloration of the produced polymer can be suppressed. When producing polyimide, known methods can be used for the reaction conditions; for example, the addition reaction can be carried out by heat treatment at an appropriate temperature and time. The heat treatment time is preferably 1 to 12 hours. One example is a condition in which the mixture is heated at 60°C for 4 hours. The heat treatment temperature is preferably 40°C to 100°C.

[0045] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The evaluation methods for each example and comparative example are shown below.

[0046] (1) Evaluation of the content of solvent (B-1), solvent (B-2), and compound (C) in the composition For solvent (B-1), solvent (B-2), and compound (C), each reagent was used as a standard, and 0.20 g of each standard was weighed into a 10 mL volumetric flask. The solution was then diluted to a volume with N-methylpyrrolidone to create a 20,000 ppm standard stock solution. The 20,000 ppm standard solution was appropriately diluted with N-methylpyrrolidone to prepare standard solutions of 10,000 ppm, 1,000 ppm, 100 ppm, 10 ppm, and 1 ppm, and a calibration curve for gas chromatography (GC) analysis was created. When solvent (B-1) was N-methylpyrrolidone, a standard stock solution diluted to a volume with tetrahydrofuran was used.

[0047] Next, 0.10 g of the composition obtained in each production example was weighed into a 1 mL volumetric flask, N-methylpyrrolidone was added to bring it to a fixed volume, and then N-methylpyrrolidone was added again to dilute it fivefold to obtain the sample solution. When the solvent (B-1) was N-methylpyrrolidone, it was diluted with tetrahydrofuran to a fixed volume to obtain the sample solution.

[0048] Next, GC / FID analysis was performed using a gas chromatography (GC) system GC2010 (Shimadzu Corporation), with an Rxi-624Sil MS column (RESTEK), column temperature held at 40°C for 1 minute, then increased to 300°C at 20°C / min and held at 300°C for 9 minutes, split ratio of 1 / 20, inlet temperature of 300°C, injection volume of 1 μL, flow rate controlled at constant pressure of 122.1 kPa, flame ionization detector, and detector temperature of 300°C. The content was calculated from the percentage of each separated peak area. Here, the percentage of peak area represents the ratio of each peak area to the sum of the separated peak area values, which is set to 100.

[0049] (2) Evaluation of coloration during storage of the composition 0.20 g of the composition obtained in each production example was added to 3.80 g of N-methylpyrrolidone and shaken for 1 hour. The solution was then immediately placed in a quartz cell and the transmittance at a wavelength of 450 nm was measured using a UV-vis measuring device U-2910 (manufactured by Hitachi High-Tech Corporation).

[0050] Furthermore, the compositions obtained in each manufacturing example were placed in aluminum bags, sealed under atmospheric conditions, and stored at 15°C and 40°C. After 6 months, 9 months, and 12 months, they were removed, and an N-methylpyrrolidone solution was prepared for each sample in the same manner as described above, and the transmittance was measured.

[0051] As an indicator of whether discoloration during storage was suppressed, the transmittance value of each stored sample was calculated, with the transmittance value before storage set to 100. The closer these values ​​are to 100, the better the discoloration during storage was suppressed.

[0052] In the following examples, commercially available reagents were used for each compound. The molecular weight of each compound was measured by liquid chromatography-mass spectrometry (LC / MS). A liquid chromatography system LC-30A (Shimadzu Corporation) was used, with a mass spectrometer Q Exactive (Thermo Fisher Scientific), an ODS column, an ammonium acetate aqueous solution-acetonitrile mobile phase, a flow rate of 0.3 mL / min, an injection volume of 3 μL, electrospray ionization, and negative ion detection.

[0053] <Diamine Compound (A)> A-1: ​​2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (molecular weight 366, manufactured by Tokyo Chemical Industry Co., Ltd.) A-2 to A-10: See <Synthesis Example 1> to <Synthesis Example 9>

[0054]

[0055] A-11 to A-18: See <Synthesis Example 10> to <Synthesis Example 17>

[0056]

