JP2005255981A - Diamine, polymer, liquid crystal aligned film, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve a problem that, in order to make a liquid crystal aligned film show required characteristics, an aligned film is proposed, the film aiming at an improvement of electric characteristics by introducing an amide bond into a polyimide main chain which constitues the aligned film, and rising a dielectric constant, but the polyimide having such an N-unsubstituted amide group shows a low solubility to a solvent. <P>SOLUTION: A diamine is used as a starting material of polyimide production, the diamine being represented by formula (1) (wherein R<SP>1</SP>is a 1-30C alkyl in which optional -CH<SB>2</SB>- may be substituted with phenylene, cyclohexylene, a divalent condensed ring group, a divalent heterocyclic group, -O-, -OCO-, -COO, or -CH=CH-; and X<SP>1</SP>and X<SP>2</SP>are a single bond, or each a 1-20C alkylene in which optional -CH<SB>2</SB>- may be substituted with phenylene, cyclohexylene, the divalent condensed ring group, the divalent heterocyclic group, -O-, -S-, -OCO-, -COO, or -CH=CH-). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel diamine, a polyamic acid which is a polyimide precursor obtained using this diamine as one of the raw materials, polyimide, polyamide, polyamideimide, a liquid crystal aligning agent containing at least one of these polymers, and this The present invention relates to a liquid crystal alignment film manufactured using a liquid crystal aligning agent. Furthermore, this invention relates to the liquid crystal display element containing this liquid crystal aligning film. The term “liquid crystal aligning agent” in the present invention means a polymer-containing composition used for forming a liquid crystal aligning film.

  Liquid crystal display elements are changing from Twisted Nematic (TN) to Super Twisted Nematic (STN) in response to demands for screen enlargement, colorization, display quality such as contrast and color development, and improved response speed. Furthermore, it has been developed into a TFT type display element in which a thin film transistor (TFT) is attached to each pixel. In recent years, driving methods for TFT-type display elements have been improved. For example, in-plane switching (IPS) and vertical alignment (VA) systems have been developed to further increase the viewing angle. In addition, an optically compensated bend (OCB) system having a response speed capable of moving images has been developed.

  The liquid crystal alignment film plays two roles of aligning liquid crystal molecules in a certain direction and tilting with respect to the substrate plane in the liquid crystal display element. The tilt of the liquid crystal molecules with respect to the substrate plane is called the pretilt angle. This name will be used hereinafter in this specification. This liquid crystal alignment film is a polyimide thin film with a high glass transition point (Tg) and excellent chemical resistance and heat resistance in order to minimize the temporal, chemical and thermal degradation of molecular alignment. It is mainly used as the material. In this liquid crystal alignment film, a polyamic acid or polyimide solution is usually applied to a glass substrate with an electrode by a spinner method or a printing method, and the substrate is heated to dehydrate and ring polyamic acid, or a solvent of the polyimide solution is removed. A polyimide thin film is obtained by evaporation, and further obtained through an alignment treatment step such as rubbing. The two substrates having the liquid crystal alignment film thus obtained are bonded to face each other, the pressure inside the assembled cell is reduced, and then immersed in liquid crystal to inject liquid crystal into the cell through the opening. A display element is created.

The liquid crystal alignment film is required to bring the following characteristics to the liquid crystal display element.
(A) Giving an appropriate pretilt angle to the liquid crystal molecules. Moreover, this pretilt angle is stable against environmental changes such as conditions in the cell manufacturing process such as rubbing and cleaning, and the ambient temperature of the liquid crystal cell.
(B) No alignment defects of liquid crystal molecules are generated.
(C) An appropriate voltage holding ratio (Voltage Holding Ratio: VHR) is given to the liquid crystal display element.
(D) When an arbitrary image is displayed on the liquid crystal display element for a long time and then changed to another image, a phenomenon called “burn-in” in which the previous image remains as an afterimage hardly occurs.
(E) It is not affected by other materials used at the same time for the liquid crystal cell.

  In recent years, polyimide is widely used for liquid crystal alignment films because of its excellent heat resistance and chemical resistance. However, the conventional liquid crystal alignment film has a problem that the image sticking phenomenon occurs. In particular, a liquid crystal alignment film used for a TFT type liquid crystal display element is required to have a high voltage holding ratio and hardly cause a burn-in phenomenon.

  A method of mixing two or more types of liquid crystal aligning agents in which polymers having different surface energy values when thinned are dissolved in a solvent in order to effectively develop the characteristics required for the liquid crystal aligning film (hereinafter referred to as polymer blend) Is often done. For example, Patent Document 1 describes an example in which a resin coating film is formed from a solution (same as the above liquid crystal aligning agent) in which two or more component polymers are mixed. This example uses the characteristic that a component having a low surface tension tends to segregate spontaneously on the film surface. That is, the surface tension of the resin coating film exhibiting good liquid crystal alignment characteristics is reduced to 2 dyne / cm or more smaller than the surface tension of the resin coating film exhibiting good electrical characteristics. In this method, a resin exhibiting liquid crystal alignment is formed, and a liquid crystal alignment film having a structure mainly composed of a resin component that exhibits good electrical characteristics is obtained inside the film.

In addition, liquid crystal alignment films have been proposed in which electrical characteristics are improved by introducing an amide bond into the polyimide main chain constituting the liquid crystal alignment film to increase the dielectric constant (see Patent Document 2 and Patent Document 3). reference). However, such a polyimide having an N-unsubstituted amide group has a problem of low solubility in a solvent.
JP-A-8-43831 JP-A-5-224212 JP-A-5-224213

  An object of the present invention is to provide a novel diamine having an amide group and a polymer using the diamine as a raw material. By using this polymer, the above-mentioned characteristics (A) to (E) are satisfied, and the problem of polyimide having an N-unsubstituted amide group is further solved.

  The present inventors have found that hydrogen bonding between polymers such as polyamic acid having N-unsubstituted amide group, polyimide, polyamideimide and the like is a cause of lowering solubility in a solvent. Further, it has been found that using a diamine having an N-substituted amide group, particularly an N-alkylamide group, as a polymer raw material gives an anti-seizure effect to a liquid crystal alignment film obtained using the polymer. The present invention has the following configuration.

ここに、Ｒ^１は炭素数１〜３０のアルキルであり、このアルキル中の任意の−ＣＨ_２−はフェニレン、シクロへキシレン、２価の縮合環基、２価のヘテロ環基、−Ｏ−、−ＯＣＯ−、−ＣＯＯまたは−ＣＨ＝ＣＨ−で置き換えられてもよく、そしてこのアルキル中の任意の水素はハロゲンで置き換えられてもよく；前記のフェニレン、シクロへキシレン、２価の縮合環基および２価のヘテロ環基において、任意の水素はハロゲン、炭素数１〜４のアルキル、炭素数１〜４のフッ素化アルキルまたは炭素数１〜４のアルコキシで置き換えられてもよく；Ｘ¹およびＸ^２は独立して単結合または炭素数１〜２０のアルキレンであり、このアルキレン中の任意の−ＣＨ_２−はフェニレン、シクロへキシレン、２価の縮合環基、２価のヘテロ環基、−Ｏ−、−Ｓ−、−ＯＣＯ−、−ＣＯＯまたは−ＣＨ＝ＣＨ−で置き換えられてもよく、そしてこのアルキレン中の任意の水素はフッ素で置き換えられてもよく；Ｘ^２が単結合の時は、Ｘ^１中のアミノフェニル基に結合する−ＣＨ_２−が−Ｏ−または−Ｓ−で置き換えられることはなく；アミノフェニル基において、ベンゼン環へのアミノ基の結合位置は任意であり、そしてベンゼン環の任意の水素はフッ素、炭素数１〜１０のアルキル、炭素数１〜１０のフッ素化アルキル、または炭素数１〜１０のアルコキシで置き換えられてもよい。 [1] Diamine represented by formula (1):

Here, R ¹ is alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is phenylene, cyclohexylene, a divalent fused ring group, a divalent heterocyclic group, —O—. , -OCO-, -COO or -CH = CH-, and any hydrogen in the alkyl may be replaced by halogen; phenylene, cyclohexylene, divalent fused ring And in the divalent heterocyclic group, any hydrogen may be replaced by halogen, alkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms; X ¹ and X ² are independently a single bond or a C 1-20 alkylene, arbitrary -CH 2 _- in the alkylene phenylene, cyclohexylene, divalent condensed ring group, a divalent heterocyclic group -O -, - S -, - OCO -, - COO or -CH = CH- may be replaced by, and any of the alkylene hydrogen may be replaced by fluorine; ^{X 2} is a single bond Sometimes, —CH ₂ — bonded to the aminophenyl group in X ¹ is not replaced by —O— or —S—; in the aminophenyl group, the position of the amino group bonded to the benzene ring is arbitrary. , And any hydrogen in the benzene ring may be replaced by fluorine, alkyl having 1 to 10 carbons, fluorinated alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons.

[2] R ¹ is alkyl having 1 to 20 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,7-diyl, fluorene. -2,7-diyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, quinoline-3,7-diyl, -O-, -OCO-, -COO or -CH = CH -And any hydrogen in the alkyl may be replaced by fluorine; in the above 1,4-phenylene, any hydrogen is fluorine, alkyl having 1 to 4 carbons, carbon number Optionally substituted with 1 to 4 fluorinated alkyl or 1 to 4 carbon alkoxy; X ¹ and X ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, -C H ₂ − represents 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,7-diyl, fluorene-2,7-diyl, pyridine-2,5-diyl, 1,3-dioxane-2, 5-diyl, quinoline-3,7-diyl, —O— or —CH═CH— may be replaced, and any hydrogen in the alkylene may be replaced with fluorine; X ² is a single bond In this case, —CH ₂ — bonded to the aminophenyl group in X ¹ is not replaced by —O—; in the aminophenyl group, the bonding position of the amino group to the benzene ring is the bonding position of X ¹ and X a para or meta position with respect to each of the ^second coupling position, and any hydrogen fluorine benzene ring, alkyl of 1 to 5 carbon atoms, a fluorinated alkyl or C1-5 carbons 1 5 may be replaced by alkoxy, diamine according to [1] term.

[3] R ¹ is alkyl having 1 to 10 carbon atoms, and arbitrary —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, — O—, —OCO—, —COO or —CH═CH— may be replaced, and any hydrogen in the alkyl may be replaced with fluorine; X ¹ and X ² are independently a single bond Or alkylene having 1 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by 1,4-phenylene, 1,4-cyclohexylene, —O— or —CH═CH—. Well, and any hydrogen in the alkylene may be replaced by fluorine; when X ² is a single bond, —CH ₂ — bonded to the aminophenyl group in X ¹ is not replaced by —O—. None; In the minophenyl group, the bonding position of the amino group to the benzene ring is para or meta with respect to each of the bonding position of X ^{1 and} the bonding position of X ² , and any hydrogen of the benzene ring is fluorine, methyl or The diamine according to item [1], which may be substituted with methoxy.

[4] The diamine according to item [1], wherein X ¹ and X ² are both single bonds.

[5] R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, — O—, —OCO—, —COO or —CH═CH— may be replaced, and any hydrogen in the alkyl may be replaced with fluorine; X ¹ and X ² are both single bonds And in the aminophenyl group, the bonding position of the amino group to the benzene ring is para or meta with respect to each of the bonding position of X ^{1 and} the bonding position of X ² , and any hydrogen of the benzene ring is The diamine according to item [1], which may be substituted with fluorine, methyl or methoxy.

[6] R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, — O—, —OCO—, —COO or —CH═CH— may be replaced, and any hydrogen in the alkyl may be replaced with fluorine; X ¹ is alkylene having 1 to 10 carbons. And any —CH ₂ — in the alkylene may be replaced by 1,4-phenylene, 1,4-cyclohexylene, —O— or —CH═CH—, and any hydrogen in the alkylene. may be is replaced by fluorine, and in the alkylene, -CH 2 that bind to the aminophenyl group _- is not be replaced by -O-; the aminophenyl group; there are X ² represents a single bond There are, bonding position of the amino group on the benzene ring is para or meta position with respect to each of the coupling position of the coupling position and X ² of X ^1, and any hydrogen in the benzene ring is fluorine, methyl or methoxy The diamine according to item [1], which may be replaced.

[7] R ¹ is alkyl having 1 to 10 carbon atoms, and arbitrary —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, — O—, —OCO—, —COO or —CH═CH— may be replaced, and any hydrogen in the alkyl may be replaced with fluorine; X ¹ and X ² are independently carbon atoms 1-10 alkylene, any —CH ₂ — in the alkylene may be replaced by 1,4-phenylene, 1,4-cyclohexylene, —O— or —CH═CH—, and this arbitrary hydrogen in the alkylene may be replaced by fluorine; in-aminophenyl group, para to the respective coupling position of the coupling position and X ² of the coupling position X ¹ of the amino group on the benzene ring Other is a meta-position, and any hydrogen in the benzene ring fluorine, it may be replaced by methyl or methoxy, diamine according to [1] term.

[8] R ¹ is alkyl having 1 to 10 carbon atoms, and arbitrary —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, — O -, - OCO -, - COO or it may be replaced by -CH = CH-, and any hydrogen in the alkyl may be replaced by fluorine; X ¹ represents a single bond; ^{X 2} is An alkylene having 1 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by 1,4-phenylene, 1,4-cyclohexylene, —O— or —CH═CH—. , and any hydrogen may be replaced by fluorine in the alkylene; Pas at aminophenyl group, for each bonding position of the amino group on the benzene ring of the coupling position of the coupling position and X ² of X ¹ A position or meta-position, and any hydrogen in the benzene ring fluorine, may be replaced by methyl or methoxy, diamine according to [1] term.

