JP5761428B2 - New diamine compounds - Google Patents

Description

The present invention is new diamine compounds, in particular, relates to useful novel diamine compound in the preparation of the polyamic acid.

Currently, as a liquid crystal alignment film of a liquid crystal display element, a liquid crystal alignment treatment agent (also referred to as a liquid crystal alignment agent) mainly composed of a polyimide precursor such as polyamic acid or a solution of soluble polyimide is applied to a glass substrate or the like and fired. A so-called polyimide-based liquid crystal alignment film is mainly used.
The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal, but the liquid crystal display element is used because of the demands for suppressing the decrease in contrast of the liquid crystal display element and reducing the afterimage phenomenon as the liquid crystal display element becomes more precise. In the alignment film, characteristics such as a high voltage holding ratio, a small residual charge when a DC voltage is applied, and / or a quick relaxation of the residual charge accumulated by the DC voltage are becoming increasingly important.

  On the other hand, the liquid crystal alignment film is often subjected to a so-called rubbing treatment in which a polymer film obtained from a liquid crystal alignment agent formed on an electrode substrate is rubbed with a cloth made of rayon or the like under pressure. . However, in the process of rubbing treatment, a part of the polymer film may be peeled off, or the surface of the liquid crystal alignment film may be damaged due to rubbing treatment, so-called film scraping may occur. Is considered to be one of the causes of deteriorating the characteristics of the liquid crystal display element and further reducing the yield.

  As another method that replaces the rubbing treatment, there is a method called photo-alignment in which a polymer film is irradiated with polarized or non-polarized ultraviolet rays (see, for example, Patent Document 1). In general, photoreactive groups such as cinnamate, coumarin, and azobenzene are introduced into the polymer of the liquid crystal alignment film used in this method. In this method, the above-described problems such as film scraping due to the lavink process do not occur.

  Another method for aligning liquid crystals is to irradiate ultraviolet rays while applying an electric field to liquid crystal molecules after a liquid crystal panel is produced. In this method, a photopolymerizable compound is generally added to the liquid crystal composition in advance (see, for example, Patent Document 2). In addition, a method of introducing a photoreactive group into a polymer of a liquid crystal alignment film is also known in the same manner as the alignment by light irradiation (for example, see Non-Patent Document 1).

JP 2003-114437 A JP 2003-307720 A SID Digest (Society of Information, Digest) 2010, Methanol (144 g), 595 pages

An object of the present invention is to provide a novel diamine compound having a photoreactive group , particularly a novel diamine compound useful for producing a polyamic acid suitable for a liquid crystal aligning agent.

As a result of intensive studies in order to achieve the above object, the present inventors have found a novel diamine compound having uracil or thymine (also referred to as 5-methyluracil) as a photoreactive group. The present invention has been completed based on the knowledge that a polyimide precursor using a diamine compound as a raw material and / or a liquid crystal aligning agent containing the polyimide precursor has excellent characteristics.
The present invention has the gist described below.

1. A diamine compound represented by the formula [1] or the formula [2].

（式中、Ｒ^１は単結合を表し、Ｒ^２は単結合又は−Ｏ−を表し、Ｒ^３は単結合、又は非置換若しくはフッ素原子によって置換されている炭素数１〜２０のアルキレン若しくはフェニレンを表し、Ｒ^４は非置換又はフッ素原子によって置換されている炭素数１〜２０のアルキル基を表し、Ｒ^５は水素原子又はメチル基を表す。
２．前記式[１]又は式[２] におけるＲ^４が炭素数１〜１０のアルキル基である上記１に記載のジアミン化合物。
３．前記式[１]又は式[２] におけるＲ^５がメチル基である上記１又は２に記載のジアミン化合物。

(Wherein, ^{R 1} represents a single bond, ^{R 2} represents a single bond or -O-, ^{R 3} is a single bond, or unsubstituted or alkylene or phenylene having 1 to 20 carbon atoms which is substituted by fluorine atoms R ⁴ represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and R ⁵ represents a hydrogen atom or a methyl group.
2. 2. The diamine compound according to 1 above, wherein R ⁴ in formula [1] or formula [2] is an alkyl group having 1 to 10 carbon atoms.
3. The diamine compound according to 1 or 2 above, wherein R ⁵ in the formula [1] or formula [2] is a methyl group.

５．請求項１〜４のいずれかに記載のジアミン化合物とテトラカルボン酸無水物とを反応させて得られるポリアミック酸、又は該ポリアミック酸をイミド化したポリイミド。 4). The diamine compound in any one of Claims 1-3 represented by following formula [3], following formula [4], or following formula [5].

5. The polyamic acid obtained by making the diamine compound and tetracarboxylic anhydride in any one of Claims 1-4 react , or the polyimide which imidized this polyamic acid .

According to this invention, the novel diamine compound used as raw material monomers, such as photoreactive polyamide, polyamic acid, polyamic acid ester, a polyimide, is provided. In particular , it is useful for producing a polyimide precursor and / or a liquid crystal aligning agent containing a polyimide obtained from the polyimide precursor, and has a novel uracil or thymine (also referred to as 5-methyluracil) as a photoreactive group. Diamine compounds are provided .

According to the present invention, a novel diamine compound used as a photoreactive port polyamic acid of which the raw material monomer. In particular , it is useful for producing a polyimide precursor and / or a liquid crystal aligning agent containing a polyimide obtained from the polyimide precursor, and has a novel uracil or thymine (also referred to as 5-methyluracil) as a photoreactive group. Diamine compounds are provided .

  Specific examples of the carbocycle or heterocycle include, but are not limited to, the following examples.

R ^{4 in} Formula [1] and Formula [2] is preferably an alkyl group having 1 to 10 carbon atoms. Moreover, when using as a raw material of the liquid crystal aligning agent for vertical alignment, in order to improve vertical alignment property, the structure containing a linear C1-C20 alkyl group or the following carbon rings is preferable. .
Specific examples of the carbocycle and the heterocycle are the same as the specific examples shown for R ³ . When used as a raw material for a liquid crystal aligning agent for vertical alignment, a linear alkyl group having 1 to 20 carbon atoms or a structure containing the following carbocycle is preferable in order to enhance vertical alignment.

また、式[１]及び式[２]中のＲ^５は水素原子又はメチル基である。

Further, R ⁵ in the formulas [1] and [2] is a hydrogen atom or a methyl group.

  Among the diamine compounds represented by the formula [1] or [2], the diamine compounds of the following formulas [3] to [5] are particularly preferable compounds because they can be synthesized relatively easily.

[Method for synthesizing specific diamine]
The method for synthesizing the diamine compound represented by the formula [1] is not particularly limited. For example, a dinitro compound represented by the following formula [6] is synthesized, and then the nitro group of the dinitro compound is reduced to form an amino acid. It can be obtained by converting to a group. ^R 1 to R ⁵ in the formula [6] are as defined for ^R 1 to R ⁵ of the formula [1].

The method for reducing the nitro group of the dinitro compound represented by the formula (6) is not particularly limited. For example, palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum carbon sulfide, reduced iron, iron chloride. In addition, there is a method in which tin, tin chloride, zinc or the like is used as a catalyst and reduced with hydrogen gas, hydrazine, hydrogen chloride, ammonium chloride or the like in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane, an alcohol solvent, or water.
In addition, when R ³ or R ⁴ in Formula [6] includes a non-aromatic unsaturated bond, a reduction reaction in which the non-aromatic unsaturated bond is not hydrogenated can be used. If the non-aromatic unsaturated bond is not hydrogenated, the method is not particularly limited. For example, reduced iron, iron chloride, tin, tin chloride, zinc, etc. are used as a catalyst, and ethyl acetate, toluene, tetrahydrofuran, dioxane, etc. There is a method of reducing with hydrazine, hydrogen chloride, ammonium chloride or the like in a solvent such as an alcohol solvent or water.

When R ¹ , R ² and R ³ in the formula [6] are all single bonds, a method for obtaining a dinitro compound of the formula [6] includes a corresponding dinitrophenyl group-containing halogen-substituted derivative and uracil containing R ⁵ A method of reacting a derivative with an alkali in the presence of an alkali can be mentioned. Here, the step of introducing R ⁴ may be before or after reacting the dinitrophenyl group-containing compound and the compound having a uracil structure, but when priority is given to avoiding by-products, It is preferable to introduce it before the reaction or to carry out the reaction in a state where the nitrogen atom of the uracil structure into which R ⁴ is introduced is protected with a protecting group such as tert-butoxycarbonyl group, and then introduce it after that. In the case where priority is given to the convenience, it is preferably introduced after the reaction.

