Amino compound, polyamic acid and polyimide using said amino compound, and methods for producing them

Abstract

To provide: an amino compound which can reduce the dielectric loss tangent of a cured product of resin composition; a polyamic acid and a polyimide that are based on the amino compound; and a method for producing them.SOLUTION: The amino compound has at least two substituents comprising a structure represented by general formula (1) in the figure, and also has at least two primary amino groups bonded to a methylene group. (In formula (1), X represents a bonding position.)SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an amino compound, a polyamic acid and a polyimide using the amino compound, and methods for producing them. [Background technology]

[0002] The amount of data transmitted by electronic devices, such as smartphones, is expected to increase further in the future, and communication frequencies are becoming higher to speed up data transmission. In order to increase communication frequencies, it is necessary to suppress transmission loss, and materials with low dielectric constants and low dielectric loss tangents are needed.

[0003] Diamine compounds having alkyl groups have been proposed to improve dielectric properties (Patent Document 1). Patent Document 1 states that the large free volume of diamine compounds enables the achievement of low dielectric constants and low dielectric loss tangents. However, the method using linear alkyl groups, which is considered preferable in this patent, does not ensure sufficient free volume, limiting the achievement of low dielectric constants and low dielectric loss tangents. Patent Document 2 discloses that a cured product obtained by curing a monofunctional epoxy ester or ether compound having a branched alkyl moiety can have a lower dielectric constant than the cured product of the original epoxy resin. However, because it is limited to monofunctional epoxy ester or ether compounds, there are limitations to providing a more versatile low dielectric constant. Furthermore, it does not disclose whether the dielectric loss tangent can be reduced.

[0004] Recently, materials informatics (MI), which uses artificial intelligence to link the structure, physical properties, and chemical properties of materials, has become popular in materials development. Information processing techniques based on statistical mathematics, known as machine learning, are being used to advance material development. For example, numerous examples have been reported of creating estimation models that use the chemical structure of a polymer or its monomer as explanatory variables to accurately estimate the target variable, which is a polymer's physical property value. For example, Non-Patent Documents 1 and 2 disclose techniques for accurately estimating the refractive index and glass transition temperature of a polymer by creating a regression equation using structural descriptors of the monomer to numerically convert characteristic atomic arrangements and charge information within the molecule as explanatory variables and the target variable, which is the refractive index and glass transition temperature of the polymer. The applicant has also developed and published a technique for accurately estimating the dielectric constant of polyimide by creating an estimation model for the dielectric constant using a dataset of the partial molecular structure and the dielectric constant of polyimide obtained by first-principles calculations (Non-Patent Document 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-142782 [Patent Document 2] Patent No. 6823294 [Non-patent literature]

[0006] [Non-Patent Document 1] ACS Omega 2018, 3, 10, 13374-13386 [Non-patent document 2] J. Comput. Chem. Jpn., Vol. 18, No. 2, pp. 115-121 (2019) [Non-patent document 3] FY2020 Ultra-Advanced Materials Ultra-Rapid Development Fundamental Technology Project (Ultra-Ultra PJ) Results Reporting Session "Research and Development of High-Frequency Compatible Flexible Dielectric Materials" Nippon Steel Chemical & Material Summary of the Invention [Problem to be solved by the invention]

[0007] Therefore, while developing materials that contribute to low transmission loss, the inventors of the present application have investigated and adopted an evaluation model for dielectric loss tangent using the above-mentioned machine learning, and have conducted extensive research into novel amino compounds that can achieve a lower dielectric loss tangent than when amino compounds disclosed in conventional prior art are used. As a result, they have discovered that it is effective to use an amino compound that has a specific multi-branched alkyl structure and a predetermined number of primary amino groups bonded to a methylene group, and have completed the present invention.

[0008] Therefore, an object of the present invention is to provide a novel amino compound capable of achieving a low dielectric loss tangent and a polyimide using the same. Another object of the present invention is to provide a method for producing such a novel amino compound and a polyimide using the same. A further object of the present invention is to provide a method for evaluating the degree of transmission loss (e.g., dielectric loss tangent) by employing an evaluation model using machine learning in the development of such a novel amino compound and a polyimide using the same. [Means for solving the problem]

[0009] That is, the gist of the present invention is as follows. [1] An amino compound having at least two substituents containing a structure represented by the following general formula (1) and at least two primary amino groups bonded to a methylene group: [ka] [In formula (1), X represents a bonding position.] [2] The amino compound according to [1], which is represented by the following general formula (2): [ka] [In formula (2), R1 and R2 each independently represent a hydrogen atom or a substituent of the following general formula (3), and R3 represents an alkylene group having one or more carbon atoms.] [ka] [In formula (3), X represents a bonding position.] [3] The amino compound according to [1], which is represented by the following general formula (4): [ka] [In formula (4), C1~C n represents a carbon atom, C1 to C n Side chain R 11 ,R 12 ,···,R n1 ,R n2 each independently represents a hydrogen atom or a substituent having a structure of the following general formula (1), and R 11 ,R 12 ,···,R n1 ,R n2 and contains at least two or more substituents containing the structure of general formula (1), and n is an integer of 6 or more and 12 or less. [ka] [In formula (1), X represents a bonding position.] [4] A polyamic acid containing a diamine residue derived from a diamine component and a tetracarboxylic acid residue derived from a tetracarboxylic dianhydride component, A polyamic acid characterized in that the diamine component contains the amino compound according to any one of [1] to [3]. [5] A polyimide containing a diamine residue derived from a diamine component and a tetracarboxylic acid residue derived from a tetracarboxylic acid dianhydride component, A polyimide characterized in that the diamine component contains the amino compound according to any one of [1] to [3]. [6] A method for producing the amino compound according to any one of [1] to [3], comprising the following steps (a) and / or (b): (a): A compound having a substituent containing the structure of the following general formula (1) is subjected to a coupling reaction with an aliphatic dinitrile using a strong base, and then the nitrile group is converted to an amino group. (b): After obtaining an unsaturated compound having a substituent containing the structure of the following general formula (1), an ester bond, and an unsaturated double bond, a dimerization reaction is carried out via the unsaturated bond, and then a reaction is carried out to convert the ester bond in the obtained dimer of the unsaturated compound into an amide bond, followed by conversion of the amide bond into an amino group. [ka] [In formula (1), X represents a bonding position.] [7] A method for producing a polyamic acid by reacting a diamine component with a tetracarboxylic dianhydride component, A method for producing a polyamic acid, wherein the diamine component contains the amino compound according to any one of [1] to [3]. [8] A method for producing a polyimide, characterized by further imidizing the polyamic acid obtained by the method according to [7]. [Effects of the Invention]

