JP7229527B2 - Diimidodicarboxylic acid and cured epoxy resin using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a diimidedicarboxylic acid capable of obtaining an epoxy resin cured product having excellent flexibility and dielectric properties, and an epoxy resin cured product using the same.

A diimidedicarboxylic acid composed of a tricarboxylic anhydride and a diamine is industrially useful as a dicarboxylic acid raw material for polymers such as polyamideimide and polyesterimide. Imidodicarboxylic acids are disclosed in Patent Documents 1 and 2, for example.

JP-A-4-182466 International publication 2016/061291 pamphlet

However, the diimide dicarboxylic acid disclosed in Patent Documents 1 and 2 is a compound obtained by reacting a tricarboxylic anhydride and mainly an aromatic diamine, so there is a problem that the resulting polymer is brittle. In recent years, there has been a demand for resin materials exhibiting excellent dielectric properties for high frequencies, but the polymers have high dielectric properties and have limited applications.

An object of the present invention is to provide a diimidedicarboxylic acid that can give an epoxy resin cured product having excellent flexibility and dielectric properties.

As a result of intensive studies on the above-mentioned problems, the present inventors found that the above-mentioned object can be achieved by using a diimidodicarboxylic acid composed of a tricarboxylic anhydride and a diamine having 18 or more carbon atoms as a raw material. I came up with the invention.

（式中、Ｒ^１は、炭素数１８以上の炭化水素基を示す。）
＜２＞無水トリカルボン酸が、無水トリメリット酸である＜１＞に記載のジイミドジカルボン酸。
＜３＞炭素数１８以上のジアミンが、ダイマージアミンである＜１＞または＜２＞に記載のジイミドジカルボン酸。
＜４＞無水トリカルボン酸と炭素数１８以上のジアミンとを反応させてジイミドジカルボン酸を製造する方法において、無溶媒下で反応させる＜１＞～＜３＞いずれかに記載のジイミドジカルボン酸の製造方法。
＜５＞メカノケミカル効果を用いて反応させる＜４＞に記載の製造方法。
＜６＞＜１＞～＜３＞いずれかに記載のジイミドジカルボン酸とエポキシ樹脂とを含有するエポキシ樹脂組成物。
＜７＞＜１＞～＜３＞いずれかに記載のジイミドジカルボン酸とエポキシ樹脂と有機溶剤とを含有するエポキシ樹脂溶液。
＜８＞＜６＞に記載のエポキシ樹脂組成物または請求項７に記載のエポキシ樹脂溶液を硬化してなるエポキシ樹脂硬化物。 That is, the gist of the present invention is as follows.
<1> A diimide dicarboxylic acid represented by the general formula (1) consisting of a tricarboxylic anhydride and a diamine having 18 or more carbon atoms.

(In the formula, R ¹ represents a hydrocarbon group with 18 or more carbon atoms.)
<2> The diimidedicarboxylic acid according to <1>, wherein the tricarboxylic anhydride is trimellitic anhydride.
<3> The diimide dicarboxylic acid according to <1> or <2>, wherein the diamine having 18 or more carbon atoms is a dimer diamine.
<4> Production of the diimide dicarboxylic acid according to any one of <1> to <3>, wherein the reaction is performed in the absence of a solvent in the method for producing a diimide dicarboxylic acid by reacting a tricarboxylic anhydride with a diamine having 18 or more carbon atoms. Method.
<5> The production method according to <4>, wherein the reaction is performed using a mechanochemical effect.
<6> An epoxy resin composition containing the diimide dicarboxylic acid according to any one of <1> to <3> and an epoxy resin.
<7> An epoxy resin solution containing the diimide dicarboxylic acid according to any one of <1> to <3>, an epoxy resin, and an organic solvent.
<8> A cured epoxy resin obtained by curing the epoxy resin composition according to <6> or the epoxy resin solution according to claim 7.

ADVANTAGE OF THE INVENTION According to this invention, the diimide dicarboxylic acid which can obtain the epoxy resin hardened|cured material which has the outstanding flexibility and dielectric properties can be provided.

一般式（１）において、Ｒ^１は、炭素数１８以上の炭化水素基である。 <Diimidodicarboxylic acid>
The diimidedicarboxylic acid of the present invention is a diimidedicarboxylic acid represented by the general formula (1) and is composed of a tricarboxylic anhydride and a diamine having 18 or more carbon atoms.