ここに、Ｒ^１は炭素数１〜３０のアルキルであり、このアルキル中の任意の−ＣＨ_２−はフェニレン、シクロへキシレン、２価の縮合環基、２価のヘテロ環基、−Ｏ−、−ＯＣＯ−、−ＣＯＯまたは−ＣＨ＝ＣＨ−で置き換えられてもよく、そしてこのアルキル中の任意の水素はハロゲンで置き換えられてもよく；前記のフェニレン、シクロへキシレン、２価の縮合環基および２価のヘテロ環基において、任意の水素はハロゲン、炭素数１〜４のアルキル、炭素数１〜４のフッ素化アルキルまたは炭素数１〜４のアルコキシで置き換えられてもよく；Ｘ¹およびＸ^２は独立して単結合または炭素数１〜２０のアルキレンであり、このアルキレン中の任意の−ＣＨ_２−はフェニレン、シクロへキシレン、２価の縮合環基、２価のヘテロ環基、−Ｏ−、−Ｓ−、−ＯＣＯ−、−ＣＯＯまたは−ＣＨ＝ＣＨ−で置き換えられてもよく、そしてこのアルキレン中の任意の水素はフッ素で置き換えられてもよく；Ｘ^２が単結合の時は、Ｘ^１中のアミノフェニル基に結合する−ＣＨ_２−が−Ｏ−または−Ｓ−で置き換えられることはなく；アミノフェニル基において、ベンゼン環へのアミノ基の結合位置は任意であり、そしてベンゼン環の任意の水素はフッ素、炭素数１〜１０のアルキル、炭素数１〜１０のフッ素化アルキル、または炭素数１〜１０のアルコキシで置き換えられてもよい。 [9] Using one of the diamines represented by formula (1) or a diamine mixture containing at least one diamine represented by formula (1) as a diamine raw material, tetracarboxylic dianhydride, tricarboxylic acid, dicarboxylic acid Polymer obtained by using at least one of acid, tricarboxylic acid derivative and dicarboxylic acid derivative as carboxylic acid raw material:

Here, R ¹ is alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is phenylene, cyclohexylene, a divalent fused ring group, a divalent heterocyclic group, —O—. , -OCO-, -COO or -CH = CH-, and any hydrogen in the alkyl may be replaced by halogen; phenylene, cyclohexylene, divalent fused ring And in the divalent heterocyclic group, any hydrogen may be replaced by halogen, alkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms; X ¹ and X ² are independently a single bond or a C 1-20 alkylene, arbitrary -CH 2 _- in the alkylene phenylene, cyclohexylene, divalent condensed ring group, a divalent heterocyclic group -O -, - S -, - OCO -, - COO or -CH = CH- may be replaced by, and any of the alkylene hydrogen may be replaced by fluorine; ^{X 2} is a single bond Sometimes, —CH ₂ — bonded to the aminophenyl group in X ¹ is not replaced by —O— or —S—; in the aminophenyl group, the position of the amino group bonded to the benzene ring is arbitrary. , And any hydrogen in the benzene ring may be replaced by fluorine, alkyl having 1 to 10 carbons, fluorinated alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons.

[10] R ¹ is alkyl having 1 to 20 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,7-diyl, fluorene. -2,7-diyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, quinoline-3,7-diyl, -O-, -OCO-, -COO or -CH = CH -And any hydrogen in the alkyl may be replaced by fluorine; in the above 1,4-phenylene, any hydrogen is fluorine, alkyl having 1 to 4 carbons, carbon number Optionally substituted with 1 to 4 fluorinated alkyls or 1 to 4 carbon alkoxy; X ¹ and X ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, of -CH ₂ - is 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,7-diyl, fluorene-2,7-diyl, pyridine-2,5-diyl, 1,3-dioxane -2 , 5-diyl, quinoline-3,7-diyl, -O- or may be replaced by -CH = CH-, and any hydrogen may be replaced by fluorine in the alkylene; ^{X 2} is a single At the time of bonding, —CH ₂ — bonded to the aminophenyl group in X ¹ is not replaced by —O—; in the aminophenyl group, the bonding position of the amino group to the benzene ring is the bonding position of X ¹ and a para or meta position with respect to each of the bonding position of X ^2, and any hydrogen fluorine benzene ring, alkyl of 1 to 5 carbon atoms, 1 to 5 carbon atoms fluorinated alkyl or carbonitrides, May be replaced by the number 1-5 alkoxy, [9] The polymer according to claim.

[11] R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, — O—, —OCO—, —COO or —CH═CH— may be replaced, and any hydrogen in the alkyl may be replaced with fluorine; X ¹ and X ² are independently a single bond Or alkylene having 1 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by 1,4-phenylene, 1,4-cyclohexylene, —O— or —CH═CH—. Well, and any hydrogen in the alkylene may be replaced by fluorine; when X ² is a single bond, —CH ₂ — bonded to the aminophenyl group in X ¹ is not replaced by —O—. None; In the aminophenyl group, the bonding position of the amino group to the benzene ring is para-position or meta-position with respect to each of the bonding position of X ^{1 and} the bonding position of X ² , and any hydrogen of the benzene ring is fluorine, methyl Or the polymer as described in the item [9], which may be replaced by methoxy.

[12] The polymer according to item [9], wherein X ¹ and X ² are both a single bond.

[13] The polymer according to item [9], wherein the carboxylic acid raw material is at least one of tetracarboxylic dianhydrides.

これらの式において、環Ｂ^１は独立してシクロヘキサン環またはベンゼン環であり；環Ｂ^２はシクロヘキサン環、シクロヘキセン環またはベンゼン環であり；Ｇ^１は単結合、炭素数１〜１２のアルキレン、１，４−フェニレンまたは１，４−シクロヘキシレンであり、；Ｇ^２は単結合、−ＣＨ_２−、−ＣＨ_２ＣＨ_２−、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−Ｃ（ＣＨ_３）_２−または−Ｃ（ＣＦ_３）_２−であり、そしてＧ^２の環Ｂ^１への結合位置は、２−オキサプロパン−１，３−ジオイルの結合位置以外の任意の位置であり；Ｘ^３は単結合または−ＣＨ_２−であり；Ｘ^４は単結合、−ＣＨ_２−、−ＣＨ_２ＣＨ_２−または−ＣＨ＝ＣＨ−であり；Ｒ^２は独立して水素、メチル、エチルまたはフェニルであり；Ｒ^３は水素またはメチルである。 [14] The polymer according to item [9], wherein the carboxylic acid raw material is at least one selected from a compound represented by any one of formulas (A1) to (A9) and naphthalenetetracarboxylic dianhydride:

In these formulas, ring B ¹ is independently a cyclohexane ring or a benzene ring; ring B ² is a cyclohexane ring, cyclohexene ring or benzene ring; G ¹ is a single bond, alkylene having 1 to 12 carbon atoms, 1 , 4-phenylene or 1,4-cyclohexylene; G ² is a single bond, —CH ₂ —, —CH ₂ CH ₂ —, —O—, —CO—, —S—, —SO—, — C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —, and the bonding position of G ² to ring B ¹ is any position other than the bonding position of 2-oxapropane-1,3-dioyl. X ³ is a single bond or —CH ₂ —; X ⁴ is a single bond, —CH ₂ —, —CH ₂ CH ₂ — or —CH═CH—; R ² is independently hydrogen, methyl, ethyl or phenyl; ^{R 3} is The elementary or methyl.

[15] The polymer according to item [9], wherein the carboxylic acid raw material is at least one of a tricarboxylic acid, a dicarboxylic acid, a tricarboxylic acid derivative, and a dicarboxylic acid derivative.

[16] A polymer obtained by replacing the hydrogen of the amide bond (—CO—NH—) with an alkyl having 1 to 10 carbon atoms, starting from the polymer according to the item [15].

[17] The polymer according to item [9], wherein the carboxylic acid raw material is at least one of a tetracarboxylic dianhydride and at least one of a tricarboxylic acid, a dicarboxylic acid, a tricarboxylic acid derivative, and a dicarboxylic acid derivative.

これらの式において、環Ｂ^１は独立してシクロヘキサン環またはベンゼン環であり；環Ｂ^２はシクロヘキサン環、シクロヘキセン環またはベンゼン環であり；Ｇ^１は単結合、炭素数１〜１２のアルキレン、１，４−フェニレンまたは１，４−シクロヘキシレンであり、；Ｇ^２は単結合、−ＣＨ_２−、−ＣＨ_２ＣＨ_２−、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ−、−Ｃ（ＣＨ_３）_２−または−Ｃ（ＣＦ_３）_２−であり、そしてＧ^２の環Ｂ^１への結合位置は、２−オキサプロパン−１，３−ジオイルの結合位置以外の任意の位置であり；Ｘ^３は単結合または−ＣＨ_２−であり；Ｘ^４は単結合、−ＣＨ_２−、−ＣＨ_２ＣＨ_２−または−ＣＨ＝ＣＨ−であり；Ｒ^２は独立して水素、メチル、エチルまたはフェニルであり；Ｒ^３は水素またはメチルである。 [18] The polymer according to item [17], wherein the tetracarboxylic dianhydride is a compound represented by any one of formulas (A1) to (A9).

In these formulas, ring B ¹ is independently a cyclohexane ring or a benzene ring; ring B ² is a cyclohexane ring, cyclohexene ring or benzene ring; G ¹ is a single bond, alkylene having 1 to 12 carbon atoms, 1 , 4-phenylene or 1,4-cyclohexylene; G ² is a single bond, —CH ₂ —, —CH ₂ CH ₂ —, —O—, —CO—, —S—, —SO—, — C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —, and the bonding position of G ² to ring B ¹ is any position other than the bonding position of 2-oxapropane-1,3-dioyl. X ³ is a single bond or —CH ₂ —; X ⁴ is a single bond, —CH ₂ —, —CH ₂ CH ₂ — or —CH═CH—; R ² is independently hydrogen, methyl, ethyl or phenyl; ^{R 3} is The elementary or methyl.

[19] A liquid crystal aligning agent that contains at least one of the polymers described in the item [9] or at least one of the polymers described in the item [16], and may contain other polymers.

[20] The liquid crystal aligning agent according to the item [19], wherein the other polymer is at least one selected from polyamic acid, partially imidized polyamic acid, polyimide, polyamide and polyamideimide.

[21] It contains at least one of the polymers described in [13], may contain other polymers, and the other polymers may be polyamic acid, partially imidized polyamic acid, polyimide, or a mixture thereof. A certain liquid crystal aligning agent.

[22] A liquid crystal aligning agent containing at least one of the polymers according to the item [13] and containing no other polymer.

[23] In the polymer according to the item [13], the ratio of the N-substituted amide bond to the total of the imide bond, amide bond and N-substituted amide bond constituting the main chain is 0.1 to 0.5 in molar ratio. The liquid crystal aligning agent as described in the item [22], which is a polymer of

[24] A liquid crystal alignment film formed using the liquid crystal aligning agent according to the item [19].

[25] A liquid crystal alignment film that is formed using the liquid crystal aligning agent according to the item [19] and that is provided with liquid crystal alignment ability by irradiation with linearly polarized ultraviolet rays.

ここに、Ｒ^１は炭素数１〜３０のアルキルであり、このアルキル中の任意の−ＣＨ_２−はアリーレン、シクロへキシレン、−Ｏ−、−ＯＣＯ−、−ＣＯＯまたは−ＣＨ＝ＣＨ−で置き換えられてもよく、そしてこのアルキル中の任意の水素はハロゲンで置き換えられてもよく；前記のアリーレンにおいて、任意の−ＣＨ＝は−Ｎ＝で置き換えられてもよく、そして任意の水素はハロゲン、炭素数１〜４のアルキル、炭素数１〜４のフッ素化アルキル、または炭素数１〜４のアルコキシで置き換えられてもよく；前記のシクロヘキシレンにおいて、隣り合わない任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく；アミノフェニル基において、ベンゼン環へのアミノ基の結合位置は任意であり、そしてベンゼン環の任意の水素はフッ素、炭素数１〜１０のアルキル、炭素数１〜１０のフッ素化アルキルまたは炭素数１〜１０のアルコキシで置き換えられてもよい。 [26] Using a diamine mixture containing one of the diamines represented by formula (1-1) or at least one of the diamines represented by formula (1-1) as a diamine raw material, tetracarboxylic dianhydride, Formed using a liquid crystal aligning agent containing at least one of a polymer obtained by using at least one of a tricarboxylic acid, a dicarboxylic acid, a tricarboxylic acid derivative and a dicarboxylic acid derivative as a carboxylic acid raw material, and irradiates linearly polarized ultraviolet light Liquid crystal alignment film to which liquid crystal alignment ability is imparted by:

Here, R ¹ is alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is arylene, cyclohexylene, —O—, —OCO—, —COO or —CH═CH—. And any hydrogen in the alkyl may be replaced with a halogen; in the arylene, any —CH═ may be replaced with —N═, and any hydrogen is a halogen. , Cycloalkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms, or alkoxy having 1 to 4 carbon atoms; in the cyclohexylene, any —CH ₂ — that is not adjacent to each other is -O- may be substituted; in the aminophenyl group, the bonding position of the amino group to the benzene ring is arbitrary, and any hydrogen of the benzene ring is fluorine, carbon C 1 -C 10 alkyl, may be replaced by fluorinated alkyl or a C 1-10 alkoxy having 1 to 10 carbon atoms.

[27] R ¹ is alkyl having 1 to 10 carbon atoms; in the aminophenyl group, the bonding position of the amino group to the benzene ring is the bonding position of —CH═CH— and the bonding position of —N (R ¹ ) —. The liquid crystal alignment film according to the item [26], which is in a para position or a meta position with respect to each of these groups, and any hydrogen in the benzene ring may be replaced with fluorine, methyl or methoxy.

[28] A liquid crystal display device comprising the liquid crystal alignment film according to any one of [24] to [27].

  The polyamic acid, polyimide, polyamide or polyamideimide obtained using the diamine of the present invention is excellent in solubility in a solvent. And the liquid crystal aligning film obtained using these polymers has a small residual charge in the liquid crystal display element obtained by using this polymer (the image sticking phenomenon hardly occurs), a high voltage holding ratio, and a wide range from 0 to 90 degrees. Excellent characteristics such as having an arbitrary pretilt angle are provided.

First, terms used in the present invention will be described.
“Other diamine” is defined as a diamine not represented by formula (1). “Other polymer” is defined as a polymer that does not use the diamine represented by formula (1) as one of the raw materials. “Arbitrary” indicates that not only the position but also the number is arbitrary. The expression that any A may be replaced by B, C, or D means that one A may be replaced by B, C, or D, and any of the plurality of A is B, C In addition to the meaning that any one of D and D may be replaced, it means that at least two of A replaced by B, A replaced by C, and A replaced by D may be mixed. Have. Note that the description that any —CH ₂ — is replaced by —O— does not include the case where a plurality of consecutive —CH ₂ — are replaced by —O—. In any case, the alkyl and alkylene in the present invention may be a straight-chain group or a branched group. This is the case when any hydrogen in these groups is replaced with a halogen or a cyclic group, or when any —CH ₂ — is replaced with —O—, —CH═CH—, cycloalkylene, or the like. Also applies.

