JP5930238B2 - Composition, liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a composition used for forming a resin film, a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film. Is.

  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. This 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. In that case, since these compositions usually use a solvent having a high boiling point such as N-methyl-2-pyrrolidone (also referred to as NMP) or γ-butyrolactone (also referred to as γ-BL), it is about 200 to 300 ° C. It is necessary to bake at a high temperature (for example, refer to Patent Document 1).

JP 09-278724 A

  When forming a liquid crystal alignment film using a liquid crystal aligning agent containing a polyimide-based polymer, the baking process requires a high temperature among the processes for manufacturing a liquid crystal display element for the reasons described above. This is because a liquid crystal aligning agent containing a polyimide-based polymer uses NMP or γ-BL as a solvent to dissolve the polyimide-based polymer, and therefore requires a high temperature. However, when a plastic substrate that is thin and lightweight but has low heat resistance is used instead of a normal glass substrate as the substrate of the liquid crystal display element, firing at a lower temperature is required. Similarly, in order to suppress deterioration of the color characteristics of the color filter of the liquid crystal display element due to baking at a high temperature, and further to reduce energy costs in the production of the liquid crystal display element, baking at a low temperature is necessary. Become.

  Moreover, a liquid crystal aligning film is formed by apply | coating a liquid-crystal aligning agent to a board | substrate, and baking a coating film then. At that time, the liquid crystal alignment treatment agent is wetted with respect to the substrate for the purpose of enhancing the coating property (also referred to as coating property) of the liquid crystal alignment film, that is, suppressing the occurrence of pinholes due to repellency and foreign matter. There is a need to increase the spreadability.

Then, an object of this invention is to provide the composition which has the said characteristic. That is, an object of the present invention is to provide a composition that can form a resin film by baking at a low temperature in a composition containing a polyimide-based polymer. And when forming a resin film, it aims at providing the composition which the applicability | paintability to a board | substrate improves.
Another object of the present invention is to provide a liquid crystal aligning agent that can form a liquid crystal aligning film by firing at a low temperature in the liquid crystal aligning agent using the above composition. And when forming a liquid crystal aligning film, it aims at providing the liquid crystal aligning agent which the applicability | paintability to a board | substrate improves.
An object of the present invention is to provide a liquid crystal alignment film that meets the above requirements. That is, it aims at providing the liquid crystal aligning film which can be formed by baking at low temperature, and providing the liquid crystal aligning film which the applicability | paintability to a board | substrate improves.
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 diligent research, the present inventor has selected from a polyimide precursor or a polyimide obtained by reacting a diamine component containing a solvent having a specific structure and a diamine compound having a carboxyl group with a tetracarboxylic dianhydride component. It has been found that a composition containing at least one kind of polymer is extremely effective for achieving the above object, and the present invention has been completed.

  That is, the present invention has the following gist.

(1) It is a composition containing the following (A) component, (B) component, and (C) component , and the following (A) component is 55 mass%-of the whole solvent contained in the said composition. A composition, which is 99% by mass .

  Component (A): at least one solvent selected from the following formula [1a] or [1b].

(In formula [1a], X ¹ represents an alkyl group having 1 to 3 carbon atoms, and in formula [1b], X ² represents an alkyl group having 1 to 3 carbon atoms).

  Component (B): at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone.

  Component (C): At least one polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group with a tetracarboxylic dianhydride component.

(3) The diamine compound having a carboxyl group as the component (C) is a diamine compound having a structure represented by the following formula [2], described in (1) or (2) above Composition.

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

(4) The composition according to (1) or (2) above, wherein the diamine compound having a carboxyl group as the component (C) is a diamine compound having a structure represented by the following formula [2a]. object.

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

(5) The diamine compound having a carboxyl group is 20 mol% to 100 mol% in the total diamine used for the component (C), as described in (3) or (4) above Composition.

(6) Any of (1) to (5) above, wherein the diamine component of the component (C) contains at least one diamine compound selected from the structure represented by the following formula [2b] A composition according to claim 1.

(In the formula [2b], Y represents the structure of the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5] 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 amine 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 an alkyl group having 8 to 22 carbon atoms, and in formula [2b-4], Y ⁸ and Y ⁹ are each independently a hydrocarbon having 1 to 6 carbon atoms. A group of formula [2b During ^{5], Y 10} represents an alkyl group having 1 to 8 carbon atoms).

(7) The tetracarboxylic dianhydride component of the component (C) is a compound represented by the following formula [3], according to any one of (1) to (6) above Composition.

(In the formula [3], Z ¹ is a group having at least one 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.

(8) As component (D), 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol The composition according to any one of (1) to (7) above, which contains at least one solvent selected from monopropyl ether, diethylene glycol isopropyl ether, and diethylene glycol monobutyl ether.

(9) A resin film obtained from the composition according to any one of (1) to (8) above.

(10) A liquid crystal aligning agent obtained from the composition according to any one of (1) to (8) above.

(11) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to (10).

(12) A liquid crystal alignment film obtained by an ink jet method using the liquid crystal aligning agent according to (10).

(13) A liquid crystal display element comprising the liquid crystal alignment film according to (11) or (12).

(14) 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 as described in (11) or (12) above, which is used for a liquid crystal display device produced through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

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

(16) 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 as described in (11) or (12) above, which is used for a liquid crystal display device produced through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

(17) A liquid crystal display device comprising the liquid crystal alignment film according to (16).

  Contains at least one polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component containing a solvent having a specific structure of the present invention and a diamine compound having a carboxyl group with a tetracarboxylic dianhydride component The composition to be formed can form a resin film by baking at a low temperature. In addition, the composition of the present invention has improved wet spreading properties on the substrate, and can suppress the occurrence of pinholes due to repellency and foreign matter on the resin film.

  Moreover, the liquid crystal aligning agent which consists of a composition of this invention can form a liquid crystal aligning film by baking at low temperature. And this liquid-crystal aligning agent improves the wet-spreading property to a board | substrate, and can suppress generation | occurrence | production of the pinhole accompanying the repellency and foreign material on a liquid crystal aligning film. 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 uses the following components (A), (B) and (C) containing a composition, a liquid crystal aligning agent, a resin film obtained using the composition, and the liquid crystal aligning agent. The obtained liquid crystal alignment film is a liquid crystal display element having the liquid crystal alignment film.
Component (A): at least one solvent selected from the following formula [1a] or [1b] (also referred to as a specific alcohol solvent).