In general formula (1), R ¹ is a hydrocarbon group having 18 or more carbon atoms.

Examples of the tricarboxylic anhydride used in the present invention include trimellitic anhydride (1,2,4-benzenetricarboxylic acid-1,2-anhydride) and 1,2,3-benzenetricarboxylic acid-1,2-anhydride. things are mentioned. Among them, trimellitic anhydride is preferred because of its high versatility.

Examples of diamines having 18 or more carbon atoms used in the present invention include octadecanediamine (18 carbon atoms), nonadecanediamine (19 carbon atoms), icosanediamine (20 carbon atoms), and henicosanediamine (21 carbon atoms). , docosane diamine (22 carbon atoms), tricosane diamine (23 carbon atoms), tetracosane diamine (24 carbon atoms), pentacosane diamine (25 carbon atoms), hexacosane diamine (26 carbon atoms), heptacosane diamine ( 27 carbon atoms), octacosane diamine (28 carbon atoms), nonacosane diamine (29 carbon atoms), triacontanediamine (30 carbon atoms), hentriacontanediamine (31 carbon atoms), dotriacontanediamine (32 carbon atoms) ), tritriacontanediamine (33 carbon atoms), tetratriacontanediamine (34 carbon atoms), pentatriacontanediamine (35 carbon atoms), and dimer diamine (36 carbon atoms). Among them, dimer diamine (having 36 carbon atoms) is preferable because it has high versatility and improves the flexibility of the obtained epoxy resin cured product. The diamine having 18 or more carbon atoms may be hydrogenated, or may have a double bond or a triple bond. Moreover, the diamine having 18 or more carbon atoms may have a branch or an unsaturated bond. A diamine having 18 or more carbon atoms preferably has a high purity. Commercial products of dimer diamine include "Versamin 551" manufactured by BASF Japan, "Versamin 552" manufactured by Cognis Japan (hydrogenated product of Versamin 551), "PRIAMINE 1075" manufactured by Croda Japan, and manufactured by Croda Japan. "PRIAMINE 1074" can be mentioned. Among the above diamines having 18 or more carbon atoms, one type may be used alone, or two or more types may be used in combination.

<Method for producing diimidodicarboxylic acid>
The method for producing the diimide dicarboxylic acid represented by the general formula (1) is not particularly limited, but since a step such as solvent recovery is not required, tricarboxylic anhydride and a diamine having 18 or more carbon atoms are reacted in the absence of a solvent. After that, it is preferable to carry out a heat imidization reaction. As a method of reacting in the absence of a solvent, for example, a solid tricarboxylic anhydride is heated to a temperature below the melting point of the obtained diimidedicarboxylic acid and above the melting point of the diamine having 18 or more carbon atoms, and the tricarboxylic anhydride is converted into the solid. A method of reacting by adding a diamine having 18 or more carbon atoms in a liquid state so as to maintain the state, and a method of reacting tricarboxylic anhydride and a diamine having 18 or more carbon atoms using a mechanochemical effect. .

In the case of the former method, a method of dividing the diamine having 18 or more carbon atoms into two or more portions and adding the divided portions in a plurality of portions is preferable, and a method of dropping is more preferable.

The latter method utilizing the mechanochemical effect is a method of expressing the mechanochemical effect by utilizing the mechanical energy generated when pulverizing the raw material compound used in the reaction.

The mechanochemical effect refers to the application of mechanical energy (compressive force, shearing force, impact force, grinding force, etc.) to a raw material compound in a solid state under a reaction environment to pulverize the raw material compound and form It is the effect of activating the pulverization interface. This causes a reaction between functional groups. Reactions between functional groups usually occur between two or more starting compound molecules. For example, the reaction between functional groups may occur between two starting compound molecules with different chemical structures, or between two starting compound molecules with the same chemical structure. Reaction between functional groups does not occur only between a limited set of two starting compound molecules, but usually occurs between another set of two starting compound molecules. A new reaction between the functional groups may occur between the compound molecule generated by the reaction between the functional groups and the raw material compound molecule. The reaction between the functional groups is usually a chemical reaction, whereby the functional groups of each starting compound molecule form a bonding group (particularly a covalent bond) between two starting compound molecules to form another A compound molecule is generated.