  The diamine of the present invention is represented by the formula (1). In the following description, the diamine represented by the formula (1) may be represented by diamine (1). Diamine (1) can be easily synthesized by the following method. Organic Syntheses (Jphn Wiley & Sons, Inc), Organic Reactions (Organic Reactions, John Wiley & Sons, Inc), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry By referring to the methods described in the lecture (Maruzen) etc. and combining them appropriately, the desired end group, ring and linking group can be introduced into the starting material. In the scheme shown below, the symbol and the bonding position of the substituent to the benzene ring are as defined in Formula (1).

式（Ｓ−１）で表されるカルボン酸と塩化チオニルを、Ｎ，Ｎ−ジメチルホルムアミド存在下、トルエン中で加熱還流させることにより、式（Ｓ−２）で表されるカルボン酸クロライドが得られる。 <Synthesis of carboxylic acid chloride>

The carboxylic acid chloride represented by the formula (S-2) is obtained by heating and refluxing the carboxylic acid represented by the formula (S-1) and thionyl chloride in toluene in the presence of N, N-dimethylformamide. It is done.

化合物（Ｓ−３）と、化合物（Ｓ−４）とを極性溶剤中で反応させることにより式（Ｓ−５）で表されるＮ−置換アミンが得られる。 <Synthesis of N-substituted amine (1)>

An N-substituted amine represented by the formula (S-5) is obtained by reacting the compound (S-3) and the compound (S-4) in a polar solvent.

ケミストリー・オブ・マテリアルズ（１９９５）、７（１０）、１８４３−８に記載の方法に従い、化合物（Ｓ−６）と式（Ｓ−７）で表される臭素を有する化合物とを塩基中で反応させることにより式（Ｓ−５）で表されるＮ−置換アミンが得られる。パラジウム触媒存在下で化合物（Ｓ−６）と化合物（Ｓ−７）を反応させることによっても化合物（Ｓ−５）が得られる。 <Synthesis of N-substituted amine (2)>

According to the method described in Chemistry of Materials (1995), 7 (10), 1843-8, the compound (S-6) and the compound having bromine represented by the formula (S-7) in a base By reacting, an N-substituted amine represented by the formula (S-5) is obtained. Compound (S-5) can also be obtained by reacting compound (S-6) and compound (S-7) in the presence of a palladium catalyst.

前記の化合物（Ｓ−２）と化合物（Ｓ−５）をピリジン（Ｐｙ）の存在下、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）中で反応させることにより、化合物（Ｓ−８）が得られる。このときの反応温度は室温から加熱還流温度までの範囲から任意に選択できる。 <Synthesis of N-Substituted Amide (1)>

Compound (S-8) is obtained by reacting compound (S-2) and compound (S-5) in N, N-dimethylformamide (DMF) in the presence of pyridine (Py). The reaction temperature at this time can be arbitrarily selected from the range from room temperature to heating reflux temperature.

前記の化合物（Ｓ−２）と化合物（Ｓ−６）をピリジン存在下、Ｎ，Ｎ−ジメチルホルムアミド中で室温から加熱還流条件下で反応させることにより、化合物（Ｓ−９）が得られる。化合物（Ｓ−９）を水素化ナトリウム存在下で、前記の化合物（Ｓ−７）と反応させることにより化合物（Ｓ−８）が得られる。 <Synthesis of N-Substituted Amide (2)>

The compound (S-9) is obtained by reacting the compound (S-2) and the compound (S-6) in the presence of pyridine in N, N-dimethylformamide under room temperature to reflux conditions. Compound (S-8) is obtained by reacting compound (S-9) with compound (S-7) in the presence of sodium hydride.

  The nitro group can be reduced to diamine (1) by reacting compound (S-8) with hydrogen in the presence of palladium / carbon or treating with hydrochloric acid in the presence of iron.

R ¹ in formula (1) is alkyl having 1 to 30 carbons. Arbitrary —CH ₂ — in this alkyl is replaced by phenylene, cyclohexylene, divalent fused ring group, divalent heterocyclic group, —O—, —OCO—, —COO or —CH═CH—. May be. Any hydrogen in the alkyl may be replaced with a halogen. In the phenylene, cyclohexylene, divalent fused ring group and divalent heterocyclic group, any hydrogen is halogen, alkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms or 1 to 1 carbon atoms. It may be replaced by 4 alkoxy. Examples of fused or heterocyclic groups are naphthalene 2,7-diyl, fluorene-2,7-diyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl and quinoline-3, 7-Diyl.

In order to obtain a liquid crystal alignment film having a high voltage holding ratio, R ¹ is alkyl, alkoxy, alkenyl, alkenyloxy, or diamine (1) in which any hydrogen is replaced with fluorine in these groups, as a polymer raw material It is preferable that Examples of such R ¹ are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, methoxymethyl, methoxyethyl , Methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, butoxymethyl, pentoxymethyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl , 3-pentenyl, 4-pentenyl, 2-propenyloxy, 2-butenyloxy, or 2-pentenyloxy, 1-propynyl, 1-pentynyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 1,1,2-trifluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, perfluoroethyl, 3-fluoropropyl, 1,1,2,3,3 , 3-hexafluoropropyl, 1,2,2,3,3,3-hexafluoropropyl, perfluoropropyl. Of these, methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl are more preferred.

In order to obtain a liquid crystal alignment film having a high voltage holding ratio, it is also preferable that any —CH ₂ — in the example of R ¹ is a group that can be replaced by phenylene or cyclohexylene. Examples of preferred phenylene and cyclohexylene for maintaining the linearity of R ¹ are 1,4-phenylene, 1,3-phenylene, 1,4-cyclohexylene and 1,3-cyclohexylene. In particular, 1,4-phenylene and 1,4-cyclohexylene are preferred.

From the liquid crystal aligning agent containing a polymer obtained by using diamine (1) in which R ¹ is alkyl having 1 to 5 carbon atoms, a liquid crystal aligning film having a characteristic that the residual charge is low and seizure hardly occurs is obtained. Preferred examples of such alkyl are methyl, ethyl, propyl, butyl, pentyl, isopropyl and tert-butyl. Such a polymer using diamine as a raw material can be suitably used as a component having a large surface energy when a plurality of different types of polymers are used in combination in a liquid crystal aligning agent. That is, when this liquid crystal aligning agent is applied to a substrate, such a polymer is considered to be unevenly distributed on the substrate side. Therefore, in the liquid crystal alignment film obtained from the liquid crystal aligning agent containing such a polymer, it is considered that the main electric characteristics of the liquid crystal alignment film such as voltage holding ratio and residual charge characteristics are influenced.

The polymer obtained when R ¹ is a diamine (1), which is alkyl having 6 to 30 carbon atoms, is suitable as a component having a small surface energy when a plurality of different types of polymers are used in combination in a liquid crystal aligning agent. Can be used. That is, when this liquid crystal aligning agent is applied to a substrate, such a polymer is considered to be unevenly distributed on the air interface side. Therefore, in the liquid crystal alignment film obtained from the liquid crystal aligning agent containing such a polymer, it is thought that it plays the role which influences the characteristics in a liquid crystal-alignment film interface, such as a pretilt angle and the response speed of a liquid crystal molecule. Any —CH ₂ — in the alkyl may be replaced by 1,4-phenylene or 1,4-cyclohexylene.

  In the two aminophenyl groups included in formula (1), any hydrogen in the benzene ring is replaced with fluorine, alkyl having 1 to 10 carbons, fluorinated alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons. May be. When it is desired to prevent the liquid crystal alignment film from being scraped, these substituents preferably have 1 to 5 carbon atoms. More preferred substituents are methyl and methoxy. And the coupling | bonding position of an amino group is arbitrary. The bonding position is preferably para-position or meta-position, and para-position is most preferable in order to maintain the linearity of the polymer.

  Sealing agents such as epoxy resins are often used around liquid crystal display elements for the purpose of bonding glass substrates and sealing liquid crystals. At this time, impurities from these resins may be adsorbed on the liquid crystal alignment film, resulting in display defects. In order to prevent this, it is preferable to use diamine (1) in which at least one hydrogen of the aminophenyl group is fluorine, trifluoromethyl or trifluoromethoxy as a liquid crystal alignment film material.

X ¹ and X ² are each independently a single bond or alkylene having 1 to 20 carbon atoms. In this alkylene, arbitrary —CH ₂ — is phenylene, cyclohexylene, divalent condensed ring group, divalent heterocyclic group, —O—, —S—, —OCO—, —COO or —CH═CH. -May be replaced, and any hydrogen may be replaced by fluorine. Preferred examples of this alkylene have 1 to 10 carbon atoms, and arbitrary —CH ₂ — is 1,4-phenylene, 1,4-cyclohexylene, naphthalene 2,7-diyl, fluorene-2, Optionally substituted with 7-diyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, quinoline-3,7-diyl, —O— or —CH═CH— In which alkylene is optionally substituted with fluorine. However, when X ² is a single bond, —CH ₂ — bonded to the aminophenyl group in X ¹ is not replaced by —O— or —S—. In order to obtain a liquid crystal alignment film having excellent rubbing resistance and low residual charge, X ¹ and X ² are each independently a single bond, alkylene having 1 to 3 carbons, or alkenylene having 2 to 3 carbons. It is preferable to produce a polymer using (1). In order to obtain a liquid crystal alignment film having excellent alignment properties, a polymer is produced using diamine (1) in which at least one of X ¹ and X ² is alkylene having 4 to 10 carbon atoms or alkenylene having 4 to 10 carbon atoms. It is preferable to do. Furthermore, diamine (1) in which at least one of X ¹ and X ² is a group having 1,4-cyclohexylene or 1,4-cyclohexylene is used as a raw material for a polymer from which a liquid crystal alignment film having a high voltage holding ratio can be obtained. Is preferred. When X ¹ or X ² is a group having a configuration, the configuration is preferably trans in order to maintain the linearity of the polymer.

The following formulas (I) to (IV) are examples that further embody the formula (1).

In these formulas, R ¹ is alkyl having 1 to 20 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,7-diyl. Fluorene-2,7-diyl, pyridine-2, 5-diyl, 1,3-dioxane-2,5-diyl, quinoline-3,7-diyl, -O-, -OCO-, -COO or- CH = CH- may be replaced and any hydrogen in the alkyl may be replaced with a halogen. Arbitrary hydrogen in this 1,4-phenylene may be replaced by halogen, alkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms. In the aminophenyl group, the bonding position of the amino group to the benzene ring is para-position or meta-position, and any hydrogen of the benzene ring is fluorine, alkyl having 1 to 5 carbons, fluorinated alkyl having 1 to 5 carbons Alternatively, it may be replaced with alkoxy having 1 to 5 carbon atoms. X ¹ and X ² are each independently alkylene having 1 to 10 carbon atoms, and any —CH ₂ — in the alkylene is 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2 , 7-diyl, fluorene-2,7-diyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, quinoline-3,7-diyl, -O- or -CH = CH- And any hydrogen in the alkylene may be replaced with fluorine.

A preferred example of R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, — O—, —OCO—, —COO or —CH═CH— may be replaced, and any hydrogen in the alkyl may be replaced with fluorine. Preferred examples of X ¹ and X ² are alkylene having 1 to 10 carbon atoms, and any —CH ₂ — in the alkylene is 1,4-phenylene, 1,4-cyclohexylene, —O— or —CH. ═CH— may be replaced, and any hydrogen in the alkylene may be replaced with fluorine. Fluorine, alkyl having 1 to 5 carbon atoms, fluorinated alkyl having 1 to 5 carbon atoms, and 1 to 1 carbon atoms are defined as being a substituent of the benzene ring in formulas (I) to (IV). Preferred examples of 5 alkoxy are fluorine, methyl and methoxy.

Specific examples of the compound represented by each of formula (I) to formula (IV) are shown below.

In the IPS liquid crystal display element, it is necessary to adjust the pretilt angle of liquid crystal molecules to 0 to 3 degrees. In order to obtain a liquid crystal alignment film suitable for such a liquid crystal display element, it is preferable to use a compound that does not have a group having a large structure at a lateral position of liquid crystal molecules. That is, it is preferable to use a diamine (1) in which R ¹ in the formula (1) is alkyl having 1 to 3 carbon atoms and does not have a large substituent at the lateral position of the ring. Examples of such diamine (1) include (I-1) to (I-7), (I-9) to (I-13), (II-1), (II-) among the above specific examples. 2), (II-4), (II-7), (II-9), (II-10), (II-14), (II-15), (II-17), (II-19) , (II-22), (II-26), (II-29), (II-30), (II-38), (II-39), (II-42), (II-45) to (II) II-49), (III-1), (III-2), (III-4), (III-6) to (III-8), (IV-1), (IV-2) and (IV- 5). Among these, the alignment film using (I-1), (I-2) or (I-3) as a raw material can adjust the pretilt angle of the liquid crystal molecules to 0 to 3 degrees, and the time Since there is almost no change in the pretilt angle over time and long-time driving, it is particularly preferable as an alignment film material for IPS liquid crystal display elements.

In a TN-TFT or OCB type liquid crystal display element, it is necessary to adjust the pretilt angle of liquid crystal molecules to 3 to 25 degrees. Examples of preferred diamine (1) for obtaining a liquid crystal alignment film suitable for such a liquid crystal display element include (I-8), (I-14) to (I-17), ( II-3), (II-6), (II-11), (II-16), (II-20), (II-21), (II-24), (II-27), (II- 28), (II-33), (II-35), (II-40), (II-41), (II-43), (II-44), (II-50), (II-51) , (III-5), (IV-3), (IV-4) and (IV-6) to (IV-8). Among these, those of R ¹ in formula (1) is an organic group having 4 to 7 carbon atoms is more preferred. An alignment film obtained using such a diamine (1) as a raw material can adjust the pretilt angle of the liquid crystal molecules to 3 to 25 degrees, and the pretilt angle is hardly changed over time and for a long time. Therefore, it is particularly preferable as an alignment film material for a TN-TFT or OCB type liquid crystal display element.

  In a VA liquid crystal display element, it is necessary to adjust the pretilt angle of liquid crystal molecules to 90 degrees. In order to obtain a liquid crystal alignment film suitable for such a liquid crystal display element, it is preferable to use a compound having a group having a large structure at a lateral position of liquid crystal molecules. That is, preferable examples of the diamine (1) include (I-18) to (I-21), (II-5), (II-8), (II-12), (II-) among the above specific examples. 13), (II-18), (II-23), (II-25), (II-31), (II-32), (II-34), (II-36), (II-37) , (III-3), (IV-9) and (IV-10). Among these, the alignment film using (I-19), (I-20) or (I-21) as a raw material can adjust the pretilt angle of the liquid crystal molecules to 90 degrees, and the time elapses. Since there is almost no change in the pretilt angle due to long-time driving, it is particularly preferable as an alignment film material for a VA liquid crystal display element.