[0010] The amino compound of the present invention can achieve a low dielectric loss tangent for a cured product of a resin composition, such as a polyimide. Furthermore, the manufacturing method of the present invention can produce such an amino compound. Furthermore, the present invention can evaluate the degree of low transmission loss (e.g., low dielectric loss tangent) of an amino compound and a cured product of a resin composition using the same through a dielectric loss tangent evaluation model using machine learning. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a 1H-NMR spectrum of Compound A obtained in Example 1. [Figure 2] FIG. 2 is an ESI-MS spectrum of Compound A obtained in Example 1. [Figure 3] FIG. 3 is a graph comparing the measured and estimated values ​​of the dielectric loss tangent for four types of polyimide materials not included in the training data in creating an estimation model for the dielectric loss tangent. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, an embodiment of the present invention will be described.

[0013] <Amino compounds> The amino compound of the present invention has at least two substituents containing a structure represented by the following general formula (1), and has at least two primary amino groups bonded to methylene groups. [ka] [In formula (1), X represents a bonding position.]

[0014] The amino compound of the present invention contains at least two structures represented by formula (1) in the molecule, and the presence of such a large fatty (hydrocarbon) chain can reduce the dielectric loss tangent of the molecule itself and the cured product of the resin composition using the compound, thereby contributing to the improvement of dielectric properties. The reason for this is presumed to be as follows. In other words, the structure represented by formula (1) is a large fatty (hydrocarbon) chain, which is thought to increase the free volume of the molecule. Increasing the free volume is thought to reduce the proportion of polar amino groups and groups derived from them (e.g., imide groups in the case of polyimide). This is thought to reduce the dipole moment of the molecule (and the resin) as a whole. Regarding the dielectric loss tangent, when a voltage is applied to a resin (dielectric), the dipole moment moves in response to the electric field, converting part of the electrical energy into heat and resulting in loss (dielectric loss). The dielectric loss tangent is an index of this electrical energy loss. Therefore, it is thought that increasing the free volume and reducing the dipole moment, as described above, are effective.

[0015] The substituent containing the structure represented by formula (1) may be the group of formula (1) itself, or the structure represented by formula (1) may be bonded to another group, which may or may not contain formula (1), via the bonding position X. Examples of substituents when the other group also contains formula (1) include, but are not limited to, the substituent of formula (3) below. Here, the "other group" is not limited to the above, and is preferably a group containing few or no polar groups other than amino groups, more preferably a hydrocarbon group that may have heteroatoms, and even more preferably a group consisting only of aliphatic hydrocarbons. Most preferably, the substituent is composed only of aliphatic hydrocarbons having one or more structures represented by formula (1). That is, the entire molecule of the amino compound is preferably an amino compound consisting only of aliphatic hydrocarbons (excluding the amino group) having 2 to 12 structures represented by formula (1). By setting the number of structures represented by formula (1) within the preferred range, the bulkiness around the amino group can be relatively suppressed, which is preferable because it does not reduce the reactivity when used as a resin raw material. [ka] [In formula (3), X represents a bonding position.]

[0016] The amino compound of the present invention also has at least two primary amino groups bonded to a methylene group. It is believed that by having a primary amino group bonded to a methylene group, the bulkiness of the structure near the amino group can be reduced compared to when the amino group is bonded to a methine or quaternary carbon, and as a result, it is believed that reaction (approach) with other functional groups (e.g., acid anhydride groups, epoxy groups, etc.) via the amino group becomes more likely to occur compared to when the carbon next to the amino group is a tertiary or quaternary carbon.

[0017] Furthermore, it is preferable that the compound has at least two such amino groups, since it can be used as a material for industrially useful resins such as polyimide, polyamide, epoxy, etc. Preferably, the amino compound has 2 to 4 such amino groups, more preferably 2, for reasons such as economic efficiency (or difficulty) in producing the amino compound.

[0018] The amino compound of the present invention having the above-described structural characteristics is not particularly limited, but examples thereof include those represented by the following general formula (2) or (4) from the viewpoints of the arrangement of the structure represented by formula (1) and the predictability, rationality, and efficiency of the production (synthesis) method. [ka]

[0019] Here, in formula (2), R1 and R2 each independently represent a hydrogen atom or a substituent of the general formula (3). To reduce the dielectric loss tangent, it is preferable to have many structures represented by formula (1), and it is preferable that both R1 and R2 are substituents of formula (3). On the other hand, from the viewpoint of the reactivity of the amino group with other functional groups, as described above, either or both of R1 and R2 may be a hydrogen atom, and these can be appropriately set or changed depending on the object of the present invention (such as reducing the dielectric loss tangent).

