JP6501073B2 - Liquid crystal aligning agent and liquid crystal display device using the same - Google Patents

Description

  The present invention relates to a liquid crystal alignment treatment agent used in the production of a liquid crystal display device, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display device using the liquid crystal alignment film.

  Liquid crystal display devices are currently widely used as display devices that realize thinness and lightness. Usually, a liquid crystal alignment film is used in this liquid crystal display element to determine the alignment state of the liquid crystal.

  One of the characteristics required of the liquid crystal alignment film is control of so-called pretilt angle of liquid crystal, which keeps the orientation inclination angle of liquid crystal molecules with respect to the substrate surface at an arbitrary value. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film. Among the techniques for controlling the pretilt angle by the structure of the polyimide, the method of using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle according to the usage ratio of this diamine, and thus obtain the target pretilt angle. Is relatively easy, and is useful as a means for increasing the pretilt angle (see, for example, Patent Document 1). In addition, the diamine component for increasing the pretilt angle of the liquid crystal in this way has also been studied for the purpose of improving the stability and process dependency of the pretilt angle, and the side chain structure used herein is phenyl Those containing a ring structure such as a group or a cyclohexyl group have been proposed (see, for example, Patent Document 2).

  In addition, with a high definition of the liquid crystal display element, the liquid crystal alignment film used also has a high voltage holding ratio and a DC voltage from the viewpoint of suppression of the contrast drop of the liquid crystal display element and reduction of the afterimage phenomenon. The characteristic that the accumulated charge at the time of application is small or the relaxation of the accumulated charge by DC voltage is quicker has become increasingly important.

  A liquid crystal aligning agent containing a tertiary amine of a specific structure in addition to a polyamic acid or an imide group-containing polyamic acid is used as a polyimide liquid crystal aligning film having a short time until the residual image generated by a direct current voltage disappears. The thing (for example, refer patent document 3), the thing using the liquid-crystal aligning agent containing the soluble polyimide which used the specific diamine which has a pyridine skeleton etc. as a raw material (refer patent document 4), etc. are known. Also, a compound containing one carboxylic acid group in the molecule in addition to the polyamic acid, its imidated polymer, etc., as having a high voltage holding ratio and a short time until the residual image generated by the direct current voltage disappears Using a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing one carboxylic acid anhydride group in the molecule and a compound containing one tertiary amino group in the molecule (eg, Patent Document 5) is known.

Japanese Patent Application Laid-Open No. 2-282726 Unexamined-Japanese-Patent No. 9-278724 JP-A-9-316200 JP 10-104633 A JP-A-8-76128

  The liquid crystal alignment film is also used to control the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal. In particular, since it is necessary to vertically align liquid crystals in VA (Vertical Alignment) mode or PSA (Polymer Sustained Alignment) mode, etc., the liquid crystal alignment film has the ability to vertically align liquid crystals (vertical alignment or high pretilt). (Also called horns) is required. Furthermore, the liquid crystal alignment film has become important not only for its high vertical alignment but also for its stability. In particular, a liquid crystal display element using a backlight having a large calorific value and a large light irradiation amount to obtain high luminance, for example, a car navigation system or a large television, is exposed to high temperature and light irradiation for a long time May be used or left in an environment. Under such severe conditions, when the vertical alignment is lowered, problems such as an initial display characteristic can not be obtained or unevenness in display occurs.

  Furthermore, also with regard to the voltage holding ratio, which is one of the electrical characteristics of the liquid crystal display element, high stability under the above-described severe conditions is also required. That is, when the voltage holding ratio decreases due to light irradiation from the backlight, burn-in failure (also referred to as line burn-in), which is one of the display defects of the liquid crystal display element, tends to occur. A high liquid crystal display element can not be obtained. Therefore, in addition to good initial characteristics, the liquid crystal alignment film is also required to have a low voltage retention rate, for example, even after being exposed to light irradiation for a long time. Furthermore, also with respect to surface burn-in, which is another burn-in failure, there is a demand for a liquid crystal alignment film in which the relaxation of the residual charge accumulated by the DC voltage is quickened by light irradiation from the backlight.

  Then, an object of this invention is to provide the liquid-crystal aligning agent which has the said characteristic. That is, an object of the present invention is to provide a liquid crystal alignment film capable of expressing a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. In addition, it is an object of the present invention to provide a liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio even after being exposed to light irradiation for a long time and quickly reducing the residual charge accumulated by a direct current voltage.

  In addition, it is providing the liquid crystal display element which has said liquid crystal aligning film, and the liquid-crystal aligning agent which can provide said liquid crystal aligning film.

  Another object of the present invention is to provide a liquid crystal display device provided with a liquid crystal alignment film meeting the above-mentioned requirements.

  As a result of intensive studies, the present inventors have found that a liquid crystal alignment treatment agent having two polymers having a specific structure is extremely effective for achieving the above object, and completes the present invention. It reached.

That is, the present invention has the following gist.
(1) The liquid-crystal aligning agent containing the following (A) component and (B) component.
Component (A): A polymer containing at least one selected from a polyimide precursor having a structure containing a nitrogen atom and a polyimide.
Component (B): A polymer containing at least one selected from a polyimide precursor and a polyimide having a structure represented by the following formula [2].
In addition, the structure shown by following formula [3] is contained in at least any one of the polymer of (A) component and the (B) component.

（式［２］中、Ｙ^１およびＹ^７はそれぞれ独立して、単結合、炭素数１〜１０のアルキレン基、−Ｏ−、−Ｎ（Ｒ^１）−（Ｒ^１は水素原子または炭素数１〜３のアルキレン基を示す）、−ＣＯＮ（Ｒ^２）−（Ｒ^２は水素原子または炭素数１〜３のアルキレン基を示す）、−Ｎ（Ｒ^３）ＣＯ−（Ｒ^３は水素原子または炭素数１〜３のアルキレン基を示す）、−ＣＨ_２Ｏ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の有機基を示し、Ｙ^２およびＹ^６はそれぞれ独立して、炭素数１〜１０のアルキレン基を示し、Ｙ^３およびＹ^５はそれぞれ独立して、水素原子または炭素数１〜１０のアルキレン基を示し、Ｙ^４は酸素原子または硫黄原子を示す）。

(In formula [2], Y ¹ and Y ⁷ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R ¹ )-(R ¹ is a hydrogen atom or carbon number 1 to 3 represents an alkylene group), -CON (R ² )-(wherein R ² represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), -N (R ³ ) CO- (R ³ represents a hydrogen atom) Or an alkylene group of 1 to 3 carbon atoms), at least one organic group selected from -CH ₂ O-, -COO- and -OCO-, and Y ² and Y ⁶ are each independently carbon And each of Y ³ and Y ⁵ independently represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, and Y ⁴ represents an oxygen atom or a sulfur atom).

（式［３］中、Ｂ^１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−または−ＯＣＯ−を示し、Ｂ^２は単結合または−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を示し、Ｂ^３は単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−または−ＯＣＯ−を示し、Ｂ^４はベンゼン環、シクロヘキサン環または複素環から選ばれる２価の環状基、またはステロイド骨格を有する炭素数１７〜５１の２価の有機基を示し、前記環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、Ｂ^５はベンゼン環、シクロヘキサン環または複素環から選ばれる２価の環状基を示し、これらの環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、ｎは０〜４の整数を示し、Ｂ^６は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基または炭素数１〜１８のフッ素含有アルコキシル基を示す）。

(In formula [3], B ¹ is a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- B ² represents a single bond or-(CH ₂ ) _b- (b is an integer of 1 to 15), B ³ represents a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15) ), —O—, —CH ₂ O—, —COO— or —OCO—, and B ⁴ is a carbon having a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a steroid skeleton And an arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or a fluorine containing 1 to 3 carbon atoms. It may be substituted by an alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. , B ⁵ represents a divalent cyclic group selected from benzene ring, cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, 1 to 3 carbon atoms It may be substituted by an alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4, and B ⁶ represents a carbon number 1-18 alkyl group, C1-C18 fluorine-containing alkyl group, C1-C18 alkoxyl group, or C1-C18 fluorine-containing alkoxyl group is shown).

(2) The liquid crystal orientation according to the above (1), wherein the structure having a nitrogen atom in the component (B) is at least one structure selected from the structures represented by the following formulas [1a] to [1c] Processing agent.

（式［１ａ］中、Ｘ^１はベンゼン環または窒素含有芳香族複素環を示し、Ｘ^２は水素原子または炭素数１〜１２の脂肪族基で置換されたジ置換アミノ基を示し、式［１ｂ］中、Ｘ^３およびＸ^７はそれぞれ独立して、炭素原子を６〜１５個有し、かつベンゼン環を１〜２個有する芳香族基を示し、Ｘ^４およびＸ^６はそれぞれ独立して、水素原子または炭素数１〜５のアルキレン基を示し、Ｘ^５は炭素数２〜５のアルキレン基またはビフェニル基を示し、ｍは０または１の整数を示し、式［１ｃ］中、Ｘ^８およびＸ^１０はそれぞれ独立して、下記の式［１ｃ−ａ］および式［１ｃ−ｂ］で示される構造から選ばれる少なくとも１種の構造を示し、Ｘ^９は炭素数１〜５のアルキレン基またはベンゼン環を示す）。

(In the formula [1a], X ¹ represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, and X ² represents a hydrogen atom or a disubstituted amino group substituted with a C 1 to C 12 aliphatic group, 1 b], X ³ and X ⁷ each independently represent an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, and X ⁴ and X ⁶ each independently are , A hydrogen atom or an alkylene group of 1 to 5 carbon atoms, X ⁵ represents an alkylene group of 2 to ⁵ carbon atoms or a biphenyl group, m represents an integer of 0 or 1, and in the formula [1c], X ⁸ And X ¹⁰ each independently represents at least one structure selected from the structures represented by the following Formula [1c-a] and Formula [1c-b], and X ⁹ is an alkylene group having 1 to 5 carbon atoms Or a benzene ring is shown).

(3) The polymer according to the above (1) or (2), wherein the polymer of the component (A) is a polymer obtained by using a diamine compound represented by the following formula [1-1] as a part of the raw material The liquid-crystal aligning agent of description.

（式［１−１］中、Ｘ^Ａは前記式［１ａ］〜式［１ｃ］で示される構造から選ばれる少なくとも１種の構造を有する有機基を示し、Ａ^１およびＡ^２はそれぞれ独立して、水素原子または炭素数１〜５のアルキレン基を示す）。

(In the formula [1-1], X ^A represents an organic group having at least one structure selected from the structures represented by the above formulas [1a] to [1c], and A ¹ and A ² are each independently A hydrogen atom or an alkylene group of 1 to 5 carbon atoms).

(4) The liquid crystal according to the above (3), wherein the diamine compound is a polymer obtained by using a diamine compound represented by the following formula [1a-1] to formula [1c-1] as a part of the raw material Alignment treatment agent.

（式［１ａ−１］中、Ｘ^１はベンゼン環または窒素含有芳香族複素環を示し、Ｘ^２は水素原子または炭素数１〜１２の脂肪族基で置換されたジ置換アミノ基を示し、式［１ｂ−１］中、Ｘ^３およびＸ^７はそれぞれ独立して、炭素原子を６〜１５個有し、かつベンゼン環を１〜２個有する芳香族基を示し、Ｘ^４およびＸ^６はそれぞれ独立して、水素原子または炭素数１〜５のアルキレン基を示し、Ｘ^５は炭素数２〜５のアルキレン基またはビフェニル基を示し、ｍは０または１の整数を示し、式［１ｃ−１］中、Ｘ^８およびＸ^１０はそれぞれ独立して、前記式［１ｃ−ａ］および式［１ｃ−ｂ］で示される構造から選ばれる少なくとも１種の構造を示し、Ｘ^９は炭素数１〜５のアルキレン基またはベンゼン環を示し、式［１ａ−１］〜式［１ｃ−１］中、Ａ^１〜Ａ^６はそれぞれ独立して、水素原子または炭素数１〜５のアルキレン基を示す）。

(In the formula [1a-1], X ¹ represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, and X ² represents a hydrogen atom or a disubstituted amino group substituted with a C 1-12 aliphatic group, In the formula [1b-1], X ³ and X ⁷ each independently represent an aromatic group having 6 to 15 carbon atoms and one or two benzene rings, and X ⁴ and X ⁶ each represents an aromatic group Each independently represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, X ⁵ represents an alkylene group having 2 to ⁵ carbon atoms or a biphenyl group, m represents an integer of 0 or 1, and 1], X ⁸ and X ¹⁰ each independently represent at least one structure selected from the structures represented by the above formulas [1c-a] and [1c-b], and X ⁹ has 1 carbon atom And an alkylene group of 5 to 5 or a benzene ring, represented by the formula [1a-1] [1c-1] ^in, A 1 to A ⁶ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms).

(5) The liquid crystal alignment treatment agent according to the above (4), wherein the diamine compound is at least one diamine compound selected from diamine compounds represented by the following Formula [1-1a] to Formula [1-4a]: .

（式［１−３ａ］中、Ｒ^１は水素原子または炭素数１〜５のアルキレン基を示し、式［１−４ａ］中、ｎは１〜１０の整数を示し、式［１−１ａ］〜式［１−４ａ］中、Ａ^１〜Ａ^８はそれぞれ独立して、水素原子または炭素数１〜５のアルキレン基を示す）。

(In the formula [1-3a], R ¹ represents a hydrogen atom or an alkylene group having 1 to 5 carbon atoms, and in the formula [1-4a], n represents an integer of 1 to 10, and the formula [1-1a] ~ formula [1-4a] ^in, a 1 to a ⁸ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms).

(6) The polymer of the said (B) component is a polymer obtained by using the diamine compound shown by following formula [2-1] for a part of raw material of said (1)-said (5) The liquid-crystal aligning agent as described in any.

（式［２−１］中、Ｙ^Ａは前記式［２］で示される構造を有する有機基を示し、Ａ^１およびＡ^２はそれぞれ独立して、水素原子または炭素数１〜５のアルキレン基を示す）。

(In formula [2-1], Y ^A represents an organic group having a structure represented by formula [2], and A ¹ and A ² each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms Show).

(7) The liquid-crystal aligning agent as described in said (6) whose said diamine compound is a polymer obtained by using the diamine compound shown by following formula [2a] for a part of raw material.

（式［２ａ］中、Ｙ^１およびＹ^７はそれぞれ独立して、単結合、炭素数１〜１０のアルキレン基、−Ｏ−、−Ｎ（Ｒ^１）−（Ｒ^１は水素原子または炭素数１〜３のアルキレン基を示す）、−ＣＯＮ（Ｒ^２）−（Ｒ^２は水素原子または炭素数１〜３のアルキレン基を示す）、−Ｎ（Ｒ^３）ＣＯ−（Ｒ^３は水素原子または炭素数１〜３のアルキレン基を示す）、−ＣＨ_２Ｏ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の有機基を示し、Ｙ^２およびＹ^６はそれぞれ独立して、炭素数１〜１０のアルキレン基を示し、Ｙ^３およびＹ^５はそれぞれ独立して、水素原子または炭素数１〜１０のアルキレン基を示し、Ｙ^４は酸素原子または硫黄原子を示し、Ａ^１およびＡ^２はそれぞれ独立して、水素原子または炭素数１〜５のアルキレン基を示す）。

(In formula [2a], Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R ¹ )-(wherein R ¹ is a hydrogen atom or carbon number 1 to 3 represents an alkylene group), -CON (R ² )-(wherein R ² represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), -N (R ³ ) CO- (R ³ represents a hydrogen atom) Or an alkylene group of 1 to 3 carbon atoms), at least one organic group selected from -CH ₂ O-, -COO- and -OCO-, and Y ² and Y ⁶ are each independently carbon And Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkylene group having 1 to 10 carbon atoms; Y ⁴ represents an oxygen atom or a sulfur atom; A ¹ and A ² each independently represent a hydrogen atom or a C1-5 It represents an alkylene group).

(8) The liquid crystal alignment treatment agent according to the above (7), wherein the diamine compound is at least one diamine compound selected from diamine compounds represented by the following formulas [2-1a] to [2-3a]: .

（式［２−１ａ］〜式［２−３ａ］中、Ａ^１〜Ａ^６はそれぞれ独立して、水素原子または炭素数１〜５のアルキレン基を示す）。

(In Formula [2-1a] to Formula [2-3a], A ^{1 to} A ⁶ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms).

(9) The above (1) to (8) wherein a diamine compound represented by the following formula [3a] is used as part of the raw material for at least one polymer of the (A) component and the (B) component The liquid-crystal aligning agent in any one of these.

（式［３ａ］中、Ｂは前記式［３］を示し、Ａ^１およびＡ^２はそれぞれ独立して、水素原子または炭素数１〜５のアルキレン基を示し、ｍは１〜４の整数を示す）。

(In formula [3a], B represents the above formula [3], A ¹ and A ² each independently represent a hydrogen atom or an alkylene group of 1 to 5 carbon atoms, and m is an integer of 1 to 4 Show).

(10) At least one selected from a polyimide precursor and a polyimide obtained by using a tetracarboxylic acid component represented by the following formula [4]: (A) Component polymer and (B) component polymer The liquid-crystal aligning agent in any one of said (1)-(9) which is a polymer of these.

（式［４］中、Ｚは下記の式［４ａ］〜式［４ｋ］で示される構造から選ばれる少なくとも１種の構造を示す）。

(In Formula [4], Z shows at least 1 type of structure chosen from the structure shown by following formula [4a]-Formula [4k]).

