JP6299977B2 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

The present invention relates to a liquid crystal aligning agent used in the manufacture of the liquid crystal display device, the present invention relates to a liquid crystal display device using this liquid crystal alignment film obtained from the liquid crystal alignment treating agent and the liquid crystal alignment film.

  A resin film made of an organic material such as a polymer material is widely used as an interlayer insulating film or a protective film in an electronic device because of its ease of formation and insulation performance. Among them, in a liquid crystal display element well known as a display device, a resin film made of an organic material is used as a liquid crystal alignment film.

  Currently, a polyimide organic film having excellent durability is used as a resin film that is industrially used. In particular, this polyimide organic film is also used as a liquid crystal alignment film of a liquid crystal display element. The polyimide organic film is formed from a composition containing a polyimide precursor, polyamic acid or polyimide. That is, the polyimide organic film is formed by applying a composition containing polyamic acid or polyimide onto a substrate and performing a baking process (see, for example, Patent Document 1).

  The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. However, as liquid crystal display elements have become higher in definition, the liquid crystal alignment film used in the liquid crystal alignment film has a high voltage holding ratio and a direct current voltage from the viewpoint of suppressing the decrease in contrast of the liquid crystal display elements and reducing the afterimage phenomenon. The characteristic that the accumulated charge when applied is small or the relaxation of the accumulated charge by the DC voltage is fast has become important. On the other hand, in order to shorten the time until the afterimage generated by the DC voltage disappears with a high voltage holding ratio, in addition to the polyamic acid or its imidized polymer, one carboxylic acid is included in the molecule. Liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing an acid group, a compound containing one carboxylic anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (For example, see Patent Document 2) is known.

JP 09-278724 A Japanese Patent Laid-Open No. 08-76128

  Along with the recent improvement in performance of liquid crystal display elements, liquid crystal display elements are used in in-vehicle applications such as car navigation systems and meter panels, and also in smartphones and tablet computers. In such applications, in order to improve visibility in the vehicle or outdoors, there are cases where the backlight is used with a high light amount or a backlight with a high calorific value. In addition, in applications such as smartphones and tabred computers, it is often used outdoors, so that the liquid crystal display element is likely to receive a lot of external light such as sunlight including ultraviolet rays.

  When the liquid crystal display element is irradiated with light such as backlight or ultraviolet light, peripheral members in the liquid crystal display element, for example, organic members such as color filters and column spacers may be decomposed. Along with this, the voltage holding ratio characteristic is lowered, and line burn-in, which is a display defect of the liquid crystal display element, occurs, and the reliability of the liquid crystal display element is lowered.

  Therefore, the liquid crystal alignment film is required to have a good voltage holding ratio even when the peripheral member of the liquid crystal display element is decomposed by light irradiation to the liquid crystal display element. In particular, even if an insulating film made of an organic member under the liquid crystal alignment film is decomposed by light irradiation, it is required that this characteristic be good.

  Moreover, the composition which consists of a normal polyimide-type polymer has low transparency of a resin film, and when it receives light, such as an ultraviolet ray in connection with it, it will become easy to decompose | disassemble a resin film. Therefore, it is necessary to increase the transparency of the resin film and suppress decomposition.

Then, this invention aims at providing the liquid-crystal aligning agent which has the said characteristic. That is, an object of the present invention is to provide a liquid crystal aligning agent using a composition in which the resin film has high transparency and can suppress decomposition of the resin film by light such as ultraviolet rays.

  Further, the present invention provides a liquid crystal alignment film using the above-described composition, wherein the liquid crystal alignment film has an excellent voltage holding ratio even when light is irradiated in a state where an insulating film made of an organic member is present under the liquid crystal alignment film. It aims at providing the liquid-crystal aligning agent used as this.

  Furthermore, an object of the present invention is to provide a liquid crystal display device provided with a liquid crystal alignment film that meets the above-described requirements.

  As a result of earnest research, the present inventor has at least one polymer selected from a cellulose-based polymer having a specific structure and a polyimide precursor obtained by reacting a diamine component with a tetracarboxylic acid component or a polyimide. The present invention has been completed by finding that a composition containing a salt is extremely effective for achieving the above object.

That is, the present invention has the following gist.
(1) A liquid crystal aligning agent obtained from a composition containing the following components (A) and (B):

  (A) Component: A polymer having a structure represented by the following formula [1].

（式［１］中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５およびＸ^６は、それぞれ独立して、下記の式［１ａ］〜式［１ｍ］から選ばれる構造の基を示し、ｎは１００〜１００００００の整数を示す）。

(In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a group having a structure selected from the following formulas [1a] to [1m]. N represents an integer of 100 to 1000000).

（式［１ｃ］〜式［１ｍ］中、Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０、Ｘ^１１、Ｘ^１２、Ｘ^１３およびＸ^１４は、それぞれ独立して、ベンゼン環、メチレン基、エチレン基、ｎ−プロピレン基、イソプロピレン基またはブチレン基を示し、式［１ｈ］中、ｎは０〜３の整数を示し、式［１ｉ］中、ｍは０〜３の整数を示す）。

(In the formulas [1c] to [1m], X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently a benzene ring, methylene group, ethylene group , N-propylene group, isopropylene group or butylene group , in formula [1h], n represents an integer of 0 to 3, and in formula [1i], m represents an integer of 0 to 3.

  (B) component: At least 1 type of polymer chosen from the polyimide precursor obtained by making a diamine component and a tetracarboxylic-acid component react, and a polyimide.

(2) The liquid crystal aligning agent according to (1) above, wherein the diamine component in the polymer of the component (B) contains a diamine compound having a structure represented by the following formula [2a].

（式［２ａ］中、ａは０〜４の整数を示す）。

(In formula [2a], a represents an integer of 0 to 4).

(3) The liquid crystal aligning agent according to (1), wherein the diamine component in the polymer of the component (B) includes a diamine compound having a structure represented by the following formula [2a-1].

（式［２ａ−１］中、ａは０〜４の整数を示し、ｎは１〜４の整数を示す）。

(In formula [2a-1], a represents an integer of 0 to 4, and n represents an integer of 1 to 4).

(4) The above (1) to (3), wherein the diamine component in the polymer of the component (B) contains at least one selected from diamine compounds having a structure represented by the following formula [2b]. ) The liquid crystal aligning agent according to any one of

（式［２ｂ］中、Ｙは下記の式［２ｂ−１］、式［２ｂ−２］、式［２ｂ−３］、式［２ｂ−４］または式［２ｂ−５］から選ばれる構造の置換基を示し、ｍは１〜４の整数を示す）。

(In the formula [2b], Y has a structure selected from the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4], or formula [2b-5]. Represents a substituent, and m represents an integer of 1 to 4.

（式［２ｂ−１］中、ａは０〜４の整数を示し、式［２ｂ−２］中、Ｙ^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、Ｙ^２は単結合または−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）を示し、Ｙ^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、Ｙ^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１２〜２５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、Ｙ^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、Ｙ^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し、式［２ｂ−３］中、Ｙ^７は−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−または−ＮＨＣＯ−を示し、Ｙ^８は炭素数８〜２２のアルキル基を示し、式［２ｂ−４］中、Ｙ^９およびＹ^１０はそれぞれ独立して炭素数１〜１２の炭化水素基を示し、式［２ｂ−５］中、Ｙ^１１は炭素数１〜５のアルキル基を示す）。

(Wherein [2b-1], a represents an integer of 0 to 4, wherein [2b-2], ^{Y 1} is a single _{bond, - (CH 2) a -} (a is an integer from 1 to 15 ), —O—, —CH ₂ O—, —COO— or —OCO—, Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15), Y ³ represents a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—, Y ⁴ represents a benzene ring, A divalent cyclic group selected from a cyclohexane ring or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, wherein any hydrogen atom on the cyclic group has 1 to 3 carbon atoms An alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkyl group having 1 to 3 carbon atoms. Kokishiru group or a fluorine atom may be substituted with, Y ⁵ represents a divalent cyclic group selected from benzene ring, cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic group, carbon atoms 1 Or an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, 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, and n is 0 indicates to 4 integer, ^{Y 6} represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxyl group having 1 to 18 alkoxyl group or a carbon of 1 to 18 carbon atoms In formula [2b-3], Y ⁷ represents —O—, —CH ₂ O—, —COO—, —OCO—, —CONH— or —NHCO—, and Y ⁸ has 8 to 22 carbon atoms. Represents an alkyl group, In formula [2b-4], Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and in formula [2b-5], Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms. Show).

(5) The (1) to (4) above, wherein the tetracarboxylic acid component in the polymer of the component (B) contains at least one selected from compounds represented by the following formula [3]. The liquid-crystal aligning agent in any one of.

（式［３］中、Ｚ^１は下記の式［３ａ］〜式［３ｊ］から選ばれる構造の基である）。

(In formula [3], Z ¹ is a group having a structure selected from the following formulas [3a] to [3j]).

（式［３ａ］中、Ｚ^２〜Ｚ^５は水素原子、メチル基、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［３ｇ］中、Ｚ^６およびＺ^７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 [3a], Z ^{2 to} Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [3g], Z ⁶ and Z ⁷ are A hydrogen atom or a methyl group, which may be the same or different.

(6) Any of the above (1) to (5) containing at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone as the component (C) A liquid crystal alignment treatment agent according to claim 1 .

(7) Any of the above (1) to (6) containing at least one solvent selected from the solvents represented by the following formulas [D-1] to [D-3] as the component (D) A liquid crystal alignment treatment agent according to claim 1 .

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

(In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and the formula [D-3 ], D < ³ > shows a C1-C4 alkyl group.

(8) As component (E), at least one solvent selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether is contained. The liquid crystal aligning agent according to any one of (1) to (7) above.

(9) A liquid crystal alignment film obtained by using the liquid crystal aligning agent as described in (1) to (8 ) above.

(10) A liquid crystal alignment film obtained by an ink jet method using the liquid crystal aligning agent described in (1) to (8 ) above.

(11) A liquid crystal display device having the liquid crystal alignment film according to (9) or (10) .

(12) A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (9) or (10) , wherein the liquid crystal alignment film is used for a liquid crystal display device produced through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(13) A liquid crystal display element comprising the liquid crystal alignment film according to (12) .

(14) A liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (9) or (10) , wherein the liquid crystal alignment film is used for a liquid crystal display device produced through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

(15) A liquid crystal display device comprising the liquid crystal alignment film according to (14) .

  A composition containing at least one polymer selected from a cellulose-based polymer having a specific structure of the present invention and a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component is a resin film. The transparency of the resin is high, and decomposition of the resin film accompanying light irradiation can be suppressed.

  In addition, the liquid crystal alignment treatment agent comprising the composition of the present invention forms a liquid crystal alignment film having an excellent voltage holding ratio even when irradiated with light in the presence of an insulating film made of an organic member under the liquid crystal alignment film. Can do. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained thereby can have high reliability.

  As a result of intensive studies, the inventor has obtained the following knowledge and completed the present invention.

The present invention relates to a composition containing the following components (A) and (B), a liquid crystal alignment treatment agent, a resin film obtained using the composition, and a liquid crystal alignment film obtained using the liquid crystal alignment treatment agent. Furthermore, the present invention relates to a liquid crystal display element having the liquid crystal alignment film.
Component (A): a polymer having a structure represented by the following formula [1] (also referred to as a specific cellulose polymer).