In the present invention, the thermal imidization reaction is a method in which a tricarboxylic anhydride and a diamine having 18 or more carbon atoms are reacted in the absence of a solvent and then heated to 250 to 350° C. in a nitrogen atmosphere.

<Epoxy resin solution>
The epoxy resin solution of the present invention can be obtained by dissolving the diimidedicarboxylic acid represented by the general formula (1) and the epoxy resin in an organic solvent.

The epoxy resin used in the epoxy resin solution of the present invention is an organic compound having two or more epoxy groups in one molecule. Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, bisphenyl type epoxy resin, dicyclopentadiene type epoxy resin, phenol Novolac type epoxy resins, cresol novolac type epoxy resins, isocyanurate type epoxy resins, alicyclic epoxy resins, acrylic acid-modified epoxy resins, polyfunctional epoxy resins, brominated epoxy resins and phosphorus-modified epoxy resins can be mentioned. Among the above epoxy resins, one type may be used alone, or two or more types may be used in combination. The epoxy equivalent of the epoxy resin is preferably 100-3000 eq/mol, more preferably 150-300 eq/mol.

The organic solvent used in the epoxy resin solution of the present invention is not particularly limited as long as the curing agent and the epoxy resin can be dissolved uniformly, and non-halogenated solvents are preferred from the viewpoint of environmental impact. Examples of such non-halogenated solvents include amide compounds such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone. All of these non-halogenated solvents are useful as general purpose solvents. One of the above organic solvents may be used alone, or two or more thereof may be used in combination.

The epoxy resin solution of the present invention may contain a curing accelerator. Although the curing accelerator is not particularly limited, for example, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole; 4-dimethylaminopyridine, benzyldimethylamine, 2-(dimethylaminomethyl ) tertiary amines such as phenol and 2,4,6-tris(dimethylaminomethyl)phenol; and organic phosphines such as triphenylphosphine and tributylphosphine. Among the above hardening accelerators, one kind may be used alone, or two or more kinds may be used in combination.

The amount of the curing accelerator is preferably 0.01 to 2% by mass with respect to the total amount of the epoxy resin solution, and is 0.01 to 1% because the heat resistance and dielectric properties of the cured epoxy resin are improved. % by mass is preferable, and 0.05 to 0.5% by mass is more preferable.

The method for producing the epoxy resin solution of the present invention is not particularly limited, but may be, for example, either an individual dissolution method or a batch dissolution method. The individual dissolution method is preferable from the viewpoint of obtaining a uniform resin solution in a short time. The separate dissolution method is a method in which the diimidedicarboxylic acid and the epoxy resin are preliminarily mixed with an organic solvent and dissolved, and then mixed. The simultaneous dissolution method is a method of simultaneously mixing diimide dicarboxylic acid and an epoxy resin in an organic solvent and dissolving them. In the individual dissolution method and batch dissolution method, the mixing temperature is not particularly limited, but is preferably 80 to 180°C, more preferably 100 to 160°C. Heating to achieve the above mixing temperature may be, for example, reflux heating of the organic solvent.

In the epoxy resin solution of the present invention, the amount of diimidodicarboxylic acid to be blended improves the heat resistance and dielectric properties of the resulting epoxy resin cured product. , preferably 0.5 to 1.5 equivalent ratio, more preferably 0.7 to 1.3 equivalent ratio. The functional group equivalent weight of diimidodicarboxylic acid can be calculated from the content of carboxyl groups.

<Epoxy resin composition>
The epoxy resin composition of the present invention can be obtained by mixing the diimidedicarboxylic acid represented by the general formula (1) and an epoxy resin.

The epoxy resin used in the epoxy resin composition of the present invention is the same as the epoxy resin used in the epoxy resin solution.

The epoxy resin composition of the present invention may contain a curing accelerator. The curing accelerator and compounding amount used in the epoxy resin composition are the same as in the case of the epoxy resin solution.

The blending amount of imide dicarboxylic acid in the epoxy resin composition of the present invention is also the same as in the case of the epoxy resin solution.