（式［４ａ］中、Ｚ^１〜Ｚ^４は水素原子、メチル基、エチル基、プロピル基、塩素原子またはベンゼン環を示し、それぞれ同じであっても異なってもよく、式［４ｇ］中、Ｚ^５およびＺ^６は水素原子またはメチル基を示し、それぞれ同じであっても異なってもよい）。

(In the formula [4a], Z ^{1 to} Z ^{4 each} represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, which may be the same or different, and in the formula [4g], Z ⁵ and Z ⁶ represents a hydrogen atom or a methyl group, may or may not be respectively the same).

(11) A tetracarboxylic acid having at least one structure wherein the tetracarboxylic acid component is selected from the structures in which Z in the formula [4] is represented by the formula [4a] and the formula [4e] to the formula [4g] The liquid-crystal aligning agent as described in said (10) which is a component.

(12) In the polymer of the component (A), the diamine compound represented by the formula [1a-1] to the formula [1c-1] is 5 mol% to 95 mol% in 100 mol% of all diamine components. The liquid-crystal aligning agent in any one of said (4)-(11) which is it.

(13) In the polymer of the component (B), the diamine compound represented by the formula [2a] is 5 mol% to 95 mol% in 100 mol% of all diamine components, The liquid-crystal aligning agent in any one of 12).

(14) Any of the above (1) to (13), wherein the polymer of the component (B) is 0.5 parts by mass to 950 parts by mass with respect to 100 parts by mass of the polymer of the component (A) Liquid crystal alignment treatment agent described in.

(15) The above (1) to (14) containing at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone as a solvent for a liquid crystal alignment treatment agent The liquid-crystal aligning agent in any one of.

(16) As a solvent for a liquid crystal alignment treatment agent, at least one selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether The liquid-crystal aligning agent in any one of said (1)-(15) which contains 1 type of solvent.

(17) At least one kind of substitution selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group in a liquid crystal alignment treatment agent The liquid crystal aligning agent according to any one of the above (1) to (16), which contains at least one crosslinkable compound selected from a crosslinkable compound having a group and a crosslinkable compound having a polymerizable unsaturated bond.

(18) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of (1) to (17) above.

The liquid crystal aligning film obtained by the inkjet method using the liquid-crystal aligning agent in any one of said (1)-(17).

The liquid crystal display element which has a liquid crystal aligning film as described in said (18) or said (19).

(21) A liquid crystal composition is provided which has a liquid crystal layer between a pair of substrates provided with electrodes, and which contains a polymerizable compound which is polymerized by at least one of active energy rays and heat. The liquid crystal alignment film according to the above (18) or (19), which is used for a liquid crystal display device manufactured through the step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(22) A liquid crystal display device having the liquid crystal alignment film as described in (21) above.

(23) A liquid crystal alignment film having a liquid crystal layer is provided between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy ray and heat is disposed between the pair of substrates. The liquid crystal alignment film according to the above (18) or (19), which is used for a liquid crystal display device manufactured through the step of polymerizing the polymerizable group while applying a voltage between the electrodes.

(24) A liquid crystal display device having the liquid crystal alignment film as described in (23) above.

  The liquid crystal aligning agent containing two kinds of at least one polymer selected from the polyimide precursor or the polyimide having the specific structure of the present invention has a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time The liquid crystal aligning film which can be expressed can be obtained. In addition, even after exposure to light irradiation for a long time, the liquid crystal alignment film can suppress the decrease in the voltage holding ratio and quickly reduce the residual charge accumulated by the direct current voltage. Therefore, the liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be suitably used for a large screen and high definition liquid crystal television.

  Hereinafter, the present invention will be described in detail.

  The present invention is a liquid crystal alignment treatment agent containing the following components (A) and (B), a liquid crystal alignment film obtained using the liquid crystal alignment treatment agent, and a liquid crystal display device having the liquid crystal alignment film. is there.

The liquid-crystal aligning agent containing the following (A) component and (B) component.
Component (A): A polymer containing at least one selected from a polyimide precursor having a structure containing a nitrogen atom and a polyimide (also referred to as a specific polymer (A)).
Component (B): a polyimide precursor having a structure (also referred to as a specific structure (2)) represented by the following formula [2] and a polymer containing at least one selected from polyimides (specific polymer (B) Also called).

  In addition, the structure (it is also called a specific side chain structure) shown by following formula [3] is contained in at least any one of the polymer of (A) component and (B) component.

（式［２］中、Ｙ^１およびＹ^７はそれぞれ独立して、単結合、炭素数１〜１０のアルキレン基、−Ｏ−、−Ｎ（Ｒ^１）−（Ｒ^１は水素原子または炭素数１〜３のアルキレン基を示す）、−ＣＯＮ（Ｒ^２）−（Ｒ^２は水素原子または炭素数１〜３のアルキレン基を示す）、−Ｎ（Ｒ^３）ＣＯ−（Ｒ^３は水素原子または炭素数１〜３のアルキレン基を示す）、−ＣＨ_２Ｏ−、−ＣＯＯ−および−ＯＣＯ−から選ばれる少なくとも１種の有機基を示し、Ｙ^２およびＹ^６はそれぞれ独立して、炭素数１〜１０のアルキレン基を示し、Ｙ^３およびＹ^５はそれぞれ独立して、水素原子または炭素数１〜１０のアルキレン基を示し、Ｙ^４は酸素原子または硫黄原子を示す）。

(In formula [2], Y ¹ and Y ⁷ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R ¹ )-(R ¹ is a hydrogen atom or carbon number 1 to 3 represents an alkylene group), -CON (R ² )-(wherein R ² represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), -N (R ³ ) CO- (R ³ represents a hydrogen atom) Or an alkylene group of 1 to 3 carbon atoms), at least one organic group selected from -CH ₂ O-, -COO- and -OCO-, and Y ² and Y ⁶ are each independently carbon And each of Y ³ and Y ⁵ independently represents a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, and Y ⁴ represents an oxygen atom or a sulfur atom).

（式［３］中、Ｂ^１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−または−ＯＣＯ−を示し、Ｂ^２は単結合または−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を示し、Ｂ^３は単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−または−ＯＣＯ−を示し、Ｂ^４はベンゼン環、シクロヘキサン環または複素環から選ばれる２価の環状基、またはステロイド骨格を有する炭素数１７〜５１の２価の有機基を示し、前記環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、Ｂ^５はベンゼン環、シクロヘキサン環または複素環から選ばれる２価の環状基を示し、これらの環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、ｎは０〜４の整数を示し、Ｂ^６は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基または炭素数１〜１８のフッ素含有アルコキシル基を示す）。

(In formula [3], B ¹ is a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- B ² represents a single bond or-(CH ₂ ) _b- (b is an integer of 1 to 15), B ³ represents a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15) ), —O—, —CH ₂ O—, —COO— or —OCO—, and B ⁴ is a carbon having a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a steroid skeleton And an arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or a fluorine containing 1 to 3 carbon atoms. It may be substituted by an alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. , B ⁵ represents a divalent cyclic group selected from benzene ring, cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, 1 to 3 carbon atoms It may be substituted by an alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4, and B ⁶ represents a carbon number 1-18 alkyl group, C1-C18 fluorine-containing alkyl group, C1-C18 alkoxyl group, or C1-C18 fluorine-containing alkoxyl group is shown).

  In the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention, the reason why the problems of the present invention are solved is not necessarily clear, but is considered to be substantially as follows.

  That is, the specific side chain structure represented by the formula [3] contained in at least one of the specific polymer (A) and the specific polymer (B) of the present invention has a benzene ring and a cyclohexyl ring at the side chain site. Or a heterocyclic ring or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton. The side chain structure of the ring and the organic group exhibits a rigid structure as compared with the side chain structure of a long chain alkyl group which is a prior art for aligning liquid crystals vertically. As a result, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent having the specific side chain structure of the present invention has higher and stable vertical alignment of the liquid crystal compared to the conventional long chain alkyl side chain structure. You can get it.

  In addition, the specific side chain structure of the present invention is more stable to light such as ultraviolet light as compared with the side chain structure of a conventional long chain alkyl group. Therefore, the specific side chain structure of the present invention can lower the voltage holding ratio and suppress the decomposition product of the side chain component that causes the residual charge to be accumulated by the direct current voltage, even when exposed to light irradiation for a long time .

  Furthermore, the interaction between the nitrogen atom in the structure containing the nitrogen atom contained in the specific polymer (A) of the present invention and the carboxyl group (COOH group) in the specific polymer (B), and the specific polymer ( It is considered that charge transfer occurs between the nitrogen atom in the above-mentioned formula [2] in B) and the carboxyl group in the specific polymer (A). Along with that, the accumulated residual charge can be efficiently transferred between molecules of the polymer. That is, it is considered that the release of the residual charge due to the DC voltage can be promoted.

  In addition, it is considered that the structure having a nitrogen atom in the specific polymer (A) of the present invention can trap an ionic impurity component which is a factor to reduce the voltage holding ratio. That is, the liquid crystal display element can trap ionic impurities generated by being exposed to light irradiation for a long time, and the decrease in the voltage holding ratio can be suppressed accordingly.

  From the above points, the liquid crystal aligning agent containing two kinds of at least one polymer selected from the polyimide precursor or the polyimide having the specific structure of the present invention is exposed to high temperature and light irradiation for a long time, A liquid crystal alignment film capable of expressing a stable pretilt angle can be obtained. In addition, even after exposure to light irradiation for a long time, the liquid crystal alignment film can suppress the decrease in the voltage holding ratio and quickly reduce the residual charge accumulated by the direct current voltage.

<Structure with nitrogen atom>
The specific polymer (A) of the present invention is a polymer containing at least one selected from a polyimide precursor and a polyimide having a structure containing a nitrogen atom.

  Specific examples of the structure containing a nitrogen atom include structures represented by the following formulas [1a] to [1c].

In formula [1a], X ¹ represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring.

In formula [1a], X ² represents a hydrogen atom or a disubstituted amino group substituted with a C 1-12 aliphatic group.

In the formula [1a], when X ² is a hydrogen atom, X ¹ represents a nitrogen-containing aromatic heterocyclic ring, and X ² is a disubstituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms And X ¹ represents a benzene ring.

In formula [1b], X ³ and X ⁷ each independently represent an aromatic group having 6 to 15 carbon atoms and one or two benzene rings.

In formula [1b], X ⁴ and X ⁶ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

Wherein [1b], ^{X 5} represents an alkylene group or a biphenyl group having 2 to 5 carbon atoms.

  In formula [1b], m is an integer of 0 or 1.

In Formula [1c], X ⁸ and X ¹⁰ each independently represent at least one structure selected from the structures represented by Formula [1c-a] and Formula [1c-b] below.

In formula [1c], X ⁹ represents a C1-C5 alkylene group or a benzene ring.

<Specific structure (2)>
The specific polymer (B) of the present invention is a polymer containing at least one selected from a polyimide precursor having a specific structure represented by the following formula [2] and a polyimide.

In formula [2], Y ¹ and Y ⁷ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -S-, -N (R ¹ )-(R ¹ is a hydrogen atom) Or an alkylene group having 1 to 3 carbon atoms), -CON (R ² )-(R ² represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), -N (R ³ ) CO- (R ³ represents a hydrogen atom or an alkylene group having 1 to 3 carbon _{atoms), - CH 2 O -,} - COO- represents at least one organic group selected from and -OCO-. Among them, a single bond, -O-, -S-, -OCO- or -COO- is preferable. More preferable is a single bond, -O- or -S- from the viewpoint of liquid crystal alignment and film hardness of the liquid crystal alignment film.

Wherein [2], ^{Y 2} and ^{Y 6} independently represents an alkylene group having 1 to 10 carbon atoms. Especially, a C1-C3 alkylene group is preferable, and the structure may be either linear or branched. Specifically, from the point of liquid crystal alignment and film hardness of the liquid crystal alignment film, methylene group (-CH _2- ), ethylene group (-CH ₂ CH ₂ ) having a free rotation site and small steric hindrance. -), propylene (- _{(CH 2) 3} -) or an isopropyl group _{(-C (CH 2) 2 -} ) is preferred.

Wherein [2], ^{Y 3} and ^{Y 5} each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Especially, a hydrogen atom or a C1-C3 alkyl group is preferable. Particularly preferred is a hydrogen atom.

In formula [2], Y ⁴ represents an oxygen atom or a sulfur atom. Among them, oxygen atom is preferable from the viewpoint of film hardness of the liquid crystal alignment film.

<Specific side chain structure>
The specific side chain structure represented by the formula [3] contained in at least one of the specific polymer (A) and the specific polymer (B) of the present invention is a structure represented by the following formula [3] is there.

In formula [3], B ¹ represents a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- . Among them, from the viewpoint of availability of raw materials and easiness of synthesis, a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO -Is preferred. More preferred is a single _{bond, - (CH 2) a -} (a is an integer of 1 to _{10), - O -, - CH} 2 O- or -COO-.

Wherein [3], ^{B 2} is a single bond or - indicates a (b is an integer of _{1~15) - (CH 2) b} . Among them, a single bond or-(CH ₂ ) _b- (b is an integer of 1 to 10) is preferable.

In formula [3], B ³ represents a single bond,-(CH ₂ ) _c- (wherein c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- . Among them, a single bond,-(CH ₂ ) _c- (wherein c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable from the viewpoint of easiness of synthesis. More preferred is a single _{bond, - (CH 2) c -} (c is an integer of 1 to _{10), - O -, - CH} 2 O- or -COO-.

In formula [3], B ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted by an alkoxyl group of the number 1-3, a fluorine-containing alkyl group having a carbon number of 1-3, a fluorine-containing alkoxyl group having a carbon number of 1-3, or a fluorine atom. Further, B ⁴ may be a divalent organic group selected from organic groups 17-51 carbon atoms having a steroid skeleton. Among them, an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable from the viewpoint of easiness of synthesis.

In formula [3], B ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, carbon It may be substituted by an alkoxyl group of the number 1-3, a fluorine-containing alkyl group having a carbon number of 1-3, a fluorine-containing alkoxyl group having a carbon number of 1-3, or a fluorine atom. Among these, a benzene ring or a cyclohexane ring is preferable.

  In formula [3], n shows the integer of 0-4. Among them, 0 to 3 are preferable in terms of availability of raw materials and easiness of synthesis. 0 to 2 is more preferable.

In formula [3], B ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms . Among them, alkyl groups having 1 to 18 carbon atoms, fluorine-containing alkyl groups having 1 to 10 carbon atoms, alkoxyl groups having 1 to 18 carbon atoms or fluorine-containing alkoxyl groups having 1 to 10 carbon atoms are preferable. More preferably, it is a C1-C12 alkyl group or a C1-C12 alkoxyl group. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

Preferred combinations of B ^{1 to} B ⁶ and n in the formula [3] are listed in Tables 6 to 47 of pages 13 to 34 of International Publication WO 2011/132751 (published on 2011.10.27) (2 The same combination as -1)-(2-629) is mentioned. Although B ^{1 to} B ⁶ in the present invention are shown as Y ^{1 to} Y ⁶ in each table of International Publication Gazette, Y ^{1 to} Y ⁶ shall be read as B ^{1 to} B ⁶ . In addition, in (2-605) to (2-629) listed in each table of the international publication, an organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention has 12 to 12 carbon atoms having a steroid skeleton. Although indicated as 25 organic groups, an organic group having 12 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.

<Specific polymer (A) / specific polymer (B)>
The specific polymer (A) and the specific polymer (B) of the present invention are at least one polymer selected from a polyimide precursor and a polyimide (collectively referred to as a polyimide polymer). Among them, the polyimide-based polymer of the present invention is preferably a polyimide precursor or a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

  The polyimide precursor is a structure represented by the following formula [A].

（式［Ａ］中、Ｒ^１は４価の有機基であり、Ｒ^２は２価の有機基であり、Ａ^１およびＡ^２はそれぞれ独立して、水素原子または炭素数１〜５のアルキレン基を示し、Ａ^３およびＡ^４はそれぞれ独立して、水素原子、炭素数１〜５のアルキレン基またはアセチル基を示し、ｎは正の整数を示す）。

(In formula [A], R ¹ is a tetravalent organic group, R ² is a divalent organic group, and A ¹ and A ² are each independently a hydrogen atom or an alkylene having 1 to 5 carbon atoms And A ³ and A ⁴ each independently represent a hydrogen atom, an alkylene group having 1 to 5 carbon atoms, or an acetyl group, and n represents a positive integer).

  Examples of the diamine component include diamine compounds having two primary or secondary amino groups in the molecule.

  Further, examples of the tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and tetracarboxylic acid dialkyl ester dihalide compounds.

In order to obtain a polyamic acid in which A ¹ and A ² in the formula [A] are hydrogen atoms, a diamine compound having two primary or secondary amino groups in the molecule, a tetracarboxylic acid compound or a tetracarboxylic acid compound is preferable. It can be obtained by reacting with a carboxylic acid anhydride.

In order to obtain a polyamic acid alkyl ester in which A ¹ and A ² in the formula [A] are an alkylene group having 1 to 5 carbon atoms, the diamine compound, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or It can be obtained by reacting with a tetracarboxylic acid dialkyl ester dihalide compound. Further, the polyamic acid obtained by the method, it is also possible to introduce an alkylene group having 1 to 5 carbon atoms for A ¹ and A ² of the formula [A].

  The specific polymer (A) of the present invention is a polymer having a structure containing a nitrogen atom. Especially, it is preferable that it is a structure shown by said Formula [1a]-Formula [1c].