（式［１］中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５およびＸ^６は、それぞれ独立して、下記の式［１ａ］〜式［１ｍ］から選ばれる少なくとも１種の構造の基を示し、ｎは１００〜１００００００の整数を示す）。

(In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are each independently at least one structure selected from the following formulas [1a] to [1m]. And n represents an integer of 100 to 1,000,000).

（式［１ｃ］〜式［１ｍ］中、Ｘ^７、Ｘ^８、Ｘ^９、Ｘ^１０、Ｘ^１１、Ｘ^１２、Ｘ^１３およびＸ^１４は、それぞれ独立して、ベンゼン環、メチレン基、エチレン基、ｎ−プロピレン基、イソプロピレン基またはブチレン基を示し、式［１ｈ］中、ｎは０〜３の整数を示し、式［１ｉ］中、ｍは０〜３の整数を示す）。

(In the formulas [1c] to [1m], X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently a benzene ring, methylene group, ethylene group , N-propylene group, isopropylene group or butylene group , in formula [1h], n represents an integer of 0 to 3, and in formula [1i], m represents an integer of 0 to 3.

  Component (B): At least one polymer selected from a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component (also referred to as a specific polyimide polymer).

  The specific cellulose polymer of the present invention has higher transparency than a polyimide polymer. Therefore, the resin film obtained from the composition of the present invention is less likely to absorb light such as ultraviolet rays than that obtained from a normal polyimide polymer, and accordingly, the resin film is less likely to be decomposed.

  Moreover, since the composition of this invention contains the specific polyimide-type polymer excellent in light resistance and heat resistance with the specific cellulose polymer, the stability of the resin film with respect to light and heat becomes higher.

  Since the specific cellulose polymer of the present invention has many OH groups (hydroxyl groups) and COOH groups (carboxylic acid groups), it can trap ionic impurities such as metals and low molecular weight organic compounds. Therefore, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention becomes a liquid crystal alignment film having an excellent voltage holding ratio even when light is irradiated in a state where an insulating film made of an organic member is present under the liquid crystal alignment film. .

  In addition, since the liquid-crystal aligning agent of this invention contains the specific polyimide type polymer, the ability to orient a liquid crystal (it is also called liquid crystal orientation) and a pretilt angle are provided with the characteristic of the voltage retention mentioned above. A liquid crystal alignment film having excellent characteristics can also be formed.

  From the above points, the composition of the present invention can form a highly transparent resin film. And the liquid-crystal aligning agent obtained from the composition of this invention is excellent in a voltage holding | maintenance rate even if it irradiates light in the state which has the insulating film which consists of an organic member under a liquid-crystal aligning film, Furthermore, liquid-crystal aligning It is possible to form a liquid crystal alignment film having excellent properties and a property for imparting a pretilt angle.

  Hereinafter, embodiments of the present invention will be described in more detail.

<Specific cellulose polymer>
The specific cellulose polymer as the component (A) of the present invention is a polymer having a structure represented by the following formula [1].

In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently have at least one structure selected from the following formulas [1a] to [1m]. Indicates a group.

In the formulas [1c] to [1m], X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently a benzene ring, methylene group, ethylene group, n -Represents a propylene group, an isopropylene group or a butylene group .

  In the formula [1h], n represents an integer of 0 to 3. Of these, an integer of 0 or 1 is preferable.

  In formula [1i], m represents an integer of 0 to 3. Of these, an integer of 0 or 1 is preferable.

In formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a structure selected from formula [1a] to formula [1m]. May be one type or two or more types. In particular, it is preferable to use two or more types from the viewpoints of solubility of a specific cellulose polymer in a solvent and applicability of a composition or a liquid crystal aligning agent. It is particularly preferable to use the structure of the formula [1a] and the structures of the formulas [1b] to [1m]. Furthermore, it is preferable to use the structure of formula [1a] and the structure of formula [1c], the structure of formula [1d], the structure of formula [1e], the structure of formula [1h], or the structure of formula [1i].

  In the formula [1], n represents an integer of 100 to 1,000,000. Especially, 100-500,000 are preferable from the point of the handleability at the time of adjusting the solubility to the solvent of a specific cellulose polymer, and a composition or a liquid-crystal aligning agent. More preferred is 100 to 100,000.

  Specific examples of the specific cellulose polymer of the present invention include the following, but are not limited to these examples.

  For example, cellulose, methylcellulose, ethylcellulose, propylcellulose, butylcellulose, methylethylcellulose, acetylcellulose, cellulose propionate, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose Phthalate, methylaminocellulose, ethylaminocellulose, propylaminocellulose, benzylcellulose, tribenzoylcellulose, cellulose acetate butyrate, cellulose acetate propionate, carboxymethylcellulose, carboxymethylethylcellulose or carboxymethyl Le hydroxyethyl cellulose and the like. Among them, methylcellulose, ethylcellulose, propylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose phthalate, benzylcellulose, cellulose acetate propionate, carboxymethylethylcellulose or carboxy Methyl hydroxyethyl cellulose is preferred. More preferred is methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose phthalate or carboxymethylethylcellulose. Particularly preferred are methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose or hydroxypropylmethylcellulose phthalate.

  These specific cellulose derivatives are generally available. Moreover, there is no restriction | limiting in particular in the method of introduce | transducing the structure shown by Formula [1b]-Formula [1m], The existing method can be used.

For example, to introduce the structure of formula [1b], a method of reacting in the presence of an alkali to cellulose and benzyl chloride, to introduce the structure of formula [1c] is a halogen compound having a cellulose and X ⁷ a method of reacting in the presence of an alkali, to introduce the structure of formula [1d], a method of reacting the method and cellulose and acetic anhydride is reacted with an acid chloride compound having the structure of cellulose and X ⁸ in the presence of an alkali In the case of introducing the structure of the formula [1e], a method in which cellulose and a halogen compound having a structure of X ⁹ -OH are reacted in the presence of an alkali. In the case of introducing the structure of the formula [1f], cellulose and X a method of reacting in the presence of an alkali and a halogen compound having the structure ¹⁰ -COOH, the case of introducing the structure of formula [1 g], the cellulose A method of reacting in the presence of an alkali and a halogen compound having the structure ¹¹ -NH _2, the case of introducing the structure of formula [1h], a method of reacting a cellulose with phthalic acid, introducing the structure of formula [1i] If you are a method of reacting a halogen compound having a cellulose and X ¹² and phthalic acid skeleton in the presence of an alkali, to introduce the structure of formula [1k] can include a method of reacting a cellulose with maleic anhydride It is done.

  These specific cellulosic polymers represented by the formula [1] are the solubility and coating properties of the specific cellulosic polymer of the present invention in a solvent, the orientation of liquid crystals when used as a liquid crystal alignment film, the voltage holding ratio, One type or a mixture of two or more types can be used in accordance with characteristics such as accumulated charge.

<Specific polyimide polymer>
The specific polyimide polymer which is the component (B) of the present invention is a polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

  The polyimide precursor has 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は水素原子または炭素数１〜８のアルキル基を示し、それぞれ同じであっても異なってもよく、Ａ^３およびＡ^４は水素原子、炭素数１〜５のアルキル基またはアセチル基を示し、それぞれ同じであっても異なってもよく、ｎは正の整数を示す）。

(In the formula [A], R ¹ is a tetravalent organic group, R ² is a divalent organic group, A ¹ and A ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, A ³ and A ⁴ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, and may be the same or different, and n is a positive integer. Show).

  The diamine component is a diamine compound having two primary or secondary amino groups in the molecule, and the tetracarboxylic acid component is a tetracarboxylic acid compound, tetracarboxylic dianhydride, or tetracarboxylic acid dihalide compound. And tetracarboxylic acid dialkyl ester compounds or tetracarboxylic acid dialkyl ester dihalide compounds.

  The reason why the specific polymer of the present invention can be obtained relatively easily by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as raw materials. Therefore, a polyamic acid having a structural formula of a repeating unit represented by the following formula [D] or a polyimide obtained by imidizing the polyamic acid is preferable.

（式［Ｂ］および式［Ｃ］中、Ｒ^１およびＲ^２は式［Ａ］で定義したものと同意義である）。

(In formula [B] and formula [C], R ¹ and R ² are as defined in formula [A]).

（式［Ｄ］中、Ｒ^１およびＲ^２は式［Ａ］で定義したものと同意義である）。

(In formula [D], R ¹ and R ² have the same meaning as defined in formula [A]).

In addition, the polymer of the formula [D] obtained as described above is added to the alkyl group having 1 to 8 carbon atoms of A ¹ and A ^{2 represented by} the formula [A] and the formula [A] by a usual synthesis method. it is also possible to introduce an alkyl group or an acetyl group having 1 to 5 carbon atoms of a ³ and a ⁴ are shown.

<Diamine component>
A known diamine compound can be used as the diamine component for producing the specific polyimide polymer that is the component (B) of the present invention.

  Among them, it is preferable to use a diamine compound having a structure represented by the following formula [2a].

  In formula [2a], a represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis | combination.

  Specific examples of the diamine compound having a structure represented by the formula [2a] include a diamine compound represented by the following formula [2a-1].

  In formula [2a-1], a represents an integer of 0 to 4. Among these, 0 or 1 is preferable from the viewpoint of availability of raw materials and ease of synthesis.

  In the formula [2a-1], n represents an integer of 1 to 4. Among these, 1 is preferable from the viewpoint of ease of synthesis.

  Although the method to manufacture the diamine compound shown by the formula [2a] of this invention is not specifically limited, What is shown below is mentioned as a preferable method. As an example, a diamine compound represented by the formula [2a-1] is obtained by synthesizing a dinitro compound represented by the following formula [2a-A], further reducing the nitro group and converting it to an amino group. It is done.

（式［２ａ−Ａ］中、ａは０〜４の整数を示し、ｎは１〜４の整数を示す）。

(In formula [2a-A], a represents an integer of 0 to 4, and n represents an integer of 1 to 4).

  The method for reducing the dinitro group of the dinitro compound represented by the formula [2a-A] is not particularly limited, and is usually palladium-carbon in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent. There is a method in which platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, or the like is used as a catalyst and reacted under hydrogen gas, hydrazine, or hydrogen chloride.

  Examples of the diamine compound represented by the formula [2a] of the present invention further include diamine compounds represented by the following formulas [2a-2] to [2a-5].

In formula [2a-2], 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) shows a CO-. Among these, from the viewpoint of ease of synthesis, a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH -, -NHCO-, -COO- or -OCO- are preferred. More preferred is a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —NH— or —N (CH ₃ ) —.

In formula [2a-2], m ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4. Among ^them, m 1 + ^{m 2} is 1 or 2 are preferred.

In formula [2a-3], m ³ and m ⁴ each represent an integer of 1 to 5. Of these, 1 or 2 is preferable from the viewpoint of ease of synthesis.

In formula [2a-4], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. Especially, a C1-C3 linear alkyl group is preferable.

In formula [2a-4], m ⁵ represents an integer of 1 to 5. Of these, 1 or 2 is preferable.

In the formula [2a-5], A ³ 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) shows a CO-. Among them, a single bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ — , -COO- or -OCO- is preferable. More preferred is —O—, —CO—, —NH—, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO— or —OCO—.