When R ² and R ³ of the formula [6] is not a single bond, a method of obtaining a dinitro compound of the formula [6], to the dinitrophenyl group-containing compound containing R ^1, via R ^2, R ³ may be mentioned.
When R ^{2 of the} formula [6] is not a single bond, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —N (CH ₃ ) —, —CON ( CH ₃ ) — and —N (CH ₃ ) CO— are linking groups selected from these, and these linking groups can be formed by ordinary organic synthetic chemistry techniques.
For example, when R ² in formula [6] is —O—, it has a corresponding dinitrophenyl group-containing halogen substituent or dinitrophenyl group-containing sulfonate group substituent, and a uracil structure containing R ³ and R ^5. A method of reacting a hydroxyl group-substituted product with an alkali, or a method of reacting a dinitrophenyl group-containing hydroxyl group-substituted product with a halogen or sulfonate-substituted derivative having a uracil structure containing R ³ and R ⁵ in the presence of an alkali, etc. Is mentioned.

When R ^{2 in the} formula [6] is —NH— or —N (CH ₃ ) —, the corresponding dinitrophenyl group-containing halogen group-substituted product, or dinitrophenyl group-containing sulfonate group-substituted product, R ³ , and A method of reacting an amino group-substituted product having a uracil structure containing R ⁵ in the presence of an alkali, or a dinitrophenyl group-containing amino group-substituted product, and an amino group-substituted product having a uracil structure containing R ³ and R ⁵ And the like in the presence of an alkali.
When R ^{2 in} Formula [6] is —CONH— or —CON (CH ₃ ) —, the corresponding dinitrophenyl group-containing acid chloride, and an amino group-substituted product having a uracil structure containing R ³ and R ⁵ Or a corresponding dinitrophenyl group-containing carboxylic acid and an amino group-substituted product having a uracil structure containing R ³ and R ⁵ in the presence of a dehydration condensing agent. Can be mentioned.

When R ^{2 in} formula [6] is —NHCO— or —N (CH ₃ ) CO—, the corresponding dinitrophenyl group-containing amino group-substituted product, and an acid having a uracil structure containing R ³ and R ⁵ A method of reacting a chloride compound in the presence of an alkali, or a method of reacting a corresponding dinitrophenyl group-containing amino group-substituted product and a carboxylic acid having a uracil structure containing R ³ and R ⁵ in the presence of a dehydration condensing agent. Etc.
When R ^{2 of the} formula [6] is —COO—, a corresponding dinitrophenyl group-containing acid chloride and a hydroxyl group-substituted product having a uracil structure containing R ³ and R ⁵ in the presence of an alkali; Alternatively, a method of reacting a corresponding dinitrophenyl group-containing carboxylic acid with a hydroxyl group-substituted product having a uracil structure containing R ³ and R ⁵ in the presence of a dehydration condensing agent can be used.

When R ^{2 of} formula [6] is —OCO—, a corresponding dinitrophenyl group-containing hydroxyl group-substituted product and an acid chloride compound having a uracil structure containing R ³ and R ⁵ are reacted in the presence of an alkali; Alternatively, there may be mentioned a method in which the corresponding dinitrophenyl group-containing hydroxyl group-substituted product and a carboxylic acid having a uracil structure containing R ³ and R ⁵ are reacted in the presence of a dehydration condensing agent.
As described above, when R ³ is bonded to a dinitrophenyl group-containing compound containing R ¹ via R ² , the step of introducing R ⁴ is a compound having a dinitrophenyl group-containing compound and a uracil structure In order to avoid the formation of by-products, it may be introduced before the reaction, or after the reaction, or the nitrogen atom of the uracil structure into which R ⁴ is introduced may be substituted with a tert-butoxycarbonyl group. It is preferable that the reaction is carried out in a state protected with a protecting group such as, and then introduced.

As another method for obtaining the dinitro compound of the formula [6] when R ² and R ³ of the formula [6] are not single bonds, a dinitrophenyl group-containing compound containing R ¹ , R ² , and R ³ On the other hand, a method of directly bonding a compound having a uracil structure containing R ⁵ to R ³ is mentioned.
Specific examples of this method include a method in which a dinitrophenyl group-containing halogen or sulfonate substituent containing R ¹ , R ² and R ³ is reacted with a compound having a uracil structure containing R ⁵ in the presence of an alkali. Is mentioned.
When the carbon atom of R ³ bonded to the uracil group is an sp ² hybrid carbon atom such as ethenylene group or phenylene group, or an sp hybrid carbon atom such as ethynylene group, R ¹ , R ² , and R ³ are A method of reacting a halogen- or sulfonate-containing substituent containing dinitrophenyl with a compound having a uracil structure containing R ⁵ in the presence of a palladium catalyst and an alkali, or a dinitrophenyl group containing R ¹ , R ² , and R ³ For example, the compound having a uracil structure containing boric acid and R ⁵ is reacted in the presence of a copper catalyst.

As described above, when the relative R ^{1, R 2,} and dinitrophenyl group-containing compound containing R ^3, directly to R ^3, which bind the compound having a uracil structure containing R ^5, introducing the R ⁴ The step may be performed before or after reacting the dinitrophenyl group-containing compound and the compound having a uracil structure. However, in order to avoid the formation of by-products, the step may be introduced before the reaction, or R ⁴ may be used. It is preferable to carry out the reaction in a state where the nitrogen atom of the uracil structure to be introduced is protected with a protecting group such as a tert-butoxycarbonyl group and then introduce it.

The method for bonding R ⁴ onto the nitrogen atom of the uracil structure is not particularly limited, and examples thereof include a method of reacting a compound having a uracil structure with a halogen or sulfonate substituent of R ^{4 in} the presence of an alkali.
When the carbon atom of R ⁴ bonded to the uracil structure is an sp ² hybrid carbon atom such as ethenylene group or phenylene group, or an sp hybrid carbon atom such as ethynylene group, a compound having a uracil structure and R ⁵ And a method of reacting a halogen-substituted sulfonate with a palladium catalyst and an alkali, or reacting a compound having a uracil structure with a boric acid derivative of R ^{5 in} the presence of a copper catalyst.

On the other hand, the method for synthesizing the diamine compound represented by the formula [2] is not particularly limited. For example, a dinitro compound represented by the following formula [7] is synthesized, and then the nitro group of the dinitro compound is reduced. It can be obtained by converting it to an amino group. ^R 1 to R ⁵ in the formula [7] is the same as the definition of ^R 1 to R ⁵ of the formula [2].

The method for reducing the nitro group of the dinitro compound represented by the formula [7] is not particularly limited, and the same method as exemplified in the method for reducing the nitro group represented by the formula [6] should be used. Can do.
The method for obtaining the dinitro compound of formula [7] is not particularly limited. In the method for obtaining the dinitro compound of formula [6], a compound having a uracil structure in which the positions of R ³ and R ⁴ on the uracil structure are exchanged is used. Except for the above, in the method for obtaining the dinitro compound of the formula [6], the exemplified method can be used.

[Liquid crystal aligning agent]
The liquid crystal aligning agent of the present invention is a polyimide precursor obtained by reacting a diamine compound containing any one of the diamine compounds represented by the above formula [1] and the above formula [2] with a tetracarboxylic acid derivative. Body and / or polyimide.
Below, the tetracarboxylic acid derivative made to react with the diamine compound containing a diamine compound is demonstrated.

[Tetracarboxylic acid derivative]
Preferred examples of the tetracarboxylic acid derivative are represented by any of the following formulas [8] to [10].

  Of the tetracarboxylic acid derivatives, a polyamic acid is obtained by reacting a tetracarboxylic acid anhydride represented by the formula [8] with a diamine. Moreover, polyamic acid ester is obtained by making the tetracarboxylic-acid diester dichloride represented by Formula [9] or the tetracarboxylic-acid diester represented by Formula [10] react with diamine. And a polyimide can be synthesize | combined by imidating this polyamic acid or polyamic acid ester.

In formula [9] and formula [10], R ⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a 2-propyl group, a butyl group, and a tert-butyl group. In general, the polyamic acid ester has a higher temperature at which imidization proceeds as the number of carbon atoms of its alkyl group increases. Accordingly, the alkyl group is preferably a methyl group or an ethyl group, and particularly preferably a methyl group, from the viewpoint of ease of imidization by heat.