<Epoxy resin cured product>
By heating the epoxy resin solution or the epoxy resin composition of the present invention, the diimide dicarboxylic acid and the epoxy resin can be reacted to obtain the epoxy resin cured product of the present invention. The heating temperature (curing temperature) is preferably 80 to 350°C, more preferably 130 to 300°C. The heating time (curing time) is preferably 1 minute to 20 hours, more preferably 5 minutes to 10 hours. In addition, when heating an epoxy resin solution, an organic solvent is distilled off by heating.

From the viewpoint of dielectric properties, the dielectric constant of the epoxy resin cured product of the present invention is preferably 2.5 or less, more preferably 2.2 or less, and even more preferably 2.1 or less. From the viewpoint of dielectric properties, the dielectric loss tangent of the cured epoxy resin product of the present invention is preferably 0.016 or less, more preferably 0.010 or less, and further preferably 0.006 or less. preferable. A cured epoxy resin having a dielectric constant of 2.5 or less and a dielectric loss tangent of 0.016 or less is obtained by curing an epoxy resin and a diimidedicarboxylic acid obtained by reacting a tricarboxylic anhydride with a diamine having 18 or more carbon atoms. can be obtained by

From the viewpoint of flexibility, the tensile modulus of the epoxy resin cured product of the present invention is preferably 1700 MPa or less, more preferably 1400 MPa or less. A cured epoxy resin having a tensile modulus of 1700 MPa or less can be obtained by curing a diimidedicarboxylic acid obtained by reacting an epoxy resin, tricarboxylic anhydride and a diamine having 18 or more carbon atoms.

The diimidedicarboxylic acid of the present invention can be suitably used as a raw material for polyamideimide, polyesterimide, and the like. Moreover, the epoxy resin composition, epoxy resin solution, and epoxy resin cured product of the present invention can be suitably used as printed wiring boards, build-up laminates, and semiconductor sealing materials.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these. The diimidedicarboxylic acid, epoxy resin solution, and cured epoxy resin were evaluated by the following methods.

A. Raw materials (1) Tricarboxylic anhydride/trimellitic anhydride: manufactured by Tokyo Chemical Industry Co., Ltd.
(2) Diamine/hydrogenated dimer diamine: "PRIAMINE 1075" manufactured by Croda Japan Co., Ltd.

(3) Epoxy resin/Bisphenol A type: "jER828" manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 184 to 194 g/eq
· Novolac type: Nippon Kayaku Co., Ltd. "EOCN-1020-55", o-cresol novolak type epoxy resin, epoxy equivalent 195 g / eq
(4) Curing accelerator 2-ethyl-4-methylimidazole: manufactured by Tokyo Chemical Industry Co., Ltd.

(5) Diimidodicarboxylic Acid Synthesis Example 1
A sample obtained by mixing trimellitic anhydride and hydrogenated dimer diamine at a molar ratio of 66.6/33.4 is mixed and pulverized for 1 minute at a rotation speed of 9000 rpm using a Wonder Crusher WC-3C manufactured by Osaka Chemical Co., Ltd. was repeated three times to carry out the mechanochemical treatment.
The treated sample was transferred to a glass container, and an imidation reaction was performed in an inert oven DN411I manufactured by Yamato Scientific Co., Ltd. under a nitrogen atmosphere at 300° C. for 2 hours to obtain a diimide dicarboxylic acid.

Synthesis Examples 2-4
The same operation as in Synthesis Example 1 was performed except that the diamine component was changed to the diamine shown in Table 1, mechanochemical treatment and imidization reaction were performed, and diimide dicarboxylic acid was obtained.

Table 1 shows the composition and evaluation of the diimidedicarboxylic acids obtained in Synthesis Examples 1-4.

B. Evaluation [Evaluation of diimidedicarboxylic acid]
(1) Confirmation of Reaction Infrared spectroscopy (IR) was used to measure under the following conditions to confirm the presence or absence of absorption near 1778 cm ⁻¹ and 1714 cm ⁻¹ .
Infrared spectroscopy (IR)
Apparatus: System 2000 infrared spectrometer manufactured by Perkin Elmer Method: KBr method Accumulation times: 64 scans (resolution 4 cm ^-1 )
If both absorption near 1778 cm ⁻¹ and near 1714 cm ⁻¹ can be confirmed, the reaction is evaluated as progressed and marked as “○”. It was evaluated as not progressing, and was set as "x".