  Although there is no restriction | limiting in particular in the method to introduce | transduce the structure containing a nitrogen atom in a specific polymer (A), The diamine compound which has a structure shown by said Formula [1a]-Formula [1c] is used for a part of raw materials Is preferred.

  Specifically, it is preferable to use a diamine compound (also referred to as a specific diamine compound (1)) represented by the following formula [1-1].

In formula [1-1], X ^A represents an organic group having 5 to 50 carbon atoms having at least one structure selected from the structures represented by formulas [1a] to [1c].

In formula [1-1], A ¹ and A ² each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

  More specifically, it is preferable to use diamine compounds represented by the following formulas [1a-1] to [1c-1].

In formula [1a-1], X ¹ represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring.

In formula [1a-1], X ² represents a hydrogen atom or a disubstituted amino group substituted with a C 1-12 aliphatic group.

In the formula [1a-1], when X ² is a hydrogen atom, X ¹ represents a nitrogen-containing aromatic heterocyclic ring, and X ² is a di-substituted amino group substituted with an aliphatic group having 1 to 12 carbon atoms In the case, X ¹ represents a benzene ring.

In formula [1b-1], X ³ and X ⁷ each independently represent an aromatic group having 6 to 15 carbon atoms and one or two benzene rings.

In formula [1b-1], X ⁴ and X ⁶ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

Wherein [1b-1], ^{X 5} represents an alkylene group or a biphenyl group having 2 to 5 carbon atoms.

  M shows an integer of 0 or 1 in a formula [1 b-1].

In Formula [1c-1], X ⁸ and X ¹⁰ each independently represent at least one structure selected from the structures represented by Formula [1c-a] and Formula [1c-b] below.

In formula [1c-1], X ⁹ represents a C1-C5 alkylene group or a benzene ring.

  As a specific diamine compound of the specific diamine compound (1) of this invention, the diamine compound shown by following formula [1-1a]-a formula [1-4a] is mentioned.

R < ¹ > shows a hydrogen atom or a C1-C5 alkylene group in Formula [1-3a].

  In formula [1-4a], n shows the integer of 1-10.

In formulas [1-1a] to [1-4a], A ^{1 to} A ⁸ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

  Especially, it is preferable to use the diamine compound shown by said Formula [1-3a] or Formula [1-4a].

  The specific diamine compound (1) in the specific polymer (A) of the present invention is preferably 1 mol% to 95 mol% in 100 mol% of all diamine components. Especially, 5 mol%-95 mol% are preferable. More preferably, it is 20 mol% to 80 mol%.

  The specific diamine compound (1) of the present invention is the solubility of the specific polymer (A) of the present invention in the solvent, the coatability of the liquid crystal alignment treatment agent, the liquid crystal alignment in the liquid crystal alignment film, the voltage retention rate, Depending on the characteristics such as accumulated charge, one kind or a mixture of two or more kinds can also be used.

  The specific polymer (B) of the present invention is a polymer having a specific structure (2).

  Although there is no restriction | limiting in particular in the method to introduce | transduce the specific structure (2) of this invention in a specific polymer (B), It is preferable to use the diamine compound which has a specific structure (2) for a diamine component. It is particularly preferable to use a diamine compound having a structure represented by the formula [2].

  Specifically, it is preferable to use a diamine compound (also referred to as a specific diamine compound (2)) represented by the following formula [2-1].

Wherein [2-1], ^{Y A} represents an organic group having a structure represented by the formula [2].

In formula [2-1], A ¹ and A ² each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

  More specifically, it is preferable to use a diamine compound represented by the following formula [2a].

In formula [2a], Y ¹ and Y ⁷ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -S-, -N (R ¹ )-(R ¹ is a hydrogen atom) Or an alkylene group having 1 to 3 carbon atoms), -CON (R ² )-(R ² represents a hydrogen atom or an alkylene group having 1 to 3 carbon atoms), -N (R ³ ) CO- (R ³ represents a hydrogen atom or an alkylene group having 1 to 3 carbon _{atoms), - CH 2 O -,} - COO- represents at least one organic group selected from and -OCO-. Among them, a single bond, -O-, -S-, -OCO- or -COO- is preferable. More preferably, it is a single bond, -O- or -S-, which is as flexible as possible and has a small steric hindrance, in terms of liquid crystal alignment and film hardness.

Wherein [2a], ^{Y 2} and ^{Y 6} independently represents an alkylene group having 1 to 10 carbon atoms. Especially, a C1-C3 alkylene group is preferable, and the structure may be either linear or branched. Specifically, from the point of liquid crystal alignment and film hardness of the liquid crystal alignment film, methylene group (-CH _2- ), ethylene group (-CH ₂ CH ₂ ) having a free rotation site and small steric hindrance. -), propylene (- _{(CH 2) 3} -) or an isopropyl group _{(-C (CH 2) 2 -} ) is preferred.

In formula [2a], Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Especially, a hydrogen atom or a C1-C3 alkyl group is preferable. Particularly preferred is a hydrogen atom.

In formula [2a], Y ⁴ represents an oxygen atom or a sulfur atom. Among them, oxygen atom is preferable from the viewpoint of film hardness of the liquid crystal alignment film.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and Y ^{7 in} the formula [2a] are as shown in Table 1 below.

  Among them, a combination represented by the formula [2-1a], the formula [2-2a], the formula [2-4a], the formula [2-5a], the formula [2-7a] and the formula [2-8a] is preferable .

In formula [2a], A ¹ and A ² each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms.

  As a specific diamine compound of the specific diamine compound (2) of this invention, the diamine compound shown by following formula [2-1a]-a formula [2-3a] is mentioned.

（式［２−１ａ］〜式［２−３ａ］中、Ａ^１〜Ａ^６はそれぞれ独立して、水素原子または炭素数１〜５のアルキレン基を示す）。

(In Formula [2-1a] to Formula [2-3a], A ^{1 to} A ⁶ each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms).

  The specific diamine compound (2) in the specific polymer (B) of the present invention is preferably 1 mol% to 95 mol% in 100 mol% of all diamine components. Especially, 5 mol%-95 mol% are preferable. More preferably, it is 20 mol% to 80 mol%.

  The specific diamine compound (2) of the present invention is the solubility of the specific polymer (B) of the present invention in the solvent, the coatability of the liquid crystal alignment treatment agent, the liquid crystal alignment in the liquid crystal alignment film, the voltage retention rate, Depending on the characteristics such as accumulated charge, one kind or a mixture of two or more kinds can also be used.

  At least one of the specific polymer (A) and the specific polymer (B) of the present invention contains a specific side chain structure.

  The method for introducing the specific side chain structure of the present invention into the specific polymer (A) or the specific polymer (B) is not particularly limited, but it is preferable to use a diamine compound having a specific side chain structure for the diamine component .

  Specifically, it is preferable to use a diamine compound represented by the following formula [3a] (also referred to as a specific side chain type diamine compound).

In Formula [3a], B shows said Formula [3]. A preferable combination of ^B 1 .about.B ⁶ and n in the formula [3] are the same as described above.

In formula [3a], A ¹ and A ² each independently represent a hydrogen atom or an alkylene group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkylene group having 1 or 2 carbon atoms is preferable.

  In formula [3a], m represents an integer of 1 to 4. Among them, 1 is preferable.

  Specific examples of the specific side chain type diamine compound of the present invention include diamine compounds represented by the following formulas [3a-1] to [3a-31], and further, these amino groups are secondary amino groups. Some diamine compounds are mentioned.

（式［３ａ−１］〜式［３ａ−３］中、Ｒ^１、Ｒ^３およびＲ^５はそれぞれ独立して、−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−または−ＣＨ_２ＯＣＯ−を示し、式［３ａ−１］〜式［３ａ−３］中、Ｒ^２、Ｒ^４およびＲ^６はそれぞれ独立して、炭素数１〜２２の直鎖状または分岐状アルキレン基、炭素数１〜２２の直鎖状または分岐状アルコキシル基、炭素数１〜２２の直鎖状または分岐状フッ素含有アルキレン基またはフッ素含有アルコキシル基を示す）。

(In the formula [3a-1] to the formula [3a-3], R ¹ , R ³ and R ⁵ are each independently -O-, -OCH _2- , -CH ₂ O-, -COOCH ₂ -or -CH ₂ OCO-, and in the formulas [3a-1] to [3a-3], R ² , R ⁴ and R ⁶ are each independently a linear or branched alkylene having 1 to 22 carbon atoms And a group, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms, or a fluorine-containing alkoxyl group).

（式［３ａ−４］〜式［３ａ−６］中、Ｒ^１、Ｒ^３およびＲ^５はそれぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−または−ＣＨ_２−を示し、式［３ａ−４］〜式［３ａ−６］中、Ｒ^２、Ｒ^４およびＲ^６はそれぞれ独立して、炭素数１〜２２の直鎖状または分岐状アルキレン基、炭素数１〜２２の直鎖状または分岐状アルコキシル基、炭素数１〜２２の直鎖状または分岐状フッ素含有アルキレン基またはフッ素含有アルコキシル基を示す）。

(In the formulas [3a-4] to [3a-6], R ¹ , R ³ and R ⁵ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -COOCH _{2- , -CH 2 OCO -, - CH} 2 O -, - OCH 2 - or -CH ₂ - indicates, wherein [3a-4] ~ formula ^{[3a-6], R 2} , R 4 and ^{R 6} each Independently, a linear or branched alkylene group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms Or a fluorine-containing alkoxyl group is shown).

（式［３ａ−７］および式［３ａ−８］中、Ｒ^１およびＲ^３はそれぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２−、−Ｏ−または−ＮＨ−を示し、Ｒ^２およびＲ^４はそれぞれ独立して、フッ素基、シアノ基、トリフルオロメタン基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基または水酸基を示す）。

(In the formula [3a-7] and the formula [3a-8], R ¹ and R ³ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -COOCH _2- , -CH ₂ OCO-, -CH ₂ O-, -OCH _2- , -CH _2- , -O- or -NH-, and R ² and R ⁴ each independently represent a fluorine group, a cyano group or a trifluoromethane group , A nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group).

（式［３ａ−９］および式［３ａ−１０］中、Ｒ^１およびＲ^２はそれぞれ独立して、炭素数３〜１２の直鎖状または分岐状アルキレン基を示し、１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である）。

(In the formula [3a-9] and the formula [3a-10], R ¹ and R ² each independently represent a linear or branched alkylene group having 3 to 12 carbon atoms, 1,4-cyclohexylene (Cis-trans isomerism of (each is a trans isomer)).

（式［３ａ−１１］および式［３ａ−１２］中、Ｒ^１およびＲ^２はそれぞれ独立して、炭素数３〜１２の直鎖状または分岐状アルキレン基を示し、１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である）。

(In the formula [3a-11] and the formula [3a-12], R ¹ and R ² each independently represent a linear or branched alkylene group having 3 to 12 carbon atoms, 1,4-cyclohexylene (Cis-trans isomerism of (each is a trans isomer)).

（式［１ａ−１３］中、Ａ_４はフッ素原子で置換されていてもよい炭素数３〜２０の直鎖状または分岐状アルキル基であり、Ａ_３は１，４−シクロへキシレン基または１，４−フェニレン基であり、Ａ_２は酸素原子または−ＣＯＯ−＊（ただし、「＊」を付した結合手がＡ_３と結合する）であり、Ａ_１は酸素原子または−ＣＯＯ−＊（ただし、「＊」を付した結合手が（ＣＨ_２）ａ_２）と結合する）である。また、ａ_１は０または１の整数であり、ａ_２は２〜１０の整数であり、ａ_３は０または１の整数である）。

(In the formula [1a-13], A ₄ represents a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ represents a 1,4-cyclohexylene group or It is a 1,4-phenylene group, A ₂ is an oxygen atom or -COO- * (however, a bond with "*" is bonded to A ₃ ), A ₁ is an oxygen atom or -COO- * (However, the bond with “*” is bonded to (CH ₂ ) a ₂ ). Also, _{a 1} is an integer of 0 or 1, _{a 2} is an integer of 2 to 10, _{a 3} is an integer of 0 or 1).

  In the above formulas [3a-1] to [3a-31], the diamine compound having a particularly preferable structure is represented by formulas [3a-1] to [3a-6] and formulas [3a-9] to [3a-13]. Or Formula [3a-22]-Formula [3a-31].

  The specified side chain type diamine compound of the present invention may be used for at least one of the specified polymer (A) and the specified polymer (B), or may be used for both specified polymers. Especially, it is preferable to use for a specific polymer (A).

  It is preferable that the specific side chain type diamine compound in the specific polymer (A) and / or the specific polymer (B) of this invention is 10 to 80 mol% of the whole diamine component. Particularly preferred is 10 mol% or more and 70 mol% or less.

  The specific side chain type diamine compound of the present invention is the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in the solvent, the coating property of the liquid crystal alignment treatment agent, and the liquid crystal in the liquid crystal alignment film. Depending on the properties such as the orientation, the voltage holding ratio, and the accumulated charge, it is possible to use one kind or a mixture of two or more kinds.

  As the diamine component of the specific polymer (A) and the specific polymer (B) of the present invention, as long as the effects of the present invention are not impaired, the specific diamine compound (1), the specific diamine compound (2) and the specific side chain type Other diamine compounds (also referred to as other diamine compounds) other than the diamine compound can also be used.

  Specifically, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4, 4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamino Biphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3 4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 3,4'-diaminodiphenylether, 2,2 ' -Diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl- Bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4′-thiodianiline, 3,3′-thiodianiline, 4,4′-diaminodiphenylamine, 3,3′-diaminodiphenylamine, 3,4'-Diaminodipheny Amine, 2,2′-diaminodiphenylamine, 2,3′-diaminodiphenylamine, N-methyl (4,4′-diaminodiphenyl) amine, N-methyl (3,3′-diaminodiphenyl) amine, N-methyl ( 3,4'-Diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3 ' -Diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene , 7-Diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, Bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-amino) Phenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4′- 1,4-phenylenebis (methylene)] dianiline, 4,4 ′-[1,3-phenylenebis (methylene)] dianiline, 3,4 ′-[1,4-phenylenebis (methylene)] dianiline, 3, 4 '-[1,3-phenylenebis (methylene)] dianiline, 3,3'-[1,4-phenylenebis (methylene)] dianiline, 3,3 '-[1,3-phenylenebis (methylene)] Dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-amino 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4) -Aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N '-(1,4-phenylene) bis (4-aminobenzamido), N, N'-(1,3-phenylene) bis (4-aminobenzamido), N, N '-(1,4-phenylene) bis (3-aminobenzamido), N, N'-(1,3-phenylene) bis (3-aminobenzamido), N, N '-Bis (4-aminophenyl) terephthalamide, N, N'-bis (3-aminophenyl) terephthalamide, N, N'-bis (4- Aminophenyl) isophthalamide, N, N′-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4′-bis (4-aminophenoxy) diphenyl sulfone, 2 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) ) Hexafluoropropane, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4- (4) Aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) ) Propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3- (3) Aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8 -Bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-amino) Phenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) Dodecane, 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane or 1 , 12-diaminododecane and diamine compounds in which these amino groups are secondary amino groups are listed. Be

  Furthermore, a diamine compound having a carboxyl group (COOH group) or a hydroxyl group (OH group) can also be used in the diamine compound.

  Specifically, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, Mention may be made of 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid. Among them, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid is preferable. Moreover, the diamine compound shown by following formula [3 b-1]-formula [3 b-4] and the diamine compound whose these amino groups are secondary amino groups can also be used.

（式［３ｂ−１］中、Ａ^１は単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−または−Ｎ（ＣＨ_３）ＣＯ−を示し、ｍ^１およびｍ^２はそれぞれ独立して、０〜４の整数を示し、かつｍ^１＋ｍ^２は１〜４の整数を示し、式［３ｂ−２］中、ｍ^３およびｍ^４はそれぞれ独立して、１〜５の整数を示し、式［３ｂ−３］中、Ａ^２は炭素数１〜５の直鎖または分岐アルキレン基を示し、ｍ^５は１〜５の整数を示し、式［３ｂ−４］中、Ａ^３およびＡ^４はそれぞれ独立して、単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）_２−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−または−Ｎ（ＣＨ_３）ＣＯ−を示し、ｍ^６は１〜４の整数を示す）。

(Wherein ^{[3b-1], A} 1 is a single _{bond, -CH 2 -, - C 2} H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, _{-O -, - CO -, -} NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON ( CH ₃ ) — or —N (CH ₃ ) CO—, m ¹ and m ² each independently represent an integer of 0 to 4 and m ¹ + m ² represents an integer of 1 to 4, In [3b-2], m ³ and m ⁴ each independently represent an integer of 1 to 5, and in the formula [3b-3], A ² represents a linear or branched alkylene group having 1 to 5 carbon atoms. indicates, ^{m 5} represents an integer of 1 to 5, wherein [3b-4], ^{a 3} and ^{a 4} are each independently a single _{bond, -CH 2 -, - C 2} H 4 - _{-C (CH 3) 2 -,} - CF 2 -, - C (CF 3) 2 -, - O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO- _{, -CH 2 O -, - OCH} 2 -, - COO -, - OCO -, - CON (CH 3) - or -N _(CH 3) CO- indicates, ^{m 6} is an integer of 1 to 4) .

  In addition, diamine compounds having a nitrogen-containing heterocycle represented by the following formula [3c] and diamine compounds in which these amino groups are secondary amino groups can also be used in the diamine compound.