[0057] <Solvent (B-1)> B-1a: Tetrahydrofuran (hereinafter sometimes referred to as THF) (For high-performance liquid chromatography (HPLC) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) B-1b: Dimethylacetamide (For residual solvent testing manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) B-1c: N-methylpyrrolidone (For HPLC manufactured by Sigma-Aldrich) B-1d: Butyl acetate (For HPLC manufactured by Sigma-Aldrich) B-1e: Isopropyl alcohol (For HPLC manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) B-1f: Methanol (For HPLC manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) B-1g: Dimethylformamide (For HPLC manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) B-1h: 3-Methoxy-N,N-dimethylpropanamide (Manufactured by Tokyo Chemical Industry Co., Ltd.) B-1i: Acetonitrile (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., for HPLC) B-1j: Methyl ethyl ketone (manufactured by Sigma-Aldrich, for HPLC) B-1k: Ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., for HPLC) B-1l: Acetone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., for HPLC) <Solvent (B-2)> B-2m: Heptane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., for HPLC) B-2n: Toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., for HPLC) B-2o: Benzene (manufactured by Sigma-Aldrich, for HPLC) B-2p: Hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., for HPLC) B-2q: n-Octane (manufactured by Tokyo Chemical Industries, Ltd., for HPLC) B-2r: Methylcyclohexane (manufactured by Tokyo Chemical Industries, Ltd., for HPLC) B-2s: Xylene (manufactured by Sigma-Aldrich, for HPLC) B-2t: Cyclohexane (manufactured by Fujifilm Wako Pure Chemical Corporation, for HPLC) B-2u: 2,2,4-Trimethylpentane (manufactured by Fujifilm Wako Pure Chemical Corporation, for HPLC) <Compound (C)> C-1: Ditertically butylhydroxytoluene (molecular weight 220, manufactured by Tokyo Chemical Industries, Ltd.) C-2: 4-Tertically butylcatechol (molecular weight 166, manufactured by Tokyo Chemical Industries, Ltd.) C-3: Tertically butylhydroquinone (molecular weight 166, manufactured by Fujifilm Wako Pure Chemical Corporation, Wako Special Grade) C-4: Hydroquinone (molecular weight 110, manufactured by Fujifilm Wako Pure Chemical Corporation, Special Grade) C-5: 4-Methoxyphenol (molecular weight 124, manufactured by Tokyo Chemical Industry Co., Ltd.) C-6: 1,4-Benzoquinone (molecular weight 108, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade) C-7: 2,4-di-tert-butylphenol (molecular weight 206, manufactured by Tokyo Chemical Industries, Ltd.) C-8: 6-tert-butyl-2,4-xylenol (molecular weight 178, manufactured by Tokyo Chemical Industries, Ltd.) C-9: 2-tert-butyl-1,4-benzoquinone (molecular weight 164, manufactured by Tokyo Chemical Industries, Ltd.) <C, ｇ H ｈ O ｉ Compounds with a molecular weight greater than 300 in the solid state at atmospheric pressure and 23°C as shown (C')> (g, h, and i are natural numbers greater than or equal to 1.) C'-10: 4,4'-butylidenebis(6-tert-butyl-metacresol) (molecular weight 382, ​​manufactured by Tokyo Chemical Industry Co., Ltd.) <Synthesis Example 1 Synthesis of Diamine Compound (A-2)> 17.5 g (0.05 mol) of 4,4'-(9H-fluorene-9,9-diyl)bisphenol was placed in a 500 ml four-necked flask fitted with a stirrer, dropping funnel, thermometer, and Liebig condenser, and dissolved in 200 ml of THF. Subsequently, while cooling with ice to keep the internal temperature below 10°C, a mixed acid mixture of 7.7 g of 90% concentrated nitric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 22.7 g of 95% concentrated sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 2.0 g of ultrapure water was added from a dropping funnel over 10 minutes. 60 minutes after the start of the mixed acid addition, 23.8 g of special grade sodium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and the mixture was stirred while cooling for another 60 minutes. After adding 100 ml of ultrapure water, solid-liquid separation was performed using a Kiriyama funnel and aspirator. The resulting solid was thoroughly washed with ultrapure water, concentrated using a rotary evaporator, and recrystallized in THF solution. The recrystallized solid was added to a 500 ml glass flask fitted with a hydrogen balloon and a pressure release stopcock, and dissolved in 300 ml of THF. Then, 2 g of 5% palladium-carbon was added and the mixture was vigorously stirred. Hydrogen was introduced using a balloon, and the reduction reaction was carried out at room temperature. After about two hours, the reaction was terminated when it was confirmed that the balloon would not deflate any further. After the reaction was complete, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain the diamine compound (A-2) (molecular weight 380).

[0058] <Synthesis Example 2: Synthesis of Diamine Compound (A-3)> The same procedure as in Synthesis Example 1 was followed, except that 17.5 g (0.05 mol) of 4,4'-(9H-fluorene-9,9-diyl)bisphenol in Synthesis Example 1 was replaced with 13.5 g (0.05 mol) of 2,2-bis(4-hydroxyphenyl)-4-methylpentane to obtain diamine compound (A-3) (molecular weight 300).