In formula [2a-5], m ⁶ represents an integer of 1 to 4. Of these, 1 is preferable from the viewpoint of ease of synthesis.

  The diamine compound represented by the formula [2a-1] to the formula [2a-5] is preferably 20 mol% to 100 mol%, more preferably 30 mol% to 80 mol%, based on the total diamine component. It is preferable that

  The diamine compound represented by the formula [2a-1] to the formula [2a-5] is a liquid crystal when the specific polyimide polymer of the present invention is dissolved in a solvent, the coating property of the composition, or a liquid crystal alignment film. One kind or a mixture of two or more kinds can be used according to the properties such as the orientation, voltage holding ratio, and accumulated charge.

  As a diamine component for producing the specific polyimide polymer of the present invention, a diamine compound represented by the following formula [2b] is preferably used.

  In formula [2b], Y is at least one selected from the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4], or formula [2b-5]. The substituent of a structure is shown, m shows the integer of 0-4.

  In formula [2b-1], a represents an integer of 0 to 4. Especially, the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis | combination.

In formula [2b-2], Y ¹ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. Indicates. Among these, from the viewpoint of availability of raw materials and ease 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—.

In formula [2b-2], Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15). Among these, a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.

In formula [2b-2], Y ³ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. Indicates. Among these, from the viewpoint of ease of synthesis, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, or —COO— is preferable. 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 [2b-2], Y 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. , An alkoxyl group having 1 to 3 carbon atoms, 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. Furthermore, Y ⁴ may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton. Of these, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable from the viewpoint of ease of synthesis.

In Formula [2b-2], Y 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. , An alkoxyl group having 1 to 3 carbon atoms, 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. Of these, a benzene ring or a cyclohexane ring is preferable.

  In formula [2b-2], n represents an integer of 0 to 4. Especially, 0-3 are preferable from the point of the availability of a raw material and the ease of a synthesis | combination. More preferably, it is 0-2.

In Formula [2b-2], Y 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. Indicates. Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are 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.

As a preferred combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2b-2] for constituting the substituent Y in the formula [2b], International Publication The same combinations as (2-1) to (2-629) listed in Tables 6 to 47 of the 13th to 34th items of WO2011 / 132751 (published 2011.10.27) are mentioned. In each table of International Publication, ^Y 1 to Y ⁶ in the present invention is shown as Y1 to Y6, Y1 to ^Y6, shall read Y 1 to Y ^6.

In formula [2b-3], Y ⁷ represents —O—, —CH ₂ O—, —COO—, —OCO—, —CONH— or —NHCO—. Of these, —O—, —CH ₂ O—, —COO— or —CONH— is preferable. More preferred is —O—, —COO— or —CONH—.

In formula [2b-3], Y ⁸ represents an alkyl group having 8 to 22 carbon atoms.

In formula [2b-4], Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group having 1 to 12 carbon atoms.

In formula [2b-5], Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms.

  Although the method to manufacture the diamine compound shown by the formula [2b] of this invention is not specifically limited, What is shown below is mentioned as a preferable method. As an example, the diamine compound represented by the formula [2b] can be obtained by synthesizing a dinitro compound represented by the following formula [2b-A], further reducing the nitro group and converting it to an amino group.

（式［２ｂ−Ａ］中、Ｙは前記式［２ｂ−１］、式［２ｂ−２］、式［２ｂ−３］、式［２ｂ−４］または式［２ｂ−５］から選ばれる少なくとも１つの構造の置換基を示し、ｍは０〜４の整数を示す）。

(In Formula [2b-A], Y is at least selected from Formula [2b-1], Formula [2b-2], Formula [2b-3], Formula [2b-4], or Formula [2b-5]. 1 represents a substituent having one structure, and m represents an integer of 0 to 4.

There is no particular limitation on the method for reducing the dinitro group of the dinitro compound represented by the formula [2b-A], and usually in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent, palladium-carbon, There is a method in which platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, or the like is used as a catalyst and reacted under hydrogen gas, hydrazine, or hydrogen chloride.
Although the specific structure of the diamine compound shown by the formula [2b] of this invention is given to the following, it is not limited to these examples.
That is, as the diamine compound represented by the formula [2b], m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol In addition to 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, and 4,6-diaminoresorcinol, diamine compounds having structures represented by the following formulas [2b-6] to [2b-46] are exemplified. be able to.

（式［２ｂ−６］〜式［２ｂ−９］中、Ａ^１は、炭素数１〜２２のアルキル基またはフッ素含有アルキル基を示す）。

(In Formula [2b-6] to Formula [2b-9], A ¹ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

（式［２ｂ−３４］〜式［２ｂ−３６］中、Ｒ^１は−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−またはＣＨ_２ＯＣＯ−を示し、Ｒ^２は炭素数１〜２２のアルキル基、アルコキシ基、フッ素含有アルキル基またはフッ素含有アルコキシ基を示す）。

(In the formulas [2b-34] to [2b-36], R ¹ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or CH ₂ OCO—, and R ² represents carbon. An alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group represented by formulas 1 to 22).

（式［２ｂ−３７］〜式［２ｂ−３９］中、Ｒ^３は−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−または−ＣＨ_２−を示し、Ｒ^４は炭素数１〜２２のアルキル基、アルコキシ基、フッ素含有アルキル基またはフッ素含有アルコキシ基を示す）。

(In the formulas [2b-37] to [2b-39], R ³ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ — or — CH ₂ - indicates, ^{R 4} represents an alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group having 1 to 22 carbon atoms).

（式［２ｂ−４０］および式［２ｂ−４１］中、Ｒ^５は−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２−または−Ｏ−であり、Ｒ^６はフッ素基、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である）。

(In the formulas [2b-40] and [2b-41], R ⁵ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, — CH ₂ — or —O—, and R ⁶ is a fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group).

（式［２ｂ−４２］および式［２ｂ−４３］中、Ｒ^７は炭素数３〜１２のアルキル基を示す。なお、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が好ましい）。

(In the formulas [2b-42] and [2b-43], R ⁷ represents an alkyl group having 3 to 12 carbon atoms. Note that the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer. preferable).

（式［２ｂ−４４］および式［２ｂ−４５］中、Ｒ^８は炭素数３〜１２のアルキル基を示す。なお、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が好ましい）。

(In the formulas [2b-44] and [2b-45], R ⁸ represents an alkyl group having 3 to 12 carbon atoms. In addition, the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer. preferable).

（式［２ｂ−４６］中、Ｂ^４はフッ素原子で置換されていてもよい炭素数３〜２０のアルキル基を示し、Ｂ^３は１，４−シクロへキシレン基または１，４−フェニレン基を示し、Ｂ^２は酸素原子または−ＣＯＯ−＊（但し、「＊」を付した結合手がＢ^３と結合する）を示し、Ｂ^１は酸素原子または−ＣＯＯ−＊（但し、「＊」を付した結合手が（ＣＨ_２）ａ^２と結合する）を示す。また、ａ^１は０または１の整数を示し、ａ^２は２〜１０の整数を示し、ａ^３は０または１の整数を示す）。

(In the formula [2b-46], B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and B ³ represents a 1,4-cyclohexylene group or a 1,4-phenylene group. B ² represents an oxygen atom or —COO— * (where a bond marked with “*” binds to B ³ ), and B ¹ represents an oxygen atom or —COO— * (where “*” bond marked with represents a _(CH 2) bind to ^{a 2).} Further, ^{a 1} represents an integer of 0 or 1, ^{a 2} represents an integer of 2 to 10, ^{a 3} is 0 or 1 Indicates an integer).

  Among the diamine compounds represented by the formula [2b], the composition using the diamine compound in which the substituent Y in the formula [2b] is represented by the formula [2b-2] Can be high. Further, when the liquid crystal alignment film is used, the pretilt angle of the liquid crystal can be increased. At that time, for the purpose of enhancing these effects, among the above diamine compounds, the diamines represented by the formula [2b-28] to the formula [2b-39] or the formula [2b-42] to the formula [2b-46]. It is preferable to use a compound. More preferred are diamine compounds represented by the formula [2b-24] to [2b-39] or the formula [2b-42] to the formula [2b-46]. Moreover, in order to improve these effects, it is preferable that these diamine compounds are 5 mol% or more and 80 mol% or less of the whole diamine component. More preferably, these diamine compounds are 5 mol% or more and 60 mol% of the whole diamine component from the viewpoint of the applicability of the composition and the liquid crystal alignment treatment agent and the electric characteristics as the liquid crystal alignment film.

  The diamine compound represented by the formula [2b] is used for the solubility and coating property of the specific polyimide polymer of the present invention in a solvent, liquid crystal alignment in the case of forming a liquid crystal alignment film, voltage holding ratio, accumulated charge, etc. Depending on the characteristics, one kind or a mixture of two or more kinds can be used.

  As a diamine component for producing the specific polyimide-based polymer of the present invention, a diamine compound other than the diamine compound represented by the formula [2a-1] to the formula [2a-5] and the diamine compound represented by the formula [2b] (Also referred to as other diamine compounds) can be used as the diamine component. Specific examples of other diamine compounds are shown below, but are not limited to these examples.

  For example, 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'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diamino Biphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-dia Nodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyl Dianiline, 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′-diaminodiphenylamine, 2,2′-diaminodiphenylamine, 2,3′-diaminodiphenylamine, N-methyl (4,4′-diaminodipheny ) 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, 1,7-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-amino) Phenyl) 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-aminophenyl) 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-aminobenzoate), 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-aminobenzamide), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1,4-phenylene) bis (3-aminobenzamide), N, N '-(1,3-phenylene) bis (3-aminobenzamide), 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) L) anthracene, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 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-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-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-aminophenoxy) 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-methyl) (Cyclohexyl) 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, 1,12-diaminododecane and the like can be mentioned.

  Examples of other diamine compounds include those having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in the diamine side chain, and those having a macrocyclic substituent composed of these. . Specifically, diamine compounds represented by the following formulas [DA1] to [DA13] can be exemplified.

（式［ＤＡ１］〜式［ＤＡ６］中、Ａ^１は−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ル基または炭素数１〜２２の直鎖状もしくは分岐状のフッ素含有アルキル基を示す）。

(In Formula [DA1] to Formula [DA6], A ¹ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or —NH—, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms).

（式［ＤＡ７］中、ｐは１〜１０の整数を示す）。

(In formula [DA7], p represents an integer of 1 to 10).

  As long as the effects of the present invention are not impaired, diamine compounds represented by the following formulas [DA8] to [DA13] can also be used as other diamine compounds.

（式［ＤＡ１０］中、ｍは０〜３の整数を示し、式［ＤＡ１３］中、ｎは１〜５の整数を示す）。

(In the formula [DA10], m represents an integer of 0 to 3, and in the formula [DA13], n represents an integer of 1 to 5).

  Furthermore, a diamine compound represented by the following formula [DA14] can also be used as long as the effects of the present invention are not impaired.