In the formula [3c], D ¹ represents -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )- or -N _(CH 3) shows a CO-. Among them, -O -, - NH -, - CONH -, - NHCO -, - CH 2 O -, - OCO -, - CON (CH 3) - or -N _(CH 3) CO- is a diamine compound It is preferable because it is easy to synthesize. More preferred, -O -, - NH -, - CONH -, - NHCO -, - CH 2 O -, - OCO- or -CON (CH ₃₎ - is. Particularly preferred is, -O -, - CONH- or _-CH 2 is O-.

In formula [3c], D ² represents a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a nonaromatic cyclic hydrocarbon group or an aromatic hydrocarbon group.

  The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have a unsaturated bond. Especially, a C1-C10 alkylene group is preferable.

  Specific examples of the nonaromatic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotrino ring. Decane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecane ring, bicycloheptane ring, decahydronaphthalene ring And norbornene ring or adamantane ring. Among them, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring is preferable.

  Specific examples of the aromatic hydrocarbon group include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring or phenalene ring. Among them, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring is preferable.

As preferable D ² in the formula [3c], a single bond, an alkylene group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, It is a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring. Among them, a single bond, an alkylene group of 1 to 5 carbon atoms, a cyclohexane ring or a benzene ring is preferable.

In formula [3c], D ³ is a single bond, -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ ) - or _{-N (CH 3) CO -,} - O (CH 2) m - show the (m is an integer of 1 to 5). Among them, a single bond, -O -, - COO -, - OCO- or _{-O (CH 2) m - (} m is an integer of 1 to 5) is preferred. More preferred is a single bond, -O -, - OCO- or -O _{(CH 2)} m - is (m is an integer of 1 to 5).

In the formula [3c], D ⁴ is a nitrogen-containing aromatic heterocycle, which is an aromatic heterocycle containing at least one structure selected from the following formula [a], formula [b] and formula [c] is there.

（式［ｃ］中、Ｚは炭素数１〜５のアルキレン基を示す）。

(In formula [c], Z shows a C1-C5 alkylene group).

  More specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring , Triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, chinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring or acridine ring etc. be able to. Among them, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring or a benzimidazole ring is preferable. More preferred is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring.

Moreover, D ³ in the formula [3c] can expressions included in the D ⁴ [a], is preferably bonded with a substituent nonadjacent the formula [b] and the formula [c].

  In the formula [3c], n is an integer of 1 to 4, and preferably 1 or 2 from the viewpoint of the reactivity with the tetracarboxylic acid component.

A particularly preferable combination of D ^{1 to} D ⁴ and n in the formula [3c] is that D ¹ represents -CONH-, D ² represents an alkyl group having 1 to 5 carbon atoms, D ³ represents a single bond, D It is a diamine compound in which ⁴ represents an imidazole ring or a pyridine ring and n represents 1.

The bonding position of the two amino groups (—NH ₂ ) in the formula [3c] is not limited. Specifically, with respect to the side-chain linking group (B ¹ ), the 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions on the benzene ring Position or position of 3, 5 can be mentioned. Among them, from the viewpoint of reactivity when synthesizing a polyamic acid, the positions of 2, 4, 2, 5 or 3, 5 are preferable. The positions of 2, 4 or 2, 5 are more preferable in consideration of the ease of synthesis of the diamine compound.

  Furthermore, as other diamine compounds, diamine compounds represented by the following formulas [3d-1] to [3d-13] and diamine compounds in which these amino groups are secondary amino groups can also be used.

（式［３ｄ−１］〜式［３ｄ−４］中、Ａ^１〜Ａ^４はそれぞれ独立して、炭素数１〜２２のアルキレン基またはフッ素含有アルキレン基を示す）。

(In Formula [3d-1] to Formula [3d-4], A ^{1 to} A ⁴ each independently represent an alkylene group having 1 to 22 carbon atoms or a fluorine-containing alkylene group).

（式［３ｄ−５］中、Ａ^１およびＡ^３はそれぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−または−ＮＨ−を示し、Ａ^２は炭素数１〜２２の直鎖状もしくは分岐状のアルキレン基または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキレン基を示し、式［３ｄ−６］中、Ａ^４およびＡ^６はそれぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−または−ＮＨ−を示し、Ａ^５は炭素数１〜２２の直鎖状もしくは分岐状のアルキレン基または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキレン基を示す）。

(In the formula [3d-5], A ¹ and A ³ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO- or- NH ^2- represents A-, and A ² represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms, represented by the formula [3d-6] Among them, A ⁴ and A ⁶ each independently represent —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or —NH—, and A ⁵ Represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms).

（式［３ｄ−７］中、Ａ^１およびＡ^３はそれぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−または−ＮＨ−を示し、Ａ^２は炭素数１〜２２の直鎖状もしくは分岐状のアルキレン基または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキレン基を示し、式［３ｄ−８］中、Ａ^４およびＡ^６はそれぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−または−ＮＨ−を示し、Ａ^５は炭素数１〜２２の直鎖状もしくは分岐状のアルキレン基または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキレン基を示す）。

(In the formula [3d-7], A ¹ and A ³ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO- or- NH ^2- represents A-, and A ² represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms, represented by the formula [3d-8] Among them, A ⁴ and A ⁶ each independently represent —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or —NH—, and A ⁵ Represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms).

（式［３ｄ−９］中、Ａ^１およびＡ^３はそれぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−または−ＮＨ−を示し、Ａ^２は炭素数１〜２２の直鎖状もしくは分岐状のアルキレン基または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキレン基を示し、式［３ｄ−１０］中、Ａ^４およびＡ^６はそれぞれ独立して、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−または−ＮＨ−を示し、Ａ^５は炭素数１〜２２の直鎖状もしくは分岐状のアルキレン基または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキレン基を示す）。

(In the formula [3d-9], A ¹ and A ³ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO- or- A — ² represents NH—, and A ² represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms, and the formula [3d-10] Among them, A ⁴ and A ⁶ each independently represent —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or —NH—, and A ⁵ Represents a linear or branched alkylene group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkylene group having 1 to 22 carbon atoms).

（式［３ｄ−１１］中、ｐは１〜１０の整数を示す）。

(In the formula [3d-11], p represents an integer of 1 to 10).

  The other diamine compounds of the present invention are the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in the solvent, the coatability of the liquid crystal alignment treatment agent, the liquid crystal alignment in the liquid crystal alignment film, Depending on the characteristics such as the voltage holding ratio and the accumulated charge, one type or two or more types may be mixed and used.

  The specific polymer (A) and the specific polymer (B) of the present invention, that is, tetracarboxylic acid components for producing these polyimide polymers are tetracarboxylic acid dianhydrides represented by the following formula [4] It is preferable to use a product. At that time, not only the tetracarboxylic acid dianhydride represented by the formula [4] but also the tetracarboxylic acid derivative thereof tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid dialkyl ester di A halide compound can also be used (tetracarboxylic acid dianhydride represented by the formula [4] and derivatives thereof are generically referred to as a specific tetracarboxylic acid component).

（式［４］中、Ｚは下記の式［４ａ］〜式［４ｋ］で示される構造から選ばれる少なくとも１種の構造を示す）。

(In Formula [4], Z shows at least 1 type of structure chosen from the structure shown by following formula [4a]-Formula [4k]).

Wherein [4a], Z ¹ ~Z ⁴ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, or may be different from one another respectively the same.

Wherein [4g], Z ⁵ and Z ⁶ represents a hydrogen atom or a methyl group, may or may not be respectively identical.

  Among Z in the formula [4], in view of easiness of synthesis and easiness of polymerization reactivity when producing a polymer, the formula [4a], the formula [4c] to the formula [4g] or the formula [4k The tetracarboxylic acid dianhydride of the structure shown by these] and its tetracarboxylic acid derivative are preferable. More preferred are those having a structure represented by formula [4a] or formula [4e] to formula [4g]. Particularly preferred are tetracarboxylic acid dianhydrides having a structure represented by [4a], formula [4e] or formula [4f] and tetracarboxylic acid derivatives thereof.

  The specific tetracarboxylic acid component in the specific polymer (A) and the specific polymer (B) of the present invention is preferably 1 mol% to 100 mol% in 100 mol% of all tetracarboxylic acid components. Especially, 5 mol%-95 mol% are preferable. More preferably, it is 20 mol% to 80 mol%.

  The specific tetracarboxylic acid component of the present invention is the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in the solvent, the coating property of the liquid crystal alignment treatment agent, the liquid crystal alignment film Depending on the properties such as orientation, voltage holding ratio, and accumulated charge, one or more types may be mixed and used.

  In the polyimide polymer of the specific polymer (A) and the specific polymer (B) of the present invention, other tetracarboxylic acid components other than the specific tetracarboxylic acid component may be used as long as the effects of the present invention are not impaired. You can also.

  Other tetracarboxylic acid components include tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds or tetracarboxylic acid dialkyl ester dihalide compounds shown below.

  That is, as other tetracarboxylic acid components, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4' Benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1, 1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, biphenyl (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4' -Diphenyl sulfone tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid.

  The other tetracarboxylic acid component of the present invention is the solubility of the specific polymer (A) and the specific polymer (B) of the present invention in the solvent, the coating property of the liquid crystal alignment treatment agent, and the liquid crystal in the liquid crystal alignment film. Depending on the properties such as orientation, voltage holding ratio, and accumulated charge, one or more types may be mixed and used.

<Method for producing specific polymer (A) / specific polymer (B)>
In the present invention, the specific polymer (A) and the specific polymer (B), that is, methods for producing these polyimide polymers are not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acid dianhydride and its derivative is reacted with a diamine component consisting of one or more diamine compounds. And a method of obtaining a polyamic acid. Specifically, a method of polycondensing a tetracarboxylic acid dianhydride with a primary or secondary diamine compound to obtain a polyamic acid, a dehydration polycondensation reaction between a tetracarboxylic acid and a primary or secondary diamine compound A method of obtaining a polyamic acid or a method of polycondensing a tetracarboxylic acid dihalide and a primary or secondary diamine compound to obtain a polyamic acid is used.

  In order to obtain a polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid in which a carboxylic acid group is dialkylesterified and a primary or secondary diamine compound, a tetracarboxylic acid dihalide in which a carboxylic acid group is dialkylesterified, and A method of polycondensation with a primary or secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester is used.

  In order to obtain a polyimide, the method of ring-closing the above-mentioned polyamic acid or polyamic acid alkyl ester to make a polyimide is used.

  The reaction of the diamine component with the tetracarboxylic acid component is usually carried out in a solvent with the diamine component and the tetracarboxylic acid component. It will not specifically limit, if the produced | generated polyimide precursor melt | dissolves as a solvent used in that case. Although the specific example of the solvent used for reaction is given to the following, it is not limited to these examples.

  For example, mention may be made of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone. Be When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D-1] to formula [D-3] The indicated solvents can be used.

（式［Ｄ−１］中、Ｄ^１は炭素数１〜３のアルキレン基を示し、式［Ｄ−２］中、Ｄ^２は炭素数１〜３のアルキレン基を示し、式［Ｄ−３］中、Ｄ^３は炭素数１〜４のアルキレン基を示す）。

(In the formula [D-1], D ¹ represents an alkylene group of 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkylene group of 1 to 3 carbon atoms; In the above, D ³ represents a C 1-4 alkylene group).

  These solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, it may be used by mixing with the above-mentioned solvent in the range which the generated polyimide precursor does not precipitate. Further, since water in the solvent inhibits the polymerization reaction and causes hydrolysis of the formed polyimide precursor, it is preferable to use the solvent which has been dehydrated and dried.

  When the diamine component and the tetracarboxylic acid component are reacted in a solvent, a solution in which the diamine component is dispersed or dissolved in the solvent is stirred, and the tetracarboxylic acid component is added as it is or dispersed in the solvent. On the contrary, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in a solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, and the like can be mentioned. May be used. Moreover, when making it react using two or more types of diamine components or tetracarboxylic acid components, respectively, you may make it react in the state mixed beforehand, you may make it react separately separately, and the low molecular weight product made to react further separately May be mixed and reacted as a polymer. Although the polymerization temperature in that case can select any temperature of -20 degreeC-150 degreeC, Preferably it is the range of -5 degreeC-100 degreeC. The reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a polymer of high molecular weight, if the concentration is too high the viscosity of the reaction solution will be too high and uniform stirring will be difficult It becomes. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction may be performed at high concentration, and then solvent may be added.

  In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the formed polyimide precursor increases as the molar ratio approaches 1.0.

  The polyimide of the present invention is a polyimide obtained by ring-closing the above-mentioned polyimide precursor, and in this polyimide, the ring-closing rate (also referred to as imidization rate) of the amic acid group does not necessarily have to be 100%. It can be adjusted arbitrarily according to the purpose.

  Examples of the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, or catalyst imidization in which the catalyst is added to the solution of the polyimide precursor.

  The temperature for thermally imidizing the polyimide precursor in a solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidization reaction out of the system.

  Catalytic imidization of the polyimide precursor may be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 ° C to 250 ° C, preferably at 0 ° C to 180 ° C. it can. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic acid group, and the amount of the acid anhydride is 1 to 50 moles of the amic acid group. Preferably, it is 3 molar times to 30 molar times. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferable because it has a suitable basicity to allow the reaction to proceed. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned. Among them, acetic anhydride is preferable because it facilitates purification after completion of the reaction. The imidation ratio by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

  When the produced polyimide precursor or polyimide is recovered from the reaction solution of polyimide precursor or polyimide, the reaction solution may be introduced into a solvent and precipitated. As a solvent used for precipitation, methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like can be mentioned. The polymer precipitated by charging in a solvent may be recovered by filtration and then dried at normal temperature or under heating under normal pressure or reduced pressure. In addition, when the precipitated and recovered polymer is redissolved in a solvent and the operation of reprecipitating and recovering is repeated twice to ten times, impurities in the polymer can be reduced. As the solvent in this case, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and it is preferable to use three or more solvents selected from these, because the efficiency of purification is further improved.

<Liquid crystal aligning agent>
The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and a liquid crystal alignment film containing a specific polymer (A), a specific polymer (B) and a solvent. It is a coating solution for forming.

  As the specific polymer (A) of the present invention, any polyimide polymer of polyamic acid, polyamic acid alkyl ester and polyimide may be used. Among them, polyamic acid alkyl ester or polyimide is preferable. More preferably, it is a polyimide.

  As the specific polymer (B) of the present invention, any polyimide polymer of polyamic acid, polyamic acid alkyl ester and polyimide may be used. Among them, polyamic acid or polyamic acid alkyl ester is preferable. More preferably, it is a polyamic acid.

  The ratio of the specific polymer (A) to the specific polymer (B) in the liquid crystal alignment treatment agent of the present invention is 0.5 mass of the specific polymer (B) with respect to 100 parts by mass of the specific polymer (A) It is preferably part to 950 parts by mass. Among them, 10 parts by mass to 900 parts by mass are preferable, and 10 parts by mass to 400 parts by mass are more preferable.

  All polymer components in the liquid crystal alignment treatment agent of the present invention may be all the specific polymer (A) and the specific polymer (B) of the present invention, and other polymers are mixed. It is good. As a polymer of other than that, the polyimide polymer which does not have a structure which has a tertiary nitrogen atom of this invention, and the polyimide polymer which does not have a specific structure (2) are mentioned. Furthermore, cellulose polymers, acrylic polymers, methacrylic polymers, polystyrenes, polyamides or polysiloxanes may also be mentioned. At that time, the content of other polymers other than that is 0.5 parts by mass with respect to 100 parts by mass of the specific polymer of the specific polymer (A) and the specific polymer (B) of the present invention. 30 parts by mass. Especially, 1 mass part-20 mass parts are preferred.

  Moreover, it is preferable that content of the solvent in the liquid-crystal aligning agent of this invention is 70 mass%-99.9 mass%. This content can be suitably changed with the coating method of a liquid-crystal aligning agent, and the film thickness of the liquid crystal aligning film made into the objective.

  The solvent used for the liquid-crystal aligning agent of this invention will not be specifically limited if it is a solvent (it is also called a good solvent) in which a specific polymer (A) and a specific polymer (B) are dissolved. Specific examples of the good solvent are listed below, but are not limited to these examples.

  For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone And cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone and the like.

  Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone are preferably used.

  Furthermore, when the solubility to the solvent of specific polymer (A) and specific polymer (B) is high, it is preferable to use the solvent shown by said Formula [D-1]-Formula [D-3].

  It is preferable that the good solvent in the liquid-crystal aligning agent of this invention is 20 mass%-99 mass% of the whole solvent contained in a liquid-crystal aligning agent. Among these, 20% by mass to 90% by mass is preferable. More preferably, it is 30% by mass to 80% by mass.

  The liquid crystal alignment treatment agent of the present invention uses a solvent (also referred to as a poor solvent) that improves the coating property and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied, as long as the effects of the present invention are not impaired. be able to. Specific examples of the poor solvent are listed below, but the present invention is not limited to these examples.

  For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol , 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Ethanedi 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentane Diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2 Heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methyl pentyl acetate, 2-ethyl butyl acetate, 2-ethyl hexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate 2- (methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (Butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate Tart, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, milk Methyl, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropion Ethyl acid, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid The isoamyl ester or the solvent represented by the formula [D-1] to the formula [D-3] can be exemplified.

  Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether or dipropylene glycol dimethyl ether is preferably used.