  In the formulas [8] to [10], X is a tetravalent organic group and is not particularly limited. Preferable specific examples of X include (X-1) to (X-46) shown below.

[Other diamine compounds]
When obtaining the liquid crystal aligning agent of the present invention, as long as the effects of the present invention are not impaired, other diamine compounds represented by the following formula [11] other than the specific diamine compound can be used in combination as the diamine component. .

式[１１]中、Ｙは２価の有機基であり、特に限定されるものではない。Ｙの好ましい具体例を示すならば、（Ｙ−１）〜（Ｙ−９７）が挙げられる。

In the formula [11], Y is a divalent organic group and is not particularly limited. If the preferable example of Y is shown, (Y-1)-(Y-97) will be mentioned.

[Synthesis of Polyimide Precursor 1 (Polyamic Acid)]
A polyamic acid (hereinafter also referred to as a polymer) can be synthesized by a polycondensation reaction between a tetracarboxylic dianhydride and a diamine compound (hereinafter also referred to as a monomer).

具体的には、テトラカルボン酸二無水物とジアミンを有機溶媒存在下で−２０℃〜１５０℃、好ましくは０℃〜５０℃において、３０分〜２４時間、好ましくは１〜１２時間反応させることによって合成することができる。

Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 12 hours. Can be synthesized.

The solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the monomer and the resulting polymer. These may be used alone or in combination of two or more. It may be used. The concentration of the polymer in the reaction system is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight body is easily obtained.
The polyamic acid obtained as described above can be recovered by precipitating the polymer by pouring into the poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine | purified by performing precipitation several times, washing | cleaning with a poor solvent, and normal temperature or heat-drying can be obtained. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

[Synthesis of polyimide precursor 2 (polyamic acid ester)]
The polyamic acid ester can be synthesized by any of the methods (A) to (C) shown below.
(A) When synthesizing polyamic acid ester from polyamic acid Polyamic acid ester can be synthesized by esterifying polyamic acid obtained from tetracarboxylic dianhydride and diamine.

具体的には、ポリアミック酸とエステル化剤を有機溶剤の存在下で−２０℃〜１５０℃、好ましくは０℃〜５０℃において、３０分〜２４時間、好ましくは１〜４時間反応させることによって合成することができる。

Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be synthesized.

  As the esterifying agent, those that can be easily removed by purification are preferred, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-tert-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene and the like. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents per 1 mol of the polyamic acid repeating unit.

The solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the polymer, and these may be used alone or in combination of two or more. . The concentration at the time of synthesis is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight body is easily obtained.
(B) When synthesizing polyamic acid ester from tetracarboxylic acid diester dichloride and diamine The polyamic acid ester can be synthesized from tetracarboxylic acid diester dichloride and diamine.

具体的には、テトラカルボン酸ジエステルジクロリドとジアミンとを塩基と有機溶剤の存在下で−２０℃〜１５０℃、好ましくは０℃〜５０℃において、３０分〜２４時間、好ましくは１〜４時間反応させることによって合成することができる。

Specifically, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent are −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting.

As the base, pyridine, triethylamine, and 4-dimethylaminopyridine can be used, but pyridine is preferable because the reaction proceeds gently. The amount of the base added is preferably 2 to 4 moles relative to the tetracarboxylic acid diester dichloride from the viewpoint that it can be easily removed and a high molecular weight product can be easily obtained.
The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the monomer and polymer, and these may be used alone or in combination. The concentration at the time of synthesis is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight body is easily obtained. Moreover, in order to prevent hydrolysis of tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.

(C) When a polyamic acid is synthesized from a tetracarboxylic acid diester and a diamine The polyamic acid ester can be synthesized by condensing a tetracarboxylic acid diester and a diamine with a condensing agent.

Specifically, tetracarboxylic acid diester and diamine in the presence of a condensing agent, a base and an organic solvent are 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., 30 minutes to 24 hours, preferably 3 to 15 hours. It can be synthesized by reacting.
Examples of the condensing agent include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazi Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate, and the like. It is preferable that the addition amount of a condensing agent is 2-3 times mole with respect to tetracarboxylic-acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base added is preferably 2 to 4 moles relative to the diamine component from the viewpoint of easy removal and high molecular weight.
In the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0 to 1.0-fold mol with respect to the diamine component.
Among the three methods for synthesizing polyamic acid esters, since a high molecular weight polyamic acid ester is obtained, the synthesis methods (A) and (B) are particularly preferable.

  The polyamic acid ester solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying. Although a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.

[Molecular weight of polyimide precursor]
The molecular weight of the polyimide precursor affects the viscosity of the varnish and the physical strength of the polyimide film. The weight average molecular weight is preferably 500,000 or less from the viewpoint of obtaining good coating workability of the varnish and the coating film, and 2,000 or more is preferred from the viewpoint of obtaining a sufficiently strong polyimide film. . In the same point, it is more preferably 2,000 to 300,000, and further preferably 5,000 to 100,000. The molecular weight of the polyimide precursor can be controlled by adjusting the ratio of the diamine component used for the polymerization reaction and the tetracarboxylic acid derivative. This ratio can be exemplified by a molar ratio of 1: 0.7 to 1.2. The closer the molar ratio is to 1: 1, the higher the molecular weight of the resulting polyimide precursor.

[Synthesis of polyimide]
The polyimide of the present invention can be synthesized by imidizing the polyimide precursor. A simple and preferred method for synthesizing a polyimide from a polyimide precursor is chemical imidization in which a catalyst is added to the polyamic acid solution obtained by the reaction of a diamine component and tetracarboxylic dianhydride, This is preferable because the imidization reaction proceeds at a low temperature and the molecular weight of the polymer is hardly lowered during the imidization process.

  Chemical imidation can be performed by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As an organic solvent, the solvent used at the time of the polymerization reaction mentioned above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.

  The temperature for carrying out the imidization reaction is -20 to 200 ° C, preferably 0 to 180 ° C, and the reaction time can be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amic acid group. Is double. The imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst remains in the solution after the imidation reaction, the obtained imidized polymer is recovered by the means described below, redissolved in an organic solvent, and the liquid crystal alignment according to the present invention. It is preferable to use an agent.

  The polyimide solution obtained by the above-described method can precipitate a polymer by being poured into a poor solvent while being well stirred. The purified polyimide powder can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating. The poor solvent is not particularly limited as long as the polymer is precipitated, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.

[Liquid crystal aligning agent]
The liquid crystal aligning agent of the present invention is a varnish-like solution containing the polyimide precursor and / or polyimide (hereinafter also referred to as polymer component) obtained as described above, from which a liquid crystal alignment film is formed. Used to do.
The liquid crystal aligning agent of this invention may contain 2 or more types of polyimide precursors, 2 or more types of polyimides, and may contain both a polyimide precursor and a polyimide. Furthermore, the liquid crystal aligning agent may contain a polymer other than the polyimide precursor of the present invention or the polyimide of the present invention.

  As the simplest structural example of the liquid crystal aligning agent of this invention, the composition which consists of said polyimide precursor and / or the polymer component of a polyimide, and the organic solvent for dissolving this is mentioned. This composition may be a polyimide precursor or a reaction solution when the polyimide is synthesized, or may be a solution obtained by diluting the reaction solution with a solvent described later. When the polyimide precursor or polyimide is recovered as a powder, it may be dissolved in an organic solvent to form a polymer solution.

10-30 mass% is preferable and, as for the density | concentration of the polymer component in the case of dissolving a polyimide precursor or a polyimide powder in an organic solvent, 10-15 mass% is especially preferable. Moreover, you may heat when dissolving these. The heating temperature is preferably 20 ° C to 150 ° C, particularly preferably 20 ° C to 80 ° C.
The organic solvent for dissolving the polyimide precursor or polyimide is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples are N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl. Examples include caprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. it can. You may use these 1 type or in mixture of 2 or more types. Moreover, even if it is a solvent which cannot melt | dissolve a polymer component uniformly by itself, if it is a range which a polymer does not precipitate, you may mix with said organic solvent.