[0020] Furthermore, R3 in formula (2) is an alkylene group having 1 or more carbon atoms. R3 may be a linear alkylene group such as a methylene group, ethylene group, n-propylene group, n-butylene group, or hexylene group, preferably a linear alkylene group having about 1 to 14 carbon atoms, or may be a branched alkylene group preferably having about 1 to 14 carbon atoms, such as an isopropylene group, isobutylene group, or 2-methylpropylene group. A linear alkylene group having about 1 to 14 carbon atoms is more preferred.

[0021] The amino compound represented by formula (2) is not limited to, but examples thereof include the following compounds A to D. [ka] [ka] [ka]

[0022] The amino compound represented by the general formula (4) is represented by the following formula: [ka]

[0023] Here, in formula (4), C1 to C n represents a carbon atom, and n is an integer of 6 or more and 12 or less.

[0024] In addition, C1 to C in formula (4) n Side chain R 11 ,R 12 ,···,R n1 ,R n2 each independently represents a hydrogen atom or a substituent containing the structure of the general formula (1), and R 11 ,R 12 ,···,R n1 ,R n2The substituents containing the structure of general formula (1) are defined as above, but R 11 ,R 12 ,···,R n1 ,R n2 In the formula (1), it is preferable that the number of substituents containing the structure of the formula (1) is 2 to 8.

[0025] The amino compound represented by formula (4) is not limited to, but examples thereof include the following compounds E to G. [ka]

[0026] The amino compound of the present invention preferably has a molecular weight of not more than 2000. When the molecular weight is not more than 2000, a decrease in solubility in solvents can be prevented, making it suitable for use as a resin raw material.

[0027] When the amino compound of the present invention is used as a resin raw material, it can be used in combination with other amino compounds. In this case, the content of the amino compound of the present invention depends on the resin to be used and the application, but in order to suitably achieve a low dielectric loss tangent, it is preferably 25 mol% or more, more preferably 50 mol% or more, even more preferably 75 mol% or more, still more preferably 90 mol% or more, and most preferably 100 mol% of the total amino compounds. The amino compound of the present invention may be used as a mixture, and may be a mixture of the above-mentioned exemplary compounds.

[0028] The amino compound of the present invention is not limited in its applications, and can be used, for example, as a diamine component of polyimide, an epoxy curing agent, a polyurea raw material, an electronic device raw material, a resin modifier, a metal processing oil, a cleaning agent, an additive, or an intermediate raw material for pharmaceuticals and agricultural chemicals. In particular, the amino compound can be widely used as a raw material for electronic devices that are expected to have low transmission loss (for example, a low dielectric tangent), and is suitable as a diamine component of polyimide or an epoxy curing agent.

[0029] <Method of producing amino compounds> The method for producing the amino compound of the present invention is not limited, and known synthesis and production techniques can be used. However, for the purpose of forming an aliphatic skeleton (such as a t-butyl group, a methyl group, or a methylene group) with a large free volume and low polarity that contributes to a low dielectric loss tangent, it is generally preferred to use a method in which a compound having a substituent containing the structure of general formula (1) is used, and the compound is bonded to itself or to another alkyl chain or the like to form a carbon-carbon bond to obtain a precursor of the amino compound, and then a predetermined functional group in the precursor is converted to an amino group.

[0030] For example, the amino compounds of the general formulas (2) and (4) can be synthesized or produced by a method including, but not limited to, the following procedures, in view of the commonality of the chemical structures encompassed by each general formula. Any or all of the production methods shown below can be appropriately adopted, and known methods can also be appropriately used.

[0031] [Production Example of Amino Compound of General Formula (2)] The amino compound of general formula (2) preferably includes a step of bonding a compound having a substituent containing the structure of general formula (1) with an aliphatic dinitrile compound via a coupling reaction using a strong base, and then converting the nitrile group into an amino group.

[0032] When obtaining an amino compound of formula (2), it is preferable to use a compound having a substituent of general formula (3) as the compound having a substituent containing the structure of general formula (1), and it is also preferable to use a compound having the structure of R3 in formula (2) as the aliphatic dinitrile compound. This allows the multi-branched structure, which is the substituent containing the structure of general formula (1) (e.g., the substituent of general formula (3)), and the partial structure of R3 in general formula (2) to be separately introduced and formed, while allowing the coupling reaction using a strong base to bond and elongate the carbon chain without introducing an extra polar functional group. Furthermore, using a compound that already has a nitrile group is advantageous because it can serve as a nucleophile in the coupling reaction and as a precursor to the amino group that is ultimately converted.

[0033] Examples of compounds having a substituent containing the structure of general formula (1) include isostearyl alcohol and isostearic acid. For reasons of availability, isostearic acid (2,2,4,8,10,10-hexamethylundecane-5-carboxylic acid) is preferably used as the compound having a substituent of general formula (3). This starting material isostearic acid can be halogenated stepwise by chlorination or bromination to subsequently react with an aliphatic dinitrile. First, isostearic acid is reduced to an alcohol compound using a reducing agent. Examples of the reducing agent that can be used in this case include lithium aluminum hydride. The resulting alcohol (compound 2 below) can then be subjected to an Appel reaction using triphenylphosphine and carbon tetrachloride, carbon tetrabromide, or iodine to obtain a halide (compound 3 below (an example of a bromide)). [ka]

[0034] On the other hand, as described above, an aliphatic dinitrile compound having the R3 structure is used as a compound that has the partial structure of R3 in general formula (2) but can be later converted to an amino group. R3 is the same as defined above, and examples of the aliphatic dinitrile compound that can be used include propanedinitrile, butanedinitrile, pentanedinitrile, hexanedinitrile, heptanedinitrile, octanedinitrile, nonanedinitrile, decanedinitrile, and undecanedinitrile.