(In formula [1a], X ¹ represents an alkyl group having 1 to 4 carbon atoms, and in formula [1b], X ² represents an alkyl group having 1 to 4 carbon atoms).

  Component (B): at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone (also referred to as a specific polar solvent).

  Component (C): at least one polymer selected from a polyimide precursor or polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic dianhydride component (also referred to as a specific polymer). ).

  The specific alcohol solvent of the present invention usually has a lower boiling point compared to NMP and γ-BL used as the main solvent of the composition containing the polyimide polymer, and further dissolves the specific polymer of the present invention. Can do. Therefore, a resin film can be formed by baking at low temperature by increasing the introduction amount of the specific alcohol solvent in the entire solvent contained in the composition of the present invention.

  Furthermore, the specific alcohol solvent of the present invention usually has a lower surface tension as a solvent than solvents such as NMP and γ-BL used in compositions having a polyimide polymer. Therefore, the composition using the specific solvent has high wettability to the substrate. Therefore, it is possible to suppress the generation of pinholes accompanying the repelling on the resin film.

  Moreover, since the specific polar solvent of this invention has the high effect which melt | dissolves a specific polymer, when apply | coating to a board | substrate, generation | occurrence | production of the pinhole accompanying the foreign material on a resin film can be suppressed.

  From the above points, the composition of the present invention can form a resin film by baking at a low temperature. And the composition of this invention improves the wet-spreading property to a board | substrate, and can suppress generation | occurrence | production of the pinhole accompanying the repelling on a resin film, and a foreign material. Moreover, also in the liquid crystal aligning agent obtained from the composition of this invention, the effect mentioned above is acquired for the same reason.

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

<Specific alcohol solvent>
The specific alcohol solvent that is the component (A) of the present invention is at least one solvent selected from the following formula [1a] or [1b].

(In the formula [1a], X ¹ represents an alkyl group having 1 to 3 carbon atoms).
(In the formula [1b], X ² represents an alkyl group having 1 to 3 carbon atoms).

  Specifically, structures represented by the following formula [1a-1] to formula [1a-4] and formula [1b-1] to formula [1b-4] are given.

Among these, from the viewpoint of the boiling point and availability of the solvent, the formula [1a-1], the formula [1b-1], the formula [1b-2], or the formula [1b-3] is preferable.
The specific alcohol solvent of the present invention is preferably 50 to 99% by mass of the total solvent contained in the composition in order to enhance the above-described effect of improving the wet spreadability to the substrate. Especially, 55-99 mass% is preferable. More preferred is 55 to 95% by mass.

  The more the amount of the specific alcohol solvent of the present invention in the whole solvent in the composition, the more the effect of the present invention, that is, the resin film or the liquid crystal alignment film can be formed by baking at a low temperature. The wet spreading property of the coating solution to the substrate is enhanced, and a resin film or a liquid crystal alignment film having excellent coating properties can be obtained.

<Specific polar solvent>
The specific polar solvent which is the component (B) of the present invention is at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone.

  Of these, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferable. More preferred is γ-butyrolactone.

  The specific polar solvent according to the present invention is a pin that forms a resin film or a liquid crystal alignment film by baking at a low temperature as described above, and a pin accompanying a foreign substance on the resin film when a composition or a liquid crystal alignment treatment agent is applied to a substrate. In order to enhance the effect of suppressing the generation of holes, it is preferably 1 to 40% by mass of the total solvent contained in the composition. Especially, 1-35 mass% is preferable. More preferably, it is 1-30 mass%, More preferably, it is 5-30 mass%.

<Specific polymer>
The specific polymer which is the component (C) of the present invention is at least one selected from a polyimide precursor or a polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic dianhydride component. The polymer.
The polyimide precursor has a structure represented by the following formula [A].

(In formula [A], R ¹ is a tetravalent organic group, R ² is a divalent organic group having a carboxyl group, and A ¹ and A ² are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. And each may be the same or different, and n represents a positive integer).

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

  The specific polymer of the present invention is relatively simple by using a diamine compound having a carboxyl group represented by the following formula [B] and a tetracarboxylic dianhydride represented by the following formula [C] as raw materials. From the reason that it is obtained, 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.

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

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

<Diamine compound having a carboxyl group>
The diamine compound having a carboxyl group of the present invention is a diamine compound having a structure represented by the following formula [2] in the molecule.

  In formula [2], 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 synthesis | combination.

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

  In formula [2a], 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], 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, the diamine compound represented by the formula [2a] can be 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.

(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 having a carboxyl group of the present invention further include structures represented by the following formulas [2a-1] to [2a-4].

In formula [2a-1], A ¹ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, — O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃₎ - or -N _(CH 3) 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-1], 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-2], 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 the formula [2a-3], 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-3], m ⁵ represents an integer of 1 to 5. Of these, 1 or 2 is preferable.

In formula [2a-4], 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—.

Wherein [2a-4], ^{m 6} is an integer of 1-4. Of these, 1 is preferable from the viewpoint of ease of synthesis.

  It is preferable that the diamine compound which has a carboxyl group of this invention is 20 mol%-100 mol% in all the diamine components, More preferably, it is preferable that it is 30 mol%-100 mol%.

  The diamine compound having a carboxyl group described above has properties such as the solubility of the specific 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 situation, one kind or a mixture of two or more kinds can be used.

<Second diamine compound>
In the diamine component for producing the specific polymer of the present invention, a diamine compound represented by the following formula [2b] (also referred to as a second diamine compound) can be used as the second diamine compound.

(In formula [2b], Y represents the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5], and m represents Represents an integer of 0 to 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 an alkyl group having 8 to 22 carbon atoms.
In formula [2b-4], Y ⁸ and Y ⁹ each independently represent a hydrocarbon group having 1 to 6 carbon atoms.
In formula [2b-5], Y ¹⁰ represents an alkyl group having 1 to 8 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.