  The solvent component of the liquid crystal aligning agent of the present invention may contain, in addition to the organic solvent for dissolving the polymer component, a solvent for improving the coating film uniformity when the liquid crystal aligning agent is applied to the substrate. . As such a solvent, a solvent having a surface tension lower than that of the organic solvent is generally used. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2 -Propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-Ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, etc. It is. Two types of these solvents may be used in combination.

The polymer concentration in the liquid crystal aligning agent of the present invention can be appropriately changed according to the thickness of the liquid crystal aligning film to be formed, but it is 1% by mass or more from the viewpoint of forming a uniform and defect-free coating film. Preferably, it is preferably 10% by mass or less from the viewpoint of storage stability of the solution. In addition, the liquid crystal aligning agent of the present invention may contain various additives such as a silane coupling agent and a crosslinking agent.
The silane coupling agent is added for the purpose of improving the adhesion between the substrate on which the liquid crystal alignment agent is formed and the liquid crystal alignment film formed there. Although the specific example is given to the following, the silane coupling agent which can be used for the liquid crystal aligning agent of this invention is not limited to this.

  3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-phenylaminopropyltri Amine-based silane coupling agents such as methoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-aminopropyldiethoxymethylsilane; vinyltrimethoxysilane, vinyltriethoxysilane, Vinyl-based silane couplings such as vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane Agents: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxy cyclohexyl) Epoxy silane coupling agent such as ethyltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Methacrylic silane coupling agents such as ethoxysilane; Acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; Ureido silane cups such as 3-ureidopropyltriethoxysilane Sulfide-based silane coupling agents such as bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl Mercapto silane coupling agents such as trimethoxysilane and 3-octanoylthio-1-propyltriethoxysilane; Isocyanate silane coupling agents such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane; Aldehyde-based silane coupling agents such as butyraldehyde; triethoxysilylpropylmethylcarbamate, (3-triethoxysilylpropyl) -tert-butylcarbamate, etc. Carbamate silane coupling agent.

  The addition amount of the silane coupling agent is preferably 0.01 to 5.0% by mass with respect to the polymer component from the viewpoint that the unreacted material does not adversely affect the liquid crystal orientation and the effect of adhesion appears. 0.1 to 1.0% by mass is more preferable. When adding a silane coupling agent, it is preferable to add before adding the solvent for improving the above-mentioned coating film uniformity, in order to prevent polymer precipitation.

[Liquid crystal alignment film]
A coating film obtained by applying the liquid crystal aligning agent obtained as described above to a substrate, drying and baking, and subjecting this coating film surface to a known alignment treatment as necessary. The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, and the like can be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like is formed. Further, in the reflection type liquid crystal display element, an opaque object such as a silicon wafer can be used as long as only one substrate is used, and in this case, a material that reflects light such as aluminum can be used.

  Examples of the method for applying the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method. Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent of the present invention. Usually, in order to sufficiently remove the organic solvent contained, the organic solvent is dried at 50 ° C. to 120 ° C. for 1 minute to 10 minutes, and then baked at 150 ° C. to 300 ° C. for 5 minutes to 120 minutes. Although the thickness of the coating film after baking is not specifically limited, Since the reliability of a liquid crystal display element may fall when too thin, it is 5-300 nm, Preferably it is 10-200 nm. When the liquid crystal is horizontally aligned or tilted, the fired coating film is rubbed or photo-aligned.

[Liquid crystal display element]
After obtaining the board | substrate with a liquid crystal aligning film from the liquid crystal aligning agent of this invention with the above-mentioned method, a liquid crystal cell is produced by a known method and it is set as a liquid crystal display element.
The manufacturing method of the liquid crystal cell is not particularly limited, but for example, a pair of substrates on which the liquid crystal alignment film is formed is preferably 1 to 30 μm, more preferably 2 to 10 μm with the liquid crystal alignment film surface inside. A method is generally employed in which the spacer is fixed with a sealing agent after the spacer is sandwiched, and liquid crystal is injected and sealed. The method for enclosing the liquid crystal is not particularly limited, and examples thereof include a vacuum method of injecting liquid crystal after reducing the pressure inside the produced liquid crystal cell, and a dropping method of sealing after dropping the liquid crystal.

As another method of manufacturing a liquid crystal cell, a liquid crystal alignment agent is applied on two substrates to form a liquid crystal alignment layer, and the two substrates are arranged so that the liquid crystal alignment layers face each other. There is a method in which a liquid crystal layer is sandwiched between a plurality of substrates and an ultraviolet ray is irradiated while applying an electric field to the liquid crystal layer. The substrate used is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed on a substrate, and a substrate on which an electrode pattern or a protrusion pattern is provided. May be used. Forming a 1-10 μm line / slit electrode pattern on one side of the liquid crystal cell and using an electrode structure with no slit pattern or protrusion pattern on the opposite substrate can simplify the manufacturing process, This is preferable because high transmittance can be obtained.
The liquid crystal alignment layer is a resin film for aligning liquid crystals, and the step of forming the liquid crystal alignment layer on the substrate formed using the liquid crystal aligning agent is described in [Liquid crystal alignment film]. The applied coating method and the firing method after coating can be applied.

  The step of irradiating ultraviolet rays while applying an electric field to the liquid crystal layer is, for example, a method in which an electric field is applied to the liquid crystal layer by applying a voltage between electrodes installed on the substrate, and the ultraviolet rays are irradiated while maintaining the electric field. Is mentioned. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, and preferably 5 to 20 Vp-p. The irradiation amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less, and the lower the ultraviolet rays, the lowering of reliability that causes the destruction of the members constituting the liquid crystal display element can be suppressed, and the ultraviolet irradiation time is selected. This is preferable because the manufacturing efficiency increases.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention should not be construed as being limited thereto. Each measuring method of the molecular weight performed in the present Example is shown below.
[Molecular weight]
The molecular weight of the polymer was measured by a GPC (room temperature gel permeation chromatography) apparatus, and the number average molecular weight was calculated as a polyethylene glycol and polyethylene oxide equivalent value.
GPC device: Showa Denko (GPC-101)
Column: manufactured by Showa Denko KK (series of KD803 and KD805)
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran 10mL / L)
Flow rate: 1.0 mL / min. Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polymer laboratory Polyethylene glycol manufactured by the company (peak top molecular weight (Mp) about 12,000, 4,000, 1,000). In order to avoid the overlap of peaks, the measurement was performed by mixing four types of 900,000, 100,000, 12,000, and 1,000, and three types of 150,000, 30,000, and 4,000. Two samples of the mixed sample were measured separately.

The abbreviations of the compounds used are shown below.
DMF: N, N-dimethylformamide THF: tetrahydrofuran NMP: N-methyl-2-pyrrolidone BCS: ethylene glycol monobutyl ether CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride APC18: 2,4-diamino -1-octadecyloxybenzene

[Synthesis of Diamine Compounds [3] to [5]]
<Example 1> Diamine compound [3]: Synthesis of 1- (2,4-diaminophenyl) -3-methylthymine

以下に示す３ステップの経路でジアミン化合物［３］を合成した。

The diamine compound [3] was synthesized by the following three-step route.

First step: Synthesis of 1- (2,4-dinitrophenyl) thymine

２，４−ジニトロフルオロベンゼン（２６．６ｇ、１４３ｍｍｏｌ）、ＤＭＦ（５００ｍＬ）、及びトリエチルアミン（２９．９ｍＬ、２１５ｍｍｏｌ）の混合物を７０℃に加熱した溶液に、ＤＭＦ（１００ｍＬ）に溶解させたチミン（１６．０ｇ、１４３ｍｍｏｌ）を１時間かけて滴下した。７０℃で２時間反応させた後、減圧下でＤＭＦ（４２０ｇ）を留去し、残った溶液を水（５００ｍＬ）へ注いだ。

A solution of 2,4-dinitrofluorobenzene (26.6 g, 143 mmol), DMF (500 mL), and triethylamine (29.9 mL, 215 mmol) in a solution heated to 70 ° C. was dissolved in DMF (100 mL) with thymine ( 16.0 g, 143 mmol) was added dropwise over 1 hour. After reacting at 70 ° C. for 2 hours, DMF (420 g) was distilled off under reduced pressure, and the remaining solution was poured into water (500 mL).