（式［ＤＡ１４］中、Ａ^１は−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−または−Ｎ（ＣＨ_３）ＣＯ−より選ばれる２価の有機基であり、Ａ^２は単結合、炭素数１〜２０の脂肪族炭化水素基、非芳香族環式炭化水素基または芳香族炭化水素基であり、Ａ^３は単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−または−Ｏ（ＣＨ_２）_ｍ−（ｍは１〜５の整数である）より選ばれ、Ａ^４は窒素含有芳香族複素環であり、ｎは１〜４の整数である）。
加えて、その他ジアミン化合物として、下記の式［ＤＡ１５］および式［ＤＡ１６］で示されるジアミン化合物を用いることもできる。

(In the formula [DA14], A ¹ represents —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ). A divalent organic group selected from — or —N (CH ₃ ) CO—, and A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic group. A ³ is a hydrocarbon group, A ³ is a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ). —, —N (CH ₃ ) CO— or —O (CH ₂ ) _m — (m is an integer of 1 to 5), A ⁴ is a nitrogen-containing aromatic heterocycle, and n is 1 to 4 is an integer).
In addition, as other diamine compounds, diamine compounds represented by the following formulas [DA15] and [DA16] can also be used.

  The above-mentioned other diamine compounds have characteristics such as the solubility of the specific polyimide polymer of the present invention in a solvent, the coating property of the composition, the orientation of the liquid crystal when it is used as a liquid crystal alignment film, the voltage holding ratio, and the accumulated charge. Depending on the case, one kind or a mixture of two or more kinds may be used.

<Tetracarboxylic acid component>
As the tetracarboxylic acid component for producing the specific polyimide polymer which is the component (B) of the present invention, tetracarboxylic dianhydride represented by the following formula [3] or tetracarboxylic acid derivative tetra It is preferable to use a carboxylic acid, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound (all are collectively referred to as a specific tetracarboxylic acid component).

In the formula [3], Z ¹ is a group having a structure selected from the following formulas [3a] to [3j].

In formula [3a], Z ^{2 to} Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.

In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and may be the same or different.

In the structure represented by the formula [3] which is the specific tetracarboxylic acid component of the present invention, Z ¹ is represented by the formula [3a], from the viewpoint of ease of synthesis and polymerization reactivity when producing a polymer. A structure represented by Formula [3c], Formula [3d], Formula [3e], Formula [3f], or Formula [3g] is preferable. More preferred is a structure represented by formula [3a], formula [3e], formula [3f] or formula [3g], and particularly preferred is formula [3e], formula [3f] or formula [3g]. It is.

  It is preferable that the specific tetracarboxylic acid component of this invention is 1 mol% or more in all the tetracarboxylic acid components. More preferred is 5 mol% or more, and particularly preferred is 10 mol% or more.

  Moreover, when using the specific tetracarboxylic acid component of the structure of Formula [3e], Formula [3f], or Formula [3g], the usage-amount is made into 20 mol% or more of the whole tetracarboxylic acid component, and it is desired An effect is obtained. Preferably, it is 30 mol% or more. Further, all of the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure of the formula [3e], the formula [3f], or the formula [3g].

  As long as the effect of this invention is not impaired, other tetracarboxylic acid components other than a specific tetracarboxylic acid component can be used for the specific polyimide-type polymer of this invention. Examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and tetracarboxylic acid dialkyl ester dihalide compounds.

  That is, as other tetracarboxylic acid components, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalene Tetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic 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'-benzophenonetetracarboxylic 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, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetra Carboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1, Examples include 3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

  The specific tetracarboxylic acid component and other tetracarboxylic acid components are the solubility of the specific polyimide polymer of the present invention in the solvent, the coating property of the composition, the alignment property of the liquid crystal when used as a liquid crystal alignment film, and the voltage holding ratio. Depending on the characteristics such as accumulated charge, one kind or a mixture of two or more kinds may be used.

<Method for producing specific polyimide polymer>
In the present invention, the method for synthesizing the specific polyimide polymer is 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 acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid. Specifically, a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and primary or secondary diamine compound, dehydration polycondensation reaction of tetracarboxylic acid and primary or secondary diamine compound A method of obtaining polyamic acid by polycondensation of a tetracarboxylic acid dihalide and a primary or secondary diamine compound is used.

  In order to obtain the polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine compound, a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and 1 A method of polycondensation with a secondary 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 polyimide, a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.

  The reaction between the diamine component and the tetracarboxylic acid component is usually performed in an organic solvent with the diamine component and the tetracarboxylic acid component. The organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Although the specific example of the organic solvent used for reaction below is given, it is not limited to these examples. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone , Cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, solvents represented by the following formulas [D-1] to [D-3], and the like.

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

(In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and the formula [D-3 ], D < ³ > shows a C1-C4 alkyl group.

  These may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since the water | moisture content in an organic solvent inhibits a polymerization reaction, and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

  When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is dispersed or dissolved in the organic solvent as it is. And a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, etc. Any of these methods may be used. In addition, when reacting using a plurality of diamine components or tetracarboxylic acid components, they may be reacted in a premixed state, individually or sequentially, or further individually reacted low molecular weight substances. May be mixed and reacted to form a polymer. Although the polymerization temperature in that case can select the arbitrary 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 is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, Preferably it is 1-50 mass%, More preferably, it is 5-30 mass%. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

  In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component and 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 polyimide precursor produced increases as the molar ratio approaches 1.0.

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

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

  The temperature at which the polyimide precursor is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and is preferably performed while removing water generated by the imidization reaction from the system.

  The catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has a basicity appropriate for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

  When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be poured into a solvent and precipitated. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.

  The molecular weight of the specific polyimide polymer of the present invention was measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the resin film or liquid crystal alignment film obtained therefrom, workability at the time of film formation, and coating properties. The weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Composition / Liquid crystal aligning agent>
The composition or liquid crystal alignment treatment agent of the present invention is a coating solution for forming a resin film or a liquid crystal alignment film (also collectively referred to as a resin film), and is a specific cellulose polymer, a specific polyimide polymer, and a solvent. It is the application | coating solution for forming the resin film containing this.

  The ratio of the specific cellulose polymer and the specific polyimide polymer in the composition or the liquid crystal aligning agent of the present invention is such that when the ratio of the specific polyimide polymer is 1, the ratio of the specific cellulose polymer is 0. 1-9. Particularly preferred is 0.2-4.

  All the polymer components in the composition or the liquid crystal aligning agent of the present invention may all be the specific cellulose polymer and the specific polyimide polymer of the present invention, and other polymers are mixed. May be. In that case, content of other polymers other than that is 0.5 mass%-15 mass% of the specific polymer of this invention, Preferably they are 1 mass%-10 mass%. As other polymers, the diamine compound represented by the formula [2a-1] to the formula [2a-5], the diamine compound represented by the formula [2b] and a polyimide not using the specific tetracarboxylic acid component System polymers. Furthermore, polymers other than a cellulose polymer and a polyimide polymer, specifically, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or polysiloxane may be used.

  The organic solvent in the composition of the present invention or the liquid crystal alignment treatment agent preferably has an organic solvent content of 70 to 99.9% by mass from the viewpoint of forming a uniform resin film by coating. This content can be appropriately changed depending on the film thickness of the target resin film or liquid crystal alignment film.

  The organic solvent used in the composition or the liquid crystal aligning agent of the present invention is not particularly limited as long as it is an organic solvent (also referred to as a good solvent) that dissolves the specific cellulose polymer and the specific polyimide polymer. Although the specific example of a good solvent is given to the following, it is 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 , Cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, the solvent represented by the above-described formula [D-1] to formula [D-3], and the like can be given. These may be used alone or in combination.

  Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone (also referred to as component (C) above) are preferably used. Furthermore, when the solubility of the specific cellulose polymer and the specific polyimide polymer in the solvent is high, the solvent represented by the formula [D-1] to the formula [D-3] (also referred to as the component (D) above). It is preferable to use

  The good solvent in the composition or liquid crystal aligning agent of the present invention is preferably 10 to 100% by mass of the total solvent contained in the composition or liquid crystal aligning agent. Especially, 20-90 mass% is preferable. More preferably, it is 30-80 mass%.

  Unless the effect of this invention is impaired, the composition or liquid-crystal aligning agent of this invention improves the coating property and surface smoothness of the resin film or liquid crystal aligning film at the time of apply | coating a composition or a liquid-crystal aligning agent. An organic solvent (also referred to as a poor solvent) can be used. Although the specific example of a poor solvent is given to the following, it 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- Etanji 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-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl 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, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol dia Cetrate, 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, lactic acid 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, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate or the above formula [D -1] to a solvent represented by the formula [D-3].

  Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether (also referred to as component (E) above), or the above formula [D -1] to a solvent represented by the formula [D-3] are preferably used.

  These poor solvents are preferably 1 to 70% by mass of the whole organic solvent contained in the composition or the liquid crystal aligning agent. Especially, 1-60 mass% is preferable. More preferred is 5 to 60% by mass.

  The composition or liquid crystal aligning agent of the present invention includes 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 as long as the effects of the present invention are not impaired. A crosslinkable compound having at least one substituent selected from the group consisting of groups or a crosslinkable compound having a polymerizable unsaturated bond can also be introduced. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.

  Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, 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, tetraglycidylmetaxylenediamine, 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 [4].

  Specifically, it is a crosslinkable compound represented by the following formula [4-1] to formula [4-11].

（式［４−１］中、ｎは１〜３の整数を示す）。

(In formula [4-1], n represents an integer of 1 to 3).

（式［４−７］中、ｎは１〜３の整数を示し、式［４−８］中、ｎは１〜３の整数を示し、式［４−９］中、ｎは１〜１００の整数を示す）。

(In formula [4-7], n represents an integer of 1 to 3, in formula [4-8], n represents an integer of 1 to 3, and in formula [4-9], n represents 1 to 100. Indicates an integer).

（式［４−１１］中、ｎは１〜１０の整数を示す）。

(In the formula [4-11], n represents an integer of 1 to 10).

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

  Specifically, it is a crosslinkable compound represented by the following formula [5-1] to formula [5-37].

（式［５−２４］中、ｎは１〜１０の整数を示し、式［５−２５］中、ｎは１〜１０の整数を示す）。

(In the formula [5-24], n represents an integer of 1 to 10, and in the formula [5-25], n represents an integer of 1 to 10).

（式［５−３６］中、ｎは１〜１００の整数を示し、式［５−３７］中、ｎは１〜１０の整数を示す）。

(In the formula [5-36], n represents an integer of 1 to 100, and in the formula [5-37], n represents an integer of 1 to 10).

  Furthermore, the polysiloxane which has at least 1 type of structure shown by following formula [5-38]-formula [5-40] can also be mentioned.

（式［５−３８］〜式［５−４０］中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４およびＲ_５は、それぞれ独立して、式［５］で示される構造、水素原子、水酸基、炭素数１〜１０のアルキル基、アルコキシル基、脂肪族環または芳香族環を示し、少なくとも１つは式［５］で示される構造を示す）。

(In Formula [5-38] to Formula [5-40], R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a structure represented by Formula [5], a hydrogen atom, a hydroxyl group , An alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, at least one of which represents a structure represented by the formula [5].

  More specifically, compounds of the following formulas [5-41] and [5-42] are mentioned.

（式［５−４２］中、ｎは１〜１０の整数を示す）。

(In the formula [5-42], n represents an integer of 1 to 10).

  Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril. -Formaldehyde resin, succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group or both can be used. The melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

  Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring. Eight-substituted MW-30 (Sanwa Chemical Co., Ltd.) and Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamines, Cymel 235, 236 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 and the like Methoxymethylated etoxy 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 Cyanamide). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.