[0035] Next, the halide obtained above is reacted (coupling reaction) with an aliphatic dinitrile to obtain a compound (Compound 4 below) that serves as a precursor to an amino compound. During this reaction, the aliphatic dinitrile is subjected to a strong base to abstract the hydrogen bonded to the α-carbon of the nitrile group, thereby generating a carboanion. Examples of the strong base that can be used in this case include strong bases with low nucleophilicity, such as sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, and lithium tetramethylpiperidine. A catalyst may also be used as needed. The generated carboanion undergoes a nucleophilic coupling reaction with Compound 3, yielding Compound 4 below. The nitrile group of Compound 4 obtained in this manner is then reduced with a reducing agent (e.g., lithium aluminum hydride, borane-tetrahydrofuran complex, etc.) to convert it to a primary amino group bonded to a methylene group. This allows the production of Compound A, for example, when the aliphatic dinitrile is decanedinitrile (the number of carbon atoms in R3 is 6). [ka]

[0036] When glutaronitrile (pentanenitrile) or undecanedinitrile is used as the aliphatic dinitrile, the above-mentioned compound B or compound C can be obtained instead of compound A, respectively.

[0037] Furthermore, by mixing the compound 4 and the compound 3 and reacting them with sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, lithium tetramethylpiperidine, or the like, the following compound 5 is obtained by coupling the compound 4 with the compound 3, and similarly to the above, the nitrile group is reduced with the reducing agent and converted into a primary amino group bonded to a methylene group, thereby obtaining the above-mentioned compound D. [ka]

[0038] Although by-products may be generated in each step of the above-mentioned production method, they can be purified by conventional purification means such as column chromatography.

[0039] [Production Example of Amino Compound of General Formula (4)] The amino compound of general formula (4) preferably includes a procedure of obtaining an unsaturated compound having a substituent containing the structure of general formula (1), an ester bond, and an unsaturated double bond, followed by a dimerization reaction via the unsaturated bond, and then converting the ester bond in the obtained dimer of the unsaturated compound into an amide bond, followed by converting the amide bond into an amino group.

[0040] Here, the significance of using a compound having a substituent containing the structure of general formula (1) and the scope of the compound are the same as those described above. The compounds included in general formula (4) have the following structural characteristics: a main chain of C1 to C n Side chain R 11 ,R 12 ,···,R n1 ,R n2In the above, the compound has a structure having at least two or more substituents containing the structure of general formula (1) and has a primary amino group bonded to a methylene group at the end of the main chain. Therefore, from the viewpoint of efficiently introducing a multi-branched structure of the substituent containing the structure of general formula (1), bonding and elongating the carbon chain without introducing an extra polar functional group while suppressing side reactions, and finally converting the compound into a primary amino group bonded to a methylene group, it is efficient to follow, for example, the procedure described below.

[0041] (Production Example of Compound E) The above-mentioned compound E will be used as an example. Specifically, an aldehyde compound having a substituent containing the structure of general formula (1) is used as a starting compound, and the same or different aldehyde compounds are dimerized by aldol reaction. Examples of aldehyde compounds having a substituent containing the structure of general formula (1) include 3,5,5-trimethylhexanal. For example, 3,5,5-trimethylhexanal is dimerized by aldol reaction to obtain the following compound a. This reaction can be carried out using known procedures and conditions, as appropriate. For example, see Bulletin of the Chemical Society of Japan, 1997, vol. 70, #8, pp. 1879-1886. While an aldol reaction generally produces a mixture of structural isomers, in the present invention, the desired compound may be purified by known methods and then subjected to the synthesis procedure, or the synthesis procedure may be carried out in the form of a mixture. [ka]

[0042] Next, only the aldehyde group in the obtained compound a is converted to a carboxylic acid, and the carboxy group is simultaneously esterified to obtain the following compound b (an example of a methyl ester). Esterification can prevent side reactions in the subsequent dimerization reaction. This reaction can be carried out, for example, by the Pinnik oxidation reaction, or by a reaction using a known esterifying agent such as an alkyl halide. Furthermore, known procedures and conditions can also be appropriately adopted. For example, see Journal of Organic Chemistry; Vol. 70; nb. 1; (2005); pp. 150-160. [ka]

[0043] Alternatively, the hydroxyl group in compound a obtained above can be replaced with a substituent with good leaving ability, such as a tosyl group or a mesyl group, followed by an elimination reaction using a compound with low nucleophilicity, such as diazabicycloundecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene, or a strong base such as N,N-diisopropylethylamine, to obtain the unsaturated compound compound c shown below. For this reaction, known procedures and conditions can be appropriately employed, and reference can be made, for example, to Synthesis, 2000, #9, p. 1279. [ka]

[0044] Next, the unsaturated compound (compound c) is dimerized using a polymerization catalyst such as activated clay. Dimerization using unsaturated double bonds is preferred because it allows for carbon chain extension without leaving unnecessary polar groups. Examples of polymerization catalysts include liquid or solid Lewis acids and Bronsted acids. Solid acid catalysts, which are a type of Bronsted acid, are preferred. Examples include activated clay (preferably montmorillonite-based activated clay or bentonite-based activated clay), synthetic zeolite, silica / alumina, and silica / magnesia. This produces the following compound d, a dimer of compound c. For this reaction, known procedures and conditions can be appropriately employed; for example, see JP-A-9-12712. [ka]

[0045] The ester moiety is then hydrolyzed using sodium hydroxide or the like, followed by the formation of a primary amide. To form the amide bond, for example, urea or the like is reacted with a catalyst such as magnesium nitrate hexahydrate. This produces an amide compound (compound e) below. For this reaction, known procedures and conditions can be appropriately adopted, and reference can be made to, for example, Chem. Sci., 2020, 11, 5808-5818. [ka]

[0046] Finally, the amide can be converted to an amine using a reducing agent such as lithium aluminum hydride, to obtain the target amino compound having a primary amino group bonded to a methylene group (Compound E). For this reaction, known procedures and conditions can be appropriately employed, and reference can be made to, for example, J. Med. Chem. 2018, 61, 9, 4004-4019. Although by-products may be generated in each step of this series of production methods, they can be purified using a commonly used purification method such as column chromatography.