(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.

The method for reducing the dinitro group of the dinitro compound represented by the formula [2b-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.
Although the specific structure of the 2nd diamine compound shown by the formula [2] of this invention is given to the following, it is not limited to these examples.
That is, as the second diamine represented by the formula [2], m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5- In addition to diaminophenol, 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] Can be mentioned.

(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).

(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.

(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).

(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).

(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).

(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).

(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 second diamine compounds of the present invention, the composition using the diamine compound having a structure in which the substituent Y in the formula [2b] is represented by the formula [2b-2] increases the hydrophobicity of the resin film. be able to. 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% or less of the whole diamine component from the viewpoint of the coating properties of the composition and the liquid crystal alignment treatment agent and the electric characteristics as the liquid crystal alignment film. Especially preferably, it is 10 mol% or more and 60 mol% or less of the whole diamine component.

  The second diamine compound of the present invention depends on properties such as solubility and coating properties of the specific 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. One type or a mixture of two or more types can be used.

<Other diamine compounds>
In the specific polymer of the present invention, a diamine compound having a carboxyl group in the molecule represented by the formula [2a], the formula [2a-1] to the formula [2a-4], or In addition to the second diamine compound represented by the formula [2b], other diamine compounds (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.
That is, as other diamine compounds, 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′-diaminobiphenyl, 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'-di Minodiphenyl 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′-diaminodiphenyl) amine, N-me Ru (3,3′-diaminodiphenyl) amine, N-methyl (3,4′-diaminodiphenyl) amine, N-methyl (2,2′-diaminodiphenyl) amine, N-methyl (2,3′-diamino) Diphenyl) 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-a Nophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3 -Aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4 -Bis (4-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) anthracene, 4,4'-bis (4-a Nophenoxy) 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-amino Phenoxy) 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- Minophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4- Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diamino Examples include undecane and 1,12-diaminododecane.

  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.

(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).

(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.

(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.

(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 depend on properties such as solubility of the specific polymer of the present invention in a solvent, coating properties of the composition, liquid crystal alignment in the case of a liquid crystal alignment film, voltage holding ratio, accumulated charge, etc. One kind or a mixture of two or more kinds may be used.

<Tetracarboxylic dianhydride component>
Examples of the tetracarboxylic dianhydride component for producing the specific polymer of the present invention include a tetracarboxylic acid anhydride represented by the following formula [3] or a tetracarboxylic acid derivative thereof (specific tetracarboxylic dianhydride component). Also called).

In the formula [3], Z ¹ is a group having at least one 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 dianhydride component of the present invention, Z ¹ is represented by the formula [3] from the viewpoint of ease of synthesis and polymerization reactivity when producing a polymer. 3a], 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 dianhydride component of this invention is 1 mol% or more in all the tetracarboxylic dianhydride components. More preferred is 5 mol% or more, and particularly preferred is 10 mol% or more.

Moreover, when using the specific tetracarboxylic dianhydride component of the structure of Formula [3e], Formula [3f], or Formula [3g], the usage-amount is 20 mol% or more of the whole tetracarboxylic dianhydride component, By doing so, a desired effect can be obtained. Preferably, it is 30 mol% or more. Further, all of the tetracarboxylic dianhydride component may be a tetracarboxylic dianhydride 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 dianhydride components other than a specific tetracarboxylic dianhydride component can be used for the specific polymer of this invention.
Examples of other tetracarboxylic dianhydride components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds, and dialkyl ester dihalide compounds.
That is, as other tetracarboxylic dianhydride components, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5, 8-naphthalenetetracarboxylic 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-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridine Tetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1 , 3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

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

<Method for producing specific polymer>
In the present invention, the method for synthesizing the specific polymer is not particularly limited. Usually, it is obtained by reacting a diamine component with a tetracarboxylic dianhydride component. In general, at least one tetracarboxylic dianhydride 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 form a polyamic acid. Get. Specifically, a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and a diamine component, a method of obtaining polyamic acid by dehydration polycondensation reaction of tetracarboxylic acid and a diamine component, or tetracarboxylic acid dihalide A method is used in which a polyamic acid is obtained by polycondensation of a diamine component and diamine component.

  To obtain the polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterification of a carboxylic acid group and a diamine component, and a polycondensation of a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and a diamine component. A method 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 of the diamine component and the tetracarboxylic dianhydride component is usually performed in an organic solvent with the diamine component and the tetracarboxylic dianhydride component. The organic solvent used in that case is particularly limited as long as the specific alcohol solvent that is the component (A) of the present invention, the specific polar solvent that is the component (B), and the polyimide precursor that is generated are soluble. Not.

Examples of the solvent other than the specific alcohol solvent and the specific polar solvent of the present invention include the following solvents.
That is, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, etc. is there.

  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 dianhydride 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 dianhydride component is used as it is or in an organic solvent. A method of adding by dispersing or dissolving in a solvent, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component. These may be used alternately, and any of these methods may be used. In addition, when reacting using a plurality of diamine components or tetracarboxylic dianhydride components, they may be reacted in a premixed state, individually or sequentially, and further reacted individually. 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 to the total number of moles of the tetracarboxylic dianhydride 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 polymer of the present invention is a weight average 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 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 of the present invention or a liquid crystal alignment treatment agent using the composition is a coating solution for forming a resin film or a liquid crystal alignment film (also collectively referred to as a resin film), and includes a specific alcohol solvent, a specific polar solvent, and It is a coating solution for forming a resin film containing a specific polymer.

  All of the polymer components in the composition of the present invention or the liquid crystal alignment treatment agent using the same may be the specific polymer of the present invention. A polymer may be mixed. 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 polymer, the polyimide precursor or polyimide which does not use the diamine compound which has the said carboxyl group, the 2nd diamine compound, or a specific tetracarboxylic dianhydride component is mentioned. Furthermore, a polyimide precursor and a polymer other than polyimide, specifically, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or the like can be given.