[0059] <Synthesis Example 3: Synthesis of Diamine Compound (A-4)> The same procedure as in Synthesis Example 1 was followed, except that 17.5 g (0.05 mol) of 4,4'-(9H-fluorene-9,9-diyl)bisphenol was replaced with 12.5 g (0.05 mol) of 4,4'-sulfonyldiphenol to obtain diamine compound (A-4) (molecular weight 280).

[0060] <Synthesis Example 4: Synthesis of Diamine Compound (A-5)> The same procedure as in Synthesis Example 1 was followed, except that 17.5 g (0.05 mol) of 4,4'-(9H-fluorene-9,9-diyl)bisphenol was replaced with 11.4 g (0.05 mol) of 2,2-bis(4-hydroxyphenyl)propane to obtain diamine compound (A-5) (molecular weight 258).

[0061] <Synthesis Example 5: Synthesis of Diamine Compound (A-6)> The same procedure as in Synthesis Example 1 was followed, except that 17.5 g (0.05 mol) of 4,4'-(9H-fluorene-9,9-diyl)bisphenol was replaced with 10.7 g (0.05 mol) of 1,1-bis(4-hydroxyphenyl)ethane to obtain diamine compound (A-6) (molecular weight 244).

[0062] <Synthesis Example 6: Synthesis of Diamine Compound (A-7)> The same procedure as in Synthesis Example 1 was followed, except that 17.5 g (0.05 mol) of 4,4'-(9H-fluorene-9,9-diyl)bisphenol in Synthesis Example 1 was replaced with 13.4 g (0.05 mol) of 1,1-bis(4-hydroxyphenyl)cyclohexane to obtain diamine compound (A-7) (molecular weight 298).

[0063] <Synthesis Example 7: Synthesis of Diamine Compound (A-8)> The same procedure as in Synthesis Example 1 was followed, except that 17.5 g (0.05 mol) of 4,4'-(9H-fluorene-9,9-diyl)bisphenol in Synthesis Example 1 was replaced with 12.8 g (0.05 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane to obtain diamine compound (A-8) (molecular weight 286).

[0064] <Synthesis Example 8: Synthesis of Diamine Compound (A-9)> The same procedure as in Synthesis Example 1 was followed, except that 17.5 g (0.05 mol) of 4,4'-(9H-fluorene-9,9-diyl)bisphenol was replaced with 10.0 g (0.05 mol) of 4,4'-dihydroxydiphenylmethane to obtain diamine compound (A-9) (molecular weight 230).

[0065] <Synthesis Example 9: Synthesis of Diamine Compound (A-10)> The same procedure as in Synthesis Example 1 was followed, except that 17.5 g (0.05 mol) of 4,4'-(9H-fluorene-9,9-diyl)bisphenol was replaced with 9.3 g (0.05 mol) of 4,4'-dihydroxybiphenyl to obtain diamine compound (A-10) (molecular weight 216).

[0066] <Synthesis Example 10: Synthesis of Diamine Compound (A-11)> 18.3 g (0.05 mol) of diamine compound (A-1) was dissolved in 100 ml of acetone and 17.4 g (0.30 mol) of propylene oxide, and the mixture was cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 ml of acetone was added dropwise. After the addition was complete, the mixture was reacted at -15°C for 4 hours, and then returned to room temperature. The solution was concentrated using a rotary evaporator, and the resulting solid was recrystallized in a solution of THF and ethanol. The recrystallized solid was dissolved in 100 ml of ethanol and 300 ml of THF, and 2 g of 5% palladium-carbon was added and the mixture was vigorously stirred. Hydrogen was then introduced using a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated when it was confirmed that the balloon no longer deflated. After the reaction was complete, the palladium catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain the diamine compound (A-11) (molecular weight 604).

[0067] <Synthesis Example 11: Synthesis of Diamine Compound (A-12)> The same procedure as in Synthesis Example 10 was followed, except that 18.3 g (0.05 mol) of diamine compound (A-1) from Synthesis Example 10 was replaced with 15.0 g (0.05 mol) of diamine compound (A-3) to obtain diamine compound (A-12) (molecular weight 538).

[0068] <Synthesis Example 12: Synthesis of Diamine Compound (A-13)> The same procedure as in Synthesis Example 10 was followed, except that 18.3 g (0.05 mol) of diamine compound (A-1) from Synthesis Example 10 was replaced with 12.9 g (0.05 mol) of diamine compound (A-5) to obtain diamine compound (A-13) (molecular weight 496).