  It is preferable that these poor solvents are 1 mass%-80 mass% of the whole solvent contained in a liquid-crystal aligning agent. Among these, 10% by mass to 80% by mass is preferable. More preferably, it is 20% by mass to 70% by mass.

  The liquid crystal alignment treatment agent of the present invention has at least one substituent selected from a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group. It is preferable to introduce a crosslinkable compound or a crosslinkable compound having a polymerizable unsaturated bond. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.

  As a crosslinkable compound which has an epoxy group or an isocyanate group, for example, bisphenolacetone glycidyl ether, phenol novolak epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidyl amino diphenylene, tetraglycidyl-m-xylene diamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-aminophenol, tetraglycidyl metaxylene diamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxy) Propoxy) phenyl) ethyl) phenyl) propane or 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3) -Epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

  The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4A].

  Specifically, crosslinkable compounds represented by Formula [4a] to Formula [4k], which are published on pages 58 to 59 of International Publication WO 2011/132751 (published on 2011.10.27), can be mentioned.

  The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A].

  Specifically, crosslinkable compounds represented by Formula [5-1] to Formula [5-42], listed on pages 76 to 82 of International Publication WO 2012/014898 (2012.2.2 published), are listed. Be

  Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include, for example, amino resins having a hydroxyl group or an alkoxyl group, such as melamine resin, urea resin, guanamine resin, glycoluril. -Formaldehyde resin, succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin etc. may be mentioned. Specifically, a melamine derivative, a benzoguanamine derivative or glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group or both can be used. The melamine derivative or benzoguanamine derivative can also exist as a dimer or trimer. Those having an average of 3 or more and 6 or less of methylol groups or alkoxymethyl groups per triazine ring are preferable.

  As an example of such a melamine derivative or benzoguanamine derivative, MX-750 in which an average of 3.7 methoxymethyl groups are substituted per commercially available triazine ring, and an average of 5. 5 methoxymethyl groups per one triazine ring are exemplified. 8 substituted MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.) or methoxylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236 Such as methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254, butoxymethylated melamine such as cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as cymel 1141, cymel 1123 Methoxymethylated Etoki Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as cymel 1123-10, butoxymethylated benzoguanamine such as cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as cymel 1125-80 (above, Mitsui Cyanamide Co., Ltd.). Examples of glycolurils include butoxymethylated glycolurils such as Cymel 1170, methylolated glycolurils such as Cymel 1172, and methoxy methylolated glycolurils such as Powderlink 1174.

  Examples of the benzene or phenolic compound having a hydroxyl group or alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis and sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.

  More specifically, the crosslinkable compound represented by the formula [6-1] to the formula [6-48], which is published on pages 62 to 66 of International Publication WO 2011/132751 (published on 2011.10.27) Can be mentioned.

  Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and tri (meth) acryloyloxyethoxytrimethylol. Crosslinkable compound having three polymerizable unsaturated groups in the molecule, such as propane or glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalate neo Crosslinkable compounds having two polymerizable unsaturated groups in the molecule, such as pentyl glycol di (meth) acrylate, in addition to 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro It has one polymerizable unsaturated group such as -2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphoric acid ester or N-methylol (meth) acrylamide in the molecule A crosslinkable compound etc. are mentioned.

  In addition, a compound represented by the following formula [7A] can also be used.

（式［７Ａ］中、Ｅ^１はシクロヘキサン環、ビシクロヘキサン環、ベンゼン環、ビフェニル環、ターフェニル環、ナフタレン環、フルオレン環、アントラセン環およびフェナントレン環から選ばれる少なくとも１種を示し、Ｅ^２は下記の式［７ａ］または式［７ｂ］から選ばれる基を示し、ｎは１〜４の整数を示す）。

(In the formula [7A], E ¹ represents at least one selected from a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring and a phenanthrene ring, and E ² represents The group selected from the following formula [7a] or formula [7b] is shown, and n is an integer of 1 to 4).

  The above compounds are examples of crosslinkable compounds and are not limited thereto. In addition, the crosslinkable compound used for the liquid crystal alignment treatment agent of the present invention may be one type or a combination of two or more types.

  The content of the crosslinkable compound in the liquid crystal alignment treatment agent of the present invention is preferably 0.1 parts by mass to 150 parts by mass with respect to 100 parts by mass of all the polymer components. Especially, in order to advance a crosslinking reaction and to express the target effect, 0.1 mass part-100 mass parts are preferable with respect to 100 mass parts of all the polymer components. More preferably, it is 1 part by mass to 50 parts by mass.

  As the liquid crystal alignment treatment agent of the present invention, a compound which improves the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used as long as the effects of the present invention are not impaired.

  As a compound which improves the uniformity of the film thickness of a liquid crystal aligning film, and surface smoothness, a fluorine-type surfactant, a silicone type surfactant, a nonion type surfactant etc. are mentioned.

  More specifically, for example, F-top EF301, EF303, EF352 (above, Tochem Products, Inc.), Megafac F171, F173, R-30 (above, Dainippon Ink Co., Ltd.), Florards FC430, FC431 (above, Sumitomo 3M Ltd., Asahi Guard AG 710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (all manufactured by Asahi Glass Co., Ltd.) and the like.

  The proportion of these surfactants used is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass, with respect to 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent. 1 part by mass.

  Furthermore, the liquid crystal alignment treatment agent of the present invention is a compound which promotes charge transfer in the liquid crystal alignment film to promote charge loss of the device. It is also possible to add nitrogen-containing heterocyclic amine compounds represented by the formulas [M1] to [M156], which are listed on p. Although this amine compound may be added directly to the liquid crystal alignment treatment agent, it is added after being made into a solution with a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass with a suitable solvent. Is preferred. It will not specifically limit, if it is a solvent in which the specific polymer (A) and the specific polymer (B) which were mentioned above are dissolved as this solvent.

  The liquid crystal alignment treatment agent of the present invention includes, in addition to the above-mentioned poor solvent, crosslinkable compound, compound for improving film thickness uniformity and surface smoothness of resin film or liquid crystal alignment film, and compound for promoting charge loss. As long as the effects of the present invention are not impaired, a dielectric or a conductive substance may be added for the purpose of changing the electric properties such as the dielectric constant and the conductivity of the liquid crystal alignment film.

<Liquid crystal alignment film / Liquid crystal display element>
The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment or light irradiation. Moreover, in the case of the vertical alignment application etc., it can be used as a liquid crystal aligning film, without an orientation process. The substrate used in this case is not particularly limited as long as it is a highly transparent substrate, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of process simplification, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed. In addition, in the reflection type liquid crystal display element, an opaque substrate such as a silicon wafer can be used if it is only on one substrate, and in this case, a material that reflects light such as aluminum can also be used as an electrode.

  The coating method of the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of performing by screen printing, offset printing, flexographic printing, an inkjet method, or the like is common. Other application methods include a dip method, a roll coater method, a slit coater method, a spinner method or a spray method, and these may be used according to the purpose.

  After the liquid crystal aligning agent is applied onto the substrate, it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal aligning agent, by a heating means such as a hot plate, a thermal circulation type oven or an IR (infrared) type oven. Can evaporate the solvent at a temperature of 30 to 250 ° C. to form a liquid crystal alignment film. If the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display device, and if it is too thin, the reliability of the liquid crystal display device may be lowered. Is 10 to 100 nm. When the liquid crystal is aligned horizontally or obliquely, the liquid crystal alignment film after firing is treated by rubbing or irradiation with polarized ultraviolet light.

  The liquid crystal display device of the present invention is a liquid crystal display device produced by obtaining a liquid crystal alignment film-provided substrate from the liquid crystal alignment treatment agent of the present invention by the method described above, and then producing a liquid crystal cell by a known method.

  A liquid crystal cell is prepared by preparing a pair of substrates on which a liquid crystal alignment film is formed, dispersing spacers on the liquid crystal alignment film on one of the substrates so that the liquid crystal alignment film surface is on the inside, For example, there is a method in which a substrate of the above is attached and sealed by injecting a liquid crystal under reduced pressure, or a method in which a substrate is attached and sealed after dropping liquid crystal on the liquid crystal alignment film surface to which spacers are dispersed.

  Furthermore, the liquid crystal alignment treatment agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound polymerized with at least one of active energy rays and heat between the pair of substrates. It is preferably used also for a liquid crystal display device produced by the step of disposing a liquid crystal composition to be contained, polymerizing a polymerizable compound by at least one of irradiation of active energy rays and heating while applying a voltage between electrodes. Here, ultraviolet rays are preferable as the active energy ray. The ultraviolet light has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Also, ultraviolet light and heating may be performed simultaneously.

  The liquid crystal display device described above controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in a liquid crystal material, and after assembling a liquid crystal cell, ultraviolet light is applied to the photopolymerizable compound in a state where a predetermined voltage is applied to the liquid crystal layer. The pretilt of liquid crystal molecules is controlled by the generated polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after removing the voltage, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. In addition, since the PSA method does not require rubbing treatment, it is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by rubbing treatment.

  That is, in the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, a liquid crystal cell is produced, and a polymerizable compound The orientation of liquid crystal molecules can be controlled by polymerizing.

  As an example of preparation of a liquid crystal cell of a PSA method, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers are dispersed on the liquid crystal alignment film of one substrate so that the liquid crystal alignment film surface is inside. And then seal the liquid crystal by dropping the liquid crystal onto the surface of the liquid crystal alignment film to which the spacer is dispersed, and sealing the liquid crystal. It can be mentioned.

  In the liquid crystal, a polymerizable compound which is polymerized by heat or ultraviolet irradiation is mixed. Examples of the polymerizable compound include compounds having one or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in the molecule. At that time, the content of the polymerizable compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component. When the amount of the polymerizable compound is less than 0.01 parts by mass, the alignment control of the liquid crystal can not be performed without polymerization of the polymerizable compound, and when the amount is more than 10 parts by mass, the amount of the unreacted polymerizable compound is increased. The burn-in characteristics of the

  After producing the liquid crystal cell, while applying an alternating current or direct current voltage to the liquid crystal cell, heat or ultraviolet light is irradiated to polymerize the polymerizable compound. Thereby, the alignment of liquid crystal molecules can be controlled.

  In addition, the liquid crystal alignment treatment agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and has a polymerizable property of polymerizing between the pair of substrates by at least one of active energy ray and heat. It is preferable to use a liquid crystal display device manufactured by disposing a liquid crystal alignment film containing a group and applying a voltage between the electrodes, that is, the SC-PVA mode. Here, ultraviolet rays are preferable as the active energy ray. The ultraviolet light has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Also, ultraviolet light and heating may be performed simultaneously.

  In order to obtain a liquid crystal alignment film containing a polymerizable group which is polymerized from at least one of an active energy ray and heat, a method of adding a compound containing this polymerizable group to a liquid crystal alignment treatment agent, a weight containing a polymerizable group The method of using a united ingredient is mentioned.

  As an example of preparation of a liquid crystal cell of SC-PVA mode, a pair of substrates on which the liquid crystal alignment film of the present invention is formed is prepared, and spacers are dispersed on the liquid crystal alignment film of one substrate. The other substrate is bonded so that the inner side is inside, and the liquid crystal is injected under reduced pressure for sealing, or the liquid crystal is dropped on the liquid crystal alignment film surface to which the spacer is dispersed, and then the substrate is bonded and sealed. And the like.

  After the liquid crystal cell is manufactured, the alignment of liquid crystal molecules can be controlled by irradiating heat or ultraviolet light while applying an alternating current or a direct current voltage to the liquid crystal cell.

  As described above, the liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film capable of exhibiting a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. In addition, even after exposure to light irradiation for a long time, the liquid crystal alignment film can suppress the decrease in the voltage holding ratio and quickly reduce the residual charge accumulated by the direct current voltage. Therefore, a liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be used as a large screen, high definition liquid crystal television, a small to medium car navigation system, a smartphone, etc. It can be suitably used.

  EXAMPLES The present invention will be described in more detail by way of the following examples, but the invention is not limited thereto.

"Abbreviations used in Synthesis Examples, Examples and Comparative Examples of the Invention"
Abbreviations used in Synthesis Examples, Examples and Comparative Examples are as follows.

<Monomer for Producing Polyimide Polymer of the Present Invention>
(Specific diamine compound (1) of the present invention)
A1: Diamine compound represented by the following formula [A1] A2: Diamine compound represented by the following formula [A2] A3: Diamine compound represented by the following formula [A3]

(Specific diamine compound (2) of the present invention)
B1: Diamine compound represented by the following formula [B1]

(Specific side chain type diamine compound of the present invention)
C1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene C2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclo) Hexyl) phenoxymethyl] benzene C3: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene C4: Diamine compound represented by C4]

(Other diamine compounds)
D1: p-phenylenediamine D2: 3,5-diaminobenzoic acid D3: 1,3-diamino-4-octadecyloxybenzene

(Specific tetracarboxylic acid component of the present invention)
E1: 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride E2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride E3: the following formula [E3 Tetracarboxylic acid dianhydride E4: tetracarboxylic acid dianhydride represented by the following formula [E4] E5: tetracarboxylic acid dianhydride represented by the following formula [E5]

"Crosslinkable compound used in the present invention"
K1: Crosslinkable compound represented by the following formula [K1]

<Solvent used in the present invention>
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone γ-BL: γ-butyrolactone BCS: ethylene glycol monobutyl ether PB: propylene glycol monobutyl ether EC: diethylene glycol monoethyl ether
DME: Dipropylene glycol dimethyl ether

"Measurement of molecular weight of polyimide polymer of the present invention"
The molecular weight of the polyimide precursor and the polyimide in the synthesis example was determined using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and a column (KD-803, KD-805) (manufactured by Shodex) It measured as follows.

Column temperature: 50 ° C
Eluent: N, N'-dimethylformamide (as additive, 30 mmol / L (liter) of lithium bromide-hydrate (LiBr.H ₂ O), 30 mmol of phosphoric acid / anhydrous crystal (o-phosphoric acid) / L, tetrahydrofuran (THF) 10 ml / L)
Flow rate: 1.0 ml / min Standard sample for preparation of calibration curve: TSK Standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000 and 30,000) (made by Tosoh Corporation) and polyethylene glycol (molecular weight: about) 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

"Measurement of imidation ratio of polyimide of the present invention"
The imidation ratio of the polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder is placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) The mixture (0.53 ml) was added and sonicated to dissolve completely. This solution was subjected to proton NMR measurement at 500 MHz with an NMR measurement device (JNW-ECA 500) (manufactured by Nippon Denshi Datum Co., Ltd.). The imidation ratio is determined using a proton derived from a structure that does not change before and after imidization as a reference proton, and a peak integrated value of this proton and a proton peak derived from the NH group of amic acid appearing around 9.5 ppm to 10.0 ppm It calculated | required by the following formula using integration value.

  Imidation ratio (%) = (1−α · x / y) × 100

  In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is one NH group proton of the amic acid in the case of polyamic acid (imidation ratio is 0%) The ratio of the number of reference protons to.

"Synthesis of the polyimide polymer of the present invention"
Synthesis Example 1
E1 (4.50 g, 23.0 mmol), A1 (1.85 g, 9.30 mmol), C1 (0.88 g, 2.32 mmol) and D1 (1.26 g, 11.6 mmol) in NMP (25.5 g) The mixture was mixed and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (1) having a resin solid concentration of 25% by mass. The number average molecular weight of this polyamic acid was 24,200, and the weight average molecular weight was 86,500.

Synthesis Example 2
E1 (4.10 g, 20.9 mmol), B1 (3.16 g, 10.6 mmol), D1 (0.46 g, 4.24 mmol) and D2 (0.97 g, 6.35 mmol) in NMP (26.1 g) The mixture was mixed and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (2) having a resin solid concentration of 25% by mass. The number average molecular weight of this polyamic acid was 25,200, and the weight average molecular weight was 89,100.

Synthesis Example 3
E2 (3.96 g, 15.8 mmol), A1 (1.91 g, 9.61 mmol), C1 (6.09 g, 16.0 mmol) and D2 (0.97 g, 6.41 mmol) with NEP (32.1 g) After mixing at room temperature and reacting at 80 ° C for 5 hours, E1 (3.10 g, 15.8 mmol) and NEP (16.0 g) are added and allowed to react at 40 ° C. for 6 hours, and the resin solid concentration is 25 mass % Polyamic acid solution (3) was obtained. The number average molecular weight of this polyamic acid was 20,100, and the weight average molecular weight was 64,100.

Synthesis Example 4
After adding NEP to the polyamic acid solution (3) (30.0 g) obtained by the synthesis procedure of Synthesis Example 3 and diluting to 6 mass%, acetic anhydride (3.45 g) and pyridine (2. 50 g) was added and allowed to react at 60 ° C. for 2 hours. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (4). The imidation ratio of this polyimide was 55%, the number average molecular weight was 18,500 and the weight average molecular weight was 49,300.

Synthesis Example 5
E2 (4.47 g, 17.9 mmol), B1 (3.24 g, 10.9 mmol), C1 (2.75 g, 7.23 mmol) and D2 (2.75 g, 18.1 mmol) with NEP (33.4 g) After mixing at room temperature and reacting at 80 ° C for 5 hours, E1 (3.50 g, 17.9 mmol) and NEP (16.7 g) are added and allowed to react at 40 ° C. for 6 hours, and the resin solid concentration is 25 mass % Polyamic acid solution (5) was obtained. The number average molecular weight of this polyamic acid was 22,100, and the weight average molecular weight was 68,500.