[0047] As amino compounds encompassed by general formula (4), for example, the above-mentioned compounds F and G can also be synthesized and produced by the following procedure following the synthesis and production procedure of the above-mentioned compound E, but are not limited thereto.

[0048] (Production Example of Compound F) 3,5,5-Trimethylhexanal and acetaldehyde are reacted in a 1:1 molar ratio by aldol reaction to synthesize compound f (see below). The aldehyde is converted to a carboxylic acid by Pinnik oxidation to synthesize a methyl ester compound. The hydroxyl group is tosylated, and an elimination reaction is performed using diazabicycloundecene (DBU) to synthesize an alkene (compound g) (see below). The alkene (compound g) is dimerized using activated clay as a catalyst to obtain compound h (see below). The methyl ester moiety of compound h is hydrolyzed with sodium hydroxide, and then treated with urea using magnesium nitrate hexahydrate as a catalyst to synthesize a primary amide (compound i) (see below). The amide is then converted to an amine using lithium aluminum hydride to obtain the desired amino compound having a primary amino group bonded to a methylene group (compound F, see above). For this reaction, known procedures and conditions can be appropriately adopted, referring to the literature cited above. [ka] [ka]

[0049] (Production Example of Compound G) 3,5,5-Trimethylhexanal and acetaldehyde are reacted in a 1:1 molar ratio by aldol reaction to synthesize compound j (see below). The aldehyde is converted to a carboxylic acid by Pinnik oxidation to synthesize a methyl ester compound (see below). The hydroxyl group is tosylated, and an elimination reaction is carried out using diazabicycloundecene (DBU) to synthesize an alkene (see below). The above-listed alkene (see above, compound c) is reacted with the following alkene (see below, compound l) using activated clay as a catalyst to obtain compound m (see below). The methyl ester moiety of compound m is hydrolyzed with sodium hydroxide, and then treated with urea using magnesium nitrate hexahydrate as a catalyst to synthesize a primary amide (see below, compound n). The amide is then converted to an amine using lithium aluminum hydride to obtain the desired amino compound having a primary amino group bonded to a methylene group (see above, compound G). For this reaction, known procedures and conditions can be appropriately adopted, referring to the literature cited above. [ka] [ka] [ka]

[0050] <Polyamic acid and polyimide and methods for producing same> As described above, the amino compound of the present invention enables a low dielectric loss tangent, and is therefore suitable as a diamine component for polyamic acid and polyimide. Polyamic acid and polyimide can be obtained by a known method except for using the amino compound of the present invention as the diamine component. In this case, the amino compound of the present invention is preferably used as the diamine component in the amount described above.

[0051] As is well known, polyamic acid is composed of a tetracarboxylic acid residue, which is a tetravalent group derived from a tetracarboxylic dianhydride component, and a diamine residue, which is a divalent group derived from a diamine component. When these components are linked together and considered as one repeating unit, the polyamic acid is composed of a polymer of the repeating unit. Furthermore, the polyimide of the present invention is obtained by imidizing the polyamic acid. Both can be produced by known methods.

[0052] For example, polyimide acid, a polyimide precursor, can be obtained by dissolving a predetermined tetracarboxylic dianhydride component and a diamine component in approximately equimolar amounts in an organic solvent and then polymerizing the mixture at a temperature typically ranging from 0 to 100°C for 30 minutes to 24 hours with stirring. During the reaction, the reactants are typically dissolved so that the resulting precursor is in a concentration of 5 to 30 wt %, preferably 10 to 20 wt %, in the organic solvent. Examples of organic solvents used in the polymerization reaction include N,N-dimethylformamide, N,N-dimethylacetamide (DMAC), N-methyl-2-pyrrolidone, 2-butanone, dimethyl sulfoxide, dimethyl sulfate, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triglyme, and γ-butyrolactone. Two or more of these solvents can also be used in combination, and aromatic hydrocarbons such as xylene and toluene can also be used in combination. Furthermore, as long as the purpose is not impaired, fillers such as silicon dioxide, aluminum oxide, boron nitride, magnesium oxide, beryllium oxide, aluminum nitride, silicon nitride, aluminum fluoride, calcium fluoride, and metal salts of organic phosphinic acid and other components may be contained as necessary.

[0053] In the synthesis of polyimide acid and polyimide, the tetracarboxylic dianhydride component and the diamine component may each be used alone or in combination of two or more. In addition to using the amino compound of the present invention as the diamine component, physical properties such as thermal expansion, adhesiveness, and glass transition temperature can be controlled by selecting the type of tetracarboxylic dianhydride component and the diamine component, or by selecting the molar ratio of each when two or more acid anhydrides or diamines are used.