[0069] <Synthesis Example 13: Synthesis of Diamine Compound (A-14)> The same procedure as in Synthesis Example 10 was carried out, except that 18.3 g (0.05 mol) of diamine compound (A-1) from Synthesis Example 10 was replaced with 19.0 g (0.05 mol) of diamine compound (A-2) to obtain diamine compound (A-14) (molecular weight 618).

[0070] <Synthesis Example 14: Synthesis of Diamine Compound (A-15)> The same procedure as in Synthesis Example 10 was followed, except that 18.3 g (0.05 mol) of diamine compound (A-1) from Synthesis Example 10 was replaced with 14.0 g (0.05 mol) of diamine compound (A-4) to obtain diamine compound (A-15) (molecular weight 518).

[0071] <Synthesis Example 15: Synthesis of Diamine Compound (A-16)> The same procedure as in Synthesis Example 10 was followed, except that 18.3 g (0.05 mol) of diamine compound (A-1) from Synthesis Example 10 was replaced with 12.2 g (0.05 mol) of diamine compound (A-6) to obtain diamine compound (A-16) (molecular weight 482).

[0072] <Synthesis Example 16: Synthesis of Diamine Compound (A-17)> The same procedure as in Synthesis Example 10 was followed, except that 18.3 g (0.05 mol) of diamine compound (A-1) from Synthesis Example 10 was replaced with 14.9 g (0.05 mol) of diamine compound (A-7) to obtain diamine compound (A-17) (molecular weight 536).

[0073] <Synthesis Example 17: Synthesis of Diamine Compound (A-18)> The same procedure as in Synthesis Example 10 was followed, except that 18.3 g (0.05 mol) of diamine compound (A-1) from Synthesis Example 10 was replaced with 14.3 g (0.05 mol) of diamine compound (A-8) to obtain diamine compound (A-18) (molecular weight 524).

[0074] <Production Example 1> 49.9 g of diamine compound (A-1) was added to a 300 ml glass flask equipped with a stirrer. 50.0 mg of solvent (B-1a), 25.0 mg of solvent (B-2m), and 25.0 mg of compound (C-1) were added while stirring at room temperature. After stirring for 1 hour from the start of addition, the resulting composition (J-1) was collected. GC / FID analysis of composition (J-1) revealed that solvent (B-1a) was detected at 1000 ppm per 100 parts by weight of the total composition, solvent (B-2m) at 500 ppm, and compound (C-1) at 500 ppm. The total amount of solvent contained in 100 parts by weight of the composition was 1500 ppm.

[0075] <Production Examples 2-80> Compositions (J-2)-(J-80) were prepared by adding diamine compounds (A-2)-(A-18), solvents (B-1a)-(B-1l), solvents (B-2m)-(B-2u), compounds (C-1)-(C-9), and (C'-10) as shown in Tables 1-6 and stirring. As described above, GC / FID analysis was performed, and the content of detected solvents (B-1), solvents (B-2), compound (C), and compound (C') is shown in Tables 1-6.

[0076] <Example 1> The color of composition (J-1) during storage was evaluated. When stored at 15°C, the evaluation value was 100 for up to 12 months of storage. When stored at 40°C, the evaluation value was 100 for up to 9 months of storage, and the evaluation value for 12 months was 90.

[0077] <Examples 2-75> For compositions (J-2) to (J-75), the same coloration evaluation during storage was carried out as described above, as with composition (J-1). The evaluation results are shown in Tables 7 to 12.

[0078] <Example 76> In a 500 ml four-necked flask equipped with a stirrer and thermometer, 10.0 g of the freshly manufactured composition (J-11), 5.1 g of oxydiphthalic anhydride, and 150 ml of N-methylpyrrolidone were added and stirred under a nitrogen atmosphere for 1 hour. The reaction solution was coated to a thickness of 5 μm onto a 5 cm square Tempax glass using a spin coater MS-B100 (manufactured by Mikasa Corporation), and then heated for 3 minutes on a hot plate CHP-250DF (manufactured by AS ONE Corporation) heated to 120°C. The substrate was measured using the UV-vis measuring device used for color evaluation, and the transmittance at a wavelength of 450 nm was 100%.

[0079] Furthermore, a reaction solution was prepared in the same manner using composition (J-11) stored at 40°C for 12 months. When the substrate was coated in the same manner and its transmittance was measured, the transmittance at a wavelength of 450 nm was 100%.

[0080] <Comparative Examples 1-5> For compositions (J-76) to (J-80), coloration during storage was evaluated in the same manner as for composition (J-1). When stored at 15°C, the evaluation value after 6 months was 90, indicating coloration. When stored at 40°C, the evaluation value after 6 months was 50, indicating strong coloration.