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

  More specifically, the crosslinkable compounds represented by the formulas [6-1] to [6-48], which are published on pages 62 to 66 of International Publication No. WO2011 / 132751 (published 2011.10.27). Is 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 compounds 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 Rudi (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 hydroxypivalic acid neo Crosslinkable compounds having two polymerizable unsaturated groups in the molecule, such as pentyl glycol di (meth) acrylate, in addition, 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- Crosslink having one polymerizable unsaturated group in the molecule such as 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester or N-methylol (meth) acrylamide Compound.

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

（式［７］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、アントラセン環またはフェナントレン環からからなる群から選ばれる基を示し、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 [7], E ₁ represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring; ₂ represents a group selected from the following formula [7a] or [7b], and n represents an integer of 1 to 4.

  The said compound is an example of a crosslinkable compound, It is not limited to these. Moreover, the crosslinkable compound used for the composition or liquid crystal aligning agent of the present invention may be one kind or a combination of two or more kinds.

  The content of the crosslinkable compound in the composition or the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all the polymer components. In order for the crosslinking reaction to proceed and to achieve the desired effect, 0.1 to 100 parts by weight is more preferable, and 1 to 50 parts by weight is most preferable, with respect to 100 parts by weight of all polymer components.

  As a compound that promotes charge transfer in a liquid crystal alignment film and promotes charge release of a liquid crystal cell using the liquid crystal alignment film when a liquid crystal alignment film using the liquid crystal alignment treatment agent using the composition of the present invention is formed. It is preferable to add a nitrogen-containing heterocyclic amine compound represented by the formulas [M1] to [M156], which is described on pages 69 to 73 of International Publication No. WO2011 / 132751 (published 2011.10.27). . This amine compound may be added directly to the composition, but it may be added after a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass, with a suitable solvent. preferable. The solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polyimide polymer described above.

  Unless the effect of the present invention is impaired, the composition or the liquid crystal alignment treatment agent of the present invention has a uniform film thickness or surface smoothness of the resin film or the liquid crystal alignment film when the composition or the liquid crystal alignment treatment agent is applied. Compounds that improve can be used. Furthermore, a compound that improves the adhesion between the resin coating or the liquid crystal alignment film and the substrate can also be used.

  Examples of the compound that improves the film thickness uniformity and surface smoothness of the resin coating or the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

  More specifically, for example, F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.) and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of all the polymer components contained in the composition or the liquid crystal aligning agent. 1 part by mass.

  Specific examples of the compound that improves the adhesion between the resin coating or the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds described below.

  For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane or N, N, N Examples include ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane.

  When using a compound to be adhered to these substrates, it is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of all polymer components contained in the composition or the liquid crystal aligning agent. Is 1-20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the storage stability of the composition or the liquid crystal aligning agent may be deteriorated.

  The composition or the liquid crystal alignment treatment agent of the present invention includes the above-mentioned poor solvent, crosslinkable compound, compound that improves the uniformity of film thickness and surface smoothness of the resin film or liquid crystal alignment film, and the compound that adheres to the substrate. In addition, as long as the effects of the present invention are not impaired, a dielectric material or a conductive material for the purpose of changing electrical characteristics such as dielectric constant or conductivity of the resin film or the liquid crystal alignment film may be added.

<Resin coating>
The composition of the present invention can be used as a resin film after coating and baking on a substrate. As a substrate used in this case, a glass substrate, a silicon wafer, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used depending on a target device. The coating method of the composition is not particularly limited, but industrially, there are methods such as a dipping method, a roll coater method, a slit coater method, a spinner method, a spray method, screen printing, offset printing, flexographic printing, or an inkjet method. It is common. These can be appropriately selected according to the purpose.

  After coating the composition on the substrate, it is 30 to 300 ° C., preferably 30 to 250, depending on the solvent used in the composition by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven. The solvent can be evaporated at a temperature of 0 ° C. to form a resin film. The thickness of the resin film after baking can be adjusted to 0.01-100 micrometers according to the objective.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment treatment agent using the composition of the present invention can be used as a liquid crystal alignment film by applying alignment treatment by rubbing treatment or light irradiation after coating and baking on a substrate. In the case of vertical alignment, etc., it can be used as a liquid crystal alignment film without alignment treatment. The substrate used at this time is not particularly limited as long as it is a highly transparent substrate. 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 simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.

  The method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, an inkjet method, or the like is generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.

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

  The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.

  As a method for manufacturing a liquid crystal cell, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or a method of bonding the substrate after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacers are dispersed, and the like.

  Furthermore, the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board | substrates provided with the electrode, The polymeric compound superposed | polymerized by at least one of an active energy ray and a heat | fever between a pair of board | substrates. The liquid crystal composition is also preferably used for a liquid crystal display device produced through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes. Here, ultraviolet rays are suitable 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. Further, ultraviolet irradiation and heating may be performed simultaneously.

  The liquid crystal display element controls a 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, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound. The pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. The PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.

  That is, in the liquid crystal display element of the present invention, a liquid crystal cell is prepared 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, and a polymerizable compound is produced by at least one of irradiation with ultraviolet rays and heating. The orientation of the liquid crystal molecules can be controlled by polymerizing.

  To give an example of manufacturing a PSA type liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded and the liquid crystal is injected under reduced pressure, or the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed. Can be mentioned.

  In the liquid crystal, a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed. Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. In that case, it is preferable that a polymeric compound is 0.01-10 mass parts with respect to 100 mass parts of a liquid-crystal component, More preferably, it is 0.1-5 mass parts. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal cannot be controlled, and when it exceeds 10 parts by mass, the amount of unreacted polymerizable compound increases and the liquid crystal display element. The seizure characteristics of the steel deteriorate.

  After the liquid crystal cell is produced, the polymerizable compound is polymerized by applying heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.

  In addition, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of disposing a liquid crystal alignment film containing a group and applying a voltage between the electrodes. Here, ultraviolet rays are suitable 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. Further, ultraviolet irradiation and heating may be performed simultaneously.

  In order to obtain a liquid crystal alignment film containing a polymerizable group that polymerizes from at least one of active energy rays and heat, a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent, A method using a coalescing component may be mentioned. Since the liquid crystal aligning agent of the present invention contains a specific compound having a double bond site that reacts by heat or ultraviolet irradiation, the alignment of liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating. it can.

  If an example of liquid crystal cell production is given, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure and sealing is performed, or a method in which the substrate is attached and sealed after the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed.

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

  As described above, the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.

  The present invention will be described in more detail with reference to the following examples, but is not limited thereto.

Abbreviations used in the synthesis examples, examples and comparative examples are as follows.
(Specific cellulose polymer as component (A) of the present invention)
CE-1: Hydroxyethyl cellulose (manufactured by WAKO)
CE-2: Hydroxypropyl methylcellulose phthalate (manufactured by ACROS)

(Diamine compound represented by the formula [2a] of the present invention)
A1: 3,5-Diaminobenzoic acid (diamine compound represented by the following formula [A1])
A2: 2,5-diaminobenzoic acid (diamine compound represented by the following formula [A2])

(Diamine compound represented by the formula [2b] of the present invention)
B1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene (diamine compound represented by the following formula [B1])
B2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl] benzene (diamine compound represented by the following formula [B2])
B3: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene (diamine compound represented by the following formula [B3])
B4: Diamine compound represented by the following formula [B4] B5: 1,3-diamino-4-octadecyloxybenzene (diamine compound represented by the following formula [B5])
B6: Diamine compound represented by the following formula [B6]

(Other diamine compounds)
C1: p-phenylenediamine (diamine compound represented by the following formula [C1])
C2: m-phenylenediamine (diamine compound represented by the following formula [C2])

(Tetracarboxylic acid component)
D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [D1])
D2: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [D2])
D3: Tetracarboxylic dianhydride represented by the following formula [D3] D4: Tetracarboxylic dianhydride represented by the following formula [D4]

(Solvent as component (C) of the present invention)
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone γ-BL: γ-butyrolactone

(Solvent as component (D) of the present invention)
PGME: Propylene glycol monomethyl ether (solvent represented by the formula [D-1] of the present invention)
PCS: ethylene glycol monopropyl ether (solvent represented by the formula [D-2] of the present invention)
DEEE: Diethylene glycol monoethyl ether (solvent represented by the formula [D-3] of the present invention)

(Solvent which is component (E) of the present invention)
BCS: Ethylene glycol monobutyl ether PB: Propylene glycol monobutyl ether

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

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

(Measurement of imidization ratio of polyimide)
The imidation ratio of polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)). (Mixed product) (0.53 ml) was added and completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.

Imidation ratio (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

“Synthesis of Specific Polyimide Polymer as Component (B) of the Present Invention”
<Synthesis Example 1>
D1 (9.00 g, 45.9 mmol) and A1 (6.98 g, 45.9 mmol) were mixed in NMP (48.0 g) and reacted at 40 ° C. for 8 hours to obtain a polyamide having a resin solid content concentration of 25% by mass. An acid solution (1) was obtained. The number average molecular weight of this polyamic acid was 26,900, and the weight average molecular weight was 78,100.

<Synthesis Example 2>
D2 (8.17 g, 32.7 mmol) and A2 (6.21 g, 40.8 mmol) were mixed in NMP (26.4 g), reacted at 80 ° C. for 5 hours, and then D1 (1.60 g, 8 .16 mmol) and NMP (21.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

  After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting to 6% by mass, acetic anhydride (4.85 g) and pyridine (3.70 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 4 hours. Reacted. This reaction solution was put into methanol (800 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (2). The imidation ratio of this polyimide was 54%, the number average molecular weight was 19,800, and the weight average molecular weight was 44,300.

<Synthesis Example 3>
D2 (6.25 g, 25.0 mmol), B1 (6.79 g, 17.8 mmol) and A1 (2.72 g, 17.9 mmol) were mixed in NMP (29.5 g) and reacted at 80 ° C. for 5 hours. After that, D1 (2.10 g, 10.7 mmol) and NMP (24.1 g) were added and reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution (3) having a resin solid content concentration of 25 mass%. . The number average molecular weight of this polyamic acid was 23,500, and the weight average molecular weight was 65,600.

<Synthesis Example 4>
After adding NMP to the polyamic acid solution (3) (30.0 g) obtained in Synthesis Example 3 and diluting to 6% by mass, acetic anhydride (6.75 g) and pyridine (4.90 g) were used as imidization catalysts. In addition, the mixture was reacted at 90 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (4). The imidation ratio of this polyimide was 82%, the number average molecular weight was 17,500, and the weight average molecular weight was 40,100.

<Synthesis Example 5>
D2 (6.63 g, 26.5 mmol), B1 (5.05 g, 13.3 mmol), A1 (2.52 g, 16.6 mmol) and C1 (0.36 g, 3.33 mmol) to NMP (26.2 g) After mixing at 80 ° C. for 5 hours, D1 (1.30 g, 6.63 mmol) and NMP (21.4 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.

  After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting to 6% by mass, acetic anhydride (4.78 g) and pyridine (3.73 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 4 hours. Reacted. This reaction solution was put into methanol (800 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (5). The imidation ratio of this polyimide was 55%, the number average molecular weight was 17,200, and the weight average molecular weight was 41,600.