Synthesis Example 6
After adding NEP to the polyamic acid solution (5) (30.0 g) obtained by the synthesis procedure of Synthesis Example 5 and diluting to 6% by mass, acetic anhydride (3.40 g) and pyridine (2. 65 g) was added and reacted at 60 ° C. for 2 hours. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (6). The imidation ratio of this polyimide was 58%, the number average molecular weight was 19,800, and the weight average molecular weight was 52,900.

Synthesis Example 7
E2 (1.37 g, 5.46 mmol), A2 (1.18 g, 5.53 mmol), C2 (2.91 g, 7.38 mmol), D1 (0.20 g, 1.84 mmol) and D2 (0.56 g, 3.69 mmol) is mixed in NMP (17.4 g) and reacted at 80 ° C. for 5 hours, after which E1 (2.50 g, 12.8 mmol) and NMP (8.72 g) are added, and 6 ° C. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

  After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass%, acetic anhydride (4.45 g) and pyridine (3.30 g) are added as an imidation catalyst, and it is 3 hours at 80 ° C. It was made to react. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (7). The imidation ratio of this polyimide was 80%, the number average molecular weight was 17,100, and the weight average molecular weight was 47,800.

Synthesis Example 8
E2 (1.37 g, 5.46 mmol), B1 (1.38 g, 4.61 mmol), C2 (1.09 g, 2.77 mmol) and D2 (1.68 g, 11.1 mmol) in NMP (16.0 g) After mixing at room temperature and reacting at 80 ° C for 5 hours, E1 (2.50 g, 12.8 mmol) and NMP (8.02 g) are added and allowed to react at 40 ° C. for 6 hours, and the resin solid concentration is 25 mass % Polyamic acid solution was obtained.

  After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.35 g) are added as an imidation catalyst, It was allowed to react for 5 hours. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (8). The imidation ratio of this polyimide was 81%, the number average molecular weight was 18,800 and the weight average molecular weight was 49,800.

Synthesis Example 9
E3 (7.20 g, 32.1 mmol), A2 (2.78 g, 13.0 mmol), C2 (5.14 g, 13.0 mmol) and D2 (0.99 g, 6.51 mmol), NEP (48.3 g) The mixture was mixed and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (9) having a resin solid concentration of 25% by mass. The number average molecular weight of this polyamic acid was 21,200, and the weight average molecular weight was 65,400.

Synthesis Example 10
After adding NEP to the polyamic acid solution (9) (30.0 g) obtained by the synthesis procedure of Synthesis Example 9 and diluting to 6 mass%, acetic anhydride (3.40 g) and pyridine (2. 63 g) was added and reacted at 60 ° C. for 2 hours. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (10). The imidation ratio of this polyimide was 57%, the number average molecular weight was 18,200 and the weight average molecular weight was 48,300.

Synthesis Example 11
E3 (3.85 g, 17.2 mmol), A3 (0.53 g, 2.61 mmol), C4 (2.14 g, 4.35 mmol) and D2 (1.59 g, 10.4 mmol) in NMP (24.3 g) The mixture was mixed and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

  After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass%, acetic anhydride (3.90 g) and pyridine (2.65 g) are added as an imidation catalyst, It was allowed to react for 5 hours. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (11). The imidation ratio of this polyimide was 68%, the number average molecular weight was 17,500, and the weight average molecular weight was 47,900.

Synthesis Example 12
E4 (1.64 g, 5.46 mmol), B1 (1.65 g, 5.53 mmol), C1 (1.40 g, 3.69 mmol), D1 (0.20 g, 1.84 mmol) and D2 (1.12 g, 7.38 mmol) is mixed in NMP (17.0 g) and allowed to react at 80 ° C. for 6 hours, after which E1 (2.50 g, 12.8 mmol) and NMP (8.52 g) are added and 6 at 40 ° C. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

  After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass%, acetic anhydride (4.15 g) and pyridine (2.95 g) are added as an imidation catalyst, and 3 hours at 70 ° C. It was made to react. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (12). The imidation ratio of this polyimide was 64%, the number average molecular weight was 18,100, and the weight average molecular weight was 49,600.

Synthesis Example 13
E4 (2.87 g, 9.56 mmol), A3 (0.98 g, 4.84 mmol), C3 (2.44 g, 5.65 mmol), D1 (0.26 g, 2.42 mmol) and D2 (0.49 g, 3.23 mmol) is mixed in NEP (16.6 g) and reacted at 80 ° C. for 6 hours, after which E1 (1.25 g, 6.37 mmol) and NEP (8.30 g) are added and 6 at 40 ° C. The reaction was carried out for a time to obtain a polyamic acid solution having a resin solid concentration of 25% by mass.

  NEP is added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, then acetic anhydride (4.55 g) and pyridine (3.35 g) are added as an imidization catalyst, and the mixture is heated at 80 ° C. for 3 hours It was made to react. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (13). The imidation ratio of this polyimide was 81%, the number average molecular weight was 16,300 and the weight average molecular weight was 45,100.

Synthesis Example 14
E4 (3.57 g, 11.9 mmol), A1 (1.37 g, 6.89 mmol), C4 (1.70 g, 3.44 mmol) and D2 (1.05 g, 6.89 mmol) in NMP (17.4 g) After mixing at room temperature and reacting at 80 ° C for 6 hours, E1 (1.00 g, 5.10 mmol) and NMP (8.69 g) are added and allowed to react at 40 ° C. for 6 hours, and the resin solid concentration is 25 mass % Polyamic acid solution was obtained.

  NEP is added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, then acetic anhydride (3.75 g) and pyridine (2.35 g) are added as an imidation catalyst, and 3 hours at 80 ° C. It was made to react. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (14). The imidation ratio of this polyimide was 53%, the number average molecular weight was 17,800, and the weight average molecular weight was 48,900.

Synthesis Example 15
E2 (1.73 g, 6.91 mmol), A1 (0.70 g, 3.50 mmol), A2 (0.75 g, 3.50 mmol), C2 (2.76 g, 7.00 mmol) and D2 (0.53 g, After mixing 3.50 mmol) in NMP (17.3 g) and reacting at 80 ° C. for 6 hours, E5 (2.20 g, 10.4 mmol) and NMP (8.67 g) are added, and the reaction is carried out at 80 ° C. 6 The reaction was carried out for a time to obtain a polyamic acid solution (15) having a resin solid concentration of 25% by mass. The number average molecular weight of this polyamic acid was 20,100, and the weight average molecular weight was 62,600.

Synthesis Example 16
E2 (0.88 g, 3.54 mmol), B1 (1.60 g, 5.37 mmol), C1 (1.36 g, 3.58 mmol) and D2 (1.36 g, 8.95 mmol) in NMP (16.4 g) After mixing at room temperature and reacting at 80 ° C for 6 hours, E5 (3.00 g, 14.1 mmol) and NMP (8.21 g) are added and allowed to react at 80 ° C. for 6 hours, and the resin solid concentration is 25 mass % Polyamic acid solution (16) was obtained. The number average molecular weight of this polyamic acid was 21,600, and the weight average molecular weight was 65,100.

Synthesis Example 17
After adding NMP to the polyamic acid solution (16) (30.0 g) obtained by the synthesis procedure of Synthesis Example 16 and diluting to 6 mass%, acetic anhydride (4.50 g) and pyridine (3. 3) as an imidization catalyst are prepared. 30 g) was added and allowed to react at 80 ° C. for 3 hours. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (17). The imidation ratio of this polyimide was 81%, the number average molecular weight was 18,800, and the weight average molecular weight was 52,200.

Synthesis Example 18
E2 (1.73 g, 6.91 mmol), A3 (0.89 g, 4.38 mmol), C3 (2.65 g, 6.13 mmol) and D2 (1.07 g, 7.00 mmol) with NEP (17.1 g) After mixing at room temperature and reacting at 80 ° C for 6 hours, E5 (2.20 g, 10.4 mmol) and NEP (8.54 g) are added and allowed to react at 80 ° C. for 6 hours, and the resin solid concentration is 25 mass % Polyamic acid solution was obtained.

  After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass%, acetic anhydride (4.10 g) and pyridine (3.05 g) are added as an imidation catalyst, and It was allowed to react for 5 hours. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (18). The imidation ratio of this polyimide was 74%, the number average molecular weight was 17,900, and the weight average molecular weight was 48,300.

Synthesis Example 19
E2 (0.80 g, 3.18 mmol), A1 (0.96 g, 4.83 mmol), C1 (3.37 g, 8.86 mmol) and D2 (0.37 g, 2.42 mmol) in NMP (16.4 g) After mixing at room temperature and reacting at 80 ° C for 6 hours, E5 (2.70 g, 12.7 mmol) and NMP (8.20 g) are added and allowed to react at 80 ° C. for 6 hours, and the resin solid concentration is 25 mass % Polyamic acid solution was obtained.

  After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass%, acetic anhydride (3.75 g) and pyridine (2.55 g) are added as an imidation catalyst, and 2 hours at 60 ° C. It was made to react. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (19). The imidation ratio of this polyimide was 55%, the number average molecular weight was 16,800, and the weight average molecular weight was 46,200.

Synthesis Example 20
E1 (5.00 g, 25.5 mmol), C1 (0.98 g, 2.58 mmol) and D1 (2.51 g, 23.2 mmol) are mixed in NMP (25.5 g) and reacted at 40 ° C. for 8 hours The reaction was carried out to obtain a polyamic acid solution (20) having a resin solid concentration of 25% by mass. The number average molecular weight of this polyamic acid was 25,800, and the weight average molecular weight was 88,900.

Synthesis Example 21
E1 (5.00 g, 25.5 mmol), D1 (1.96 g, 18.1 mmol) and D2 (1.18 g, 7.75 mmol) are mixed in NMP (24.4 g) and reacted at 40 ° C. for 8 hours The reaction was carried out to obtain a polyamic acid solution (21) having a resin solid concentration of 25% by mass. The number average molecular weight of this polyamic acid was 27,100, and the weight average molecular weight was 90,100.

Synthesis Example 22
E2 (4.08 g, 16.3 mmol), C1 (6.29 g, 16.5 mmol), D1 (1.07 g, 9.92 mmol) and D2 (1.01 g, 6.61 mmol) with NEP (31.3 g) After mixing at room temperature and reacting at 80 ° C for 5 hours, E1 (3.20 g, 16.3 mmol) and NEP (15.7 g) are added and allowed to react at 40 ° C. for 6 hours, and the resin solid concentration is 25 mass % Polyamic acid solution (22) was obtained. The number average molecular weight of this polyamic acid was 22,500, and the weight average molecular weight was 66,900.

Synthesis Example 23
NEP is added to the polyamic acid solution (22) (30.0 g) obtained by the synthesis procedure of Synthesis Example 22 and diluted to 6% by mass, and then acetic anhydride (3.40 g) and pyridine (2. 50 g) was added and allowed to react at 60 ° C. for 2 hours. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (23). The imidation ratio of this polyimide was 55%, the number average molecular weight was 19,200 and the weight average molecular weight was 50,600.

Synthesis Example 24
E2 (4.72 g, 18.9 mmol), C1 (2.91 g, 7.64 mmol), D1 (1.24 g, 11.5 mmol) and D2 (2.91 g, 19.1 mmol) with NEP (31.0 g) After mixing at room temperature and reacting at 80 ° C for 5 hours, E1 (3.70 g, 18.9 mmol) and NEP (15.5 g) are added and allowed to react at 40 ° C. for 6 hours, and the resin solid concentration is 25 mass % Polyamic acid solution (24) was obtained. The number average molecular weight of this polyamic acid was 23,000, and the weight average molecular weight was 68,800.

Synthesis Example 25
NEP was added to the polyamic acid solution (24) (30.0 g) obtained by the synthesis procedure of Synthesis Example 24 and diluted to 6 mass%, and then acetic anhydride (3.40 g) and pyridine (2. 65 g) was added and reacted at 60 ° C. for 2 hours. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (25). The imidation ratio of this polyimide was 57%, the number average molecular weight was 20,100, and the weight average molecular weight was 54,100.

Synthesis Example 26
E2 (2.04 g, 8.16 mmol), A1 (0.99 g, 4.96 mmol), D2 (0.50 g, 3.31 mmol) and D3 (3.11 g, 8.26 mmol) with NEP (16.5 g) After mixing at room temperature and reacting at 80 ° C for 5 hours, E1 (1.60 g, 8.16 mmol) and NEP (8.25 g) are added and allowed to react at 40 ° C. for 6 hours, and the resin solid concentration is 25 mass % Polyamic acid solution was obtained.

  NEP is added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, then acetic anhydride (3.45 g) and pyridine (2.65 g) are added as an imidization catalyst, and 2 hours at 60 ° C. It was made to react. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (26). The imidation ratio of this polyimide was 54%, the number average molecular weight was 17,600 and the weight average molecular weight was 49,200.

Synthesis Example 27
E2 (2.23 g, 8.92 mmol), B1 (1.62 g, 5.42 mmol), D2 (1.38 g, 9.04 mmol) and D3 (1.36 g, 3.62 mmol) with NEP (16.7 g) After mixing for 5 hours at 80 ° C., E1 (1.75 g, 8.92 mmol) and NEP (8.34 g) are added and allowed to react for 6 hours at 40 ° C., and the resin solid concentration is 25 mass. % Polyamic acid solution was obtained.

  NEP is added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, then acetic anhydride (3.45 g) and pyridine (2.65 g) are added as an imidization catalyst, and 2 hours at 60 ° C. It was made to react. The reaction solution was poured into methanol (460 ml) and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (27). The imidation ratio of this polyimide was 57%, the number average molecular weight was 18,600 and the weight average molecular weight was 51,500.

  The polyimide polymers of the present invention are shown in Tables 2 to 4.

＊１：ポリアミド酸。

* 1: Polyamic acid.

＊１：ポリアミド酸。

* 1: Polyamic acid.

＊１：ポリアミド酸。

* 1: Polyamic acid.

"Production of liquid crystal aligning agent of the present invention"
In Examples 1 to 19 and Comparative Examples 1 to 8 described below, production examples of the liquid crystal alignment treatment agent will be described. In addition, this liquid crystal aligning agent is also used for evaluation.

  The liquid crystal aligning agent of this invention is shown in Tables 5-7.

  "Evaluation of inkjet coatability of liquid crystal aligning agent", "Production of liquid crystal cell and evaluation of pretilt angle (normal cell)", "Voltage" using the liquid crystal aligning agent obtained in Examples and Comparative Examples of the present invention Evaluation of retention rate (normal cell), "evaluation of relaxation of residual charge (normal cell)" and "production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" were performed.

"Evaluation of inkjet coating properties of liquid crystal aligning agent"
The liquid crystal aligning agent (4) obtained in Example 4 of the present invention, the liquid crystal aligning agent (9) obtained in Example 9, and the liquid crystal aligning agent (15) obtained in Example 15 are It pressure-filtered with a membrane filter with a hole diameter of 1 micrometer, and evaluated ink jet coatability. HIS-200 (manufactured by Hitachi Plant Technologies, Ltd.) was used as the inkjet coater. Coating is performed on ITO (indium tin oxide) deposited substrate cleaned with pure water and IPA, with a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, a coating speed of 40 mm / sec, from coating to temporary drying For 60 seconds, and preliminary drying was performed on a hot plate at 70 ° C. for 5 minutes.

  The coating properties of the obtained substrate with a liquid crystal alignment film were confirmed. Specifically, the coating film was visually observed under a sodium lamp to confirm the presence or absence of a pinhole. As a result, no pinhole was observed on the coating film in any of the liquid crystal alignment films obtained in any of the examples, and a liquid crystal alignment film having excellent coating film properties was obtained.

"Production of liquid crystal cell and evaluation of pretilt angle (normal cell)"
The liquid crystal aligning agent obtained in Examples and Comparative Examples of the present invention was subjected to pressure filtration with a membrane filter with a pore diameter of 1 μm to prepare a liquid crystal cell (usually cell). This solution is spin-coated on the ITO surface of a 40 x 30 mm ITO electroded substrate (40 mm x 30 mm, thickness 0.7 mm) washed with pure water and IPA, and heated for 5 minutes at 100 ° C on a hot plate. Heat treatment was carried out at 230 ° C. for 30 minutes in a heat circulating clean oven to obtain an ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm. The liquid crystal aligning agent (4) obtained in Example 4 of the present invention, the liquid crystal aligning agent (9) obtained in Example 9, and the liquid crystal aligning agent (15) obtained in Example 15 A substrate with a liquid crystal alignment film is prepared under the same conditions as the above-mentioned "evaluation of the ink jet coatability of a liquid crystal alignment treatment agent", and then heat treated at 230 ° C for 30 minutes in a heat circulating clean oven, An ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained.

  The coated film surface of this ITO substrate was rubbed with a rubbing apparatus with a roll diameter of 120 mm using a rayon cloth under conditions of a roll rotation speed of 1000 rpm, a roll advancing speed of 50 mm / sec, and a pressing amount of 0.1 mm.

  Two obtained ITO substrates with a liquid crystal alignment film were prepared, combined by sandwiching a 6 μm spacer with the liquid crystal alignment film surface inside, and the periphery was adhered with a sealing agent to produce an empty cell. A nematic liquid crystal was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (usually a cell).

  In the liquid crystal cell using the liquid crystal aligning agent (1) obtained in Example 1 and the liquid crystal aligning agent (21) obtained in Comparative Example (1), MLC-2003 (Merck Japan Ltd.) was used as a liquid crystal. Company company) was used. Moreover, MLC-6608 (made by Merck Japan) was used for the liquid crystal for the cell using the liquid-crystal aligning agent obtained by the other Example and the comparative example.