Next, the polymer of the present invention will be described.
The polymer of the present invention is a polycondensation polymer obtained from a diamine raw material and a carboxylic acid raw material, and is a polymer characterized by using diamine (1) as one of the raw materials. The diamine (1) may be used alone or as a mixture of two or more diamines (1). Furthermore, a mixture of at least one of diamine (1) and at least one of other diamines can also be used. The carboxylic acid raw material is at least one of tetracarboxylic dianhydride, tricarboxylic acid, dicarboxylic acid, tricarboxylic acid derivative and dicarboxylic acid derivative. When diamine (1) is reacted with tetracarboxylic dianhydride in a solvent, a solution containing polyamic acid, partially imidized polyamic acid or a mixture thereof is obtained, and this solution is used as it is as a liquid crystal aligning agent. Can be used as Furthermore, a solution containing polyimide is obtained by subjecting these polyamic acids, partially imidized polyamic acids, or a mixture thereof to a dehydration reaction or a ring closure reaction. This solution can also be used as a liquid crystal aligning agent as it is. By distilling off the solvent in these solutions, polyamic acid, partially imidized polyamic acid, a mixture of polyamic acid and partially imidized polyamic acid, or polyimide can be obtained. Two or more diamines (1) and tetracarboxylic dianhydrides may be used. The diamine (1) can be used in combination with other diamines.

  A polyamide is obtained by reacting the diamine (1) with a tricarboxylic acid, a dicarboxylic acid or a derivative of these acids. Polyamideimide is obtained by reacting diamine (1), tetracarboxylic dianhydride, and a mixture of tricarboxylic acid, dicarboxylic acid or derivatives of these acids. Examples of derivatives of tricarboxylic acids are tricarboxylic acid trichlorides, tricarboxylic acid trialkyl esters and tricarboxylic acid dialkyl esters. Examples of derivatives of dicarboxylic acids are dicarboxylic acid dichlorides and dialkyl esters of dicarboxylic acids. Also in the production of polyamide and polyamideimide, the same solvent as in the case of reaction with the above tetracarboxylic dianhydride is used, and solutions that can be used as liquid crystal aligning agents are obtained. At this time, two or more diamines (1) may be used, and other diamines may be used in combination. Two or more tetracarboxylic dianhydrides, tricarboxylic acids, dicarboxylic acids, tricarboxylic acid derivatives and dicarboxylic acid derivatives may be used. In the case of this polyamide, the object of the present invention can be further improved by replacing hydrogen of the amide bond (—CO—NH—) with alkyl having 1 to 10 carbon atoms.

A more preferable polymer of the present invention is a polymer obtained from one of diamine (1) or a diamine mixture containing at least one of diamine (1) and at least one of tetracarboxylic dianhydrides. Preferred examples of the tetracarboxylic dianhydride used at this time are shown below. In the following formula, ring B ¹ is independently a cyclohexane ring or a benzene ring. Ring B ² is cyclohexane ring, cyclohexene ring or a benzene ring. G ¹ is a single bond, alkylene having 1 to 12 carbons, 1,4-phenylene or 1,4-cyclohexylene. G ² is a single _{bond, -CH 2 -, - CH 2} CH 2 -, - O -, - CO -, - S -, - SO -, - C (CH 3) 2 - or -C _{(CF 3) 2} -And the bonding position of G ² to ring B ¹ is an arbitrary position other than the bonding position of 2-oxapropane-1,3-dioyl. X ³ is a single bond or —CH ₂ —. X ⁴ is a single bond, —CH ₂ —, —CH ₂ CH ₂ — or —CH═CH—. R ² is independently hydrogen, methyl, ethyl or phenyl. R ³ is hydrogen or methyl.

Specific examples of the tetracarboxylic dianhydride used in the present invention are shown below.

  When other diamines are used in combination, the preferred proportion of diamine (1) based on the total amount of diamines used is 0.5 mol% or more. Within this range, the effect of the present invention is clearly recognized.

Examples of other diamines that can be used in combination with the diamine (1) are aliphatic diamines, alicyclic diamines, and aromatic diamines. Specific examples of these diamines are shown below.

ここに、Ｒ^７はメチレン、フェニレンまたはアルキル置換されたフェニレンであり；Ｒ^８およびＲ^９は独立して炭素数１〜３のアルキルまたはフェニルであり；ｈは１〜６の整数であり；そして、ｋは１〜１０の整数である。 Another example of the other diamine that can be used in combination with the diamine (1) is a diamine having a siloxane bond. A preferred example of the diamine is a compound represented by the formula (2).

Where R ⁷ is methylene, phenylene or alkyl-substituted phenylene; R ⁸ and R ⁹ are independently alkyl or phenyl having 1 to 3 carbon atoms; h is an integer from 1 to 6; , K is an integer of 1-10.

  Examples of solvents used in the production of the polymers of the present invention are N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), ethylene glycol mono Butyl ether (BC), ethylene glycol monoethyl ether and γ-butyrolactone (GBL). These solvents may be used as a mixture. These solvents can also be used as a solvent for the reaction product. Solvents that can be used in the present invention are not limited to these solvent examples. Any solvent can be used as long as it dissolves the polymer of the present invention and does not impair the object of the present invention.

  The liquid crystal aligning agent of this invention is a solution containing the polymer of this invention. This solution may be a reaction liquid obtained when the polymer of the present invention is produced, and a solid obtained by distilling off the solvent from the reaction solution (hereinafter referred to as a reaction product) is reacted with this reaction. It may be a solution dissolved in a solvent different from that used in the above.

  Examples of preferred liquid crystal aligning agents of the present invention are polymers obtained by reacting one of diamine (1) or a diamine mixture containing at least one of diamine (1) with at least one of tetracarboxylic dianhydrides. It is a liquid crystal aligning agent containing. The effect of the present invention is exhibited by introducing an N-substituted amide bond into the main chain. Therefore, the liquid crystal aligning agent containing the polymer obtained only using diamine (1) is the most preferable. In the polymer obtained from diamine (1) and tetracarboxylic dianhydride, the ratio of the N-substituted amide bond to the total of the imide bond, amide bond and N-substituted amide bond constituting the main chain is 0 in molar ratio. .5. That is, when using other diamines, it is desirable that this molar ratio is close to 0.5. And since the effect of this invention is acquired, the range of a preferable molar ratio is 0.1 or more.

  In order to further improve the properties of the liquid crystal alignment film, among the polymers of the present invention, a liquid crystal alignment agent containing polyamic acid or polyimide and polyamide may be used. At this time, polyamideimide may be used instead of polyamide. And in the liquid crystal aligning agent containing this polymer mixture, the preferable compounding ratio of this polyamide or polyamideimide is 0.01-30 weight% with respect to the whole polymer. A more preferable range of this ratio is 0.01 to 10% by weight, and a particularly preferable range is 0.1 to 5% by weight.

  In addition to the polymer of the present invention, other polymers can be used for the liquid crystal aligning agent of the present invention. Examples of other polymers are polyamic acid, polyimide, polyamide, and polyamideimide, and other types of polymers may be used. Preferred examples of other polymers are polyamic acid, partially imidized polyamic acid and polyimide, and a mixture thereof may be used. When other polymers are used, the preferred content is 1 to 99% by weight based on the total amount of polymers contained in the liquid crystal aligning agent. A more preferable range of this ratio is 5 to 95% by weight, and a further preferable range is 10 to 90% by weight.

  A desirable ratio of the total amount of the polymer in the liquid crystal aligning agent is 0.1 to 50% by weight with respect to the total weight of the liquid crystal aligning agent. A more preferable range of this range is 0.5 to 30% by weight, and a particularly preferable range is 1 to 10% by weight. By using a liquid crystal aligning agent containing a liquid crystal aligning agent containing a polymer in such a concentration range, a liquid crystal display element in which the above-described display unevenness is hardly generated can be obtained without impairing the alignment.

  An organosilicon compound can be added to the liquid crystal aligning agent of the present invention for the purpose of improving the adhesion of the liquid crystal aligning film to the glass substrate. Examples of this organosilicon compound are aminopropyltrimethoxysilane, aminopropyltriethoxysilane, vinyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, dimethylpolysiloxane, polydimethylsiloxane and polydiphenylsiloxane. The addition ratio of the organosilicon compound is 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the polymer contained in the liquid crystal aligning agent.

  The liquid crystal alignment film of the present invention is effective in almost all liquid crystal display elements. When used in a liquid crystal display element for TFTs that requires a high voltage holding ratio, the effects of the present invention such as prevention of image sticking and occurrence of poor alignment are remarkably recognized. Pretilt angle suitable for each display method when used in any of TFT liquid crystal display elements, IPS liquid crystal display elements, TN liquid crystal display elements, OCB liquid crystal display elements, and VA liquid crystal display elements Can be given.

  The example of the manufacturing method of the liquid crystal aligning film of this invention is shown next. That is, the liquid crystal aligning agent of the present invention is applied to a glass substrate with a transparent electrode by a brush coating method, a dipping method, a spinner method, a spray method, an ink jet method or a printing method, and then the temperature of the glass substrate is set to 50 to 150 ° C. The solvent is preferably evaporated at 80 to 120 ° C. Thereafter, a polymer thin film is formed on the surface of the glass substrate by setting the temperature to 150 to 400 ° C., preferably 180 to 280 ° C. The liquid crystal alignment film of the present invention can be obtained by rubbing the surface of this film in one direction with a cloth or the like.

  An example of another method for imparting liquid crystal alignment ability to a polymer thin film is a method of irradiating a thin film of a photosensitive polymer coated on a glass substrate with linearly polarized ultraviolet rays or laser light. According to this method, since other members do not contact the thin film on the substrate, there are advantages such as no generation of static electricity and no contamination of impurities.

In order to obtain such a photosensitive polymer thin film, it is preferable to use, as a raw material, a diamine in which at least one of R ¹ , X ¹ and X ^{2 in} the formula (1) is a group having —C═C—. Particularly preferred is diamine (1), wherein at least one of X ¹ and X ² is a group having —C═C—. Specifically, (I-15), (II-6), (II-9), (II-12), (II-15), (II-21), (II-29), (II- 34), (II-38), (II-40), (III-5), (IV-4) and (IV-8). Among these, more preferred examples are (II-9), (II-12), (II-15), (II-38), (II-40), (III-5) and (IV-4). Particularly preferred examples are (II-9), (II-15), (II-38) and (IV-4).

  If the glass substrate surface is treated with a silane coupling agent before applying the liquid crystal alignment agent of the present invention to the glass substrate with a transparent electrode, the liquid crystal alignment film formed on the glass substrate surface is bonded to the substrate. Improves.

Any liquid crystal composition may be used for the liquid crystal display element of the present invention. The liquid crystal alignment film of the present invention is suitable for producing a TFT element. The TFT element having the liquid crystal alignment film of the present invention includes Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Application Laid-Open No. 5-501735, Japanese Patent Application Laid-Open No. 2001-48822, Japanese Patent Application Laid-Open No. 2001-192657, and Japanese Patent Application Laid-Open No. In particular, a fluorine-based liquid crystal composition having a high voltage holding ratio, which includes a compound having a —OCF ₃ group at a terminal, a compound having 1 to 3 or more fluorine atoms, and the like, which are described in JP-A No. 2555956, etc. Preferably used.

Examples of the synthesis of the diamine of the present invention, examples of the synthesis of the polyamic acid using the diamine, and examples of the liquid crystal alignment film using the polyamic acid will be specifically illustrated below. It is not limited to examples. First, the evaluation method of the liquid crystal display element used in the Example is shown. The physical property values were measured according to the method described in Standard of Electronic Industries Association of Japan, EIAJ • ED-2521A, or a modified method thereof. The measured values of various physical properties in the examples are values at 25 ° C.
(1) Pretilt angle It measured by the crystal rotation method. The wavelength of light used for the measurement is 589 nm.
(2) Residual charge (burn-in)
Residual charges were measured by the method described in “Miyake et al., Shingaku Giho, EID91-111, p19”. This residual charge was used as an index for baking. In other words, the more residual charge, the easier it is to burn. The voltage applied to the liquid crystal cell at the time of measurement was an alternating voltage in which 50 mV, 1 kHz alternating current and a ± 10 V triangular wave with a frequency of 0.0036 Hz were superimposed.
(3) Voltage holding ratio The voltage holding ratio was measured by the method described in “Mizushima et al., 14th Liquid Crystal Discussion Group Proceedings, p78”. The AC pulse voltage used for the measurement had a gate width of 69 μs, a frequency of 30 Hz, and a wave height of ± 4.5V.
(4) Adsorption of impurities from the sealing material etc. to the liquid crystal alignment film (Vth unevenness)
When a voltage was applied to the liquid crystal cell to perform display, the portion that had a display defect was visually observed.