<Synthesis Example 6>
D2 (5.17 g, 20.7 mmol), B2 (4.07 g, 10.3 mmol), A1 (2.09 g, 13.7 mmol) and B6 (2.10 g, 10.3 mmol) as NMP (26.6 g) After mixing at 80 ° C. for 5 hours, D1 (2.70 g, 13.8 mmol) and NMP (21.8 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. % Polyamic acid solution was obtained.

  After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting to 6% by mass, acetic anhydride (4.80 g) and pyridine (3.75 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 4 hours. Reacted. This reaction solution was put into methanol (800 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (6). The imidation ratio of this polyimide was 52%, the number average molecular weight was 17,600, and the weight average molecular weight was 41,300.

<Synthesis Example 7>
D2 (4.34 g, 17.3 mmol), B3 (4.50 g, 10.4 mmol), A2 (3.17 g, 20.8 mmol) and C2 (0.37 g, 3.42 mmol) into NMP (26.0 g) After mixing at 80 ° C. for 5 hours, D1 (3.40 g, 17.3 mmol) and NMP (21.3 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid content concentration of 25 mass. % Polyamic acid solution was obtained.

  After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6% by mass, acetic anhydride (6.74 g) and pyridine (4.90 g) were added as an imidization catalyst, and the mixture was stirred at 90 ° C. for 3 hours. Reacted. This reaction solution was put into methanol (700 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (7). The imidation ratio of this polyimide was 78%, the number average molecular weight was 18,500, and the weight average molecular weight was 42,100.

<Synthesis Example 8>
D2 (6.12 g, 24.5 mmol), B4 (2.26 g, 4.59 mmol) and A2 (3.96 g, 26.0 mmol) were mixed in NMP (22.3 g) and reacted at 80 ° C. for 6 hours. After that, D1 (1.20 g, 6.12 mmol) and NMP (18.3 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25 mass%.

  After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting to 6% by mass, acetic anhydride (4.82 g) and pyridine (3.75 g) were added as an imidization catalyst, and 3. The reaction was allowed for 5 hours. This reaction solution was put into methanol (800 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (8). The imidation ratio of this polyimide was 50%, the number average molecular weight was 16,200, and the weight average molecular weight was 38,100.

<Synthesis Example 9>
D3 (7.70 g, 34.3 mmol), B1 (3.92 g, 10.3 mmol) and A1 (3.66 g, 24.1 mmol) were mixed in NMP (45.8 g) and reacted at 40 ° C. for 5 hours. Thus, a polyamic acid solution having a resin solid content concentration of 25% by mass was obtained.

  After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting to 6% by mass, acetic anhydride (4.70 g) and pyridine (3.60 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 4 hours. Reacted. This reaction solution was put into methanol (800 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (9). The imidation ratio of this polyimide was 54%, the number average molecular weight was 17,300, and the weight average molecular weight was 41,000.

<Synthesis Example 10>
D3 (7.50 g, 33.5 mmol), B5 (3.78 g, 10.0 mmol), B6 (1.36 g, 6.69 mmol) and A1 (2.55 g, 16.8 mmol) NMP (45.6 g) Then, the mixture was reacted at 40 ° C. for 5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

  After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting to 6% by mass, acetic anhydride (4.80 g) and pyridine (3.75 g) were added as imidization catalysts, and the mixture was heated at 80 ° C. for 4 hours. Reacted. This reaction solution was put into methanol (800 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 55%, the number average molecular weight was 18,100, and the weight average molecular weight was 39,900.

<Synthesis Example 11>
D4 (5.51 g, 18.4 mmol), B2 (3.62 g, 9.17 mmol), C2 (0.66 g, 6.10 mmol) and A1 (2.33 g, 15.3 mmol) with NMP (24.0 g) After mixing at 80 ° C. for 5 hours, D1 (2.40 g, 12.2 mmol) and NMP (19.6 g) were added, and the mixture was reacted at 40 ° C. for 5 hours. % Polyamic acid solution was obtained.

  After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting to 6% by mass, acetic anhydride (4.80 g) and pyridine (3.70 g) were added as an imidization catalyst, and 4. The reaction was allowed for 5 hours. This reaction solution was put into methanol (800 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (11). The imidation ratio of this polyimide was 60%, the number average molecular weight was 16,800, and the weight average molecular weight was 37,500.

<Synthesis Example 12>
D4 (5.66 g, 18.9 mmol), B1 (4.31 g, 11.3 mmol), B6 (2.30 g, 11.3 mmol) and A1 (2.30 g, 15.1 mmol) with NMP (30.2 g) After mixing at 80 ° C. for 5 hours, D1 (3.70 g, 18.9 mmol) and NMP (24.7 g) were added and reacted at 40 ° C. for 5 hours to give a resin solid content concentration of 25 mass. % Polyamic acid solution (12) was obtained. The number average molecular weight of this polyamic acid was 23,500, and the weight average molecular weight was 66,900.

<Synthesis Example 13>
After adding NMP to the polyamic acid solution (12) (30.0 g) obtained in Synthesis Example 12 and diluting to 6% by mass, acetic anhydride (6.70 g) and pyridine (4.80 g) were used as imidization catalysts. In addition, the mixture was reacted at 90 ° C. for 3.5 hours. This reaction solution was put into methanol (700 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (13). The imidation ratio of this polyimide was 81%, the number average molecular weight was 15,800, and the weight average molecular weight was 37,500.

  Specific polyimide polymers of the present invention are shown in Table 1.

＊１：ポリアミド酸。

* 1: Polyamic acid.

“Production of Composition and Liquid Crystal Alignment Treatment Agent of the Present Invention”
In Examples 1 to 19 and Comparative Examples 1 to 5 described below, production examples of the composition are described. These compositions are also used for evaluation of liquid crystal aligning agents.

  Tables 2 to 4 show the compositions and liquid crystal aligning agents of the present invention.

  Using the compositions or liquid crystal alignment treatment agents obtained in the examples and comparative examples of the present invention, "Evaluation of transparency of resin film", "Evaluation of ink jet coatability of liquid crystal alignment treatment agent", "Preparation of liquid crystal cell And “Evaluation of liquid crystal alignment (ordinary cell)”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)” and “Evaluation of voltage holding ratio on insulating film coated substrate”. The conditions are as follows.

"Evaluation of transparency of resin film"
The compositions obtained in Examples and Comparative Examples of the present invention were pressure filtered through a membrane filter having a pore diameter of 1 μm, and the transparency of the resin coating was evaluated. This solution was spin-coated on a 40 × 50 mm quartz substrate and heat-treated at 100 ° C. for 5 minutes on a hot plate to obtain a quartz substrate with a polyimide resin coating having a thickness of 100 nm.

  Using the obtained quartz substrate with a resin coating, an ultraviolet-visible absorption spectrum having a wavelength of 300 to 750 nm was measured with an ultraviolet-visible spectrophotometer (UV-2550) (manufactured by Shimadzu Corporation). Among these, the higher the transmittance at wavelengths of 310 nm and 340 nm, the better the transparency of the resin film.

  Tables 5 to 7 show the results of the transparency of the resin films obtained in Examples and Comparative Examples.

"Evaluation of inkjet coating properties of liquid crystal alignment treatment agents"
The liquid crystal aligning agent (7) obtained in Example 7 of the present invention and the liquid crystal aligning agent (13) obtained in Example 13 were subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm, and evaluation of ink jet coatability was performed. Went. HIS-200 (manufactured by Hitachi Plant Technology) was used for the ink jet coater. Application is on an ITO (indium tin oxide) vapor-deposited substrate cleaned with pure water and IPA (isopropyl alcohol), the application area is 70 × 70 mm, the nozzle pitch is 0.423 mm, and the scan pitch is 0.5 mm. The speed was 40 mm / second, the time from application to temporary drying was 60 seconds, and temporary drying was performed on a hot plate at 70 ° C. for 5 minutes.

"Preparation of liquid crystal cell and evaluation of liquid crystal alignment (normal cell)"
The liquid crystal aligning agent obtained in Examples and Comparative Examples of the present invention was pressure filtered through a membrane filter having a pore diameter of 1 μm to produce a liquid crystal cell. This solution was spin coated on the ITO surface of a 30 × 40 mm ITO electrode substrate (length 40 mm × width 30 mm, thickness 0.7 mm) washed with pure water and IPA, and heated at 100 ° C. for 5 minutes on a hot plate. Heat treatment was performed to obtain an ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm. The surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm.

  Two obtained ITO substrates with a liquid crystal alignment film were prepared, combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface inside, and a sealant (XN-1500T) (manufactured by Mitsui Chemicals, Inc.) was printed. Next, after bonding the other substrate and the liquid crystal alignment film face each other, the sealing agent was cured by heat treatment at 120 ° C. for 90 minutes in a heat-circulating clean oven to produce an empty cell. . 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 (ordinary cell).

  In addition, the liquid crystal aligning agent (1) and liquid crystal aligning agent (2) obtained in Example 1 and Example 2, the liquid crystal aligning agent (20) obtained in Comparative Example 1 and Comparative Example 2, and the liquid crystal aligning agent In the liquid crystal cell using the treating agent (21) and the liquid crystal aligning agent (24) obtained in Comparative Example 5, nematic liquid crystal (MLC-2003) (manufactured by Merck Japan Ltd.) was used as the liquid crystal.

  Moreover, the liquid crystal aligning agent (3)-liquid crystal aligning agent (6) obtained in Example 3-Example 6, and the liquid crystal aligning agent (8)-liquid crystal aligning obtained in Example 8-Example 12 Treatment agent (12), liquid crystal alignment treatment agent obtained in Examples 14 to 19 (14) to liquid crystal alignment treatment agent (19) and liquid crystal alignment treatment agents obtained in Comparative Examples 3 and 4 (22 ) And a liquid crystal cell using the liquid crystal alignment agent (23), nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Ltd.) was used as the liquid crystal.

  Liquid crystal alignment was evaluated using the liquid crystal cell obtained above. The liquid crystal alignment was confirmed by observing the liquid crystal cell with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) to check for the presence of alignment defects. Specifically, those in which no alignment defect was observed were considered to be excellent in this evaluation (shown as good in Tables 8 to 10).

  Tables 8 to 10 show the results of liquid crystal alignment obtained in Examples and Comparative Examples.

"Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)"
The liquid crystal aligning agent (6) obtained in Example 6, the liquid crystal aligning agent (9) obtained in Example 9 and the liquid crystal aligning agent (16) obtained in Example 16 were used as a membrane having a pore diameter of 1 μm. A liquid crystal cell was prepared and the liquid crystal alignment was evaluated using a solution that was filtered under pressure with a filter and stored at −15 ° C. for 48 hours. This solution was washed with pure water and IPA at the center with a 10 × 10 mm ITO electrode substrate with a pattern spacing of 20 μm (vertical 40 mm × width 30 mm, thickness 0.7 mm) and at the center with a 10 × 40 mm ITO electrode substrate Spin coating was performed on the ITO surface (length 40 mm × width 30 mm, thickness 0.7 mm), and heat treatment was performed on a hot plate at 100 ° C. for 5 minutes to obtain a polyimide coating film having a thickness of 100 nm. After the coated surface was washed with pure water, it was heat-treated at 100 ° C. for 15 minutes in a heat circulation type clean oven to obtain a substrate with a liquid crystal alignment film.