[0081] <Comparative Example 6> In a 500 ml four-necked flask equipped with a stirrer and thermometer, 6.2 g of the composition (J-79) immediately after production, 8.9 g of oxydiphthalic anhydride, and 150 ml of N-methylpyrrolidone were added and stirred under a nitrogen atmosphere for 1 hour. The reaction solution was coated to a thickness of 5 μm onto a 5 cm square Tempax glass using a spin coater MS-B100 (manufactured by Mikasa Corporation), and then heated for 3 minutes on a hot plate CHP-250DF (manufactured by AS ONE Corporation) heated to 120°C. The substrate was measured using the UV-vis measuring device used for color evaluation, and the transmittance at a wavelength of 450 nm was 70%.

[0082] Furthermore, a reaction solution was prepared in the same manner using the composition (J-79) after 12 months of storage at 40°C. When the substrate was coated in the same manner and its transmittance was measured, the transmittance at a wavelength of 450 nm was 0%.

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[0096] The composition of the present invention can be suitably used as a monomer when polymerizing a polymer.

Claims

1. At least a diamine compound (A) represented by formula (1), C ａ H ｂ N ｃ O ｄ a solvent (B-1) represented by, C ｅ H ｆ a solvent (B-2) represented by and C ｇ H ｈ O ｉ A composition comprising the compound (C) represented by which is in a solid state at 23°C under atmospheric pressure and has a molecular weight of 300 or less, wherein the total amount of solvents contained in 100 parts by weight of the composition is 1 ppm or more and 20000 ppm or less. (In the chemical formulas of the solvent (B-1), the solvent (B-2) and the compound (C), a, b, e, f, g, h and i each represent a natural number of 1 or more, c and d each represent an integer of 0 or more, provided that either c or d represents 1 or more.) (In formula (1), R １ represents a trivalent to hexavalent organic group having 2 to 33 carbon atoms, R ２ and R ３ each independently represent hydrogen or a monovalent amino group having 3 to 13 carbon atoms, and j represents an integer of 1 to 4.) 2. The composition according to claim 1, wherein the solvent (B-1) comprises any of the following selected from the group consisting of methanol, ethanol, isopropyl alcohol, tetrahydrofuran, methyl ethyl ketone, butyl acetate, ethyl acetate, acetonitrile, dimethylacetamide, N-methylpyrrolidone, dimethylformamide, and 3-methoxy-N,N-dimethylpropanamide.

3. The composition according to claim 1 or 2, wherein the content of the solvent (B-1) in 100 parts by weight of the composition is 500 to 10,000 ppm.

4. The composition according to claim 1 or 2, wherein the solvent (B-2) comprises any one selected from the group consisting of hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene.

5. The composition according to claim 1 or 2, wherein the content of the solvent (B-2) in 100 parts by weight of the composition is 10 to 3000 ppm.

6. The composition according to claim 1 or 2, wherein the compound (C) comprises any one selected from the group consisting of ditertically butylhydroxytoluene, 4-tertically butylcatechol, tertically butylhydroquinone, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, 2,4-ditertically butylphenol, and 6-tertically butyl-2,4-xylenol.

7. The composition according to claim 1 or 2, wherein the content of compound (C) in 100 parts by weight of the composition is 10 to 3000 ppm.

8. The composition according to claim 1 or 2, wherein when the total content of solvent (B-1), solvent (B-2), and compound (C) in the composition is 100 parts by weight, the content of compound (C) is 1 to 50 parts by weight.

9. The composition according to claim 1 or 2, wherein the compound represented by formula (1) is the compound represented by formula (2). (In formula (2), R ２ and R ３ Each of these independently represents either hydrogen or a monovalent amino group having 3 to 13 carbon atoms. ４ R represents an ether group, a thioether group, a sulfonyl group, or a divalent organic group having 1 to 13 carbon atoms. ５ and R ６ Each of the following independently represents hydrogen or an organic group with 1 to 2 carbon atoms. k and l independently represent natural numbers 1 or 2. m and n independently represent integers from 0 to 2.

10. The composition according to claim 1 or 2, wherein the compound represented by formula (1) is the compound represented by formula (3). (In formula (3), R ４ R represents an ether group, a thioether group, a sulfonyl group, or a divalent organic group having 1 to 13 carbon atoms. ５ and R ６ Each of these independently represents either hydrogen or an organic group having 1 to 2 carbon atoms. ７ and R ８ (The symbol represents a divalent organic group with 2 to 12 carbon atoms. k and l independently represent natural numbers 1 or 2. m and n independently represent integers from 0 to 2.) 11. A polymer obtained by reacting the composition according to claim 1 or 2 with an acid anhydride.

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