３つ口フラスコに４−ニトロベンゾイルクロライド（２０ｇ：２２０ｍｍｏｌ）を入れ、温度計、冷却管および滴下漏斗を取り付けて、ＤＭＦ（２００ｍｌ）に溶解させた。そこにＮ−メチル−４−ニトロアニリン（１５ｇ：２００ｍｍｏｌ）をＤＭＦ（２００ｍｌ））とピリジン（４０ｍｌ））との混合溶剤に溶かした溶液をゆっくり滴下した。窒素雰囲気下、８０℃で８時間加熱攪拌した。放冷後、反応液を水（２００ｍｌ））中に投入し、ジクロロメタン（３００ｍｌ））で抽出した。有機層を水（３００ｍｌ））で２回洗浄した後、無水硫酸マグネシウム（３０ｇ）を有機層に加え乾燥させた。ろ過によって無水硫酸マグネシウムを取り除いた後、溶剤を減圧溜去した。得られた粗結晶を酢酸エチルから再結晶して４，４’−ジニトロ−Ｎ−メチルベンズアニリドを得た。
（収量３２ｇ、収率５３％） [Example 1]
<Synthesis of Compound (I-1)>

4-Nitrobenzoyl chloride (20 g: 220 mmol) was placed in a three-necked flask, and a thermometer, a condenser tube and a dropping funnel were attached and dissolved in DMF (200 ml). A solution prepared by dissolving N-methyl-4-nitroaniline (15 g: 200 mmol) in a mixed solvent of DMF (200 ml)) and pyridine (40 ml) was slowly added dropwise thereto. The mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water (200 ml) and extracted with dichloromethane (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from ethyl acetate to obtain 4,4′-dinitro-N-methylbenzanilide.
(Yield 32g, Yield 53%)

The obtained 4,4′-dinitro-N-methylbenzanilide (30 g: 100 mmol) was dissolved in DMF (400 ml), palladium carbon powder (3.0 g) was added thereto, and the mixture was heated at 40 ° C. under a hydrogen pressure of 800 kPa. For 12 hours. The palladium carbon powder was removed, and the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (dichloromethane: methanol = 10: 1), and the resulting crude crystals were recrystallized from ethanol to obtain 4,4′-diamino-N-methylbenzanilide. (Yield 23g, Yield 91%)
¹ H-NMR (ppm): 2.78 (s, ═N—CH ₃ , 3H), 3.74 (br, s, —NH ₂ , 4H), 6.44-7.70 (m, arm, H, 8H)

フラスコに４−ブロモニトロベンゼン（２０ｇ：１００ｍｍｏｌ）を入れ、ＮＭＰ（５０ｍｌ））に溶解させた。そこにｎ-プロピルアミン（１２ｇ：２００ｍｍｏｌ）を滴下し、窒素雰囲気下１５０℃で８時間攪拌した。放冷後、反応液を水中に投入し、トルエン（３００ｍｌ））で抽出した。有機層を水（３００ｍｌ））で２回洗浄した後、無水硫酸マグネシウム（３０ｇ）を有機層に加え乾燥させた。ろ過によって無水硫酸マグネシウムを取り除いた後、溶剤を減圧溜去した。得られた粗結晶をヘプタンから再結晶してＮ−ｎ-プロピル−４−ニトロアニリンを得た。（収量１６ｇ、収率７６％） [Example 2]
<Synthesis of Compound (I-3)>

4-Bromonitrobenzene (20 g: 100 mmol) was placed in the flask and dissolved in NMP (50 ml). N-Propylamine (12 g: 200 mmol) was added dropwise thereto, and the mixture was stirred at 150 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water and extracted with toluene (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from heptane to obtain Nn-propyl-4-nitroaniline. (Yield 16g, Yield 76%)

4-Nitrobenzoyl chloride (15 g: 80 mmol) was placed in a three-necked flask, and a thermometer, a condenser tube and a dropping funnel were attached and dissolved in DMF (150 ml). A solution obtained by dissolving Nn-propyl-4-nitroaniline (10 g: 70 mmol) obtained therein in a mixed solvent of DMF (150 ml) and pyridine (30 ml) was slowly added dropwise. The mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water (200 ml) and extracted with dichloromethane (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from ethyl acetate to obtain 4,4′-dinitro-Nn-propylbenzanilide.
(Yield 14g, Yield 61%)

The obtained 4,4′-dinitro-Nn-propylbenzanilide (13 g: 40 mmol) was dissolved in DMF (200 ml), palladium carbon powder (1.5 g) was added thereto, and the hydrogen pressure was reduced to 800 kPa under 40 kPa. Stir at 12 ° C. for 12 hours. The palladium carbon powder was removed, and the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (dichloromethane: methanol = 10: 1), and the resulting crude crystals were recrystallized from ethanol to obtain 4,4′-diamino-Nn-propylbenzanilide. (Yield 10g, Yield 89%)
¹ H-NMR (ppm): 0.96 (t, —CH ₃ , 3H), 1.63 (m, —CH ₂ —2H), 3.20 (m, —CH ₂ —2H), 3 _{.74 (br, s, -NH 2} , 4H), 6.44-7.70 (m, arm, H, 8H)

フラスコに２，３，５，６−テトラフルオロ−４−アミノ安息香酸（２５ｇ：１２０ｍｍｏｌ）をトルエン（１００ｍｌ）に溶解させた。塩化チオニル（４５ｍｌ）とＤＭＦ数滴とを加え、６時間加熱還流した。放冷後、溶剤および未反応の塩化チオニルを減圧溜去し、２，３，５，６−テトラフルオロ−４−アミノベンゾイルクロライドを得た。
（収量２７ｇ、収率９６％） [Example 3]
<Synthesis of Compound (I-7)>

2,3,5,6-tetrafluoro-4-aminobenzoic acid (25 g: 120 mmol) was dissolved in toluene (100 ml) in the flask. Thionyl chloride (45 ml) and a few drops of DMF were added, and the mixture was heated to reflux for 6 hours. After allowing to cool, the solvent and unreacted thionyl chloride were distilled off under reduced pressure to obtain 2,3,5,6-tetrafluoro-4-aminobenzoyl chloride.
(Yield 27g, Yield 96%)

  Put the obtained 3,3,5,6-tetrafluoro-4-aminobenzoyl chloride (25 g: 120 mmol) in a three-necked flask, attach a thermometer, condenser and dropping funnel, and dissolve in DMF (200 ml). It was. A solution prepared by dissolving N-methyl-4-nitroaniline (17 g: 110 mmol) in a mixed solvent of DMF (200 ml) and pyridine (50 ml) was slowly added dropwise thereto. The mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water (200 ml) and extracted with dichloromethane (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from ethyl acetate to obtain 1-amino-6-nitro-2,3,9,10-tetrafluoro-N-methylbenzanilide. (Yield 22g, Yield 53%)

The obtained 1-amino-6-nitro-2,3,9,10-tetrafluoro-N-methylbenzanilide (20 g: 60 mmol) was dissolved in DMF (300 ml), and palladium carbon powder (2.0 g) was dissolved therein. And stirred at 40 ° C. for 12 hours under a hydrogen pressure of 800 kPa. The palladium carbon powder was removed, and the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (dichloromethane: methanol = 10: 1) were performed, and the resulting crude crystals were recrystallized from ethanol to obtain 4,4′-diamino-N-butylbenzanilide.
(Yield 17g, 92% yield)
¹ H-NMR (ppm): 2.78 (s, ═N—CH ₃ , 3H), 3.74 (br, s, —NH ₂ , 2H), 4.08 (br, s, —NH ₂ , 2H), 6.44-7.39 (m, arm, H, 4H)

フラスコに、特開平１０−２５１１８６号公報に記載の方法に従い合成した４−（４−（４−ｎ−プロピルシクロヘキシル）シクロヘキシル）ブロモベンゼン（３４ｇ：９０ｍｍｏｌ）、４−ニトロアニリン（３８ｇ：２７０ｍｍｏｌ）、ｔ−ブトキシナトリウム（３４ｇ：３６０ｍｍｏｌ）、トリス（ジベンジリデンアセトン）パラジウム（１．６ｇ：１．８ｍｍｏｌ）および２−（ジ−ｔ−ブチルホスフィノ）ビフェニル（１．０ｇ：３．６ｍｍｏｌ）を入れ、トルエンに溶解させた。窒素雰囲気下８０℃で１２時間攪拌した。放冷後、反応液を水（４００ｍｌ）に投入し、トルエン（５００ｍｌ）で抽出した。有機層を飽和塩化アンモニウム水溶液（５００ｍｌ）で２回、次いで水（５００ｍｌ）で２回洗浄した後、無水硫酸マグネシウム（５０ｇ）を有機層に加え乾燥させた。ろ過によって無水硫酸マグネシウムを取り除いた後、溶剤を減圧溜去した。カラムクロマトグラフィー（トルエン）で分離精製し、得られた粗結晶をトルエンから再結晶してＮ−（４−（４−（４−ｎ−プロピルシクロヘキシル）シクロヘキシル）フェニル）−４−ニトロアニリンを得た。（収量２８ｇ、収率７３％） [Example 4]
<Synthesis of Compound (I-21)>

4- (4- (4-n-propylcyclohexyl) cyclohexyl) bromobenzene (34 g: 90 mmol), 4-nitroaniline (38 g: 270 mmol) synthesized according to the method described in JP-A-10-251186, Add t-butoxy sodium (34 g: 360 mmol), tris (dibenzylideneacetone) palladium (1.6 g: 1.8 mmol) and 2- (di-t-butylphosphino) biphenyl (1.0 g: 3.6 mmol). And dissolved in toluene. The mixture was stirred at 80 ° C. for 12 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water (400 ml) and extracted with toluene (500 ml). The organic layer was washed twice with a saturated aqueous ammonium chloride solution (500 ml) and then twice with water (500 ml), and then anhydrous magnesium sulfate (50 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (toluene), and the resulting crude crystals were recrystallized from toluene to give N- (4- (4- (4-n-propylcyclohexyl) cyclohexyl) phenyl) -4-nitroaniline. It was. (Yield 28g, Yield 73%)

  4-Nitrobenzoyl chloride (15 g: 80 mmol) was placed in a three-necked flask, and a thermometer, a condenser tube and a dropping funnel were attached and dissolved in DMF (300 ml). The obtained N- (4- (4- (4-n-propylcyclohexyl) cyclohexyl) phenyl) -4-nitroaniline (28 g: 60 mmol) was added to a mixed solvent of DMF (200 ml) and pyridine (40 ml). The dissolved solution was slowly added dropwise. The mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water (300 ml) and extracted with dichloromethane (500 ml). The organic layer was washed twice with water (500 ml), and then anhydrous magnesium sulfate (50 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from ethyl acetate to obtain 4,4'-dinitro-N- (4- (4- (4-n-propylcyclohexyl) cyclohexyl) phenyl) benzanilide. (Yield 24g, Yield 68%)

The obtained 4,4′-dinitro-N- (4- (4- (4-n-propylcyclohexyl) cyclohexyl) phenyl) benzanilide (24 g: 40 mmol) was dissolved in DMF (300 ml), and palladium carbon powder ( 2.4 g) was added, and the mixture was stirred at 40 ° C. for 12 hours under a hydrogen pressure of 800 kPa. The palladium carbon powder was removed, and the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (dichloromethane: methanol = 10: 1), the resulting crude crystals were recrystallized from ethanol to give 4,4′-diamino-N- (4- (4- (4-n-propyl). Cyclohexyl) cyclohexyl) phenyl) benzanilide was obtained. (Yield 19g, Yield 94%)
_{^{1 H-NMR (ppm):}} 1.03 (t, -CH 3, 3H), 1.28-1.73 (m, -CH 2 -, cyc.hex.-CH 2 -, - CH-, 23H ), 2.83 (m, —CH—, 1H), 3.84 (br, s, —NH ₂ , 4H), 6.38-7.98 (m, arm, H, 8H)

２−（４−ニトロフェニル）プロピオン酸（２５ｇ：１３０ｍｍｏｌ）をトルエン（１００ｍｌ）に溶解させた。塩化チオニル（４５ｍｌ）とＤＭＦ数滴とを加え、６時間加熱還流した。放冷後、溶剤および未反応の塩化チオニルを減圧溜去し、２−（４−ニトロフェニル）プロピオン酸クロライドを得た。（収量２６ｇ、収率９５％） [Example 5]
<Synthesis of Compound (II-7)>

2- (4-Nitrophenyl) propionic acid (25 g: 130 mmol) was dissolved in toluene (100 ml). Thionyl chloride (45 ml) and a few drops of DMF were added, and the mixture was heated to reflux for 6 hours. After cooling, the solvent and unreacted thionyl chloride were distilled off under reduced pressure to obtain 2- (4-nitrophenyl) propionic acid chloride. (Yield 26g, Yield 95%)

  4-Bromonitrobenzene (20 g: 100 mmol) was placed in the flask and dissolved in NMP (50 ml). Propylamine (12 g: 200 mmol) was added dropwise thereto, and the mixture was stirred at 150 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water and extracted with toluene (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from heptane to obtain N-propyl-4-nitroaniline. (Yield 15g, Yield 83%)

  The obtained 2- (4-nitrophenyl) propionic acid chloride (19 g: 90 mmol) was placed in a three-necked flask, and a thermometer, a condenser tube and a dropping funnel were attached and dissolved in DMF (200 ml). A solution prepared by dissolving the obtained N-propyl-4-nitroaniline (15 g: 80 mmol) in a mixed solvent of DMF (200 ml) and pyridine (50 ml) was slowly added dropwise. The mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water (200 ml) and extracted with dichloromethane (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from ethyl acetate to obtain 2, N-bis- (4-nitrophenyl) -N-propyl-propionamide. (Yield 21g, Yield 66%)

The obtained 2, N-bis- (4-nitrophenyl) -N-propyl-propionamide (21 g: 60 mmol) was dissolved in DMF (300 ml), palladium carbon powder (2.0 g) was added thereto, and hydrogen was added. The mixture was stirred at 40 ° C. under a pressure of 800 kPa for 12 hours. The palladium carbon powder was removed, and the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (dichloromethane: methanol = 10: 1), and the resulting crude crystals were recrystallized from ethanol to obtain 2, N-bis- (4-aminophenyl) -N-propyl-propionamide. It was.
(Yield 17g, Yield 93%)
¹ H-NMR (ppm): 1.52 (d, —CH ₃ , 3H), 2.78 (s, ═N—CH ₃ , 3H), 3.74 (br, s, —NH ₂ , 4H) 3.79 (m, -CH-, 1H), 6.41-6.87 (m, arm, H, 8H)

４−ニトロシンナミック酸（２５ｇ：１３０ｍｍｏｌ）をトルエン（１００ｍｌ）に溶解させた。塩化チオニル（４５ｍｌ）とＤＭＦ数滴とを加え、６時間加熱還流した。放冷後、溶剤および未反応の塩化チオニルを減圧溜去し、４−ニトロシンナミック酸クロライドを得た。（収量２５ｇ、収率９３％） [Example 6]
<Synthesis of Compound (II-9)>

4-Nitrocinnamic acid (25 g: 130 mmol) was dissolved in toluene (100 ml). Thionyl chloride (45 ml) and a few drops of DMF were added, and the mixture was heated to reflux for 6 hours. After cooling, the solvent and unreacted thionyl chloride were distilled off under reduced pressure to obtain 4-nitrocinnamic acid chloride. (Yield 25g, Yield 93%)

The obtained 4-nitrocinnamic acid chloride (25 g: 120 mmol) was placed in a three-necked flask, and a thermometer, a condenser tube and a dropping funnel were attached and dissolved in DMF (200 ml). A solution prepared by dissolving N-methyl-4-nitroaniline (17 g: 110 mmol) in a mixed solvent of DMF (200 ml) and pyridine (50 ml) was slowly added dropwise thereto. The mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water (200 ml) and extracted with dichloromethane (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from ethyl acetate to obtain N-methyl-3, N-bis (4-nitrophenyl) acrylamide.
(Yield 22g, Yield 60%)