[0054] Although it depends on the resin to be applied and the application, in order to suitably achieve a low dielectric loss tangent, the amino compound of the present invention is preferably contained in the diamine component at 25 mol % or more, more preferably 50 mol % or more, even more preferably 75 mol % or more, still more preferably 90 mol % or more, and most preferably 100 mol %. Here, as the diamine component other than the amino compound of the present invention, any known diamine used in the production of polyimide acid and polyimide can be used without limitation, but aromatic diamine compounds are preferred. Alternatively, diamine compounds having an aliphatic skeleton may also be used. For example, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis(4-aminophenoxy)benzophenone, 4,4'-bis(3-aminophenoxy)benzophenone (BABP), 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene (BABB), 1,4-bis(4-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, bis[4-(3-aminophenoxy)benzophenone] bis(4-(4-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 3,7-diamino-2,8-dimethylbenzothiophene sulfone, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether (4,4'-DAPE), 3,3-diaminodiphenyl ether, bis(p-β-amino-t-butylphenyl)ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(3-aminophenoxy)benzene (APB), 1,3-bis(4-aminophenoxy)benzene (TPE-R), or 1,4-bis(4-aminophenoxy)benzene. More preferably, 4,4'-diaminodiphenyl ether (4,4'-DAPE), 1,3-bis(3-aminophenoxy)benzene (APB), 1,3-bis(4-aminophenoxy)benzene (TPE-R), or 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 3,3'-dimethyl-4,4'-Diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4-diaminomesitylene, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylidine, 4,4'-methylene-2,6-diethylaniline, 2,4-toluenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-di Aminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-p-terphenyl, 3,3'-diamino- p-Terphenyl, bis(p-β-methyl-δ-aminopentyl)benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis(β-amino-t-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6 Examples of the diamine compounds include aromatic diamine compounds such as 5-amino-2-(4-aminophenyl)benzimidazole, 5-amino-2-(4-aminophenyl)benzoxazole, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine, 9,9-bis(4-aminophenyl)fluorene, 4,4'-diaminobenzanilide, 5-amino-2-(4-aminophenyl)benzimidazole, and 5-amino-2-(4-aminophenyl)benzoxazole, and aliphatic diamines such as dimer diamine, hexamethylenediamine, and pentamethylenediamine.

[0055] The tetracarboxylic acid dianhydride component may be any known tetracarboxylic acid dianhydride used in the production of polyimide acids and polyimides, but aromatic tetracarboxylic acid dianhydrides are preferred. Alternatively, an anhydride of a tetracarboxylic acid having an aliphatic skeleton may be used, such as an aliphatic chain tetracarboxylic acid dianhydride such as ethylene tetracarboxylic acid dianhydride or 1,2,3,4-butane tetracarboxylic acid dianhydride, or an alicyclic tetracarboxylic acid dianhydride such as 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, fluorenylidene bisphthalic anhydride, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride or cyclopentanone bisspironorbornane tetracarboxylic acid dianhydride. Examples of aromatic tetracarboxylic dianhydrides include 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3',3,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 4,4'-(paraphenylenedicarbonyl)diphthalic anhydride, 4,4'-(metaphenylenedicarbonyl)diphthalic anhydride, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), p-phenylenebis(trimellitate anhydride), 4,4'-oxydiphthalic dianhydride (ODPA), bis(2,3-dicarboxyphenyl)ether dianhydride, 5,5'-bis( trifluoromethyl)-3,3',4,4'-tetracarboxydiphenyl ether dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}diphenyl ether dianhydride, bis{3,5-di(trifluoromethyl)phenoxy}pyromellitic dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}benzene dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}, bis(dicarboxyphenoxy)trifluoromethylbenzene dianhydride, bis(dicarboxyphenoxy)bis(trifluoromethyl)benzene dianhydride, bis(dicarboxyphenoxy)tetrakis(trifluoromethyl)benzene dianhydride, 2,2-bis{(4-(3,4-dicarboxyphenoxy)phenyl}hexafluoropropane dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}biphenyl dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}bis(trifluoromethyl)biphenyl dianhydride, bis(dicarboxyphenoxy)bis(trifluoromethyl)biphenyl dianhydride, 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride , naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3'',4,4''-p-terphenyltetracarboxylic dianhydride, 2,2'',3,3''-p-terphenyltetracarboxylic dianhydride, 2,3,3'',4''-p-terphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane Dianhydrides, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-diphenylsulfonetetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, (trifluoromethyl)pyromellitic dianhydride, di(trifluoromethyl)pyromellitic dianhydride, di(heptafluoropropyl)pyromellitic dianhydride ) Pyromellitic dianhydride, pentafluoroethyl pyromellitic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxybiphenyl dianhydride, 2,2',5,5'-tetrakis(trifluoromethyl)-3,3',4,4'-tetracarboxybiphenyl dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxybenzophenone dianhydride, trifluoromethylbenzene dianhydride, and the like.

[0056] Furthermore, although not limited, the polyamic acid preferably has a weight-average molecular weight in the range of 20,000 to 5,000,000. A more preferred lower limit is 40,000, and an even more preferred lower limit is 60,000. A more preferred upper limit is 1,500,000, and an even more preferred upper limit is 1,000,000. When the weight-average molecular weight is equal to or greater than the lower limit, the film after imidization becomes tough, while when the weight-average molecular weight is equal to or less than the upper limit, there is an advantage in that the viscosity of the polyamic acid solution can be easily adjusted.

[0057] The synthesized polyamic acid is usually advantageously used as a reaction solvent solution, but it can be concentrated, diluted, or replaced with another organic solvent as necessary. Furthermore, polyamic acid is advantageously used because it generally has excellent solvent solubility. The method for imidizing polyamic acid is not particularly limited, and a suitable method is, for example, heat treatment in the solvent at a temperature in the range of 80 to 400°C for 1 to 24 hours.

[0058] The method for forming a polyimide film as a resin film is not particularly limited, but examples include a method in which a polyimide solution (or polyamic acid solution) is applied to a substrate, followed by heat treatment (drying and curing) to form a polyimide layer (or polyamic acid layer) on the substrate, and then peeling it off to form a polyimide film. The method for applying the polyimide solution (or polyamic acid solution) to the substrate is not particularly limited, and it can be applied using a coater such as a comma, die, knife, or lip. When forming a multilayer polyimide layer, a method in which the polyimide solution (or polyamic acid solution) is repeatedly applied to the substrate and dried is preferred. The resin film can include a single or multiple polyimide layers, and other layers (materials) may be provided as necessary.