  The precipitated solid was collected by suction filtration and washed three times with water (300 mL). 200 g of 1,2-dichloroethane was added to the obtained solid, dissolved by heating to 70 ° C., allowed to cool to room temperature, and allowed to stand for 30 minutes. The precipitated solid was collected by suction filtration, washed with 1,2-dichloroethane (50 g × 1) and 1,2-dichloroethane / ethyl acetate = 1/1 (50 g), and dried under reduced pressure at 40 ° C. for 4 hours. By performing, 1- (2,4-dinitrophenyl) thymine (26.8 g) was obtained as a yellow solid (yield 66%).

Second step: Synthesis of 1- (2,4-dinitrophenyl) -3-methylthymine

１−（２，４−ジニトロフェニル）チミン（２３．１ｇ、８２．９ｍｍｏｌ）、炭酸カリウム（１７．２ｇ、１２４ｍｍｏｌ）、ＤＭＦ（１２７ｍＬ）、及びヨウ化メチル（１１．５ｇ、１００ｍｍｏｌ）の混合物を２時間、室温で反応させた後、固体を吸引ろ過で除き、減圧下でＤＭＦを留去した。そこへ、酢酸エチル（２５０ｍＬ）を加え、水／飽和食塩水＝１／１の混合液（１００ｍＬ）で４回、及び飽和食塩水（１００ｍＬ）で洗浄し、硫酸マグネシウムで乾燥し、ろ過により硫酸マグネシウムを除き、溶媒を減圧下留去し、４０℃で４時間減圧乾燥を行うことで、１−（２，４−ジニトロフェニル）−３−メチルチミン（２２．６ｇ）を黄色固体として得た（収率８９％）。

A mixture of 1- (2,4-dinitrophenyl) thymine (23.1 g, 82.9 mmol), potassium carbonate (17.2 g, 124 mmol), DMF (127 mL), and methyl iodide (11.5 g, 100 mmol). After reacting at room temperature for 2 hours, the solid was removed by suction filtration, and DMF was distilled off under reduced pressure. Thereto, ethyl acetate (250 mL) was added, washed four times with a mixed solution (100 mL) of water / saturated saline = 1/1, and saturated brine (100 mL), dried over magnesium sulfate, and filtered to give sulfuric acid. Magnesium was removed, the solvent was distilled off under reduced pressure, and dried under reduced pressure at 40 ° C. for 4 hours to obtain 1- (2,4-dinitrophenyl) -3-methylthymine (22.6 g) as a yellow solid ( Yield 89%).

Third step: Synthesis of 1- (2,4-diaminophenyl) -3-methylthymine

１−（２，４−ジニトロフェニル）−３−メチルチミン（２０．２ｇ、６５．９ｍｍｏｌ）、及びエタノール（３２９ｍｍｏｌ）の混合物を脱気し、窒素雰囲気として、塩化第一スズ（１２５ｇ、６５９ｍｍｏｌ）を加え、２時間加熱還流を行い、室温まで放冷し、飽和炭酸水素ナトリウム水溶液（１．４Ｌ）をゆっくりと加えた。吸引ろ過により固体を除き、約５００ｇの水／エタノール混合溶媒を減圧留去し、酢酸エチル（１００ｍＬ×１０）で抽出し、有機相を硫酸マグネシウムで乾燥し、ろ過により硫酸マグネシウムを除き、溶媒を減圧下留去し、４０℃で４時間減圧乾燥を行うことで、１−（２，４−ジアミノフェニル）−３−メチルチミン（１２．１ｇ）を紫色固体として得た（収率６０％）。

A mixture of 1- (2,4-dinitrophenyl) -3-methylthymine (20.2 g, 65.9 mmol) and ethanol (329 mmol) was degassed and stannous chloride (125 g, 659 mmol) was added as a nitrogen atmosphere. The mixture was heated under reflux for 2 hours, allowed to cool to room temperature, and a saturated aqueous sodium hydrogen carbonate solution (1.4 L) was slowly added. The solid was removed by suction filtration, about 500 g of the water / ethanol mixed solvent was distilled off under reduced pressure, extracted with ethyl acetate (100 mL × 10), the organic phase was dried over magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was removed. The residue was distilled off under reduced pressure and dried under reduced pressure at 40 ° C. for 4 hours to obtain 1- (2,4-diaminophenyl) -3-methylthymine (12.1 g) as a purple solid (yield 60%).

<Example 2> Diamine compound [4]: Synthesis of 1- {4- (2,4-diaminophenoxy) phenyl} -3-heptylthymine

以下に示す６ステップの経路でジアミン化合物［４］を合成した。

The diamine compound [4] was synthesized by the following 6-step route.

First step: Synthesis of 1-tert-butoxycarbonylthymine

チミン（２５．３ｇ、２２６ｍｍｏｌ）、アセトニトリル（１．１３Ｌ）、二炭酸ジ−ｔｅｒｔ−ブチル（４９．３ｇ、２２６ｍｍｏｌ）、及び４−（Ｎ、Ｎ−ジメチルアミノ）ピリジン（０．２５４ｇ、２．２６ｍｍｏｌ）の混合物を室温で２４時間攪拌した後、溶媒を減圧留去し、真空下乾燥することで１−ｔｅｒｔ−ブトキシカルボニルチミン（４５．３ｇ）を白色固体として得た（収率８７％）。

Thymine (25.3 g, 226 mmol), acetonitrile (1.13 L), di-tert-butyl dicarbonate (49.3 g, 226 mmol), and 4- (N, N-dimethylamino) pyridine (0.254 g, 2. 26 mmol) was stirred at room temperature for 24 hours, and then the solvent was distilled off under reduced pressure and dried under vacuum to obtain 1-tert-butoxycarbonylthymine (45.3 g) as a white solid (yield 87%). .

Second step: Synthesis of 1-tert-butoxycarbonyl-3-heptylthymine

１−ｔｅｒｔ−ブトキシカルボニルチミン（２８．７ｇ、１２７ｍｍｏｌ）、ＤＭＦ（１９０ｍＬ）、１−ブロモヘプタン（２３．９ｇ、１３３ｍｍｏｌ）、及び炭酸カリウム（２６．４ｇ、１９１ｍｍｏｌ）の混合物を室温で１７時間攪拌した後、水（１．９Ｌ）に注ぎ、３０分間攪拌した。析出した固体を吸引ろ過により回収し、水（１００ｍＬ）で２回洗浄し、６０℃で３時間真空下で乾燥することで１−ｔｅｒｔ−ブトキシカルボニル−３−ヘプチルチミン（３７．６ｇ）を白色固体として得た（収率９５％）。

A mixture of 1-tert-butoxycarbonylthymine (28.7 g, 127 mmol), DMF (190 mL), 1-bromoheptane (23.9 g, 133 mmol), and potassium carbonate (26.4 g, 191 mmol) was stirred at room temperature for 17 hours. The mixture was poured into water (1.9 L) and stirred for 30 minutes. The precipitated solid was collected by suction filtration, washed twice with water (100 mL), and dried under vacuum at 60 ° C. for 3 hours to give 1-tert-butoxycarbonyl-3-heptylthymine (37.6 g) as white. Obtained as a solid (95% yield).

Third step: Synthesis of 3-heptylthymine

１−ｔｅｒｔ−ブトキシカルボニル−３−ヘプチルチミン（３７．１ｇ、１１４ｍｍｏｌ）、メタノール（２２８ｍＬ）、及び炭酸カリウム（７．９０ｇ、５７．２ｍｍｏｌ）の混合物を室温で１８時間攪拌した後、メタノールを減圧留去し、水（２００ｍＬ）を加え、酢酸エチル（２５０ｍＬ）で３回抽出し、有機相を飽和食塩水で洗浄し、硫酸マグネシウムで乾燥し、ろ過により硫酸マグネシウムを除き、溶媒を減圧下留去し、４０℃で２時間減圧乾燥を行うことで、３−ヘプチルチミン（２５．６ｇ）を無色油状物として得た（収率１００％）。

A mixture of 1-tert-butoxycarbonyl-3-heptylthymine (37.1 g, 114 mmol), methanol (228 mL), and potassium carbonate (7.90 g, 57.2 mmol) was stirred at room temperature for 18 hours, and then the methanol was reduced in pressure. Evaporate, add water (200 mL), extract three times with ethyl acetate (250 mL), wash the organic phase with saturated brine, dry over magnesium sulfate, remove the magnesium sulfate by filtration, and remove the solvent under reduced pressure. The resulting solution was dried under reduced pressure at 40 ° C. for 2 hours to give 3-heptylthymine (25.6 g) as a colorless oil (yield 100%).