N-methyl-3, N-bis (4-nitrophenyl) acrylamide (22 g: 70 mmol) and iron powder (12 g: 210 mmol) obtained in the flask were dissolved in ethanol (200 ml). The mixture was heated to reflux in a nitrogen atmosphere, and a mixed solution of hydrochloric acid (15 ml) and ethanol (50 ml) was added dropwise thereto, and the mixture was further heated to reflux for 6 hours. After removing the iron powder by filtration, a 15% aqueous sodium hydroxide solution was added to the filtrate to make the reaction mixture neutral. After allowing to cool, the mixture was extracted with dichloromethane (300 ml), the organic layer was washed twice with water (300 ml), and anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (dichloromethane: methanol = 10: 1) were performed, and the resulting crude crystals were recrystallized from ethanol to obtain N-methyl-3, N-bis (4-aminophenyl) acrylamide.
(Yield 17g, Yield 91%)
¹ H-NMR (ppm): 2.69 (s, ═N—CH ₃ , 3H), 3.79 (m, —CH—, 1H), 3.88 (br, s, —NH ₂ , 4H) , 6.44-7.39 (m, arm, H, 8H), 6.84 (s, -CH = 1H), 7.55 (s, -CH = 1H)

３つ口フラスコに４−ニトロけい皮酸（２７ｇ：１３０ｍｍｏｌ）を入れ、温度計、冷却管および滴下漏斗を取り付けて、ＤＭＦ（１００ｍｌ）に溶解させた。そこにＮ−メチル−４−ニトロアニリン（２０ｇ：１３０ｍｍｏｌ）をＤＭＦ（２００ｍｌ））とピリジン（１５ｍｌ））との混合溶剤に溶かした溶液をゆっくり滴下した。窒素雰囲気下、８０℃で８時間加熱攪拌した。放冷後、反応溶液をろ過して、得られた結晶を純水（１５０ｍＬ）で洗浄した。得られた粗結晶をＤＭＦから再結晶してＮ−メチル−４，４‘−ジニトロけい皮酸アニリドを得た。（収量２１ｇ、収率６１％） [Example 7]
<Synthesis of Compound (II-10)>

4-Nitrocinnamic acid (27 g: 130 mmol) was placed in a three-necked flask, and a thermometer, a condenser tube and a dropping funnel were attached and dissolved in DMF (100 ml). A solution prepared by dissolving N-methyl-4-nitroaniline (20 g: 130 mmol) in a mixed solvent of DMF (200 ml) and pyridine (15 ml)) was slowly added dropwise thereto. The mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction solution was filtered, and the resulting crystals were washed with pure water (150 mL). The obtained crude crystals were recrystallized from DMF to obtain N-methyl-4,4′-dinitrocinnamic acid anilide. (Yield 21g, Yield 61%)

The obtained N-methyl-4,4′-dinitrocinnamic acid anilide (21 g: 79 mmol) was dissolved in DMF (400 ml), palladium carbon powder (2.1 g) was added thereto, and the hydrogen pressure was 800 kPa. The mixture was stirred at 40 ° C. for 12 hours. The palladium carbon powder was removed, and the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (dichloromethane: methanol = 10: 1) were performed, and the resulting crude crystals were recrystallized from ethanol to obtain N-methyl-3, N-bis (4-aminophenyl) propionamide.
(Yield 19g, Yield 87%)
¹ H-NMR (ppm): 2.31 (t, —CH ₂ —3H), 2.78 (t, —CH ₂ —3H), 3.19 (s, —CH ₃ , 3H), 3 _{.56 (br, s, -NH 2} , 2H), 3.74 (br, s, -NH 2, 2H), 6.56-6.64 (m, arm, H, 4H), 6.79- 6.87 (m, arm, H, 4H)

フラスコに４−アミノ−４’−ニトロビフェニル（２５ｇ：１１５ｍｍｏｌ）を入れ、ＮＭＰ（５０ｍｌ）に溶解させた。そこにｎ−ヘプチルアミン（２７ｇ：２３０ｍｍｏｌ）を滴下し、窒素雰囲気下１５０℃で８時間攪拌した。放冷後、反応液を水に投入し、トルエン（３００ｍｌ）で抽出した。有機層を水（３００ｍｌ）で２回洗浄した後、無水硫酸マグネシウム（３０ｇ）を有機層に加え乾燥させた。ろ過によって無水硫酸マグネシウムを取り除いた後、溶剤を減圧溜去した。得られた粗結晶をヘプタンから再結晶して４−（Ｎ−ｎ−ヘプチルアミノ）−４’−ニトロビフェニルを得た。
（収量３２ｇ、収率８７％） [Example 8]
<Synthesis of Compound (IV-3)>

4-Amino-4′-nitrobiphenyl (25 g: 115 mmol) was placed in the flask and dissolved in NMP (50 ml). N-Heptylamine (27 g: 230 mmol) was added dropwise thereto, and the mixture was stirred at 150 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water and extracted with toluene (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from heptane to obtain 4- (Nn-heptylamino) -4′-nitrobiphenyl.
(Yield 32g, Yield 87%)

  4-Nitrobenzoyl chloride (10 g: 110 mmol) was placed in a three-necked flask, and a thermometer, a condenser tube and a dropping funnel were attached and dissolved in DMF (200 ml). A solution prepared by dissolving 4- (Nn-heptylamino) -4'-nitrobiphenyl (32 g: 100 mmol) in a mixed solvent of DMF (200 ml) and pyridine (40 ml) was slowly added dropwise. The mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water (200 ml) and extracted with dichloromethane (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from ethyl acetate to obtain Nn-heptyl-4-nitrophenyl-N- (4- (4-nitrobiphenylene)) benzamide. (Yield 26g, Yield 55%)

The obtained Nn-heptyl-4-nitrophenyl-N- (4- (4-nitrobiphenylene)) benzamide (26 g: 70 mmol) was dissolved in DMF (300 ml), and palladium carbon powder (2.6 g) was dissolved therein. And stirred at 40 ° C. for 12 hours under a hydrogen pressure of 800 kPa. The palladium carbon powder was removed, and the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (dichloromethane: methanol = 10: 1), and the resulting crude crystals were recrystallized from ethanol to give Nn-heptyl-4-aminophenyl-N- (4- (4-aminobiphenylene). )) Benzamide was obtained. (Yield 26g, Yield 90%)
¹ H-NMR (ppm): 0.96 (t, —CH ₃ , 3H), 1.29-1.57 (m, —CH ₂ —10H), 3.20 (d, ═N—CH _{2 -, 2H), 3.81 (br} , s, -NH 2, 4H), 6.52-7.70 (m, arm, H, 12H)

４−（４−ニトロフェニル）ブチル酸（２５ｇ：１２０ｍｍｏｌ）をトルエン（１００ｍｌ）に溶解させた。塩化チオニル（４５ｍｌ）とＤＭＦ数滴とを加え、６時間加熱還流した。放冷後、溶剤および未反応の塩化チオニルを減圧溜去し、４−（４−ニトロフェニル）ブチル酸クロライドを得た。（収量２７ｇ、収率９３％） [Example 9]
<Synthesis of Compound (II-17)>

4- (4-Nitrophenyl) butyric acid (25 g: 120 mmol) was dissolved in toluene (100 ml). Thionyl chloride (45 ml) and a few drops of DMF were added, and the mixture was heated to reflux for 6 hours. After allowing to cool, the solvent and unreacted thionyl chloride were distilled off under reduced pressure to obtain 4- (4-nitrophenyl) butyric acid chloride. (Yield 27g, Yield 93%)

  The obtained 4- (4-nitrophenyl) butyric acid chloride (27 g: 120 mmol) was placed in a three-necked flask, and a thermometer, a condenser tube and a dropping funnel were attached and dissolved in DMF (200 ml). A solution prepared by dissolving N-methyl-4-nitroaniline (17 g: 110 mmol) in a mixed solvent of DMF (200 ml) and pyridine (40 ml) was slowly added dropwise thereto. The mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water (200 ml) and extracted with dichloromethane (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from ethyl acetate to obtain N-methyl-4, N-bis (4-nitrophenyl) butyramide. (Yield 23g, Yield 61%)

The obtained N-methyl-4, N-bis (4-nitrophenyl) butyramide (23 g: 65 mmol) was dissolved in DMF (300 ml), palladium carbon powder (2.3 g) was added thereto, and the hydrogen pressure was reduced to 800 kPa. And stirred at 40 ° C. for 12 hours. The palladium carbon powder was removed, and the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (dichloromethane: methanol = 10: 1), and the resulting crude crystals were recrystallized from ethanol to obtain N-methyl-4, N-bis (4-aminophenyl) butyramide.
(Yield 17g, Yield 94%)
¹ H-NMR (ppm): 2.01-2.55 (m, —CH ₂ —, 6H), 2.73 (s, ═N—CH ₃ , 3H), 3.98 (br, s, − _{NH 2, 4H), 6.41-6.87 (} m, arm, H, 8H)

フラスコに６−ブロモ−２−ナフタレン酸（２５ｇ：１００ｍｍｏｌ）、４−ブロモフェニルボロン酸（２４ｇ：１２０ｍｍｏｌ）、炭酸ナトリウム（２２ｇ：２００ｍｍｏｌ）およびパラジウムカーボン粉末（２．５ｇ）を入れ、トルエン：ソルミックス：水＝１：１：１混合溶剤３００ｍｌ）に溶解させた。窒素雰囲気下、加熱還流して８時間攪拌した。放冷後、反応液を（水３００ｍｌ）に投入し、トルエン（３００ｍｌ）で抽出した。有機層を水（３００ｍｌ）で２回洗浄した後、無水硫酸マグネシウム（３０ｇ）を有機層に加え乾燥させた。ろ過によって無水硫酸マグネシウムを取り除いた後、溶剤を減圧溜去した。カラムクロマトグラフィー（トルエン：酢酸エチル＝１：１）で分離精製し、得られた粗結晶をトルエンから再結晶して６−（４−ブロモフェニル）−２−ナフタレン酸を得た。（収量２５ｇ、収率７７％） [Example 10]
<Synthesis of Compound (II-39)>

Put 6-bromo-2-naphthalene acid (25 g: 100 mmol), 4-bromophenylboronic acid (24 g: 120 mmol), sodium carbonate (22 g: 200 mmol) and palladium carbon powder (2.5 g) in a flask. (Mix: water = 1: 1: 1 mixed solvent 300 ml). Under a nitrogen atmosphere, the mixture was heated to reflux and stirred for 8 hours. After allowing to cool, the reaction mixture was poured into (300 ml of water) and extracted with toluene (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (toluene: ethyl acetate = 1: 1) were performed, and the resulting crude crystals were recrystallized from toluene to obtain 6- (4-bromophenyl) -2-naphthalene acid. (Yield 25g, Yield 77%)

The obtained 6- (4-bromophenyl) -2-naphthalene acid (25 g: 80 mmol) was dissolved in toluene (100 ml). To this was added thionyl chloride (45 ml) and a few drops of DMF, and the mixture was heated to reflux for 6 hours. After allowing to cool, the solvent and unreacted thionyl chloride were distilled off under reduced pressure to obtain 6- (4-bromophenyl) -2-naphthalene acid chloride.
(Yield 24g, Yield 89%)

  6- (4-Bromophenyl) -2-naphthalene acid chloride (24 g: 70 mmol) obtained in a three-necked flask was placed, a thermometer, a condenser tube and a dropping funnel were attached, and dissolved in DMF (200 ml). . A solution prepared by dissolving N-methyl-4-nitroaniline (9 g: 60 mmol) in a mixed solvent of DMF (100 ml) and pyridine (20 ml) was slowly added dropwise thereto. The mixture was heated and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water (200 ml) and extracted with dichloromethane (300 ml). The organic layer was washed twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The obtained crude crystals were recrystallized from ethyl acetate to obtain 6- (4-bromophenyl) -naphthalenic acid methyl- (4-nitrophenyl) amide. (Yield 21g, Yield 64%)

  6- (4-Bromophenyl) -naphthalenoic acid methyl- (4-nitrophenyl) amide (21 g: 45 mmol), dibenzylamine (26 g: 135 mmol), sodium t-butoxy (17 g: 180 mmol) obtained in the flask, Tris (dibenzylideneacetone) palladium (0.8 g: 0.9 mmol) and 2- (di-t-butylphosphino) biphenyl (0.5 g: 1.8 mmol) were added and dissolved in toluene. The mixture was stirred at 80 ° C. for 12 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into water (200 ml) and extracted with toluene (300 ml). The organic layer was washed twice with a saturated aqueous ammonium chloride solution (300 ml) and then twice with water (300 ml), and then anhydrous magnesium sulfate (30 g) was added to the organic layer and dried. After removing anhydrous magnesium sulfate by filtration, the solvent was distilled off under reduced pressure. The resulting crude crystals were separated and purified by column chromatography (toluene), and recrystallized from toluene to obtain 6- (4-dibenzylaminophenyl) -naphthalenoic acid methyl- (4-nitrophenyl) amide. (Yield 22g, Yield 84%)

The obtained 6- (4-dibenzylaminophenyl) -naphthalenic acid methyl- (4-nitrophenyl) amide (22 g: 40 mmol) was dissolved in DMF (300 ml), and palladium carbon powder (2.2 g) was added thereto. The mixture was stirred at 40 ° C. for 12 hours under a hydrogen pressure of 800 kPa. The palladium carbon powder was removed, and the solvent was distilled off under reduced pressure. Separation and purification by column chromatography (dichloromethane: methanol = 10: 1), and the resulting crude crystals were recrystallized from ethanol to give 6- (4-aminophenyl) -naphthalenoic acid methyl- (4-aminophenyl) amide. Obtained. (Yield 15g, Yield 92%)
¹ H-NMR (ppm): 2.81 (s, ═N—CH ₃ , 3H), 3.75 (br, s, —NH ₂ , 4H), 6.52 to 8.56 (m, arm, H, 14H)

[Example 11]
<Preparation of polyamic acid>
The compound (I-1) synthesized in Example 1 (3.2 g: 13 mmol) was placed in a flask and dissolved in NMP (50 g). Pyromellitic dianhydride (PMDA, 1.5 g: 6.5 mmol) and cyclobutanetetracarboxylic dianhydride (CBDA, 1.3 g: 6.5 mmol) were added to this solution, and the mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere. Stir. Butyl cellosolve (BC, 44 g) was added to the reaction solution, and the mixture was further stirred at room temperature for 2 hours under a nitrogen atmosphere to obtain a 6% by weight polyamic acid solution. This solution is designated as liquid crystal aligning agent A.