[0059] <About the machine learning performance evaluation prediction model> Known machine learning performance evaluation and prediction models can be used, and they can also be modified or adapted as needed depending on the purpose. For example, one example of a machine learning procedure for polymers and other compounds involves collecting molecular structure information and material properties of the polymers and their monomers, converting the molecular structure information into numerical values ​​(explanatory variables), and then calculating the relationship between the explanatory variables and the polymer's material properties (target variables) as an estimation model. Methods for converting the molecular structure of polymers and their monomers into explanatory variables include open-source libraries such as RDKit and well-known methods such as the number density ECFP method (Minami et al., MRS Advances 2018, pp. 2975-2980). Open-source machine learning libraries such as scikit-learn can be used to learn training data and create estimation models, which can be modified or adapted as needed depending on the evaluation or material development objectives. [Example]

[0060] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the scope of these examples. In the following examples, various measurements and evaluations were performed as follows unless otherwise specified.

[0061] The compounds and abbreviations used in the examples are as follows: BTDA: 3,3',4,4'-benzophenonetetracarboxylic dianhydride PMDA: Benzene-1,2,4,5-tetracarboxylic dianhydride TPE-R: 1,3-bis(4-aminophenoxy)benzene TAHQ: p-phenylenebis(trimellitate anhydride) m-TB: 2,2'-dimethylbenzidine DDA: aliphatic diamine with 36 carbon atoms (manufactured by Croda Japan Co., Ltd., trade name: PRIAMINE 1074, amine value: 210 mg KOH / g, mixture of dimer diamines with cyclic and chain structures, dimer content: 95% by weight or more) The following compounds A to I

[0062] [ka] [ka] [ka]

[0063] [ka]

[0064] [ka]

[0065] [Example 1] (Production of Compound A) Under an argon gas atmosphere, dehydrated tetrahydrofuran was charged into a reaction vessel and stirred. Next, lithium aluminum hydride was added under ice-cooling at 15°C or below. 600 g of the raw material isostearic acid (2,2,4,8,10,10-hexamethylundecane-5-carboxylic acid) was added dropwise to the mixture under ice-cooling at 5°C or below. After the dropwise addition was completed, the mixture was allowed to warm to room temperature and stirred overnight. The reaction solution was ice-cooled and diluted with 3 L of tetrahydrofuran. 600 g of sodium sulfate decahydrate was added and stirred to quench the reaction. The reaction solution was filtered, and the resulting filtrate was concentrated to obtain 501.2 g of the following compound 2 as a colorless oil. Next, under an argon gas atmosphere, compound 2, carbon tetrabromide, and 5 L of dehydrated dichloromethane were charged into a reaction vessel and stirred. To this was added dropwise 1.25 L of triphenylphosphine / dichloromethane solution at 7°C or below under ice cooling. After the dropwise addition was completed, the temperature was raised to room temperature and stirred overnight. The reaction solution was concentrated, and 1.2 L of isopropyl ether and 5 L of heptane were added to the resulting residue, followed by stirring while heating to 50°C. The solution was filtered, and the filtrate was concentrated to obtain 673 g of a crude oil. This was purified by column chromatography (SiO2, heptane) to obtain 579.9 g of the following compound 3 as a colorless oil. Next, under an argon gas atmosphere, the raw materials decanedinitrile, Compound 3, dehydrated tetrahydrofuran, and N,N'-dimethylpropyleneurea were charged into a reaction vessel and stirred. Sodium bis(trimethylsilyl)amide was added dropwise to the mixture at 5°C or below under ice cooling. After the addition was complete, the mixture was warmed to room temperature and stirred overnight. The reaction mixture was ice-cooled and quenched by adding 5.4 L of 10% aqueous ammonium chloride solution dropwise. The organic layer was separated by a separation process. The resulting organic layer was washed with saturated aqueous sodium chloride, and then dried by adding sodium sulfate as a desiccant. The desiccant was filtered off, and the filtrate was concentrated to obtain a crude oil. This was purified by column chromatography (SiO2, heptane / ethyl acetate = 10 / 1) to obtain 205.2 g of the following Compound 4 as a colorless oil. Then, under an argon gas atmosphere, the compound 4 and dehydrated diethyl ether were charged into a reaction vessel and stirred. To this was added lithium aluminum hydride under ice cooling at 8°C or below. After the addition was completed, the temperature was raised to room temperature and stirred overnight. The reaction solution was ice-cooled and quenched by sequentially adding distilled water (35 mL), 15% aqueous sodium hydroxide solution (35 mL), and distilled water (105 mL) dropwise at 12°C or below. The precipitate was filtered off. The obtained filtrate was dried by adding sodium sulfate as a desiccant. The desiccant was filtered off, and the filtrate was concentrated to obtain 201 g of a crude product of the above-mentioned compound A. 1 L of diethyl ether and activated carbon (20 g) were added to the crude product, and the mixture was stirred. The activated carbon was removed by filtration, and the filtrate was concentrated to obtain 197.7 g of the above-mentioned compound A as a light green oil.

[0066] [ka] [ka]

[0067] ( 1 H-NMR, ESI-MS) Regarding the obtained compound A, 1 Identification was carried out by H-NMR and ESI-MS measurements according to the following procedures. 1 H-NMR measurement: Compound A was dissolved in CDCl3, and the solution was transferred to an NMR tube and measured. Measurement was performed using a JEOL FT-NMR device (JNM-ECA 400). The results are as follows. The spectrum is shown in Figure 1. 1 H-NMR (400MHz, CDCl3): δ=2.7~2.4(m,4H),1.4~0.8(m,92H)

[0068] ESI-MS: Compound A was dissolved in methanol and subjected to measurement. A Waters SQD2 (single quadrupole mass spectrometer) was used. The spectrum is shown in Figure 2. Compound A was confirmed to have an m / z value of 677.7 (M+1).