Fourth step: Synthesis of 4- (tetrahydro-2H-pyran-2-yloxy) phenylboronic acid

マグネシウム（削り節状）（２４．３ｇ、９７．２ｍｍｏｌ）とヨウ素の結晶を２粒（任意量）にＴＨＦ（１０ｍＬ）を加え、室温で１分ほど攪拌した後、４−（テトラヒドロ−２Ｈ−ピラン−２−イルオキシ）ブロモベンゼン（２５．０ｇ、９７．２ｍｍｏｌ）のＴＨＦ溶液（ＴＨＦ４０．０ｍＬ）をゆっくり加え、窒素雰囲気下、室温で５分間攪拌し２時間還流させ、室温に戻すことでグリニャール試薬を調製した。別の４口フラスコにトリエチルボレート（３１．３ｇ、２９２ｍｍｏｌ）、ＴＨＦ（６００ｍＬ）を加え、窒素置換した後、−１５℃まで冷却した。

After adding magnesium (shaving node shape) (24.3 g, 97.2 mmol) and iodine crystals to 2 grains (arbitrary amount) of THF (10 mL) and stirring at room temperature for about 1 minute, 4- (tetrahydro-2H-pyran 2-yloxy) bromobenzene (25.0 g, 97.2 mmol) in THF (THF 40.0 mL) was slowly added, stirred for 5 minutes at room temperature in a nitrogen atmosphere, refluxed for 2 hours, and returned to room temperature to return to Grignard reagent. Was prepared. Triethyl borate (31.3 g, 292 mmol) and THF (600 mL) were added to another 4-neck flask, and the atmosphere was purged with nitrogen, followed by cooling to −15 ° C.

The prepared Grignard reagent was cooled to 0 ° C. and added dropwise to a THF solution of triethylborate over 30 minutes using a cannula. When the reaction was continued for 1 hour while maintaining 0 ° C. after completion of the dropwise addition, a gray solid was precipitated.
Ammonium chloride aqueous solution (10 wt%, 150 mL) was added thereto, and the mixture was stirred at room temperature for 16 hours. Add ethyl acetate (200 mL), stir for a while, extract the organic layer, wash with water and saturated brine, dry over magnesium sulfate, remove magnesium sulfate by filtration, and evaporate the solvent under reduced pressure to dilute. A pink solid was obtained. This was recrystallized with a mixed solvent of ethyl acetate and hexane 1:10 (volume ratio) to obtain 4- (tetrahydro-2H-pyran-2-yloxy) phenylboronic acid (18.3 g) as a white solid. (Yield 83%).

Fifth step: Synthesis of 1- (4-hydroxyphenyl) -3-heptylthymine

２００ｍＬ４口フラスコに、３−ヘプチルチミン（１４．９ｇ、６２．７ｍｍｏｌ）、４−（テトラヒドロ−２Ｈ−ピラン−２−イルオキシ）フェニルボロン酸（１１．６ｇ、５２．２ｍｍｏｌ）、酢酸銅（８．２０ｇ、１０４ｍｍｏｌ）、モレキュラーシーブス３Å（１５ｇ）、及び脱水ジクロロエタン（１００ｍＬ）を加え、乾燥空気を送りながら２日間激しく攪拌した。反応終了後、酢酸銅やモレキュラーシーブスなどの固形物をろ過により除き、ろ液に酢酸エチル（１００ｍＬ）を加え、水（１００ｍＬ×５）、及び飽和食塩水で洗浄し、硫酸マグネシウムで乾燥し、ろ過により硫酸マグネシウムを除き、溶媒を減圧下留去すると赤褐色の粘体が得られた。

In a 200 mL 4-neck flask, 3-heptylthymine (14.9 g, 62.7 mmol), 4- (tetrahydro-2H-pyran-2-yloxy) phenylboronic acid (11.6 g, 52.2 mmol), copper acetate (8. 20 g, 104 mmol), 3 sieves of molecular sieves (15 g), and dehydrated dichloroethane (100 mL) were added, and the mixture was vigorously stirred for 2 days while sending dry air. After completion of the reaction, solids such as copper acetate and molecular sieves were removed by filtration, ethyl acetate (100 mL) was added to the filtrate, washed with water (100 mL × 5) and saturated brine, dried over magnesium sulfate, When magnesium sulfate was removed by filtration and the solvent was distilled off under reduced pressure, a reddish brown viscous body was obtained.

  This was recrystallized with a mixed solvent of ethyl acetate and hexane 1:10 (volume ratio) to give 1- [4- (tetrahydro-2H-pyran-2-yloxy) phenyl] -3-heptylthymine (12.3 g). ) Was obtained as a white solid. This was dissolved in THF (100 mL), 1N aqueous hydrochloric acid solution was added, and the mixture was stirred at 60 ° C. for 3 hr under a nitrogen atmosphere. Then, after adjusting the pH of the reaction solution to 4 to 5 using an aqueous sodium hydrogen carbonate solution, ethyl acetate (100 mL) was added, washed with water (100 mL × 5) and saturated brine, and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, the solvent was distilled off under reduced pressure, and the residue was dried at 40 ° C. under vacuum to obtain 1- (4-hydroxyphenyl) -3-heptylthymine (9.6 g) as a light yellow viscous body. (59%).

Step 6: Synthesis of 1- {4- (2,4-dinitrophenoxy) phenyl) -3-heptylthymine

２００ｍＬ４口フラスコに、１−（４−ヒドロキシフェニル）−３−ヘプチルチミン（５．２８ｇ、２８．４ｍｍｏｌ）、２，４−ジニトロフルオロベンゼン（９．０ｇ、２８ｍｍｏｌ）、及びＴＨＦ（１００ｍＬ）を加え、最後にトリエチルアミン（３．５ｇ、３４ｍｍｏｌ）をゆっくり加え、室温で１日攪拌した。薄層クロマトグラフィーにて原料の消失を確認した後、溶媒を減圧留去し、酢酸エチル（１００ｍＬ）を加え、水（１００ｍｌ×１０）、及び飽和食塩水にて洗浄し、硫酸マグネシウムで乾燥し、ろ過により硫酸マグネシウムを除き、溶媒を減圧下留去した。残渣をシリカゲルカラムクロマトグラフィー（酢酸エチル：ヘキサン＝１：２体積比）にて精製し、溶媒を減圧下留去し、真空下４０℃で乾燥することで１−｛４−（２，４−ジニトロフェノキシ）フェニル）−３−ヘプチルチミン（１２．０ｇ）を薄黄色のガラス状固体として得た。（収率８７％）

To a 200 mL 4-neck flask, add 1- (4-hydroxyphenyl) -3-heptylthymine (5.28 g, 28.4 mmol), 2,4-dinitrofluorobenzene (9.0 g, 28 mmol), and THF (100 mL). Finally, triethylamine (3.5 g, 34 mmol) was slowly added and stirred at room temperature for 1 day. After confirming the disappearance of the raw materials by thin layer chromatography, the solvent was distilled off under reduced pressure, ethyl acetate (100 mL) was added, washed with water (100 ml × 10) and saturated brine, and dried over magnesium sulfate. The magnesium sulfate was removed by filtration, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 2 volume ratio), the solvent was distilled off under reduced pressure, and the residue was dried at 40 ° C. under vacuum to give 1- {4- (2,4- Dinitrophenoxy) phenyl) -3-heptylthymine (12.0 g) was obtained as a pale yellow glassy solid. (Yield 87%)

Seventh step: Synthesis of 1- {4- (2,4-diaminophenoxy) phenyl) -3-heptylthymine

２００ｍＬ４口フラスコに１−｛４−（２，４−ジニトロフェノキシ）フェニル）−３−ヘプチルチミン（１０．０ｇ、２０．７ｍｍｏｌ）、酸化白金（１．０ｇ）、及び１，４−ジオキサンを加え、系内を水素雰囲気にした後、室温で１日激しく攪拌した。反応終了後、酸化白金をろ別し、溶媒を減圧留去し、酢酸エチルとヘキサン１：１０（体積比）の混合溶媒にて再結晶することで１−｛４−（２，４−ジアミノフェノキシ）ブチル｝−３−ヘプチルチミン（８．４ｇ）を白色繊維状固体として得た（収率９７％）。

Add 1- {4- (2,4-dinitrophenoxy) phenyl) -3-heptylthymine (10.0 g, 20.7 mmol), platinum oxide (1.0 g), and 1,4-dioxane to a 200 mL 4-neck flask. The system was brought to a hydrogen atmosphere and then stirred vigorously at room temperature for 1 day. After completion of the reaction, platinum oxide was filtered off, the solvent was distilled off under reduced pressure, and recrystallized with a mixed solvent of ethyl acetate and hexane 1:10 (volume ratio) to give 1- {4- (2,4-diamino). Phenoxy) butyl} -3-heptylthymine (8.4 g) was obtained as a white fibrous solid (yield 97%).