[Example 12]
<Preparation of polyamide>
The flask was charged with compound (I-1) synthesized in Example 1 (6.0 g: 25 mmol), terephthalic acid 4.1 g: 25 mmol), pyridine (1 ml) and lithium chloride (6.0 g: 140 mmol), and NMP ( 200 ml). To this solution, triphenyl phosphite (19 g: 60 mmol) was added dropwise and stirred at 100 ° C. for 4 hours under a nitrogen atmosphere. After allowing to cool, the reaction mixture was poured into methanol to reprecipitate the polymer, which was separated by filtration to obtain a crude product. The crude product was washed by boiling with water (500 ml) twice and once with methanol for 30 minutes each. Vacuum drying was performed for 8 hours to obtain 10 g of polyamide. The weight average molecular weight of this polyamide was about 85,000.

[Example 13]
<Preparation of polymethylamide>
The polyamide (10 g) obtained in Example 11 was placed in a flask and dissolved in NMP (150 ml). Sodium methoxide (2.6 g: 50 mmol) was added to this solution and stirred at room temperature for 3 hours. Methyl iodide (8.4 g: 60 mmol) was added to this solution, and the mixture was further stirred at room temperature for 2 hours. The reaction mixture was poured into water to reprecipitate the polymer, which was separated by filtration and then washed twice with water (1 liter) for 30 minutes. Further, it was washed once with a water-isopropyl alcohol mixed solvent (weight ratio 1: 1, 500 ml). Vacuum drying was performed at 120 ° C. for 9 hours to obtain 8.0 g of polymethylamide. This polymethylamide is designated as polyamide A. The polymethylamide had a weight average molecular weight of about 55,000. From the NMR measurement results, it was confirmed that the substitution rate of amide hydrogen to a methyl group was 100%.

（注１）ＤＢＡは４，４’−ジアミノベンズアニリドを意味する。
（注２）ＤＤＭは４，４’−ジアミノジフェニルメタンを意味する。
（注３）実施例２２におけるジアミン欄の括弧内の数字は、ジアミン全量を基準とするモル％を示す。即ち、この実施例におけるイミド結合に対するＮ−置換アミド結合のモル比は０．１である。 [Examples 14 to 24 and Comparative Examples 1 and 2]
The aligning agent was prepared according to the method described in Example 10, except that the diamine was replaced with the compound described in Table 1 and the amount used was 13 mmol. In addition, the addition amount of BC was adjusted so that the polymer concentration in each orientation agent might be 6 weight%.
<Table 1>

(Note 1) DBA means 4,4′-diaminobenzanilide.
(Note 2) DDM means 4,4′-diaminodiphenylmethane.
(Note 3) The numbers in parentheses in the diamine column in Example 22 indicate mol% based on the total amount of diamine. That is, the molar ratio of N-substituted amide bond to imide bond in this example is 0.1.

[Example 25]
Alignment agent A (20 g) was placed in the flask, NMP (10 g) and BC (10 g) were added thereto, and the mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere to obtain a solution having a polymer concentration of about 3% by weight. This solution was dropped onto a transparent glass substrate provided with an ITO electrode on one side and applied by a spinner method (2500 rpm, 15 seconds). After application, the solvent was evaporated at 80 ° C. for 5 minutes, and then heat treatment was performed in an oven at 250 ° C. for 30 minutes to form a thin film having a thickness of 60 nm.

  A rubbing treatment was performed on the film surface to obtain a liquid crystal alignment film, and two liquid crystal alignment films were bonded so that the rubbing directions were antiparallel to assemble a liquid crystal cell having a cell thickness of 20 μm. Liquid crystal composition A was injected into the cell, subjected to an isotropic treatment at 110 ° C. for 30 hours, and cooled to room temperature to obtain a liquid crystal display element. The residual charge of this liquid crystal display element was 0.082 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 98.2% and 93.5%, respectively. The pretilt angle was 1.1 degrees. And the pretilt angle after heating this liquid crystal display element at 110 degreeC for 20 hours was 1.1 degree | times.

<Liquid crystal composition A>

[Example 26]
A liquid crystal display device was prepared according to the method described in Example 25 except that the aligning agent B was used instead of the aligning agent A. The residual charge of this element was 0.079 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 98.5% and 93.9%, respectively. The pretilt angle was 1.1 degrees. And the pretilt angle after heating at 110 degreeC for 20 hours was 1.1 degree | times.

[Example 27]
A liquid crystal display device was prepared according to the method described in Example 25 except that the aligning agent C was used instead of the aligning agent A. The residual charge of this device was 0.083 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 99.0% and 94.2%, respectively. The pretilt angle was 1.3 degrees. The pretilt angle after heating for 20 hours at 110 ° C. was 1.3 degrees.

[Example 28]
A liquid crystal display device was prepared according to the method described in Example 25 except that the aligning agent G was used instead of the aligning agent A. The residual charge of this element was 0.093 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 99.2% and 94.5%, respectively. The pretilt angle was 1.2 degrees. The pretilt angle after heating at 110 ° C. for 20 hours was 1.2 degrees.

[Example 29]
A liquid crystal display device was prepared according to the method described in Example 25 except that the aligning agent H was used instead of the aligning agent A. The residual charge of this element was 0.089 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 99.5% and 95.1%, respectively. The pretilt angle was 1.1 degrees. And the pretilt angle after heating at 110 degreeC for 20 hours was 1.1 degree | times.

[Example 30]
A liquid crystal display device was prepared according to the method described in Example 25 except that the aligning agent J was used in place of the aligning agent A. The residual charge of this device was 0.087 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 98.9% and 94.1%, respectively. The pretilt angle was 1.3 degrees. The pretilt angle after heating for 20 hours at 110 ° C. was 1.3 degrees.

[Example 31]
A liquid crystal display device was produced according to the method described in Example 25 except that the aligning agent K was used instead of the aligning agent A. The residual charge of this element was 0.084 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 99.2% and 95.0%, respectively. The pretilt angle was 4.1 degrees. The pretilt angle after heating at 110 ° C. for 20 hours was 4.0 degrees.

[Example 32]
Alignment agent D (4 g) and alignment agent N (16 g) were added to the flask, NMP (10 g) and BC (10 g) were added thereto, and the mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere. The polymer concentration was about 3% by weight. A solution was obtained. This solution was dropped onto a transparent glass substrate provided with an ITO electrode on one side and applied by a spinner method (2500 rpm, 15 seconds). After application, the solvent was evaporated at 80 ° C. for 5 minutes, and then heat treatment was performed in an oven at 250 ° C. for 30 minutes to form a thin film having a thickness of 60 nm.

  A rubbing treatment was performed on the film surface to obtain a liquid crystal alignment film, and two liquid crystal alignment films were bonded so that the rubbing directions were antiparallel to assemble a liquid crystal cell having a cell thickness of 20 μm. Liquid crystal composition A was injected into the cell, subjected to an isotropic treatment at 110 ° C. for 30 hours, and cooled to room temperature to obtain a liquid crystal display element. The residual charge of this liquid crystal display element was 0.079 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 99.1% and 95.7%, respectively. The pretilt angle was 6.5 degrees. The pretilt angle after heating at 110 ° C. for 20 hours was 6.4 degrees.

[Example 33]
A liquid crystal display device was prepared according to the method described in Example 32 except that the aligning agent F was used instead of the aligning agent D. The residual charge of this device was 0.083 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 98.8% and 94.9%, respectively. The pretilt angle was 3.8 degrees. And the pretilt angle after heating at 110 degreeC for 20 hours was 3.8 degree | times.

[Example 34]
A liquid crystal display device was prepared according to the method described in Example 32 except that the aligning agent I was used instead of the aligning agent D. The residual charge of this element was 0.079 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 98.9% and 95.0%, respectively. The pretilt angle was 10.2 degrees. And the pretilt angle after heating at 110 degreeC for 20 hours was 10.3 degree | times.

[Example 35]
A liquid crystal display device was prepared according to the method described in Example 32 except that the aligning agent E was used instead of the aligning agent D, and the liquid crystal composition B was used instead of the liquid crystal composition A. The residual charge of this element was 0.098 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 96.9% and 93.4%, respectively. The pretilt angle was 90 degrees. The pretilt angle after heating at 110 ° C. for 20 hours was 90 degrees.

<Liquid crystal composition B>

[Comparative Example 3]
A liquid crystal display device was prepared according to the method described in Example 25 except that the aligning agent M was used instead of the aligning agent A. The residual charge of this element was 0.083 V at 25 ° C., and the voltage holding ratios at 30 Hz and 0.3 Hz were 97.6% and 93.3%, respectively. The pretilt angle was 1.2 degrees. And the pretilt angle after heating at 110 degreeC for 20 hours was 1.6 degree | times. In other words, a change in the pretilt angle was observed when placed at a high temperature for a long time.

[Example 36]
<Positive polymer compatibility (1)>
Alignment agent A (10 g) and alignment agent N (90 g) were added to the flask and stirred at room temperature for 1 hour. The resulting solution was transferred to a transparent glass container and allowed to stand in a −5 ° C. refrigerator for 1 week. As a result, no turbidity was found in the solution.

[Example 37]
<Positive polymer compatibility (2)>
Alignment agent A (50 g) and alignment agent N (50 g) were added to the flask and stirred at room temperature for 1 hour. The resulting solution was transferred to a transparent glass container and allowed to stand in a −5 ° C. refrigerator for 1 week. As a result, no turbidity was found in the solution.

[Comparative Example 4]
<Positive polymer compatibility>
Alignment agent M (10 g) and alignment agent N (90 g) were added to the flask and stirred at room temperature for 1 hour. The resulting solution was transferred to a transparent glass container and allowed to stand in a −5 ° C. refrigerator for 1 week. As a result, the solution was turbid.

[Example 38]
Alignment agent G (20 g) was added to the flask, NMP (10 g) and BC (10 g) were added thereto, and the mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere to obtain a solution having a polymer concentration of about 3% by weight. This solution was dropped onto a transparent glass substrate provided with an ITO electrode on one side and applied by a spinner method (2500 rpm, 15 seconds). After application, the solvent was evaporated at 80 ° C. for 5 minutes, and then heat treatment was performed in an oven at 250 ° C. for 30 minutes to form a thin film having a thickness of 60 nm. The film surface was irradiated with 100 mJ / cm ² of linearly polarized ultraviolet light having a wavelength of around 365 nm using an ultrahigh pressure mercury lamp.

  This substrate was bonded so that the polarization direction of ultraviolet rays was parallel, and a liquid crystal cell having a cell thickness of 20 μm was assembled. Liquid crystal JC-5006 manufactured by Chisso Corporation was poured into this cell, subjected to an isotropic treatment at 110 ° C. for 30 minutes, and cooled to room temperature to obtain a liquid crystal display element. When the alignment of the liquid crystal of this liquid crystal display element was visually confirmed, it was good.

[Example 39]
Alignment agent G (20 g) was added to the flask, NMP (10 g) and BC (10 g) were added thereto, and the mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere to obtain a solution having a polymer concentration of about 3% by weight. This solution was dropped onto a transparent glass substrate provided with an ITO electrode on one side, applied by a spinner method (2500 rpm, 15 seconds), and the solvent was evaporated at 80 ° C. for 5 minutes after application. The coated surface was irradiated with 100 mJ / cm ² of linearly polarized ultraviolet light having a wavelength of around 365 nm using an ultrahigh pressure mercury lamp. After the irradiation, heat treatment was performed in an oven at 250 ° C. for 30 minutes to form a thin film having a thickness of 60 nm.

  This substrate was bonded so that the polarization direction of ultraviolet rays was parallel, and a liquid crystal cell having a cell thickness of 20 μm was assembled. Liquid crystal JC-5006 manufactured by Chisso Corporation was injected into this cell, subjected to an isotropic treatment at 110 ° C. for 30 minutes, and cooled to room temperature to obtain a liquid crystal display element. When the alignment of the liquid crystal of this liquid crystal display element was visually confirmed, it was good.

[Example 40]
Alignment agent L (20 g) was placed in the flask, NMP (10 g) and BC (10 g) were added thereto, and the mixture was stirred at room temperature for 2 hours under a nitrogen atmosphere to obtain a solution having a polymer concentration of about 3% by weight. This solution was dropped on a transparent glass substrate on which aluminum was deposited, and was applied by a spinner method (2500 rpm, 15 seconds). After application, the solvent was evaporated at 80 ° C. for 5 minutes, and then heat treatment was performed in an oven at 250 ° C. for 30 minutes to form a thin film having a thickness of 60 nm. Six circular electrode patterns having a diameter of 5 mm were formed on the obtained thin film by a vapor deposition method to prepare a dielectric constant measurement sample. The dielectric constant of the thin film was measured by the CV method using a HP16451B electrode manufactured by Yokogawa-Hewlett-Packard Co., Ltd. and an HP4284A Precision LCR meter at a frequency of 100 kHz.

[Example 41]
A dielectric constant of 3.5 was measured according to the method described in Example 40 except that the aligning agent N was used instead of the aligning agent L.

[Example 42]
<Measurement of ion content in liquid crystal>
The amount of ions (ion density) in the liquid crystal in the liquid crystal cell is an index for knowing the degree of outflow of impurity ions from the alignment film into the liquid crystal. It can be said that the smaller the ion density, the smaller the amount of impurity ions flowing out from the alignment film into the liquid crystal.
Therefore, according to the method described in Applied Physics, Vol. 65, No. 10, 1065 (1996), the amount of ions (ion density) in the liquid crystal cell produced in Example 25 was manufactured by Toyo Technica Co., Ltd. Measurement was performed in a voltage range of ± 10 V using a measurement system 6254 type and a triangular wave with a frequency of 0.01 Hz. As a result, the ion density in the liquid crystal of this liquid crystal cell was 10 pC / cm ² .

[Example 43]
The ion density in the liquid crystal of the liquid crystal cell was measured according to the method described in Example 42 except that the cell prepared in Example 25 was replaced with the cell prepared in Example 29. The result was 12 pC / cm ² . .

[Comparative Example 5]
The ion density in the liquid crystal of the liquid crystal cell was measured according to the method described in Example 42 except that the cell produced in Example 25 was replaced with the cell produced in Comparative Example 3, and was 170 pC / cm ² . .