The organic solvent in the composition of the present invention or the liquid crystal alignment treatment agent using the composition may have a content of the organic solvent of 70 to 99.9% by mass from the viewpoint of forming a uniform resin film by coating. preferable. This content can be appropriately changed depending on the film thickness of the target resin film or liquid crystal alignment film.
In the organic solvent used for the composition of the present invention or the liquid crystal alignment treatment agent using the same, all the organic solvents may be the specific alcohol solvent and the specific polar solvent of the present invention. In addition, other organic solvents may be mixed.
In that case, it is preferable that the specific alcohol solvent of this invention is 50-99 mass% of the whole solvent contained in a composition. Especially, 55-99 mass% is preferable. More preferred is 55 to 95% by mass.
Moreover, it is preferable that the specific polar solvent of this invention is 1-40 mass% of the whole solvent contained in a composition. Especially, 1-35 mass% is preferable. More preferably, it is 1-30 mass%, More preferably, it is 5-30 mass%.

  The other organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving the specific polymer. Specific examples are given below.

  For example, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone is there.

  Unless the effect of this invention is impaired, the composition of this invention or the liquid-crystal aligning agent using it is a coating film of the resin film or liquid crystal aligning film at the time of apply | coating a composition or a liquid-crystal aligning agent using the same An organic solvent that improves the property and surface smoothness, that is, a poor solvent can be used.

  Specific examples of the poor solvent for improving the coating properties and surface smoothness of the resin coating or the liquid crystal alignment film are given below.

  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, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monopropyl ether, diethylene glycol isopropyl ether or diethyl Lenglycol monobutyl ether, 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 diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-Ethoxye Xyl) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether Methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, Surface tension of solvents such as butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate A low organic solvent.

  Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl Ether or diethylene glycol monobutyl ether (also referred to as component (D) above) is preferably used.

  It is preferable that these (D) components are 1-50 mass% of the whole organic solvent contained in a composition or a liquid-crystal aligning agent using the same. Especially, 1-40 mass% is preferable. More preferably, it is 5-30 mass%, More preferably, it is 10-30 mass%.

  As long as the effects of the present invention are not impaired, the composition of the present invention or the liquid crystal alignment treatment agent using the same is 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 crosslinkable compound having at least one substituent selected from the group consisting of lower alkoxyalkyl groups, or a crosslinkable compound having a polymerizable unsaturated bond may 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].

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

(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).

(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].

(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).

(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.

(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.

(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.

  As an example of such a melamine derivative or a benzoguanamine derivative, MX-750 in which an average of 3.7 methoxymethyl groups is substituted per one triazine ring of a commercially available product, and an average of 5. methoxymethyl groups per one 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.

(Wherein [7], E ₁ represents a cyclohexane ring, bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, a group selected from the group consisting of an anthracene ring or phenanthrene ring, E 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 of this invention or the liquid-crystal aligning agent using the same may be one type, and may combine two or more types.

  The content of the crosslinkable compound in the composition of the present invention or the liquid crystal aligning agent using the same 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 above-described polymer.

  Unless the effect of this invention is impaired, the film thickness of the resin film or liquid crystal aligning film at the time of apply | coating the composition or the liquid crystal aligning agent using the composition of the present invention or a liquid crystal aligning agent using the same is used. A compound that improves the uniformity and surface smoothness of the film 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) And 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-tri Toxisilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxy Silane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyl Trimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Lopylene 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-tetraglycidyl -2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane or N, N, N ′ , N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane and the like.

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

  The composition of the present invention or a liquid crystal aligning agent using the same is in close contact with the above-mentioned poor solvent, crosslinkable compound, resin film or liquid crystal alignment film, the compound for improving the film thickness uniformity and surface smoothness, and the substrate. In addition to the compound to be added, a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant or conductivity of the resin film or the liquid crystal alignment film may be added as long as the effects of the present invention are not impaired. Good.

<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. You may use these according to the objective.

  After the composition is applied on the substrate, it is 50 to 250 ° C., preferably 80 to 200 ° C., more preferably 80 to 150 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven. The solvent can be evaporated 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 aligning agent on the substrate, it is 50 to 250 ° C., preferably 80 to 200 ° C., more preferably 80 to 200 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven. The solvent can be evaporated at 150 ° 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 the 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 irradiating 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 arranging 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 irradiating heat or ultraviolet rays while applying an AC or DC 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.
(Diamine compound having a carboxyl group)
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])

(Second diamine compound)
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]

(Component (A) of the present invention (specific alcohol solvent))
PGME: Propylene glycol monomethyl ether (solvent represented by the formula [1a-1] of the present invention)
MCS: ethylene glycol monomethyl ether (solvent represented by the formula [1b-1] of the present invention)
ECS: ethylene glycol monoethyl ether (solvent represented by the formula [1b-2] of the present invention)
PCS: ethylene glycol monopropyl ether (solvent represented by the formula [1b-3] of the present invention)

(Component (B) of the present invention (specific polar solvent))
NMP: N-methyl-2-pyrrolidone NEP: N-ethyl-2-pyrrolidone γ-BL: γ-butyrolactone (component (D) of the present invention (other organic solvents))
BCS: Ethylene 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 Polymer (Polyimide Precursor and Polyimide) as Component (C) of the Present Invention”

<Synthesis Example 1>
D1 (3.00 g, 15.3 mmol) and A1 (2.33 g, 15.3 mmol) were mixed in PGME (48.0 g), reacted at 40 ° C. for 8 hours, and the resin solid content concentration was 10.0% by mass. A polyamic acid solution (1) was obtained. The number average molecular weight of this polyamic acid was 13,500, and the weight average molecular weight was 32,100.

<Synthesis Example 2>
D2 (7.65 g, 30.6 mmol) and A2 (5.82 g, 38.3 mmol) were mixed in NMP (24.7 g), reacted at 80 ° C. for 5 hours, and then D1 (1.50 g, 7 .65 mmol) and NMP (20.2 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

  After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting to 6% by mass, acetic anhydride (4.81 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 (2). The imidation ratio of this polyimide was 55%, the number average molecular weight was 15,800, and the weight average molecular weight was 40,600.