[0069] [Example 2, Comparative Example 1] (Method for producing polyimide using compound A and acid dianhydride) BTDA, DDA, and Compound A were mixed in the amount ratios shown in Table 1, and N-methyl-2-pyrrolidone and xylene were added and mixed thoroughly at 40°C to obtain polyamic acid solutions of Example 2 and Comparative Example 1. Each of these polyamic acid solutions was heated to 190°C with stirring, and N-methyl-2-pyrrolidone and xylene were added to obtain polyimide solutions. The weight-average molecular weight (Mw) of the resulting polyimide resin was approximately 43,000 (Example 2) and approximately 58,000 (Comparative Example 1).

[0070] (Evaluation of the dielectric loss tangent of polyimide) The obtained polyimide solution was applied to one side of a release film and dried at 80° C. to obtain Polyimide Film 1. The dielectric constant and dielectric loss tangent of the resin sheet (cured resin sheet) at a predetermined frequency were measured using a Vector Network Analyzer E8363C (trade name) and an SPDR resonator manufactured by Agilent Electronics Co., Ltd. The resin sheet used for the measurement was left to stand for 48 hours under conditions of a temperature of 23°C and a humidity of 50%.

[0071] [Table 1]

[0072] [Creating an estimation model for dielectric loss tangent] Using structural descriptors of polyimide molecular structure as explanatory variables and measured data of dielectric loss tangent at 10 GHz as objective variables, we created a dielectric loss tangent estimation model by learning training data of various polyimide materials using the Lasso regression method. Using this estimation model, we estimated the dielectric loss tangents of four polyimide materials not included in the training data and compared them with the measured values. The four polyimide materials were fabricated as polyimide films using the same method as described above and evaluated. As shown in Table 2 and Figure 3, the measured and estimated dielectric loss tangents showed good agreement. The coefficient of determination calculated from the measured and estimated values ​​was 0.97. The coefficient of determination is calculated by subtracting the sum of squares of the residuals divided by the total sum of squares from 1, and is an index of how well the estimated value explains the measured value. Generally, a coefficient of determination of 0.5 or higher is considered to have explanatory power, and the closer to 1, the higher the explanatory power. Therefore, the estimation model developed here is considered to have a sufficiently high ability to explain the measured values. From the above, it is possible to accurately estimate the dielectric loss tangent from the molecular structure by using the estimation model created this time.

[0073] [Table 2]

[0074] [Examples 3 to 9, Comparative Examples 2 to 3] Then, for the structures of the amino compounds (compounds A to I) described above, the dielectric loss tangents were estimated for the following compositions using this estimated model. The results are shown in Table 3.

[0075] [Table 3]

[0076] From the results in Table 3, it was inferred that polyimide films using the amino compounds (compounds A to G) according to the present invention, each having a predetermined number of structures of general formula (1), have a superior dielectric loss tangent compared to polyimide films using known amino compounds, compound H or compound I. In other words, given the sufficiently high explanatory power of the dielectric loss tangent estimation model created this time for the actually measured values, and the fact that the difference in dielectric loss tangent as described above could be confirmed in comparison with the addition of compound A, which was actually synthesized and evaluated, it can be fully inferred that the amino compounds according to the present invention contribute to a lower dielectric loss tangent.

Claims

1. An amino compound having at least two substituents containing a structure represented by the following general formula (1) and at least two primary amino groups bonded to a methylene group, An amino compound represented by the following general formula (2): 【Chemical 1】 [In formula (1), X represents a bonding position.] 【Chemistry 2】 [In formula (2), R 1 and R 2 each independently represent a hydrogen atom or a substituent of the following general formula (3), and R 3 represents an alkylene group having one or more carbon atoms.] 【Chemistry 3】 [In formula (3), X represents a bonding position.]

2. An amino compound having at least two substituents containing a structure represented by the following general formula (1) and at least two primary amino groups bonded to a methylene group, An amino compound represented by the following general formula (4): 【Chemistry 4】 [In formula (4), C １ ~C ｎ represents a carbon atom, C １ ~C ｎ Side chain R of １１ , R １２ , ..., R ｎ１ , R ｎ２ each independently represents a hydrogen atom or a substituent having a structure of the following general formula (1), R １１ , R １２ , ..., R ｎ１ , R ｎ２ and n is an integer of 6 to 12. 【Chemistry 5】 [In formula (1), X represents a bonding position.]

3. A polyamic acid containing a diamine residue derived from a diamine component and a tetracarboxylic acid residue derived from a tetracarboxylic dianhydride component, A polyamic acid, wherein the diamine component contains the amino compound according to claim 1 or 2.

4. A polyimide containing a diamine residue derived from a diamine component and a tetracarboxylic acid residue derived from a tetracarboxylic acid dianhydride component, A polyimide characterized in that the diamine component contains the amino compound according to claim 1 or 2.

5. 3. A method for producing the amino compound according to claim 1 or 2, comprising the steps of: (a) adding a methyl group to a methyl group; (a): A compound having a substituent containing the structure of the following general formula (1) is subjected to a coupling reaction with an aliphatic dinitrile using a strong base, and then the nitrile group is converted to an amino group. (b): After obtaining an unsaturated compound having a substituent containing the structure of the following general formula (1), an ester bond, and an unsaturated double bond, a dimerization reaction is carried out via the unsaturated bond, and then a reaction is carried out to convert the ester bond in the obtained dimer of the unsaturated compound into an amide bond, followed by conversion of the amide bond into an amino group. 【Chemistry 6】 [In formula (1), X represents a bonding position.]

6. A method for producing a polyamic acid by reacting a diamine component with a tetracarboxylic dianhydride component, A method for producing a polyamic acid, wherein the diamine component contains the amino compound according to claim 1 or 2.

7. A method for producing a polyimide, comprising further imidizing the polyamic acid obtained by the method according to claim 6.

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