(2) Molecular Weight Using a high-performance liquid chromatograph mass spectrometer (LC/MS), measurement was performed under the following conditions to determine the molecular weight.
Sample: diimidodicarboxylic acid/DMSO solution (200 μg/mL)
Apparatus: microTOF2-kp manufactured by Bruker Daltonics
Column: Cadenza CD-C18 3 μm 2 mm × 150 mm
Mobile phase: (mobile phase A) 0.1% formic acid aqueous solution, (mobile phase B) methanol Gradient (B Conc.): 0 min (50%) -5.7 min (60%) -14.2 min (60 %) - 17 minutes (100%) - 21.6 minutes (100%) - 27.2 minutes (50%) - 34 minutes (50%)
Ionization method: ESI
Detection condition: Negative mode

(3) Functional group equivalent It was obtained by calculation from the molecular weight and the number of functional groups of diimidodicarboxylic acid.

[Evaluation of epoxy resin solution]
(4) Solubility of diimide dicarboxylic acid ◯: Completely dissolved within 10 minutes.
x: Although completely dissolved, it took 10 minutes to dissolve.

[Evaluation method for cured epoxy resin]
(5) Reactivity The epoxy resin solution obtained in each example and comparative example was coated on an aluminum substrate to a thickness of 300 µm, and was placed in an inert oven in a nitrogen atmosphere at 180°C for 2 hours, followed by 200°C. for 2 hours to remove the solvent and perform a curing reaction. Thereafter, the aluminum base material was removed from the aluminum base material on which the resin layer was formed to obtain a cured epoxy resin.
The epoxy resin cured product thus obtained was subjected to transmission infrared absorption spectrum (IR) measurement under the following conditions to determine the absorbance ratio of the glycidyl group and the reaction rate.
Absorption originating from glycidyl groups is usually detected in the wavenumber region of 900 to 950 cm ⁻¹ . The line connecting the bases on both sides of the absorption peaks detected at these wavenumbers is taken as the baseline, and the line from the top of the peak perpendicular to the baseline is drawn from the intersection point to the top of the peak. Absorbance was calculated as the length.
Infrared spectroscopy (IR)
Apparatus: System 2000 infrared spectrometer manufactured by Perkin Elmer Method: KBr method Accumulation times: 64 scans (resolution 4 cm ^-1 )

The details of the method for calculating the reaction rate from the absorbance ratio of glycidyl groups are as follows.
First, a sample for IR measurement was prepared by mixing the epoxy resin cured product obtained in each example with KBr powder, and the measurement was performed. It was confirmed that the intensity of the peak showing the highest absorbance in the obtained spectrum fell within the absorbance range of 0.8 to 1.0, and the absorbance α of the glycidyl group was determined. The sample was then heat treated in an oven at a temperature of 300° C. for 2 hours under a stream of nitrogen to complete the curing reaction. The cured sample was subjected to IR measurement by the same method, and the absorbance α' of the wave number due to the glycidyl group was obtained. At this time, the reaction rate of the sample was determined by the following formula and evaluated according to the following criteria. The epoxy resin solution used to prepare the samples was left at room temperature (25° C.) for 48 hours after preparation.
Reaction rate (%) = {1-(α'/α)} × 100

◎: 90% ≤ reaction rate ≤ 100% (best)
○: 80% ≤ reaction rate < 90% (good)
×: reaction rate <80% (defective)

(6) Glass transition temperature The cured epoxy resin obtained in (5) was measured using a differential scanning calorimeter (DSC) under the following conditions.
Apparatus: DSC 7 manufactured by Perkin Elmer
Heating rate: 20° C./min The temperature was raised from 25° C. to 300° C. After the temperature was lowered, the temperature was raised from 25° C. to 300° C. again, and a discontinuous change originating from the transition temperature in the obtained temperature rise curve started. The temperature was taken as the glass transition temperature.