<Synthesis Example 3>
D2 (1.91 g, 7.63 mmol), B1 (2.43 g, 6.39 mmol) and A1 (0.97 g, 6.38 mmol) were mixed in PGME (31.2 g) and reacted at 80 ° C. for 5 hours. After that, D1 (1.00 g, 5.10 mmol) and PGME (25.6 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 10.0% by mass. Obtained. The number average molecular weight of this polyamic acid was 13,900, and the weight average molecular weight was 36,500.

<Synthesis Example 4>
D2 (3.73 g, 14.9 mmol), B1 (4.73 g, 12.4 mmol) and A1 (1.89 g, 12.4 mmol) were mixed in NMP (20.3 g) and reacted at 80 ° C. for 5 hours. After that, D1 (1.95 g, 9.94 mmol) and NMP (16.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

  After adding NMP to the obtained polyamic-acid solution (40.0g) and diluting to 6 mass%, acetic anhydride (4.80g) and a pyridine (3.75g) are added as an imidation catalyst, and 4. at 80 degreeC. 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 (4). The imidation ratio of this polyimide was 60%, the number average molecular weight was 14,600, and the weight average molecular weight was 37,200.

<Synthesis Example 5>
D2 (5.61 g, 22.4 mmol), B1 (4.27 g, 11.2 mmol), A1 (2.13 g, 14.0 mmol), C1 (0.30 g, 2.77 mmol) and NMP (22.1 g) After mixing at 80 ° C. for 5 hours, D1 (1.10 g, 5.61 mmol) and NMP (18.1 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid concentration of 25. A 0% by weight 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 (5). The imidation ratio of this polyimide was 57%, the number average molecular weight was 16,500, and the weight average molecular weight was 39,900.

<Synthesis Example 6>
D2 (5.21 g, 20.8 mmol), B2 (3.52 g, 8.92 mmol), A1 (2.26 g, 14.9 mmol), B6 (1.21 g, 5.95 mmol) and NMP (23.0 g) After mixing at 80 ° C. for 5 hours, D1 (1.75 g, 8.92 mmol) and NMP (18.8 g) were added and reacted at 40 ° C. for 6 hours to give a resin solid concentration of 25. A 0% by weight 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 50%, the number average molecular weight was 18,100, and the weight average molecular weight was 42,500.

<Synthesis Example 7>
D2 (3.57 g, 14.3 mmol), B3 (3.71 g, 8.58 mmol), A2 (2.61 g, 17.2 mmol), C2 (0.31 g, 2.87 mmol) and NMP (21.4 g) After mixing at 80 ° C. for 5 hours, D1 (2.80 g, 14.3 mmol) and NMP (17.5 g) were added, and the mixture was reacted at 40 ° C. for 6 hours. A 0% by weight polyamic acid solution was obtained.

  After adding NMP to the obtained polyamic-acid solution (40.0g) and diluting to 6 mass%, acetic anhydride (4.80g) and a pyridine (3.75g) are added as an imidation catalyst, and 4. at 80 degreeC. 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 (7). The imidation ratio of this polyimide was 60%, the number average molecular weight was 19,100, and the weight average molecular weight was 43,000.

<Synthesis Example 8>
D2 (6.12 g, 24.5 mmol), B4 (2.26 g, 4.59 mmol), 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 25.0 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 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 48%, the number average molecular weight was 15,800, and the weight average molecular weight was 36,900.

<Synthesis Example 9>
D3 (6.50 g, 29.0 mmol), B1 (3.31 g, 8.70 mmol) and A1 (3.09 g, 20.3 mmol) were mixed in NMP (38.7 g) and reacted at 40 ° C. for 5 hours. Thus, a polyamic acid solution having a resin solid content concentration of 25.0% 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 (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 (9). The imidation ratio of this polyimide was 54%, the number average molecular weight was 17,500, and the weight average molecular weight was 40,100.

<Synthesis Example 10>
D3 (6.50 g, 29.0 mmol), B5 (3.28 g, 8.71 mmol), B6 (1.18 g, 5.80 mmol), A2 (2.21 g, 14.5 mmol) and NMP (39.5 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 25.0% by mass.

  After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting to 6% by mass, acetic anhydride (4.81 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 poured into methanol (900 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 16,500, and the weight average molecular weight was 38,200.

<Synthesis Example 11>
D4 (5.05 g, 16.8 mmol), B2 (3.32 g, 8.41 mmol), C2 (0.45 g, 4.16 mmol), A2 (2.35 g, 15.4 mmol) NMP (22.1 g) After mixing at 80 ° C. for 5 hours, D1 (2.20 g, 11.2 mmol) and NMP (18.1 g) were added and reacted at 40 ° C. for 5.5 hours. A 25.0 mass% 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 (3.68 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 61%, the number average molecular weight was 18,400, and the weight average molecular weight was 39,100.

<Synthesis Example 12>
D4 (4.29 g, 14.3 mmol), B1 (3.26 g, 8.57 mmol), B6 (1.74 g, 8.56 mmol), A1 (1.74 g, 11.4 mmol) and NMP (22.8 g) After mixing at 80 ° C. for 5 hours, D1 (2.80 g, 14.3 mmol) and NMP (18.7 g) were added and reacted at 40 ° C. for 5.5 hours. A 25.0 mass% 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 (4.70 g) and pyridine (3.60 g) were added as an imidization catalyst, and the mixture was heated at 80 ° 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 (12). The imidation ratio of this polyimide was 55%, the number average molecular weight was 17,500, and the weight average molecular weight was 39,300.

<Synthesis Example 13>
D1 (9.50 g, 48.4 mmol) and A1 (7.37 g, 48.4 mmol) were mixed in NMP (50.6 g), reacted at 40 ° C. for 8 hours, and the resin solid content concentration was 25.0 mass%. A polyamic acid solution (13) was obtained. The number average molecular weight of this polyamic acid was 17,300, and the weight average molecular weight was 42,900.
<Synthesis Example 14>
D2 (7.65 g, 30.6 mmol) and A2 (5.82 g, 38.3 mmol) were mixed in NMP (24.7 g), reacted at 80 ° C. for 5 hours, and then D1 (1.50 g, 7 .65 mmol) and NMP (20.2 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

  After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting to 6% by mass, acetic anhydride (4.81 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 (14). The imidation ratio of this polyimide was 55%, the number average molecular weight was 15,800, and the weight average molecular weight was 40,600.