  This substrate with a liquid crystal alignment film was combined with the liquid crystal alignment film surface inside, with a 6 μm spacer in between, and the periphery was adhered with a sealant to produce an empty cell. A nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Ltd.) was added to the empty cell by a reduced pressure injection method, and a polymerizable compound (1) represented by the following formula was added to 100% by mass of the nematic liquid crystal (MLC-6608). 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.

While applying an AC voltage of 5 V to the obtained liquid crystal cell, using a metal halide lamp with an illuminance of 60 mW, the wavelength of 350 nm or less was cut, and ultraviolet irradiation of 20 J / cm ^{2 in} terms of 365 nm was performed, and the alignment direction of the liquid crystal A liquid crystal cell (PSA cell) was controlled. The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.

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

  In the PSA cell obtained in the example, the response speed of the liquid crystal cell after the ultraviolet irradiation was higher than that of the liquid crystal cell before the ultraviolet irradiation, so that it was confirmed that the alignment direction of the liquid crystal was controlled. Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystal was uniformly aligned.

"Evaluation of voltage holding ratio on insulating film coated substrate"
(Adjustment of composition for insulating film)
In a 100 ml eggplant-shaped flask, an acrylic resin ((meth) acrylic acid / hydroxyethyl (meth) acrylate / methyl (meth) acrylate = 9 / 25.5 / 65.5 propylene glycol monomethyl ether acetate solution, solid content concentration: 22.0% by weight, weight average molecular weight 6000 (polystyrene conversion) (7.07 g), propylene glycol monomethyl ether acetate (25.1 g), KAYARDDPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) (3.30 g), I- 369 (manufactured by Ciba Specialty Chemicals) (0.30 g), ITX (manufactured by First Chemical Corporation), MegaFac R-30 (0.015 g) was added, and the mixture was stirred at 25 ° C. for 3 hours, and the composition for insulating film Got. No insoluble matter was found in the composition for insulating film, and a uniform solution was obtained.

(Preparation of insulating film coated substrate)
The insulating film composition obtained above was filtered using a 0.2 μm filter. Thereafter, this composition was washed with pure water and IPA, and a 10 × 10 mm substrate with an ITO electrode having a pattern spacing of 20 μm (length 40 mm × width 30 mm, thickness 0.7 mm) and a center 10 × 40 mm ITO It spin-coated on the ITO surface of the board | substrate with an electrode (length 40mm x width 30mm, thickness 0.7mm), and heat-processed at 110 degreeC for 5 minute (s) on the hotplate. This coating film was irradiated with ultraviolet rays having an irradiation amount of 365 m of 500 mJ / cm ² by an ultraviolet irradiation device PLA-501 (F) (manufactured by Canon Inc.), and subjected to heat treatment at 120 ° C. for 1 minute on a hot plate. did. Thereafter, a heat treatment was further performed on a hot plate at 200 ° C. for 60 minutes to obtain a substrate coated with an insulating film having a thickness of 1.12 μm.

(Production of liquid crystal cell)
A liquid crystal cell was prepared using the solution obtained by pressure-filtering the liquid crystal aligning agents obtained in Examples and Comparative Examples of the present invention with a membrane filter having a pore diameter of 1 μm and storing at −15 ° C. for 48 hours. This solution is spin-coated on the insulating film-coated surface of the insulating film-coated substrate obtained above, and heat-treated on a hot plate at 100 ° C. for 5 minutes to provide an ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm Got. The surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.1 mm.

  Two obtained ITO substrates with a liquid crystal alignment film were prepared, combined with a 6 μm spacer sandwiched with the liquid crystal alignment film surface inside, and a sealant (XN-1500T) (manufactured by Mitsui Chemicals, Inc.) was printed. Next, after bonding the other substrate and the liquid crystal alignment film face each other, the sealing agent was cured by heat treatment at 120 ° C. for 90 minutes in a heat-circulating clean oven to produce an empty cell. . 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.

(Evaluation of voltage holding ratio)
A voltage of 1V is applied to the liquid crystal cell obtained above at a temperature of 70 ° C. for 60 μs, and the voltage after 16.67 ms and 50 ms is measured. The voltage holding ratio (also referred to as VHR) Calculated). The measurement was performed using a voltage holding ratio measuring device (VHR-1) (manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ± 1 V, Pulse Width: 60 μs, Frame Period: 16.67 ms or 50 ms.

The liquid crystal cell for which the measurement of the voltage holding ratio was completed was irradiated with ultraviolet rays of 10 J / cm ^{2 in} terms of 365 nm, and then VHR was measured under the same conditions. In addition, ultraviolet irradiation was performed using the table-type UV curing device (HCT3B28HEX-1) (manufactured by SEN LIGHT CORPORATION).

  Tables 8 to 10 show the evaluation results of the voltage holding ratios of the insulating film coated substrates obtained in the examples and comparative examples.

<Example 1>
NMP (27.0 g) and BCS (26) were added to the polyamic acid solution (1) (11.5 g) and CE-2 (0.72 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 1. 2 g) was added and stirred at 50 ° C. for 6 hours to obtain a composition (1). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (1) was used for evaluation also as a liquid-crystal aligning agent (1).

  Using the obtained composition (1) and liquid crystal aligning agent (1), under the above-mentioned conditions, “Evaluation of transparency of resin film”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (normal cell)” And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 2>
Polyimide powder (2) (2.33 g) and CE-1 (1.00 g) obtained by the synthesis method of Synthesis Example 2 were added to NEP (32.7 g), PCS (5.70 g), and BCS (21.2 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (2). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (2) was used for evaluation also as a liquid-crystal aligning agent (2).

  Using the obtained composition (2) and liquid crystal aligning agent (2), under the above-mentioned conditions, “Evaluation of transparency of resin film”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (normal cell)” And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 3>
Polyamide acid solution (3) (12.6 g) having a solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 3 and CE-1, NMP (15.7 g), BCS (15.9 g), and PB (19.1 g) was added, and the mixture was stirred at 50 ° C. for 6 hours to obtain a composition (3). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (3) was used for evaluation also as a liquid-crystal aligning agent (3).

  Using the obtained composition (3) and liquid crystal aligning agent (3), under the above-mentioned conditions, “Evaluation of transparency of resin film”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (normal cell)” And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 4>
The polyamic acid solution (3) (7.80 g) and CE-2 having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 3 were mixed with NMP (26.7 g), PCS (5.61 g), and BCS. (17.7g) was added and it stirred at 50 degreeC for 6 hours, and obtained the composition (4). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (4) was used for evaluation also as a liquid-crystal aligning agent (4).

  Using the obtained composition (4) and liquid crystal aligning agent (4), "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 5>
Polyimide powder (4) (2.45 g) and CE-2 (1.05 g) obtained by the synthesis method of Synthesis Example 4 were added to NMP (9.27 g), NEP (24.7 g) and PB (28.6 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (5). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (5) was used for evaluation also as a liquid-crystal aligning agent (5).

  Using the obtained composition (5) and liquid crystal alignment treatment agent (5), under the above-mentioned conditions, “Evaluation of transparency of resin film”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (normal cell)” And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 6>
Polyimide powder (5) (2.00 g) and CE-2 (1.33 g) obtained by the synthesis method of Synthesis Example 5 were added to NMP (11.6 g), NEP (17.3 g) and PB (30.2 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (6). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (6) was used for evaluation also as a liquid-crystal aligning agent (6).

  Using the obtained composition (6) and liquid crystal aligning agent (6), "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" ”,“ Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell) ”and“ Evaluation of voltage holding ratio on insulating film coated substrate ”.

<Example 7>
Polyimide powder (5) (1.08 g) and CE-2 (0.72 g) obtained by the synthesis method of Synthesis Example 5 were added to NMP (11.7 g), NEP (17.6 g) and PB (30.0 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (7). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (7) was used for evaluation also as a liquid-crystal aligning agent (7).

  Using the obtained liquid crystal aligning agent (7), “evaluation of ink jet coatability of liquid crystal aligning agent” was performed under the above-described conditions.

<Example 8>
Polyimide powder (5) (2.15 g) and CE-2 (0.92 g) obtained by the synthesis method of Synthesis Example 5 were added to γ-BL (24.2 g), DEEE (11.7 g) and BCS (24 0.5 g) and stirred at 70 ° C. for 24 hours to obtain a composition (8). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (8) was used for evaluation also as a liquid-crystal aligning agent (8).

  Using the composition (8) and the liquid crystal aligning agent (8) obtained, "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 9>
NEP (35.9 g) and BCS (24.2 g) were added to polyimide powder (6) (2.83 g) and CE-1 (0.50 g) obtained by the synthesis method of Synthesis Example 6, and the mixture was heated to 70 ° C. The mixture was stirred for 24 hours to obtain a composition (9). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (9) was used for evaluation also as a liquid-crystal aligning agent (9).

  Using the obtained composition (9) and liquid crystal aligning agent (9), "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" ”,“ Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell) ”and“ Evaluation of voltage holding ratio on insulating film coated substrate ”.

<Example 10>
Polyimide powder (7) (1.89 g) and CE-2 (1.55 g) obtained by the synthesis method of Synthesis Example 7 were added to NEP (26.6 g), BCS (12.5 g) and PB (21.9 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (10). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (10) was used for evaluation also as a liquid-crystal aligning agent (10).

  Using the obtained composition (10) and liquid crystal aligning agent (10), under the above-mentioned conditions, “Evaluation of transparency of resin film”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (normal cell)” And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 11>
Polyimide powder (8) (1.53 g) and CE-2 (1.87 g) obtained by the synthesis method of Synthesis Example 8 were added to NMP (14.5 g), NEP (14.5 g) and PB (30.9 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (11). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (11) was used for evaluation also as a liquid-crystal aligning agent (11).

  Using the composition (11) and the liquid crystal aligning agent (11) obtained, "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 12>
Polyimide powder (8) (1.88 g) and CE-2 (1.25 g) obtained by the synthesis method of Synthesis Example 8 were added to γ-BL (24.7 g), PGME (17.8 g) and PB (18 8 g), and the mixture was stirred at 70 ° C. for 24 hours to obtain a composition (12). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (12) was used for evaluation also as a liquid-crystal aligning agent (12).

  Using the obtained composition (12) and liquid crystal aligning agent (12), "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 13>
Γ-BL (22.3 g) and PGME (39.4 g) were added to polyimide powder (8) (1.08 g) and CE-2 (0.75 g) obtained by the synthesis method of Synthesis Example 8, and 70 It stirred at 24 degreeC for 24 hours and obtained the composition (13). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (13) was used for evaluation also as a liquid-crystal aligning agent (13).

  Using the obtained liquid crystal aligning agent (13), the “evaluation of ink jet coatability of the liquid crystal aligning agent” was performed under the above-described conditions.

<Example 14>
Polyimide powder (9) (2.80 g) and CE-1 (0.70 g) obtained by the synthesis method of Synthesis Example 9 were added to NMP (35.0 g), DEEE (12.0 g) and BCS (15.9 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (14). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (14) was used for evaluation also as a liquid-crystal aligning agent (14).

  Using the obtained composition (14) and liquid crystal aligning agent (14), "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 15>
Polyimide powder (10) (2.38 g) and CE-2 (1.02 g) obtained by the synthesis method of Synthesis Example 10 were added to NEP (26.8 g), BCS (24.7 g) and PB (9.27 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (15). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (15) was used for evaluation also as a liquid-crystal aligning agent (15).