(7) Dielectric properties (dielectric constant, dielectric loss tangent)
Using an impedance analyzer, the dielectric constant and dielectric loss tangent of the epoxy resin cured product obtained in (5) were measured under the following conditions and evaluated according to the following criteria.
Apparatus: E4991A RF impedance/material analyzer manufactured by Agilent Technologies Inc. Sample dimensions: length 20 mm x width 20 mm x thickness 150 µm
Frequency: 1GHz
Measurement temperature: 23°C
Test environment: 23°C ± 1°C, 50% RH ± 5% RH

◎: dielectric constant ≤ 2.1 (best)
○: 2.1 < dielectric constant ≤ 2.2 (good)
×: 2.2 <permittivity (defective)

◎: dielectric loss tangent ≤ 0.006 (best)
○: 0.006 < dielectric loss tangent ≤ 0.010 (good)
×: 0.010 <dielectric loss tangent (defective)

(8) Tensile modulus of elasticity The epoxy resin cured product obtained in (5) was cut into a width of 10 mm and a length of 100 mm to prepare a test piece, which was measured according to ISO 178 and evaluated according to the following criteria.
◎: Tensile modulus ≤ 1400 MPa (best)
○: 1400 MPa < tensile modulus ≤ 1700 MPa (good)
×: 1700 MPa <tensile modulus (defective)

Example 1
To 60 parts by mass of a sample obtained by mixing the diimidodicarboxylic acid obtained in Synthesis Example 1 and a bisphenol A type epoxy resin at a ratio of 1.0/1.1 (equivalent ratio), 0.00 of 2-ethyl-4-methylimidazole was added. 2 parts by mass and 39.8 parts by mass of dimethylformamide were mixed and heated under reflux at 150° C. for 0.5 hours to obtain an epoxy resin solution.
The reaction rate of glycidyl groups in the epoxy resin contained in the epoxy resin solution obtained in Example 1 was 10% or less.

Examples 2-4, Comparative Examples 1 and 2
An epoxy resin solution was obtained in the same manner as in Example 1, except that the types and blending amounts of the diimide dicarboxylic acid and the epoxy resin used were changed as shown in Table 2.
The reaction rate of glycidyl groups in the epoxy resin contained in the epoxy resin solutions obtained in Examples 2 to 4 and Comparative Examples 1 and 2 was 10% or less.

Table 2 shows the composition and evaluation of the epoxy resin solutions obtained in Examples 1 to 4 and Comparative Examples 1 and 2, and the evaluation of the cured epoxy resin.

Since the epoxy resin cured products of Examples 1 to 4 used diimide dicarboxylic acid composed of tricarboxylic anhydride and diamine having 18 or more carbon atoms as a raw material, the tensile elastic modulus was 1700 MPa or less, the flexibility was high, and the dielectric constant was 2. 0.2 or less, and the dielectric loss tangent was 0.010 or less, and the dielectric properties were excellent.

The epoxy resin cured products of Comparative Examples 1 and 2 had large tensile elastic modulus, dielectric constant and dielectric loss tangent because diimidedicarboxylic acid composed of tricarboxylic anhydride and diamine having less than 18 carbon atoms was used as a raw material.

Claims (7)

A diimidedicarboxylic acid represented by the general formula (1) consisting of a tricarboxylic anhydride and a diamine having 18 or more carbon atoms, wherein the diamine is octadecanediamine, nonadecanediamine, icosanediamine, henicosanediamine, docosane Diamine, tricosanediamine, tetracosanediamine, pentacosanediamine, hexacosanediamine, heptacosanediamine, octacosanediamine, nonacosanediamine, triacontanediamine, hentriacontanediamine, dotriacontanediamine, tritriacontanediamine, tetra A diimide dicarboxylic acid selected from triacontanediamine, pentatriacontanediamine, dimer diamine, hydrogenated dimer diamine .

(In the formula, R ¹ represents a hydrocarbon group with 18 or more carbon atoms.) 2. The diimide dicarboxylic acid according to claim 1, wherein the tricarboxylic anhydride is trimellitic anhydride. 3. The diimide dicarboxylic acid according to claim 1 or 2, wherein the diamine having 18 or more carbon atoms is a dimer diamine. 4. The method for producing a diimidedicarboxylic acid according to any one of claims 1 to 3, wherein the reaction is carried out without a solvent in the method for producing a diimidedicarboxylic acid by reacting a tricarboxylic anhydride with a diamine having 18 or more carbon atoms. 5. The production method according to claim 4, wherein the reaction is performed using a mechanochemical effect. An epoxy resin composition containing the diimidedicarboxylic acid according to any one of claims 1 to 3 and an epoxy resin. An epoxy resin solution containing the diimide dicarboxylic acid according to any one of claims 1 to 3, an epoxy resin and an organic solvent.