<Synthesis Example 15>
D2 (7.37 g, 29.5 mmol), B1 (9.34 g, 24.5 mmol) and A1 (3.73 g, 24.5 mmol) were mixed in NMP (40.1 g) and reacted at 80 ° C. for 5 hours. Then, D1 (3.85 g, 19.6 mmol) and NMP (32.8 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (15) having a resin solid content concentration of 25.0 mass%. Obtained. The number average molecular weight of this polyamic acid was 19,500, and the weight average molecular weight was 46,200.

<Synthesis Example 16>
After adding NMP to the polyamic acid solution (15) (40.0 g) obtained in Synthesis Example 15 and diluting to 6% by mass, acetic anhydride (4.80 g) and pyridine (3.75 g) were used as imidization catalysts. In addition, the mixture was reacted at 80 ° C. for 4 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 (16). The imidation ratio of this polyimide was 60%, the number average molecular weight was 17,100, and the weight average molecular weight was 40,100.

<Synthesis Example 17>
D2 (3.92 g, 15.7 mmol), B1 (4.97 g, 13.1 mmol) and C1 (1.41 g, 13.0 mmol) were mixed in NMP (20.4 g) and reacted at 80 ° C. for 5 hours. After that, D1 (2.05 g, 10.5 mmol) and NMP (16.7 g) were added and reacted at 40 ° C. for 5.5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%. It was.

  After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting to 6% by mass, acetic anhydride (5.40 g) and pyridine (4.18 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 3 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 (17). The imidation ratio of this polyimide was 61%, the number average molecular weight was 16,300, and the weight average molecular weight was 39,100.

  Specific polymers (polyimide precursor and polyimide) of the present invention are shown in Table 1.

* 1: Polyamic acid.
“Production of Composition and Liquid Crystal Alignment Treatment Agent of the Present Invention”
In Examples 1 to 23 and Comparative Examples 1 to 10 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 applicability of the composition and liquid crystal alignment treatment agent", "Evaluation of ink jet coatability of the liquid crystal alignment treatment agent", “Preparation of liquid crystal cell (normal cell)”, “Evaluation of liquid crystal alignment (normal cell)”, “Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)” and “Evaluation of voltage holding ratio” . The conditions are as follows.
"Evaluation of coating properties of composition and liquid crystal alignment treatment agent"
The compositions obtained in Examples and Comparative Examples of the present invention were subjected to pressure filtration with a membrane filter having a pore size of 1 μm, and coating properties were evaluated using solutions stored at −15 ° C. for 48 hours. For the coating, a spin coater (1H-D7) (manufactured by Mikasa) was used. Application is performed by spin-coating on the ITO surface of a 30 × 40 mm ITO electrode substrate (length 40 mm × width 30 mm, thickness 0.7 mm) cleaned with pure water and IPA (isopropyl alcohol). Time was 30 seconds, and temporary drying was performed on a hot plate at 80 ° C. for 5 minutes.

  And the pinhole of the obtained resin film was evaluated. Evaluation of the pinhole of the resin film was performed by visually observing the resin film under a sodium lamp. Specifically, the number of pinholes associated with repellency and foreign matter confirmed on the resin film was counted, and the smaller the number of pinholes, the better the evaluation.

  In addition, the composition obtained by the Example and comparative example of this invention can be used for a liquid-crystal aligning agent. Therefore, the result of the coatability of the resin film obtained in the present example and the comparative example is also the result of the printability of the liquid crystal alignment film.

Tables 5 to 7 show the number of pinholes in the resin film (liquid crystal alignment film) 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 (11) obtained in Example 11 were subjected to pressure filtration with a membrane filter having a pore diameter of 1 μm, and at −15 ° C. The ink-jet coating property was evaluated using the solution stored for 48 hours. 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, the application area is 70 × 70 mm, the nozzle pitch is 0.423 mm, the scan pitch is 0.5 mm, and the application speed is 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.

  Evaluation of the pinhole of the obtained liquid crystal aligning film was performed on the same conditions as "evaluation of the applicability | paintability of a composition and a liquid-crystal aligning agent".

Table 5 shows the number of pinholes in the liquid crystal alignment film obtained in the examples.
"Production of liquid crystal cell (normal cell)"
The liquid crystal aligning agent obtained in the examples and comparative examples of the present invention was pressure filtered through a membrane filter having a pore size of 1 μm and stored at −15 ° C. for 48 hours to prepare a liquid crystal cell (ordinary 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 (normal cell).

  In addition, the liquid crystal aligning agent (1) and liquid crystal aligning agent (2) obtained in Example 1 and Example 2, and the liquid crystal aligning agent (24) obtained in Comparative Example 1- Comparative Example 5-Liquid crystal aligning In the liquid crystal cell using the treating agent (28), 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 10 were used. Treatment Agent (10), Liquid Crystal Alignment Treatment Agent (12) Obtained in Examples 12 to 23-Liquid Crystal Alignment Treatment Agent (23), and Liquid Crystal Alignment Treatment Agents Obtained in Comparative Example 6 to Comparative Example 10 (29 ) To nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Co., Ltd.) was used for the liquid crystal cell using the liquid crystal aligning agent (33).
"Evaluation of liquid crystal alignment (normal cell)"
The liquid crystal alignment was evaluated using the liquid crystal cell obtained in the above-mentioned “Preparation of liquid crystal cell (normal cell)”. 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 5 to 7).

Tables 5 to 7 show the results of the 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 (5) obtained in Example 5, the liquid crystal aligning agent (9) obtained in Example 9 and the liquid crystal aligning agent (20) obtained in Example 20 were mixed with a membrane having a pore diameter of 1 μm. Using a solution filtered under pressure with a filter and stored at −15 ° C. for 48 hours, a liquid crystal cell was prepared and liquid crystal alignment was evaluated (PSA cell). 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.) is added to the empty cell by a reduced pressure injection method, and a polymerizable compound (1) represented by the following formula is 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"
A voltage of 1 V was applied to the liquid crystal cell obtained in the above-mentioned “Preparation of liquid crystal cell (normal cell)” at a temperature of 80 ° C. for 60 μs, and the voltage after 16.67 ms and 50 ms was measured. Whether it was held was calculated as a voltage holding ratio (also referred to as VHR). 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.