<Example 3> Diamine compound [5]: Synthesis of 1- {4- (2,4-diaminophenoxy) butyl} -3-heptylthymine

以下に示す６ステップの経路でジアミン化合物［５］を合成した。

The diamine compound [5] was synthesized by the following 6-step route.

First step: Synthesis of 4- (2,4-dinitrophenoxy) butanol

２，４−ジニトロフルオロベンゼン（１８．６ｇ、１００ｍｍｏｌ）、トルエン（１００ｍＬ）、１，４−ブタンジオール（４５．１ｇ、５００ｍｍｏｌ）、及びトリエチルアミン（１２．１ｇ、１２０ｍｍｏｌ）の混合物を１００℃に加熱し２１時間反応させ、減圧下でトルエンを留去し、酢酸エチル（５００ｍＬ）を加え、水（２５０ｍＬ）で１回、水（１５０ｍＬ）で２回、及び、飽和食塩水（１５０ｍＬ）で洗浄した。その後、有機相を硫酸マグネシウムで乾燥し、ろ過により硫酸マグネシウムを除き、溶媒を減圧下留去し、４０℃で４時間減圧乾燥を行うことで、４−（２，４−ジニトロフェノキシ）ブタノール（１９．８ｇ）を黄色油状物として得た（収率７７％）。

A mixture of 2,4-dinitrofluorobenzene (18.6 g, 100 mmol), toluene (100 mL), 1,4-butanediol (45.1 g, 500 mmol), and triethylamine (12.1 g, 120 mmol) was heated to 100 ° C. The reaction was continued for 21 hours, toluene was distilled off under reduced pressure, ethyl acetate (500 mL) was added, and the mixture was washed once with water (250 mL), twice with water (150 mL), and with saturated brine (150 mL). . Thereafter, the organic phase is dried over magnesium sulfate, the magnesium sulfate is removed by filtration, the solvent is distilled off under reduced pressure, and the residue is dried under reduced pressure at 40 ° C. for 4 hours, whereby 4- (2,4-dinitrophenoxy) butanol ( 19.8 g) was obtained as a yellow oil (77% yield).

Second step: Synthesis of 4- (2,4-dinitrophenoxy) butyl methanesulfonate

４−（２，４−ジニトロフェノキシ）ブタノール（１８．０ｇ、７０．１ｍｍｏｌ）、ジクロロメタン（１７５ｍＬ）、及びトリエチルアミン（２４．３ｍＬ、１７５ｍｍｏｌ）の混合物を０℃に冷却し、メタンスルホニルクロリド（９．６３ｇ、８４．７ｍｍｏｌ）を加え、そのまま０℃で１時間撹拌した後、室温で１５時間撹拌した。析出物をセライトろ過で除き、ろ液を減圧留去し、水（１５０ｍＬ）を加え、酢酸エチル（１５０ｍＬ×３）で抽出し、有機相を飽和食塩水（１５０ｍＬ）で洗浄した。
次いで、有機相を硫酸マグネシウムで乾燥し、ろ過により硫酸マグネシウムを除き、溶媒を減圧下留去し、４０℃で４時間減圧乾燥を行うことで、メタンスルホン酸４−（２，４−ジニトロフェノキシ）ブチル（２４．５ｇ）を黄色油状物として得た（収率＞９９％）。
第３ステップ〜第５ステップは、実施例２における第１ステップ〜第３ステップと同様にして、３−ヘプチルチミンを合成した。

A mixture of 4- (2,4-dinitrophenoxy) butanol (18.0 g, 70.1 mmol), dichloromethane (175 mL), and triethylamine (24.3 mL, 175 mmol) was cooled to 0 ° C. and methanesulfonyl chloride (9. 63 g, 84.7 mmol) was added, and the mixture was stirred as it was at 0 ° C. for 1 hour and then at room temperature for 15 hours. The precipitate was removed by celite filtration, the filtrate was distilled off under reduced pressure, water (150 mL) was added, the mixture was extracted with ethyl acetate (150 mL × 3), and the organic phase was washed with saturated brine (150 mL).
Next, the organic phase was dried over magnesium sulfate, the magnesium sulfate was removed by filtration, the solvent was distilled off under reduced pressure, and the residue was dried under reduced pressure at 40 ° C. for 4 hours, whereby methanesulfonic acid 4- (2,4-dinitrophenoxy) was obtained. ) Butyl (24.5 g) was obtained as a yellow oil (yield> 99%).
In the third to fifth steps, 3-heptylthymine was synthesized in the same manner as in the first to third steps in Example 2.

Step 6: Synthesis of 1- {4- (2,4-dinitrophenoxy) butyl} -3-heptylthymine

メタンスルホン酸４−（２，４−ジニトロフェノキシ）ブチル（２２．３ｇ、６６．７ｍｍｏｌ）、ＤＭＦ（１６６ｍＬ）、３−ヘプチルチミン（１５．０ｇ、６６．７ｍｍｏｌ）、及び炭酸カリウム（１３．８ｇ、１００ｍｍｏｌ）を加え、８０℃で２０時間撹拌した。その後、反応溶液に酢酸エチル（１Ｌ）を加え、水（５００ｍＬ×３）、及び、飽和食塩水（５００ｍＬ×１）で洗浄し、有機相を硫酸マグネシウムで乾燥し、ろ過により硫酸マグネシウムを除き、溶媒を減圧下留去した。得られた粗生成物をシリカゲルカラムクロマトグラフィー（１，２−ジクロロエタン／酢酸エチル＝９／１、Ｒｆ＝０．３８）で精製し、溶媒を減圧留去し、６０℃で５時間真空乾燥を行うことで、１−｛４−（２，４−ジニトロフェノキシ）ブチル｝−３−ヘプチルチミン（２１．７ｇ）を黄色油状物として得た（収率７０％）。

4- (2,4-dinitrophenoxy) butyl methanesulfonate (22.3 g, 66.7 mmol), DMF (166 mL), 3-heptylthymine (15.0 g, 66.7 mmol), and potassium carbonate (13.8 g) , 100 mmol) and stirred at 80 ° C. for 20 hours. Thereafter, ethyl acetate (1 L) was added to the reaction solution, washed with water (500 mL × 3) and saturated brine (500 mL × 1), the organic phase was dried over magnesium sulfate, and magnesium sulfate was removed by filtration. The solvent was distilled off under reduced pressure. The resulting crude product was purified by silica gel column chromatography (1,2-dichloroethane / ethyl acetate = 9/1, Rf = 0.38), the solvent was distilled off under reduced pressure, and the residue was vacuum-dried at 60 ° C. for 5 hours. This gave 1- {4- (2,4-dinitrophenoxy) butyl} -3-heptylthymine (21.7 g) as a yellow oil (yield 70%).

Step 7: Synthesis of 1- {4- (2,4-diaminophenoxy) butyl} -3-heptylthymine

１−｛４−（２，４−ジニトロフェノキシ）ブチル｝−３−ヘプチルチミン（２１．７ｇ、４６．８ｍｍｏｌ）、１，４−ジオキサン（１８８ｍＬ）、及び５％−パラジウム／炭素（２．１７ｇ）の混合物を脱気し、水素雰囲気下、室温で６９時間撹拌した。その後、セライトろ過により固形物を除き、溶媒を減圧留去し、残渣にトルエン６０ｍＬを加え、９０℃で加熱溶解させ、熱いうちにろ過し、溶液を室温で２４時間静置した。析出した固体を吸引ろ過で回収し、４０℃で５時間真空乾燥することで、１−｛４−（２，４−ジアミノフェノキシ）ブチル｝−３−ヘプチルチミン（１２．４ｇ）を茶色粉末として得た（収率６６％）。

1- {4- (2,4-dinitrophenoxy) butyl} -3-heptylthymine (21.7 g, 46.8 mmol), 1,4-dioxane (188 mL), and 5% palladium / carbon (2.17 g) The mixture was degassed and stirred at room temperature for 69 hours under hydrogen atmosphere. Thereafter, solids were removed by Celite filtration, the solvent was distilled off under reduced pressure, 60 mL of toluene was added to the residue, heated and dissolved at 90 ° C., filtered while hot, and the solution was allowed to stand at room temperature for 24 hours. The precipitated solid was collected by suction filtration, and vacuum-dried at 40 ° C. for 5 hours to give 1- {4- (2,4-diaminophenoxy) butyl} -3-heptylthymine (12.4 g) as a brown powder. Obtained (yield 66%).