  Next, the pretilt angle of this liquid crystal cell (normal cell) was measured. The pretilt angle was measured for the liquid crystal cell after isotropic treatment (heating treatment at 95 ° C. for 5 minutes) and then heat treatment (heating treatment at 120 ° C. for 5 hours).

Furthermore, after performing the isotropic process to the liquid crystal cell produced on the conditions similar to the above, the liquid crystal cell after irradiating a 10 J / cm < ² > ultraviolet-ray in 365 nm conversion was also measured. The pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). Furthermore, ultraviolet irradiation was performed using a table-top UV curing apparatus (HCT3B28HEX-1) (manufactured by Senlight Co., Ltd.).

  The evaluation is performed after heat treatment (also referred to as high temperature treatment) or after irradiation with ultraviolet light (also referred to as ultraviolet light irradiation) with respect to a pretilt angle after isotropic treatment of liquid crystal (also referred to as Iso treatment). The smaller the change in angle, the better (Tables 8 to 10 show values of pretilt angles after Iso treatment, after high-temperature treatment, and after ultraviolet irradiation).

  Tables 8 to 10 show the results obtained in Examples and Comparative Examples.

"Evaluation of voltage holding ratio (normal cell)"
The voltage holding ratio was evaluated using a liquid crystal cell (normal cell) manufactured under the same conditions as the above-mentioned “Production of liquid crystal cell and evaluation of pretilt angle (normal cell)”. Specifically, a voltage of 1 V is applied for 60 μs at a temperature of 80 ° C. to the liquid crystal cell (normal cell) obtained by the above method, and the voltage after 50 ms is measured, and how long the voltage can be held Calculated as a voltage holding ratio (also referred to as VHR). The measurement was performed using a voltage holding ratio measuring apparatus (VHR-1) (manufactured by Toyo Corporation) with a setting of Voltage: ± 1 V, Pulse Width: 60 μs, and Flame Period: 50 ms.

Furthermore, 50 J / cm ² of ultraviolet light in terms of 365 nm is applied to the liquid crystal cell in which the measurement of the voltage holding ratio immediately after the preparation of the liquid crystal cell is finished using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlight Co., Ltd.). Irradiation was performed, and measurement of voltage retention was performed under the same conditions as described above.

  In the evaluation, the smaller the decrease in the value after irradiation with ultraviolet light, the better the value of the voltage holding ratio immediately after the liquid crystal cell production and the voltage holding ratio immediately after the liquid crystal cell production (Table 11). -In Table 13, the value of VHR immediately after liquid crystal cell preparation and after ultraviolet irradiation is shown).

  Tables 11 to 13 show the results obtained in Examples and Comparative Examples.

"Evaluation of relaxation of residual charge (normal cell)"
Using the liquid crystal cell (normal cell) manufactured under the same conditions as the above-mentioned "Production of liquid crystal cell and evaluation of pretilt angle (normal cell)", evaluation of relaxation of residual charge was performed. Specifically, after applying a DC voltage of 10 V for 30 minutes to the liquid crystal cell and shorting it for 1 second, the potential generated in the liquid crystal cell was measured for 1800 seconds. Among them, the residual charge value after 50 seconds was used to evaluate the relaxation of the residual charge. In addition, the measurement used the 6254 type liquid crystal physical-property evaluation apparatus (made by Toyo Technica Co., Ltd.).

Furthermore, 30 J / cm ² of ultraviolet light in terms of 365 nm is irradiated to the liquid crystal cell for which the measurement of the residual charge immediately after the preparation of the above liquid crystal cell is finished, using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlight Co., Ltd.) The residual charge was measured under the same conditions as above.

  In the evaluation, the smaller the value of the residual charge immediately after the liquid crystal cell production and after the ultraviolet irradiation, the better (Tables 11 to 13 show the value of the residual charge immediately after the liquid crystal cell production and after the ultraviolet irradiation).

  Tables 11 to 13 show the results obtained in Examples and Comparative Examples.

"Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)"
Liquid crystal aligning agent (3) obtained in Example 3, liquid crystal aligning agent (5) obtained in Example 5, liquid crystal aligning agent (6) obtained in Example 6, obtained in Example 8 The liquid crystal aligning agent (8) thus obtained and the liquid crystal aligning agent (16) obtained in Example 16 are pressure-filtered with a membrane filter having a pore diameter of 1 μm to prepare a liquid crystal cell and evaluate the liquid crystal alignment (PSA) Made a cell). This solution was washed with pure water and IPA at the center with a 10 × 10 mm pattern spacing 20 μm ITO electroded substrate (length 40 mm × width 30 mm, thickness 0.7 mm) and at the center 10 × 40 mm ITO electroded substrate Spin-coated on the ITO surface (40 mm long x 30 mm wide, 0.7 mm thick) and heat treated at 100 ° C for 5 minutes on a hot plate at 230 ° C for 30 minutes in a heat circulating clean oven A polyimide coating having a thickness of 100 nm was obtained.

  This liquid crystal alignment film-attached substrate was assembled with the liquid crystal alignment film surface inside, a 6 μm spacer interposed, and the periphery was adhered with a sealing agent to produce an empty cell. In this empty cell, a polymerizable compound (1) represented by the following formula is added to a nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) by a reduced pressure injection method, and 100% by mass of the nematic liquid crystal (MLC-6608) On the other hand, a liquid crystal mixed with 0.3% by mass of the polymerizable compound (1) was injected, and the injection port was sealed to obtain a liquid crystal cell.

A wavelength of 350 nm or less is cut using a metal halide lamp with an illuminance of 60 mW while applying a voltage of 5 V AC to the obtained liquid crystal cell, and UV irradiation of 20 J / cm ² is performed at 365 nm conversion. Obtained a controlled liquid crystal cell (PSA cell). The temperature in the irradiation device was 50 ° C. when the liquid crystal cell was irradiated with ultraviolet light.

  The response speed of the liquid crystal before and after the ultraviolet light irradiation of this liquid crystal cell was measured. The response speed was measured from T90 → T10 from 90% transmission to 10% transmission.

  In the PSA cell obtained in any of the examples, the response speed of the liquid crystal cell after ultraviolet light irradiation was faster than that of the liquid crystal cell before ultraviolet light irradiation, so it was confirmed that the alignment direction of the liquid crystal was controlled. . Further, it was confirmed that the liquid crystals were uniformly oriented by observation with a polarization microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) in any liquid crystal cell.

Example 1
Polyamide acid solution (1) (5.00 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 1 and polyamic acid having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 2 NMP (18.2g) and BCS (8.16g) were added to the solution (2) (3.33g), and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (1), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of relaxation of residual charge ( Normal cell) was performed.

Example 2
Polyamide acid solution (3) (4.50 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 3 and polyamic acid having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 5 NEP (14.4g) and PB (14.1g) were added to solution (5) (4.50g), and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (2). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  "Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "evaluation of voltage holding ratio (normal cell)" and "evaluation of relaxation of residual charge" using the obtained liquid crystal aligning agent (2) Normal cell) was performed.

Example 3
Polyimide powder (4) (1.15 g) obtained by the synthesis method of Synthesis Example 4 and polyimide powder (6) (1.15 g) obtained by the synthesis method of Synthesis Example 6 were NEP (21.6 g) The mixture was added and dissolved by stirring at 70 ° C. for 24 hours. PB (14.4g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (3). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  "Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "evaluation of voltage holding ratio (normal cell)", "evaluation of relaxation of residual charge" using the obtained liquid crystal aligning agent (3) "Normal cell)" and "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" were performed.

Example 4
Polyimide powder (4) (0.65 g) obtained by the synthesis method of Synthesis Example 4 and polyimide powder (6) (0.43 g) obtained by the synthesis method of Synthesis Example 6 were NEP (14.9 g) The mixture was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (5.97g), PB (8.96g) and K1 (0.032g) were added to this solution, and it stirred at 40 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (4). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal aligning agent (4), "evaluation of inkjet coatability of liquid crystal aligning agent", "preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "evaluation of voltage retention ( "Normal cell)" and "Evaluation of relaxation of residual charge (normal cell)" were performed.

Example 5
The polyimide powder (7) (1.65 g) obtained by the synthesis method of Synthesis Example 7 and the polyimide powder (8) (0.71 g) obtained by the synthesis method of Synthesis Example 8 were NMP (20.3 g) The mixture was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (12.9 g) and DME (3.69 g) were added to this solution, and the mixture was stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  "Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "evaluation of voltage holding ratio (normal cell)", "evaluation of relaxation of residual charge ( "Normal cell)" and "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" were performed.

Example 6
Polyamide acid solution (9) (3.50 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 9 and a polyamic acid having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 5 NEP (14.0 g), PB (10.3 g) and EC (3.43 g) are added to solution (5) (5.25 g), and the mixture is stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (6) I got No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (6), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)”, “evaluation of relaxation of residual charge ( "Normal cell)" and "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" were performed.

Example 7
NEP (15.0 g) was added to the polyimide powder (10) (1.75 g) obtained by the synthesis method of Synthesis Example 10, and stirred at 70 ° C. for 24 hours to be dissolved. To this solution, PB (11.0 g) and DME (1.37 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

  On the other hand, NEP (3.80 g) was added to the polyimide powder (6) (0.44 g) obtained by the synthesis procedure of Synthesis Example 6, and stirred at 70 ° C. for 24 hours for dissolution. To this solution, PB (2.70 g) and DME (0.34 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

  The two solutions obtained above were mixed, K1 (0.153 g) was further added, and the mixture was stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (7). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (7), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) was performed.

Example 8
The polyimide powder (11) (0.75 g) obtained by the synthesis procedure of Synthesis Example 11 and the polyimide powder (8) (1.39 g) obtained by the synthesis procedure of Synthesis Example 8 were NMP (6.71 g) and NEP (13.4 g) was added and dissolved by stirring at 70 ° C. for 24 hours. PB (13.4g) and K1 (0.107g) were added to this solution, and it stirred at 40 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (8). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)”, and “evaluation of relaxation of residual charge” using the obtained liquid crystal aligning agent (8) "Normal cell)" and "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" were performed.

Example 9
The polyimide powder (11) (0.55 g) obtained by the synthesis method of Synthesis Example 11 and the polyimide powder (8) (0.83 g) obtained by the synthesis method of Synthesis Example 8 were NEP (15.2 g) and γ-BL (3.79 g) was added and dissolved by stirring at 70 ° C. for 24 hours. PB (15.2g) and DME (3.79g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (9). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (9), "evaluation of inkjet coatability of liquid crystal alignment treatment agent", "preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "evaluation of voltage retention ( "Normal cell)" and "Evaluation of relaxation of residual charge (normal cell)" were performed.

Example 10
NMP (1.73 g) and NEP (6.90 g) were added to the polyimide powder (4) (1.10 g) obtained by the synthesis procedure of Synthesis Example 4 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (1.73 g) and PB (6.90 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

  On the other hand, NMP (1.73 g) and NEP (6.90 g) are added to the polyimide powder (12) (1.10 g) obtained by the synthesis method of Synthesis Example 12, and stirred at 70 ° C. for 24 hours to dissolve The To this solution, BCS (1.73 g) and PB (6.90 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

  The two solutions obtained above were mixed and stirred at 25 ° C. for 6 hours to obtain a liquid crystal aligning agent (10). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (10), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of relaxation of residual charge ( Normal cell) was performed.

Example 11
A polyimide powder (13) (1.25 g) obtained by the synthesis procedure of Synthesis Example 13 and a polyimide powder (8) (0.83 g) obtained by the synthesis procedure of Synthesis Example 8 were NEP (13.1 g) and γ-BL (3.26 g) was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (13.1g) and EC (3.26g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (11). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (11), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) was performed.

Example 12
The polyimide powder (10) (0.65 g) obtained by the synthesis method of Synthesis Example 10 and the polyimide powder (8) (1.52 g) obtained by the synthesis method of Synthesis Example 8 were NMP (17.0 g) and γ-BL (1.70 g) was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (6.79g) and PB (8.49g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (12). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (12), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of relaxation of residual charge ( Normal cell) was performed.

Example 13
Polyamide acid solution (15) (4.50 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 15 and polyamic acid having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 16 NMP (14.4 g), BCS (3.53 g), PB (10.6 g) and K1 (0.225 g) are added to solution (16) (4.50 g), and the mixture is stirred at 40 ° C. for 6 hours. A liquid crystal aligning agent (13) was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (13), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) was performed.

Example 14
Polyimide powder (7) (0.90 g) obtained by the synthesis method of Synthesis Example 7 and polyimide powder (17) (1.35 g) obtained by the synthesis method of Synthesis Example 17 were NEP (15.9 g) The mixture was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (5.29g) and PB (14.1g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (14). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (14), "Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "evaluation of voltage holding ratio (normal cell)" and "evaluation of relaxation of residual charge ( Normal cell) was performed.

Example 15
The polyimide powder (7) (0.55 g) obtained by the synthesis method of Synthesis Example 7 and the polyimide powder (17) (0.83 g) obtained by the synthesis method of Synthesis Example 17 were NMP (3.79 g) and NEP (15.2 g) was added and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (19.0 g) was added, and the mixture was stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (15). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal aligning agent (15), "evaluation of inkjet coatability of liquid crystal aligning agent", "preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "evaluation of voltage retention ( "Normal cell)" and "Evaluation of relaxation of residual charge (normal cell)" were performed.

Example 16
NMP (8.82 g) was added to the polyimide powder (18) (1.25 g) obtained by the synthesis method of Synthesis Example 18, and stirred at 70 ° C. for 24 hours for dissolution. To this solution, BCS (2.94 g) and PB (7.86 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

  On the other hand, NMP (5.88 g) was added to the polyimide powder (17) (0.83 g) obtained by the synthesis method of Synthesis Example 17, and stirred at 70 ° C. for 24 hours for dissolution. To this solution, BCS (1.96 g) and PB (5.24 g) were added and stirred at 40 ° C. for 4 hours to obtain a solution.

  The two solutions obtained above were mixed and stirred at 25 ° C. for 4 hours to obtain a liquid crystal aligning agent (16). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  "Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "evaluation of voltage holding ratio (normal cell)", "evaluation of relaxation of residual charge" using the obtained liquid crystal aligning agent (16) "Normal cell)" and "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" were performed.

Example 17
K1 (0.06 g) is added to the liquid crystal aligning agent (16) (20.0 g) obtained by the adjusting method of Example 16, and the mixture is stirred at 40 ° C. for 6 hours to obtain a liquid crystal aligning agent (17). Obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (17), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) was performed.

Example 18
Polyimide powder (19) (0.45 g) obtained by the synthesis method of Synthesis Example 19 and polyimide powder (6) (1.80 g) obtained by the synthesis method of Synthesis Example 6 were NEP (21.2 g) The mixture was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (3.53g) and PB (10.6g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (18). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (18), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of relaxation of residual charge ( Normal cell) was performed.

Example 19
Polyimide powder (19) (1.63 g) obtained by the synthesis method of Synthesis Example 19 and a polyamic acid solution (5) (6.50 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 5 Then, NEP (19.4 g) was added and dissolved by stirring at 70 ° C. for 24 hours. BCS (6.47g) and PB (6.47g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (19). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (19), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of relaxation of residual charge ( Normal cell) was performed.

Comparative Example 1
Polyamide acid solution (20) (4.95 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 20 and polyamic acid having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 21 NMP (18.0g) and BCS (8.08g) were added to the solution (21) (3.30g), and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (20). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (20), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of relaxation of residual charge ( Normal cell) was performed.

Comparative Example 2
Polyamide acid solution (3) (4.50 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 3 and a polyamic acid having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 24 NEP (14.4g) and PB (14.1g) were added to the solution (24) (4.50g), and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (21). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  "Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "evaluation of voltage holding ratio (normal cell)" and "evaluation of relaxation of residual charge" using the obtained liquid crystal aligning agent (21) Normal cell) was performed.

Comparative Example 3
Polyamide acid solution (22) (4.50 g) with a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 22 and polyamic acid with a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 5 NEP (14.4g) and PB (14.1g) were added to the solution (5) (4.50g), and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (22). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (22), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of relaxation of residual charge ( Normal cell) was performed.

Comparative Example 4
Polyamide acid solution (22) (4.50 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 22 and a polyamic acid having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 24 NEP (14.4g) and PB (14.1g) were added to the solution (24) (4.50g), and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (23). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (23), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) was performed.

Comparative Example 5
Polyimide powder (4) (1.10 g) obtained by the synthesis method of Synthesis Example 4 and polyimide powder (25) (1.10 g) obtained by the synthesis method of Synthesis Example 25 were NEP (20.7 g) The mixture was added and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.8 g) was added, and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (24). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (24), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of relaxation of residual charge ( Normal cell) was performed.

Comparative Example 6
The polyimide powder (23) (1.10 g) obtained by the synthesis method of Synthesis Example 23 and the polyimide powder (6) (1.10 g) obtained by the synthesis method of Synthesis Example 6 were combined with NEP (20.7 g) The mixture was added and dissolved by stirring at 70 ° C. for 24 hours. PB (13.8 g) was added to this solution, and the mixture was stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (25). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (25), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “Evaluation of voltage holding ratio (normal cell)” and “Evaluation of relaxation of residual charge ( Normal cell) was performed.