  Table 8 shows the results of the voltage holding ratios obtained in the examples and comparative examples.

<Example 1>
PGME (11.5 g) and NMP (1.57 g) were added to the polyamic acid solution (1) (20.0 g) having a resin solid content concentration of 10.0% by mass obtained by the synthesis method of Synthesis Example 1, and 25 The mixture was stirred at 0 ° C. for 2 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 applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 2>
PGME (21.9 g) and γ-BL (2.43 g) were added to the polyimide powder (2) (1.55 g) obtained by the synthesis method of Synthesis Example 2, and the mixture was stirred at 70 ° C. for 24 hours. A product (2) was obtained. 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 applicability of composition and liquid crystal aligning agent”, “Preparation of liquid crystal cell (normal cell) ”,“ Evaluation of liquid crystal alignment (normal cell) ”and“ Evaluation of voltage holding ratio ”.

<Example 3>
PGME (5.36 g) and NMP (1.65 g) were added to a polyamic acid solution (3) (10.5 g) having a resin solid concentration of 10.0% by mass obtained by the synthesis method of Synthesis Example 3, and 25 The mixture was stirred at 0 ° C. for 2 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 applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) ”,“ Evaluation of liquid crystal alignment (normal cell) ”and“ Evaluation of voltage holding ratio ”.

<Example 4>
To the polyamic acid solution (3) (10.0 g) having a resin solid concentration of 10.0% by mass obtained by the synthesis method of Synthesis Example 3, PGME (1.97 g), γ-BL (1.57 g), BCS (3.13 g) was added, and the mixture was stirred at 25 ° C. for 2 hours to obtain a 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), under the above-mentioned conditions, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 5>
PGME (22.6 g) and γ-BL (2.51 g) were added to the polyimide powder (4) (1.60 g) obtained by the synthesis method of Synthesis Example 4, and the mixture was stirred at 70 ° C. for 24 hours. A product (5) was obtained. 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 aligning agent (5), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) ”,“ Evaluation of liquid crystal alignment (normal cell) ”,“ Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell) ”and“ Evaluation of voltage holding ratio ”.

<Example 6>
PCS (15.0 g), γ-BL (2.51 g), and BCS (7.52 g) are added to the polyimide powder (4) (1.60 g) obtained by the synthesis method of Synthesis Example 4, and the mixture is heated to 70 ° C. And stirred 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), under the above-mentioned conditions, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 7>
PCS (21.5 g), γ-BL (7.17 g), and BCS (10.8 g) were added to the polyimide powder (4) (1.30 g) obtained by the synthesis method of Synthesis Example 4, and the mixture was heated to 70 ° C. And stirred 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>
MCS (14.6 g), NEP (3.64 g), and BCS (6.07 g) are added to the polyimide powder (5) (1.55 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 (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 obtained composition (8) and liquid crystal aligning agent (8), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 9>
PGME (15.0 g), γ-BL (7.52 g), and BCS (2.51 g) were added to the polyimide powder (5) (1.60 g) obtained by the synthesis method of Synthesis Example 5, and the mixture was heated to 70 ° C. 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), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) "," Evaluation of liquid crystal alignment (normal cell) "and" Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell) ".

<Example 10>
PGME (22.6 g) and γ-BL (2.51 g) were added to the polyimide powder (6) (1.60 g) obtained by the synthesis method of Synthesis Example 6, and the mixture was stirred at 70 ° C. for 24 hours. A product (10) was obtained. 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 applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 11>
PGME (32.3 g) and γ-BL (3.58 g) were added to the polyimide powder (6) (1.30 g) obtained by the synthesis method of Synthesis Example 6, and the mixture was stirred at 70 ° C. for 24 hours. A product (11) was obtained. 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 obtained liquid crystal aligning agent (11), “evaluation of ink jet coatability of liquid crystal aligning agent” was performed under the above-described conditions.

<Example 12>
PCS (17.6 g), NEP (5.01 g), and BCS (2.51 g) were added to the polyimide powder (6) (1.60 g) obtained by the synthesis method of Synthesis Example 6, and 24 ° C. at 24 ° C. The mixture was stirred for a time 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), under the above-mentioned conditions, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 13>
ECS (15.0 g), NMP (5.01 g), and BCS (5.01 g) were added to the polyimide powder (7) (1.60 g) obtained by the synthesis method of Synthesis Example 7, and 24 ° C. at 24 ° C. The mixture was stirred for a time to obtain a 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 composition (13) and liquid crystal aligning agent (13), under the above-mentioned conditions, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 14>
PGME (21.9 g) and γ-BL (2.43 g) were added to the polyimide powder (8) (1.55 g) obtained by the synthesis method of Synthesis Example 8, and the mixture was stirred at 70 ° C. for 24 hours. A product (14) was obtained. 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), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 15>
MCS (21.3 g), γ-BL (1.25 g), and BCS (2.51 g) are added to the polyimide powder (8) (1.60 g) obtained by the synthesis method of Synthesis Example 8, and the mixture is heated to 70 ° C. And stirred 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 obtained composition (15) and liquid crystal aligning agent (15), under the above-mentioned conditions, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 16>
PGME (22.6 g) and γ-BL (2.51 g) were added to the polyimide powder (9) (1.60 g) obtained by the synthesis method of Synthesis Example 9, and the mixture was stirred at 70 ° C. for 24 hours. A product (16) was obtained. 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), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 17>
PCS (22.6 g), γ-BL (5.01 g), and BCS (2.51 g) were added to the polyimide powder (9) (1.60 g) obtained by the synthesis method of Synthesis Example 9, and the mixture was heated to 70 ° C. And stirred for 24 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 obtained composition (17) and liquid crystal aligning agent (17), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 18>
PCS (17.6 g) and NMP (5.88 g) were added to the polyimide powder (10) (1.50 g) obtained by the synthesis method of Synthesis Example 10, and the mixture was stirred at 70 ° C. for 24 hours. 18) was obtained. 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), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 19>
PGME (23.3 g) and γ-BL (2.59 g) were added to the polyimide powder (11) (1.65 g) obtained by the synthesis method of Synthesis Example 11, and the mixture was stirred at 70 ° C. for 24 hours. A product (19) was obtained. 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 aligning agent (19), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 20>
PGME (20.1g), (gamma) -BL (2.51g), and BCS (2.51g) are added to the polyimide powder (11) (1.60g) obtained by the synthesis method of the synthesis example 11, and 70 degreeC is added. For 24 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), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) "," Evaluation of liquid crystal alignment (normal cell) "and" Preparation of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell) ".