Claims (28)

Diamine represented by formula (1):

Here, R ¹ is alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is phenylene, cyclohexylene, a divalent fused ring group, a divalent heterocyclic group, —O—. , -OCO-, -COO or -CH = CH-, and any hydrogen in the alkyl may be replaced by halogen; phenylene, cyclohexylene, divalent fused ring And in the divalent heterocyclic group, any hydrogen may be replaced by halogen, alkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms; X ¹ and X ² are independently a single bond or a C 1-20 alkylene, arbitrary -CH 2 _- in the alkylene phenylene, cyclohexylene, divalent condensed ring group, a divalent heterocyclic group -O -, - S -, - OCO -, - COO or -CH = CH- may be replaced by, and any of the alkylene hydrogen may be replaced by fluorine; ^{X 2} is a single bond Sometimes, —CH ₂ — bonded to the aminophenyl group in X ¹ is not replaced by —O— or —S—; in the aminophenyl group, the position of the amino group bonded to the benzene ring is arbitrary. , And any hydrogen in the benzene ring may be replaced by fluorine, alkyl having 1 to 10 carbons, fluorinated alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons. R ¹ is alkyl having 1 to 20 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,7-diyl, fluorene-2, Replaced with 7-diyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, quinoline-3,7-diyl, -O-, -OCO-, -COO or -CH = CH- And any hydrogen in the alkyl may be replaced by fluorine; in the aforementioned 1,4-phenylene, any hydrogen is fluorine, alkyl having 1 to 4 carbons, or carbon having 1 to 4 carbons. It may be replaced by a fluorinated alkyl or alkoxy having 1 to 4 carbon atoms; X ¹ and X ² are independently a single bond or alkylene having 1 to 10 carbon atoms, any -CH ₂ in the alkylene Is 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,7-diyl, fluorene-2,7-diyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl , Quinoline-3,7-diyl, —O— or —CH═CH—, and any hydrogen in the alkylene may be replaced with fluorine; when X ² is a single bond, —CH ₂ — bonded to the aminophenyl group in X ¹ is not replaced by —O—; in the aminophenyl group, the bonding position of the amino group to the benzene ring is the bonding position of X ^{1 and} the bonding of X ² And any hydrogen in the benzene ring is fluorine, alkyl having 1 to 5 carbons, fluorinated alkyl having 1 to 5 carbons, or aryl having 1 to 5 carbons. The diamine according to claim 1, which may be replaced with alkoxy. R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, —O—, -OCO-, -COO or -CH = CH- may be replaced, and any hydrogen in the alkyl may be replaced by fluorine; X ¹ and X ² are independently a single bond or carbon number 1-10 alkylene, any —CH ₂ — in the alkylene may be replaced by 1,4-phenylene, 1,4-cyclohexylene, —O— or —CH═CH—, and any hydrogen in the alkylene may be replaced by fluorine; X ² is at the single bond, -CH 2 that bind to the aminophenyl group in X ¹ _- are not be replaced by -O-; Aminofu In group, bonding position of the amino group on the benzene ring is para or meta position with respect to each of the coupling position of the coupling position and X ² of X ^1, and any hydrogen fluorine benzene ring, methyl or The diamine according to claim 1, which may be replaced by methoxy. The diamine according to claim 1, wherein X ¹ and X ² are both a single bond. R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, —O—, -OCO-, -COO or -CH = CH-, and any hydrogen in the alkyl may be replaced by fluorine; X ¹ and X ² are both single bonds; and In the aminophenyl group, the bonding position of the amino group to the benzene ring is para-position or meta-position with respect to each of the bonding position of X ^{1 and} the bonding position of X ² , and any hydrogen of the benzene ring is fluorine, methyl Or a diamine according to claim 1 which may be replaced by methoxy. R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, —O—, -OCO-, -COO or -CH = CH- may be replaced, and any hydrogen in the alkyl may be replaced by fluorine; X ¹ is alkylene having 1 to 10 carbons, and Any —CH ₂ — in the alkylene may be replaced by 1,4-phenylene, 1,4-cyclohexylene, —O— or —CH═CH—, and any hydrogen in the alkylene is fluorine. And in this alkylene, —CH ₂ — attached to the aminophenyl group is not replaced by —O—; X ² is a single bond; The amino group bond position to the benzene ring is para- or meta-position to each of the X ¹ bond position and X ² bond position, and any hydrogen of the benzene ring is replaced by fluorine, methyl or methoxy. The diamine according to claim 1, which may be. R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, —O—, -OCO-, -COO or -CH = CH- may be replaced, and any hydrogen in the alkyl may be replaced by fluorine; X ¹ and X ² are independently from 1 to 10 carbon atoms. And any —CH ₂ — in the alkylene may be replaced by 1,4-phenylene, 1,4-cyclohexylene, —O— or —CH═CH—, and arbitrary hydrogen may be replaced by fluorine; in-aminophenyl group, para or menu for each of the binding position of the amino group is bonded position of the coupling position and X ² of X ¹ to the benzene ring The diamine of claim 1, wherein the diamine is in the ta position and any hydrogen on the benzene ring may be replaced by fluorine, methyl or methoxy. R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, —O—, -OCO-, -COO or -CH = CH- may be replaced, and any hydrogen in the alkyl may be replaced by fluorine; X ¹ is a single bond; X ² has 1 carbon 10 is alkylene, arbitrary -CH ₂ - in the alkylene may 1,4-phenylene, 1,4-cyclohexylene, be replaced by -O- or -CH = CH-, and this Arbitrary hydrogen in alkylene may be replaced by fluorine; in the aminophenyl group, the bonding position of the amino group to the benzene ring is para-positioned to the bonding position of X ^{1 and} the bonding position of X ² respectively. The diamine according to claim 1, wherein is in the meta position and any hydrogen on the benzene ring may be replaced by fluorine, methyl or methoxy. A diamine mixture containing at least one diamine represented by formula (1) or at least one diamine represented by formula (1) is used as a diamine raw material, and tetracarboxylic dianhydride, tricarboxylic acid, dicarboxylic acid, tricarboxylic acid is used. Polymer obtained using at least one of acid derivative and dicarboxylic acid derivative as carboxylic acid raw material:

Here, R ¹ is alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is phenylene, cyclohexylene, a divalent fused ring group, a divalent heterocyclic group, —O—. , -OCO-, -COO or -CH = CH-, and any hydrogen in the alkyl may be replaced by halogen; phenylene, cyclohexylene, divalent fused ring And in the divalent heterocyclic group, any hydrogen may be replaced by halogen, alkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms; X ¹ and X ² are independently a single bond or a C 1-20 alkylene, arbitrary -CH 2 _- in the alkylene phenylene, cyclohexylene, divalent condensed ring group, a divalent heterocyclic group -O -, - S -, - OCO -, - COO or -CH = CH- may be replaced by, and any of the alkylene hydrogen may be replaced by fluorine; ^{X 2} is a single bond Sometimes, —CH ₂ — bonded to the aminophenyl group in X ¹ is not replaced by —O— or —S—; in the aminophenyl group, the position of the amino group bonded to the benzene ring is arbitrary. , And any hydrogen in the benzene ring may be replaced by fluorine, alkyl having 1 to 10 carbons, fluorinated alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons. R ¹ is alkyl having 1 to 20 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,7-diyl, fluorene-2, Replaced with 7-diyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, quinoline-3,7-diyl, -O-, -OCO-, -COO or -CH = CH- And any hydrogen in the alkyl may be replaced by fluorine; in the aforementioned 1,4-phenylene, any hydrogen is fluorine, alkyl having 1 to 4 carbons, or carbon having 1 to 4 carbons. It may be replaced by a fluorinated alkyl or alkoxy having 1 to 4 carbon atoms; X ¹ and X ² are independently a single bond or alkylene having 1 to 10 carbon atoms, any -CH ₂ in the alkylene Is 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,7-diyl, fluorene-2,7-diyl, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl , Quinoline-3,7-diyl, —O— or —CH═CH—, and any hydrogen in the alkylene may be replaced with fluorine; when X ² is a single bond, —CH ₂ — bonded to the aminophenyl group in X ¹ is not replaced by —O—; in the aminophenyl group, the bonding position of the amino group to the benzene ring is the bonding position of X ^{1 and} the bonding of X ² And any hydrogen in the benzene ring is fluorine, alkyl having 1 to 5 carbons, fluorinated alkyl having 1 to 5 carbons, or aryl having 1 to 5 carbons. 10. A polymer according to claim 9, which may be replaced with alkoxy. R ¹ is alkyl having 1 to 10 carbon atoms, and any —CH ₂ — in the alkyl is 1,4-phenylene, naphthalene-2,7-diyl, 1,4-cyclohexylene, —O—, -OCO-, -COO or -CH = CH- may be replaced, and any hydrogen in the alkyl may be replaced by fluorine; X ¹ and X ² are independently a single bond or carbon number 1-10 alkylene, any —CH ₂ — in the alkylene may be replaced by 1,4-phenylene, 1,4-cyclohexylene, —O— or —CH═CH—, and any hydrogen in the alkylene may be replaced by fluorine; X ² is at the single bond, -CH 2 that bind to the aminophenyl group in X ¹ _- are not be replaced by -O-; Aminofu In group, bonding position of the amino group on the benzene ring is para or meta position with respect to each of the coupling position of the coupling position and X ² of X ^1, and any hydrogen fluorine benzene ring, methyl or 10. A polymer according to claim 9, which may be replaced by methoxy. The polymer according to claim 9, wherein X ¹ and X ² are both a single bond.   The polymer according to claim 9, wherein the carboxylic acid raw material is at least one of tetracarboxylic dianhydrides. The polymer according to claim 9, wherein the carboxylic acid raw material is at least one selected from a compound represented by any one of formulas (A1) to (A9) and naphthalenetetracarboxylic dianhydride:

In these formulas, ring B ¹ is independently a cyclohexane ring or a benzene ring; ring B ² is a cyclohexane ring, cyclohexene ring or benzene ring; G ¹ is a single bond, alkylene having 1 to 12 carbon atoms, 1 , 4-phenylene or 1,4-cyclohexylene; G ² is a single bond, —CH ₂ —, —CH ₂ CH ₂ —, —O—, —CO—, —S—, —SO—, — C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —, and the bonding position of G ² to ring B ¹ is any position other than the bonding position of 2-oxapropane-1,3-dioyl. X ³ is a single bond or —CH ₂ —; X ⁴ is a single bond, —CH ₂ —, —CH ₂ CH ₂ — or —CH═CH—; R ² is independently hydrogen, methyl, ethyl or phenyl; ^{R 3} is The elementary or methyl.   The polymer according to claim 9, wherein the carboxylic acid raw material is at least one of a tricarboxylic acid, a dicarboxylic acid, a tricarboxylic acid derivative, and a dicarboxylic acid derivative.   The polymer obtained by using the polymer of Claim 15 as a raw material, and substituting the hydrogen of the amide bond (-CO-NH-) with the C1-C10 alkyl.   The polymer according to claim 9, wherein the carboxylic acid raw material is at least one of a tetracarboxylic dianhydride and at least one of a tricarboxylic acid, a dicarboxylic acid, a tricarboxylic acid derivative and a dicarboxylic acid derivative. The polymer according to claim 17, wherein the tetracarboxylic dianhydride is a compound represented by any one of formulas (A1) to (A9).

In these formulas, ring B ¹ is independently a cyclohexane ring or a benzene ring; ring B ² is a cyclohexane ring, cyclohexene ring or benzene ring; G ¹ is a single bond, alkylene having 1 to 12 carbon atoms, 1 , 4-phenylene or 1,4-cyclohexylene; G ² is a single bond, —CH ₂ —, —CH ₂ CH ₂ —, —O—, —CO—, —S—, —SO—, — C (CH ₃ ) ₂ — or —C (CF ₃ ) ₂ —, and the bonding position of G ² to ring B ¹ is any position other than the bonding position of 2-oxapropane-1,3-dioyl. X ³ is a single bond or —CH ₂ —; X ⁴ is a single bond, —CH ₂ —, —CH ₂ CH ₂ — or —CH═CH—; R ² is independently hydrogen, methyl, ethyl or phenyl; ^{R 3} is The elementary or methyl.   The liquid crystal aligning agent which contains at least 1 of the polymer of Claim 9, or at least 1 of the polymer of Claim 16, and may contain another polymer.   The liquid crystal aligning agent according to claim 19, wherein the other polymer is at least one selected from polyamic acid, partially imidized polyamic acid, polyimide, polyamide, and polyamideimide.   14. A liquid crystal aligning agent comprising at least one of the polymers according to claim 13, which may contain other polymers, and wherein the other polymer is a polyamic acid, a partially imidized polyamic acid, a polyimide, or a mixture thereof. .   A liquid crystal aligning agent containing at least one of the polymers according to claim 13 and containing no other polymer.   The polymer according to claim 13, wherein the ratio of the N-substituted amide bond to the total of the imide bond, amide bond and N-substituted amide bond constituting the main chain is a molar ratio of 0.1 to 0.5. The liquid crystal aligning agent of Claim 22.   The liquid crystal aligning film formed using the liquid crystal aligning agent of Claim 19.   A liquid crystal alignment film formed using the liquid crystal aligning agent according to claim 19 and imparted with liquid crystal alignment ability by irradiation with linearly polarized ultraviolet rays. A diamine mixture containing one of the diamines represented by the formula (1-1) or at least one of the diamines represented by the formula (1-1) is used as a diamine raw material, and a tetracarboxylic dianhydride, a tricarboxylic acid, A liquid crystal is formed by using a liquid crystal aligning agent containing at least one polymer obtained by using at least one of a dicarboxylic acid, a tricarboxylic acid derivative and a dicarboxylic acid derivative as a carboxylic acid raw material, and irradiating linearly polarized ultraviolet light Liquid crystal alignment film to which alignment ability is imparted:

Here, R ¹ is alkyl having 1 to 30 carbon atoms, and any —CH ₂ — in the alkyl is arylene, cyclohexylene, —O—, —OCO—, —COO or —CH═CH—. And any hydrogen in the alkyl may be replaced with a halogen; in the arylene, any —CH═ may be replaced with —N═, and any hydrogen is a halogen. , Cycloalkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms, or alkoxy having 1 to 4 carbon atoms; in the cyclohexylene, any —CH ₂ — that is not adjacent to each other is -O- may be substituted; in the aminophenyl group, the bonding position of the amino group to the benzene ring is arbitrary, and any hydrogen of the benzene ring is fluorine, carbon C 1 -C 10 alkyl, may be replaced by fluorinated alkyl or a C 1-10 alkoxy having 1 to 10 carbon atoms. R ¹ is alkyl having 1 to 10 carbon atoms; in the aminophenyl group, the bonding position of the amino group to the benzene ring is the bonding position of —CH═CH— and the bonding position of —N (R ¹ ) —, respectively. 27. The liquid crystal alignment film according to claim 26, wherein the liquid crystal alignment film is in a para position or a meta position, and any hydrogen in the benzene ring may be replaced with fluorine, methyl or methoxy. The liquid crystal display element containing the liquid crystal aligning film of any one of Claims 24-27.