Comparative Example 7
Polyimide powder (23) (1.10 g) obtained by the synthesis method of Synthesis Example 23 and polyimide powder (25) (1.10 g) obtained by the synthesis method of Synthesis Example 25 were NEP (20.7 g) The mixture was added and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (13.8 g) was added and stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (26). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (26), "Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)", "evaluation of voltage holding ratio (normal cell)" and "evaluation of relaxation of residual charge ( Normal cell) was performed.

Comparative Example 8
Polyimide powder (26) (1.10 g) obtained by the synthesis method of Synthesis Example 26 and polyimide powder (27) (1.10 g) obtained by the synthesis method of Synthesis Example 27 were NEP (20.7 g) The mixture was added and dissolved by stirring at 70 ° C. for 24 hours. PB (13.8 g) was added to this solution, and the mixture was stirred at 40 ° C. for 4 hours to obtain a liquid crystal aligning agent (27). No abnormality such as turbidity or precipitation was observed in this liquid crystal aligning agent, and it was confirmed that the solution was a uniform solution.

  Using the obtained liquid crystal alignment treatment agent (27), “Preparation of liquid crystal cell and evaluation of pretilt angle (normal cell)”, “evaluation of voltage holding ratio (normal cell)” and “evaluation of relaxation of residual charge ( Normal cell) was performed.

＊１：すべての重合体１００質量部に対する特定重合体（Ａ）の導入量（質量部）を示す。
＊２：すべての重合体１００質量部に対する特定重合体（Ｂ）の導入量（質量部）を示す。
＊３：すべての重合体１００質量部に対するその他重合体の導入量（質量部）を示す。
＊４：すべての重合体１００質量部に対する架橋性化合物の導入量（質量部）を示す。
＊５：すべての溶媒１００質量部に対する各溶媒の導入量（質量部）を示す。
＊６：液晶配向処理剤中のすべての重合体の占める割合を示す。

* 1: The introduction amount (mass part) of a specific polymer (A) with respect to 100 mass parts of all the polymers is shown.
* 2: The introduction amount (mass part) of a specific polymer (B) with respect to 100 mass parts of all the polymers is shown.
* 3: The introduction amount (parts by mass) of the other polymer with respect to 100 parts by mass of all the polymers is shown.
* 4: Indicates the introduced amount (parts by mass) of the crosslinkable compound with respect to 100 parts by mass of all the polymers.
* 5: The introduction amount (mass part) of each solvent with respect to 100 mass parts of all the solvents is shown.
* 6 Indicates the proportion of all polymers in the liquid crystal aligning agent.

＊１：すべての重合体１００質量部に対する特定重合体（Ａ）の導入量（質量部）を示す。
＊２：すべての重合体１００質量部に対する特定重合体（Ｂ）の導入量（質量部）を示す。
＊３：すべての重合体１００質量部に対するその他重合体の導入量（質量部）を示す。
＊４：すべての重合体１００質量部に対する架橋性化合物の導入量（質量部）を示す。
＊５：すべての溶媒１００質量部に対する各溶媒の導入量（質量部）を示す。
＊６：液晶配向処理剤中のすべての重合体の占める割合を示す。

* 1: The introduction amount (mass part) of a specific polymer (A) with respect to 100 mass parts of all the polymers is shown.
* 2: The introduction amount (mass part) of a specific polymer (B) with respect to 100 mass parts of all the polymers is shown.
* 3: The introduction amount (parts by mass) of the other polymer with respect to 100 parts by mass of all the polymers is shown.
* 4: Indicates the introduced amount (parts by mass) of the crosslinkable compound with respect to 100 parts by mass of all the polymers.
* 5: The introduction amount (mass part) of each solvent with respect to 100 mass parts of all the solvents is shown.
* 6 Indicates the proportion of all polymers in the liquid crystal aligning agent.

＊１：すべての重合体１００質量部に対する特定重合体（Ａ）の導入量（質量部）を示す。
＊２：すべての重合体１００質量部に対する特定重合体（Ｂ）の導入量（質量部）を示す。
＊３：すべての重合体１００質量部に対するその他重合体の導入量（質量部）を示す。
＊４：すべての重合体１００質量部に対する架橋性化合物の導入量（質量部）を示す。
＊５：すべての溶媒１００質量部に対する各溶媒の導入量（質量部）を示す。
＊６：液晶配向処理剤中のすべての重合体の占める割合を示す。

* 1: The introduction amount (mass part) of a specific polymer (A) with respect to 100 mass parts of all the polymers is shown.
* 2: The introduction amount (mass part) of a specific polymer (B) with respect to 100 mass parts of all the polymers is shown.
* 3: The introduction amount (parts by mass) of the other polymer with respect to 100 parts by mass of all the polymers is shown.
* 4: Indicates the introduced amount (parts by mass) of the crosslinkable compound with respect to 100 parts by mass of all the polymers.
* 5: The introduction amount (mass part) of each solvent with respect to 100 mass parts of all the solvents is shown.
* 6 Indicates the proportion of all polymers in the liquid crystal aligning agent.

  As can be seen from the above results, the liquid crystal alignment treatment agent of the example of the present invention has a stable pretilt angle even when subjected to high temperature treatment and ultraviolet irradiation to the liquid crystal cell as compared with the liquid crystal alignment treatment agent of the comparative example. Indicated. Furthermore, even when the ultraviolet irradiation was performed, the lowering of the voltage holding ratio was suppressed, and the relaxation of the residual charge accumulated by the direct current voltage was quick. That is, the agent for treating liquid crystal of the present invention becomes a liquid crystal alignment film capable of exhibiting a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time, and additionally, it is exposed to light irradiation for a long time Even after that, it becomes a liquid crystal alignment film which suppresses the decrease of the voltage holding ratio and quickly relieves the residual charge accumulated by the direct current voltage.

  Specifically, an example of the liquid crystal aligning agent using the specific polymer (A) and the specific polymer (B) of the present invention, and an example of the liquid crystal aligning agent using only one of them In comparison with Example 2 and Comparative Example 2 or Comparative Example 3, and Example 3 with Comparative Example 5 or Comparative Example 6. The comparative example using only the specific polymer (A) or the comparative example using only the specific polymer (B) significantly reduces the voltage holding ratio particularly to ultraviolet irradiation, as compared to the corresponding example. Furthermore, the value of residual charge also increased.

  In addition, an example of a liquid crystal alignment treatment agent using the specific polymer (A) of the present invention and the specific polymer (B), a polymer having no tertiary nitrogen atom-containing structure of the present invention, and a specific structure ( Comparative Example of Liquid Crystal Alignment Treatment Agent Using Polymer Having No 2), That is, Comparison of Example 1 and Comparative Example 1, Comparison of Example 2 and Comparative Example 4, and Example 3 and Comparative Example Comparison with 7. In these comparative examples, compared to the corresponding examples, the voltage holding ratio significantly decreased, and the residual charge value further increased, particularly with respect to ultraviolet irradiation.

  In addition, an embodiment of a liquid crystal alignment treatment agent using the specific polymer (A) and the specific polymer (B) of the present invention, and a liquid crystal alignment treatment agent using a polymer having a conventional side chain structure Comparative Example with Comparative Example, that is, Comparative Example 8 with Comparative Example 8. In this comparative example, compared with the corresponding example, the change width of the pretilt angle after the high temperature treatment and the ultraviolet irradiation is large, and the voltage holding ratio largely decreases with respect to the ultraviolet irradiation. The value of the charge also increased. Above all, the drop in the voltage holding ratio was particularly large.

  The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film capable of expressing a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. In addition, it is possible to provide a liquid crystal alignment film capable of suppressing the decrease in the voltage holding ratio even after being exposed to light irradiation for a long time, and quickly reducing the residual charge accumulated by the direct current voltage. In addition, the liquid crystal display element which has said liquid crystal aligning film, and the liquid-crystal aligning agent which can provide said liquid crystal aligning film can be provided.

  Therefore, a liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention becomes excellent in reliability, and can be suitably used for a large screen and high definition liquid crystal television etc., TN element, STN It is useful for a device, a TFT liquid crystal device, particularly a liquid crystal display device of vertical alignment type.

  Furthermore, the liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention is useful also to the liquid crystal display element which needs to irradiate an ultraviolet-ray, when producing a liquid crystal display element. That is, a liquid crystal composition is provided having a liquid crystal layer between a pair of substrates provided with electrodes, and including a polymerizable compound polymerized by at least one of an active energy ray and heat between the pair of substrates, A liquid crystal display device manufactured through the step of polymerizing the polymerizable compound while applying a voltage between the electrodes, and further comprising a liquid crystal layer between a pair of substrates provided with the electrodes, the pair of A liquid crystal produced through the step of disposing a liquid crystal alignment film containing a polymerizable group which is polymerized by at least one of active energy ray and heat between substrates, and polymerizing the polymerizable group while applying a voltage between the electrodes. It is also useful for display elements.

Claims (21)

The liquid-crystal aligning agent containing the following (A) component and (B) component.
Component (A): A polymer containing at least one selected from a polyimide precursor and a polyimide having a structure having a nitrogen atom shown below.
Component (B): A polymer containing at least one selected from a polyimide precursor and a polyimide having a structure represented by the following formula [2].
Note that at least one of the component (A) and the polymer of the component (B) contains a structure represented by the following formula [3],
The polymer of at least one of the component (A) and the component (B) is obtained by using a diamine compound represented by the following formula [3a] as a part of the raw material,
The structure having a nitrogen atom in the component (A) is at least one structure selected from the structures represented by the following formulas [1a] to [1c].

(In formula [2], Y ¹ and Y ⁷ are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R ¹ )-(R ¹ is a hydrogen atom or carbon number shows a 1-3 alkyl ^{group), - CON (R 2)} - (R 2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon ^{atoms), - N (R 3)} CO- (R 3 is a hydrogen atom Or an alkyl group of 1 to 3 carbon atoms), at least one organic group selected from -CH ₂ O-, -COO- and -OCO-, and Y ² and Y ⁶ each independently represent carbon And each of Y ³ and Y ⁵ independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y ⁴ represents an oxygen atom or a sulfur atom).

(In formula [3], B ¹ is a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- B ² represents a single bond or-(CH ₂ ) _b- (b is an integer of 1 to 15), B ³ represents a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15) ), —O—, —CH ₂ O—, —COO— or —OCO—, and B ⁴ is a carbon having a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a steroid skeleton And an arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or a fluorine containing 1 to 3 carbon atoms. It may be substituted by an alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. , B ⁵ represents a divalent cyclic group selected from benzene ring, cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic groups, an alkyl group having 1 to 3 carbon atoms, 1 to 3 carbon atoms It may be substituted by an alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, n represents an integer of 0 to 4, and B ⁶ represents a carbon number 1-18 alkyl group, C1-C18 fluorine-containing alkyl group, C1-C18 alkoxyl group, or C1-C18 fluorine-containing alkoxyl group is shown).

(In formula [3a], B represents the above formula [3], A ¹ and A ² each independently represent a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, and m is an integer of 1 to 4 Show) .

(In the formula [1a], X ¹ represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, and X ² represents a hydrogen atom or a disubstituted amino group substituted with a C 1 to C 12 aliphatic group, 1 b], X ³ and X ⁷ each independently represent an aromatic group having 6 to 15 carbon atoms and 1 to 2 benzene rings, and X ⁴ and X ⁶ each independently are , A hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X ⁵ represents an alkylene group having 2 to ⁵ carbon atoms or a biphenyl group, m represents an integer of 0 or 1, and in the formula [1c], X ⁸ And X ¹⁰ each independently represents at least one structure selected from the structures represented by the following Formula [1c-a] and Formula [1c-b], and X ⁹ is an alkylene group having 1 to 5 carbon atoms Or a benzene ring is shown).

The liquid crystal aligning agent according to claim 1, wherein the polymer of the component (A) is a polymer obtained by using a diamine compound represented by the following formula [1-1] as a part of the raw material.

(In the formula [1-1], X ^A represents an organic group having at least one structure selected from the structures represented by the above formulas [1a] to [1c], and A ¹ and A ² are each independently And represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). The liquid-crystal aligning agent of Claim 2 in which the said diamine compound contains in part the diamine compound shown by following formula [1a-1]-a formula [1c-1].

(In the formula [1a-1], X ¹ represents a benzene ring or a nitrogen-containing aromatic heterocyclic ring, and X ² represents a hydrogen atom or a disubstituted amino group substituted with a C 1-12 aliphatic group, In the formula [1b-1], X ³ and X ⁷ each independently represent an aromatic group having 6 to 15 carbon atoms and one or two benzene rings, and X ⁴ and X ⁶ each represents an aromatic group Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X ⁵ represents an alkylene group having 2 to ⁵ carbon atoms or a biphenyl group, and m represents an integer of 0 or 1; 1], X ⁸ and X ¹⁰ each independently represent at least one structure selected from the structures represented by the above formulas [1c-a] and [1c-b], and X ⁹ has 1 carbon atom And an alkylene group or benzene ring of In 1c-1], A ^{1 to} A ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). The liquid crystal aligning agent according to claim 3, wherein the diamine compound is at least one diamine compound selected from diamine compounds represented by the following Formula [1-1a] to Formula [1-4a].

(In the formula [1-3a], R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and in the formula [1-4a], n represents an integer of 1 to 10, and the formula [1-1a] In the formula [1-4a], A ^{1 to} A ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). The polymer of the said (B) component is a polymer obtained by using the diamine compound shown by following formula [2-1] for a part of raw material, The claim any one of Claims 1-4 The liquid-crystal aligning agent of description.

(In formula [2-1], Y ^A represents an organic group having a structure represented by the above formula [2], and A ¹ and A ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms Show). The liquid-crystal aligning agent of Claim 5 in which the said diamine compound contains the diamine compound shown by following formula [2a] in part.

(In formula [2a], Y ¹ and Y ⁷ each independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, -O-, -N (R ¹ )-(wherein R ¹ is a hydrogen atom or carbon number shows a 1-3 alkyl ^{group), - CON (R 2)} - (R 2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon ^{atoms), - N (R 3)} CO- (R 3 is a hydrogen atom Or an alkyl group of 1 to 3 carbon atoms), at least one organic group selected from -CH ₂ O-, -COO- and -OCO-, and Y ² and Y ⁶ each independently represent carbon And Y ³ and Y ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; Y ⁴ represents an oxygen atom or a sulfur atom; A ¹ and A ² each independently represent a hydrogen atom or alkyl of 1 to 5 carbon atoms A group). The liquid crystal aligning agent according to claim 6, wherein the diamine compound is at least one diamine compound selected from diamine compounds represented by the following formulas [2-1a] to [2-3a].

(In Formula [2-1a] to Formula [2-3a], A ^{1 to} A ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). The polymer of the component (A) and the polymer of the component (B) are at least one polymer selected from a polyimide precursor and a polyimide obtained using a tetracarboxylic acid component represented by the following formula [4] The liquid-crystal aligning agent as described in any one of Claims 1-7.

(In Formula [4], Z shows at least 1 type of structure chosen from the structure shown by following formula [4a]-Formula [4k]).

(In the formula [4a], Z ^{1 to} Z ^{4 each} represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a benzene ring, which may be the same or different, and in the formula [4g], Z ⁵ and Z ⁶ represents a hydrogen atom or a methyl group, may or may not be respectively the same).   The tetracarboxylic acid component is a tetracarboxylic acid component having at least one structure selected from the structures represented by the above formulas [4a] and [4e] to [4g] in the above formula [4] The liquid-crystal aligning agent of Claim 8.   In the polymer of the component (A), the diamine compound represented by the formula [1a-1] to the formula [1c-1] is 5 mol% to 95 mol% in 100 mol% of all diamine components. The liquid-crystal aligning agent as described in any one of Claims 3-9.   The polymer of the component (B), wherein the diamine compound represented by the formula [2a] is 5 mol% to 95 mol% in 100 mol% of all diamine components. The liquid-crystal aligning agent as described in one term.   The polymer of the said (B) component is 0.5 mass part-950 mass parts with respect to 100 mass parts of polymers of the said (A) component, It is described in any one of Claims 1-11. Liquid crystal alignment treatment agent.   The solvent for the liquid crystal alignment treatment agent according to any one of claims 1 to 12, comprising at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone. The liquid-crystal aligning agent as described in.   At least one selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether as a solvent for the liquid crystal alignment treatment agent The liquid-crystal aligning agent as described in any one of Claims 1-13 containing a solvent.   The liquid crystal alignment treatment agent has at least one substituent selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group or a lower alkoxyalkyl group. The liquid crystal aligning agent as described in any one of Claims 1-14 containing at least 1 sort (s) of crosslinkable compound chosen from a crosslinkable compound and a crosslinkable compound which has a polymerizable unsaturated bond.   The liquid crystal aligning film obtained from the liquid-crystal aligning agent as described in any one of Claims 1-12 and Claim 15.   The liquid crystal display element which has a liquid crystal aligning film of Claim 16.   A liquid crystal composition comprising a liquid crystal layer is provided between a pair of substrates provided with an electrode, and a polymerizing compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, the electrode 17. The liquid crystal alignment film according to claim 16, which is used for a liquid crystal display device manufactured through the step of polymerizing the polymerizable compound while applying a voltage between the electrodes.   A liquid crystal display device comprising the liquid crystal alignment film according to claim 18.   A liquid crystal alignment film is provided between a pair of substrates provided with an electrode, and a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, 17. The liquid crystal alignment film according to claim 16, which is used for a liquid crystal display device manufactured through the step of polymerizing the polymerizable group while applying a voltage between them.   A liquid crystal display device comprising the liquid crystal alignment film according to claim 20.