  Using the composition (15) and the liquid crystal aligning agent (15) obtained, "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (normal cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 16>
Polyimide powder (11) (2.45 g) and CE-2 (1.05 g) obtained by the synthesis method of Synthesis Example 11 were added to NEP (37.5 g), DEEE (6.02 g) and BCS (19.1 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (16). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (16) was used for evaluation also as a liquid-crystal aligning agent (16).

  Using the obtained composition (16) and liquid crystal aligning agent (16), "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" ”,“ Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell) ”and“ Evaluation of voltage holding ratio on insulating film coated substrate ”.

<Example 17>
The polyamic acid solution (12) (11.2 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 12 and CE-2 were mixed with NMP (26.3 g), BCS (12.8 g) and PB. (12.8 g) was added and stirred at 50 ° C. for 6 hours to obtain a composition (17). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (17) was used for evaluation also as a liquid-crystal aligning agent (17).

  Using the composition (17) and the liquid crystal aligning agent (17) obtained, "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Example 18>
Polyimide powder (13) (2.23 g) and CE-2 (1.20 g) obtained by the synthesis method of Synthesis Example 13 were added to NMP (30.8 g), PCS (14.7 g) and BCS (15.6 g). ) And stirred at 70 ° C. for 24 hours to obtain a composition (18). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (18) was used for evaluation also as a liquid-crystal aligning agent (18).

Using the obtained composition (18) and liquid crystal aligning agent (18), "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.
<Example 19>
Polyimide powder (13) (1.89 g) and CE-2 (1.26 g) obtained by the synthesis method of Synthesis Example 13 were added to γ-BL (24.9 g), PCS (18.0 g) and PB (18 .9 g) was added and stirred at 70 ° C. for 24 hours to obtain a composition (19). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (19) was used for evaluation also as a liquid-crystal aligning agent (19).

  Using the obtained composition (19) and liquid crystal alignment treatment agent (19), under the above-mentioned conditions, “Evaluation of transparency of resin film”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (normal cell)” And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Comparative Example 1>
NMP (21.6 g) and BCS (22.7 g) are added to the polyamic acid solution (1) (12.5 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 1, and the mixture is heated to 25 ° C. And stirred for 3 hours to obtain a composition (20). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (20) was used for evaluation also as a liquid-crystal aligning agent (20).

  Using the obtained composition (20) and liquid crystal aligning agent (20), "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Comparative example 2>
NEP (31.5 g), PCS (5.41 g) and BCS (19.9 g) are added to the polyimide powder (2) (3.12 g) obtained by the synthesis method of Synthesis Example 2, and 24 ° C. at 24 ° C. The mixture was stirred for a time to obtain a composition (21). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (21) was used for evaluation also as a liquid-crystal aligning agent (21).

  Using the composition (21) and the liquid crystal aligning agent (21) obtained, "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Comparative Example 3>
NMP (12.5 g), BCS (13.6 g) and PB (16.4 g) were added to the polyamic acid solution (3) (12.0 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 3. ) And stirred at 25 ° C. for 3 hours to obtain a composition (22). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (22) was used for evaluation also as a liquid-crystal aligning agent (22).

  Using the obtained composition (22) and liquid crystal aligning agent (22), "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Comparative Example 4>
NMP (11.6 g), NEP (17.5 g), and PB (29.1 g) were added to the polyimide powder (5) (3.20 g) obtained by the synthesis method of Synthesis Example 5, and 24 ° C. at 24 ° C. The mixture was stirred for a time to obtain a composition (23). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (23) was used for evaluation also as a liquid-crystal aligning agent (23).

  Using the composition (23) and the liquid crystal aligning agent (23) thus obtained, "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

<Comparative Example 5>
NMP (9.28 g), NEP (13.9 g) and PB (25.3 g) were added to CE-2 (2.02 g), and the mixture was stirred at 70 ° C. for 24 hours to obtain a composition (24). . In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (24) was used for evaluation also as a liquid-crystal aligning agent (24).

  Using the obtained composition (24) and liquid crystal aligning agent (24), "Evaluation of transparency of resin film", "Preparation of liquid crystal cell and evaluation of liquid crystal alignment (ordinary cell)" And “Evaluation of voltage holding ratio on insulating film coated substrate”.

＊２：組成物（液晶配向処理剤）中の重合体の占める割合を示す。

* 2: Indicates the proportion of the polymer in the composition (liquid crystal aligning agent).

＊３：組成物（液晶配向処理剤）中の重合体の占める割合を示す。

* 3: Indicates the proportion of the polymer in the composition (liquid crystal aligning agent).

＊４：組成物（液晶配向処理剤）中の重合体の占める割合を示す。

* 4: Indicates the proportion of the polymer in the composition (liquid crystal aligning agent).

＊５：均一な液晶配向は得られず、流動配向が見られた。

* 5: Uniform liquid crystal alignment was not obtained and fluid alignment was observed.

  As can be seen from the above results, the composition of the example of the present invention obtained a resin film having higher transparency than the composition of the comparative example. Specifically, using the same specific polyimide polymer as the component (B) of the present invention, the composition using the specific cellulose polymer as the component (A) of the present invention, and the specific cellulose system Comparison with a composition not using a polymer, that is, comparison between Example 1 and Comparative Example 1, comparison between Example 2 and Comparative Example 2, comparison between Example 3 and Comparative Example 3, and Example 6 And Comparison with Comparative Example 4.

  Further, in the evaluation of the voltage holding ratio in the insulating film coated substrate, the liquid crystal alignment treatment agent obtained from the composition of the present invention is more liquid crystal alignment treatment agent than the liquid crystal alignment treatment agent obtained from the composition of the comparative example. Even when light was irradiated in a state where there was an insulating film made of an organic member, a result with excellent voltage holding ratio was obtained (from evaluation of the voltage holding ratio on the insulating film coated substrate in Examples and Comparative Examples). Specifically, using the same specific polyimide polymer as the component (B) of the present invention, the composition using the specific cellulose polymer as the component (A) of the present invention, and the specific cellulose system Comparison with a composition not using a polymer, that is, comparison between Example 1 and Comparative Example 1, comparison between Example 2 and Comparative Example 2, comparison between Example 3 and Comparative Example 3, and Example 6 And Comparison with Comparative Example 4. Furthermore, the result excellent in the said voltage retention was obtained also with the comparative example 5 which does not contain a specific polyimide-type polymer.

  The composition of the present invention has high transparency of the resin film, and can suppress the decomposition of the resin film by light such as ultraviolet rays.

  In addition, the liquid-crystal aligning agent of this invention turns into a liquid-crystal aligning film which is excellent in a voltage holding rate, even if light irradiates in the state which has the insulating film which consists of an organic member under a liquid-crystal aligning film.

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

  Furthermore, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful for a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a liquid crystal display element. That is, a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and containing a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates, A liquid crystal display element manufactured through a 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 electrodes, A liquid crystal produced by placing a liquid crystal alignment film containing a polymerizable group that polymerizes at least one of active energy rays and heat between substrates and polymerizing the polymerizable group while applying a voltage between the electrodes. It is also useful for display elements.

Claims (15)

A liquid crystal aligning agent obtained from a composition containing the following components (A) and (B):
(A) Component: A polymer having a structure represented by the following formula [1].

(In the formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a group having a structure selected from the following formulas [1a] to [1m]. N represents an integer of 100 to 1000000).

(In the formulas [1c] to [1m], X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently a benzene ring, methylene group, ethylene group , N-propylene group, isopropylene group or butylene group , in formula [1h], n represents an integer of 0 to 3, and in formula [1i], m represents an integer of 0 to 3.
(B) component: At least 1 type of polymer chosen from the polyimide precursor obtained by making a diamine component and a tetracarboxylic-acid component react, and a polyimide. 2. The liquid crystal aligning agent according to claim 1, wherein the diamine component in the polymer of the component (B) includes a diamine compound having a structure represented by the following formula [2a].

(In formula [2a], a represents an integer of 0 to 4). The liquid crystal aligning agent according to claim 1, wherein the diamine component in the polymer of the component (B) includes a diamine compound having a structure represented by the following formula [2a-1].

(In formula [2a-1], a represents an integer of 0 to 4, and n represents an integer of 1 to 4). The said diamine component in the polymer of said (B) component contains at least 1 sort (s) chosen from the diamine compound of the structure shown by following formula [2b], Any one of Claims 1-3 characterized by the above-mentioned. The liquid crystal aligning agent according to one item.

(In the formula [2b], Y has a structure selected from the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4], or formula [2b-5]. Represents a substituent, and m represents an integer of 1 to 4.

(Wherein [2b-1], a represents an integer of 0 to 4, wherein [2b-2], ^{Y 1} is a single _{bond, - (CH 2) a -} (a is an integer from 1 to 15 ), —O—, —CH ₂ O—, —COO— or —OCO—, Y ² represents a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15), Y ³ represents a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—, Y ⁴ represents a benzene ring, A divalent cyclic group selected from a cyclohexane ring or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, wherein any hydrogen atom on the cyclic group has 1 to 3 carbon atoms An alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkyl group having 1 to 3 carbon atoms. Kokishiru group or a fluorine atom may be substituted with, Y ⁵ represents a divalent cyclic group selected from benzene ring, cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic group, carbon atoms 1 Or an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, 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, and n is 0 indicates to 4 integer, ^{Y 6} represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxyl group having 1 to 18 alkoxyl group or a carbon of 1 to 18 carbon atoms In formula [2b-3], Y ⁷ represents —O—, —CH ₂ O—, —COO—, —OCO—, —CONH— or —NHCO—, and Y ⁸ has 8 to 22 carbon atoms. Represents an alkyl group, In formula [2b-4], Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and in formula [2b-5], Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms. Show). The tetracarboxylic acid component in the polymer of the component (B) contains at least one selected from compounds represented by the following formula [3]. Liquid crystal aligning agent as described in.

(In formula [3], Z ¹ is a group having a structure selected from the following formulas [3a] to [3j]).

(In the formula [3a], Z ^{2 to} Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [3g], Z ⁶ and Z ⁷ are A hydrogen atom or a methyl group, which may be the same or different.   The component (C) contains at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone, according to any one of claims 1 to 5. Liquid crystal alignment treatment agent. The component (D) contains at least one solvent selected from the solvents represented by the following formulas [D-1] to [D-3], according to any one of claims 1 to 6. Liquid crystal alignment treatment agent.

(In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and the formula [D-3 ], D < ³ > shows a C1-C4 alkyl group.   The component (E) contains at least one solvent selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether. The liquid-crystal aligning agent as described in any one of Claims 7.   The liquid crystal aligning film obtained using the liquid-crystal aligning agent as described in any one of Claims 1-8.   The liquid crystal aligning film obtained by the inkjet method using the liquid-crystal aligning agent as described in any one of Claims 1-8.   The liquid crystal display element which has a liquid crystal aligning film of Claim 9 or Claim 10.   A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the electrodes 11. The liquid crystal alignment film according to claim 9, wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage therebetween.   A liquid crystal display element comprising the liquid crystal alignment film according to claim 12.   A liquid crystal layer comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates; 11. The liquid crystal alignment film according to claim 9, wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable group while applying a voltage therebetween.   A liquid crystal display element comprising the liquid crystal alignment film according to claim 14.