[Polyamide synthesis]
<Example 4> Synthesis of polyamide PA-A [adipic acid chloride / diamine (3)] The diamine compound (3) (1.00 g, 4.06 mmol) was dissolved in NMP (8.0 mL), and pyridine (0. 78 mL), cooled to 0 ° C. and adipic acid chloride (0.729 g, 3.98 mmol) was added. After stirring at 0 ° C. for 4 hours, the mixture was stirred at room temperature for 24 hours. Thereafter, NMP (18.7 mL) was added to the reaction solution and poured into water (144 mL) to precipitate a polymer. The precipitated polymer was collected by suction filtration, washed once with water (144 g), once with methanol (144 g), and three times with methanol (36 g), and vacuum-dried at 40 ° C. for 6 hours to obtain polyamide PA- A was obtained as a yellow powder (1.05 g). The number average molecular weight of the polymer was 5,204.

<Example 5> Synthesis of polyamide PA-B [adipic acid chloride / diamine (5)] The diamine compound (5) (0.800 g, 1.99 mmol) was dissolved in NMP (8.9 mL), and pyridine (0. 38 mL) was added, the mixture was cooled to 0 ° C., adipic acid chloride (0.373 g, 1.97 mmol) was added, and the mixture was returned to room temperature and stirred for 4 hours. Thereafter, NMP (9.9 mL) was added to the reaction solution and poured into water (102 mL) to precipitate a polymer. The precipitated polymer was collected by suction filtration, washed with water (102 g × 1), methanol (102 g × 1, 25 g × 3), and vacuum-dried at 40 ° C. for 6 hours, whereby polyamide PA-B was converted into a purple powder. Obtained (0.87 g). The number average molecular weight of the polymer was 5,948.

[Preparation of polyamide varnish PA]
<Example 6> Preparation of polyamide varnish PA-A-1 Polyamide PA-A (0.97 g) was dissolved in NMP (8.74 g), BCS (2.43 g) was added, and 8 wt% polyamide varnish PA was added. -A-1.
<Example 7> Preparation of polyamide varnish PA-B-1 Polyamide PA-B (0.18 g) was dissolved in NMP (1.59 g), BCS (0.44 g) was added, and 8 wt% polyamide varnish PB was added. -B-1.

[Synthesis of polyamic acid PAA]
<Example 8> Synthesis of polyamic acid PAA-A [CBDA / diamine (1) (90), APC18 (10)] Diamine (1) (0.66 g, 2.7 mmol), APC18 (0.11 g,. 30 mmol) was dissolved in NMP (5.45 mL), CBDA (0.59 g, 3.0 mmol) was added, and the mixture was reacted at room temperature for 17 hours to synthesize polyamic acid PAA-A. The number average molecular weight of the polymer was 6,865.

<Example 9> Synthesis of polyamic acid PAA-B [CBDA / diamine (2) (90), APC18 (10)] Diamine (2) (0.76 g, 1.8 mmol), APC18 (0.075 g,. 20 mmol) was dissolved in NMP (4.9 mL), CBDA (0.38 g, 2.0 mmol) was added, and the mixture was reacted at room temperature for 18 hours to synthesize polyamic acid PAA-B. The number average molecular weight of the polymer was 13,753.

<Example 10> Synthesis of polyamic acid PAA-C [CBDA / diamine (3) (90), APC18 (10)] Diamine (3) (0.98 g, 2.4 mmol), APC18 (0.10 g, 0.0. 30 mmol) was dissolved in NMP (6.4 mL), CBDA (0.53 g, 0.99 mmol) was added, and the mixture was reacted at room temperature for 18 hours to synthesize polyamic acid PAA-C. The number average molecule of the polymer was 14,571.
[Preparation of polyamic acid varnish]

<Example 11> Preparation of polyamic acid varnish PAA-A-1 To NMP solution (4.48 g) of 20 wt% PAA-A, NMP (7.22 g) and BCS (2.94 g) were added, and 6 wt. % Polyamic acid varnish PAA-A-1 was prepared.

<Example 12> Preparation of polyamic acid varnish PAA-B-1 To NMP solution (4.90 g) of 20 wt% PAA-B, NMP (3.92 g) and BCS (2.44 g) were added, and 8 wt. % Polyamic acid varnish PAA-B-1 was prepared.

<Example 13> Preparation of polyamic acid varnish PAA-C-1 To NMP solution (4.30 g) of 18 wt% PAA-C, NMP (6.15 g) and BCS (2.61 g) were added, and 6 wt. % Polyamic acid varnish PAA-C-1.

[Production and evaluation of liquid crystal cell]
<Example 14>
The polyamic acid varnish PAA-A-1 prepared in Example 11 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 × 300 microns and a line / space of 5 μm was formed. . A liquid crystal alignment film having a thickness of 100 nm was prepared by heating at 80 ° C. for 90 seconds and further at 160 ° C. for 60 minutes. Further, the same polyamic acid varnish PAA-A-1 is spin-coated on the ITO surface on which no electrode pattern is formed, and heated at 80 ° C. for 90 seconds and further at 160 ° C. for 60 minutes to form a liquid crystal alignment film having a thickness of 100 nm Was made. After spraying 6 μm bead spacers on one liquid crystal alignment film surface of these two substrates, a sealant was printed from above. Here, the other substrate was bonded with the liquid crystal alignment film surface inside, and then the sealing agent was cured to produce an empty cell. Liquid crystal MLC-6608 (trade name of Merck) was injected into this empty cell by a reduced pressure injection method to produce a liquid crystal cell.

The time variation of the luminance of the liquid crystal panel when a rectangular wave having a voltage of ± 4 V and a frequency of 1 kHz was applied to the liquid crystal cell was captured with an oscilloscope. The luminance before the voltage application was 0%, the luminance when the voltage was applied and saturated was 100%, and the time for the luminance to change from 10% to 90% was measured as the response speed. As a result, it was 800 ms.
Next, 20 J of ultraviolet light was irradiated from the outside of the liquid crystal cell in a state where a voltage of 20 Vp-p was applied to the liquid crystal cell. Thereafter, the response speed was measured again. The result was 190 ms, and an improvement in response speed was confirmed.

<Example 15>
Response speed was measured in the same manner as in Example 14 using polyamic acid varnish PAA-B-1. As a result, the initial response speed was 770 ms, the response speed after irradiation with ultraviolet light was 160 ms, and it was confirmed that the response speed was improved.
<Example 16>
The response speed was measured in the same manner as in Example 14 using polyamic acid varnish PAA-C-1. As a result, the initial response speed was 760 ms, the response speed after irradiation with ultraviolet light was 57 ms, and it was confirmed that the response speed was improved.

Diamine compounds provided in the present invention, as port polyamic acid of any material monomer, further, automobile parts, are widely used in consumer electronics field, polyamideimide, as a raw material monomer of the polymer material material, such as polyetherimide Widely used.

Claims (5)

A diamine compound represented by the following formula [1] or formula [2].

(Wherein, ^{R 1} represents a Tan'yui case, ^{R 2} represents a single bond or -O-, ^{R 3} is a single bond, or unsubstituted or alkylene having 1 to 20 carbon atoms which is substituted by fluorine atom or Represents phenylene , R ⁴ represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms substituted by a fluorine atom, and R ⁵ represents a hydrogen atom or a methyl group. The diamine compound according to claim 1, wherein R ⁴ in the formula [1] or the formula [2] is an alkyl group having 1 to 10 carbon atoms. The diamine compound according to claim 1 or 2, wherein R ⁵ in the formula [1] or the formula [2] is a methyl group. The diamine compound in any one of Claims 1-3 represented by following formula [3], following formula [4], or following formula [5].

The polyamic acid obtained by making the diamine compound and tetracarboxylic anhydride in any one of Claims 1-4 react , or the polyimide which imidized this polyamic acid .