<Example 21>
PCS (17.6 g), γ-BL (2.51 g), and BCS (5.01 g) were added to the polyimide powder (11) (1.60 g) obtained by the synthesis method of Synthesis Example 11, and the mixture was heated to 70 ° C. The mixture was stirred for 24 hours 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 obtained composition (21) and liquid crystal aligning agent (21), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 22>
PGME (22.6 g) and γ-BL (2.51 g) were added to the polyimide powder (12) (1.60 g) obtained by the synthesis method of Synthesis Example 12, and the mixture was stirred at 70 ° C. for 24 hours. A product (22) was obtained. 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), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Example 23>
MCS (17.0 g), γ-BL (1.21 g), and BCS (6.07 g) are added to the polyimide powder (12) (1.55 g) obtained by the synthesis method of Synthesis Example 12, and the mixture is heated to 70 ° C. And stirred for 24 hours 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 obtained composition (23) and liquid crystal aligning agent (23), "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell)" And “Evaluation of liquid crystal alignment (normal cell)”.

<Comparative Example 1>
NMP (17.4 g) was added to the polyamic acid solution (13) (5.50 g) having a resin solid content concentration of 25.0 mass% obtained by the synthesis method of Synthesis Example 13, and the mixture was stirred at 25 ° C. for 2 hours. A composition (24) was obtained. 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), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Comparative Example 2>
NMP (13.1 g) and BCS (4.31 g) were added to a polyamic acid solution (13) (5.50 g) having a resin solid content concentration of 25.0 mass% obtained by the synthesis method of Synthesis Example 13, and 25 The mixture was stirred at 0 ° C. for 2 hours to obtain a composition (25). 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 (25) was used for evaluation also as a liquid-crystal aligning agent (25).

  Using the obtained composition (25) and liquid crystal aligning agent (25), "Evaluation of applicability of composition and liquid crystal aligning agent" and "Preparation of liquid crystal cell (ordinary cell)" And “Evaluation of liquid crystal alignment (normal cell)”.

<Comparative Example 3>
Γ-BL (19.6 g) was added to the polyimide powder (14) (1.25 g) obtained by the synthesis method of Synthesis Example 14, and the mixture was stirred at 70 ° C. for 24 hours to obtain a composition (26). . 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 (26) was used for evaluation also as a liquid-crystal aligning agent (26).

  Using the obtained composition (26) and liquid crystal aligning agent (26), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) ”,“ Evaluation of liquid crystal alignment (normal cell) ”and“ Evaluation of voltage holding ratio ”.

<Comparative example 4>
Γ-BL (19.6 g) and BCS (4.07 g) were added to the polyimide powder (14) (1.30 g) obtained by the synthesis method of Synthesis Example 14, and the mixture was stirred at 70 ° C. for 24 hours. A product (27) was obtained. 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 (27) was used for evaluation also as a liquid-crystal aligning agent (27).

  Using the obtained composition (27) and liquid crystal aligning agent (27), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Comparative Example 5>
PGME (20.4 g) was added to the polyimide powder (14) (1.30 g) obtained by the synthesis method of Synthesis Example 14, and the mixture was stirred at 70 ° C. for 24 hours to obtain a composition (28). 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 (28) was used for evaluation also as a liquid-crystal aligning agent (28).

  Using the obtained composition (28) and liquid crystal aligning agent (28), "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (ordinary cell)" And “Evaluation of liquid crystal alignment (normal cell)”.

<Comparative Example 6>
NMP (17.4 g) is added to the polyamic acid solution (15) (5.50 g) having a resin solid content concentration of 25.0 mass% obtained by the synthesis method of Synthesis Example 15, and the mixture is stirred at 25 ° C. for 2 hours. A composition (29) was obtained. 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 (29) was used for evaluation also as a liquid-crystal aligning agent (29).

  Using the obtained composition (29) and liquid crystal aligning agent (29), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) ”,“ Evaluation of liquid crystal alignment (normal cell) ”and“ Evaluation of voltage holding ratio ”.

<Comparative Example 7>
Γ-BL (20.4 g) was added to the polyimide powder (16) (1.30 g) obtained by the synthesis method of Synthesis Example 16, and the mixture was stirred at 70 ° C. for 24 hours to obtain a composition (30). . 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 (30) was used for evaluation also as a liquid-crystal aligning agent (30).

  Using the obtained composition (30) and liquid crystal aligning agent (30), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) ”,“ Evaluation of liquid crystal alignment (normal cell) ”and“ Evaluation of voltage holding ratio ”.

<Comparative Example 8>
Γ-BL (16.3 g) and BCS (4.07 g) were added to the polyimide powder (16) (1.30 g) obtained by the synthesis method of Synthesis Example 16, and the mixture was stirred at 70 ° C. for 24 hours. A product (31) was obtained. 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 (31) was used for evaluation also as a liquid-crystal aligning agent (31).

  Using the obtained composition (31) and liquid crystal aligning agent (31), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Comparative Example 9>
PGME (19.6 g) was added to the polyimide powder (16) (1.25 g) obtained by the synthesis method of Synthesis Example 16, and the mixture was stirred at 70 ° C. for 24 hours to obtain a composition (32). 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 (32) was used for evaluation also as a liquid-crystal aligning agent (32).

  Using the obtained composition (32) and liquid crystal aligning agent (32), under the conditions described above, "Evaluation of applicability of composition and liquid crystal aligning agent", "Preparation of liquid crystal cell (normal cell) And “Evaluation of liquid crystal alignment (normal cell)”.

<Comparative Example 10>
PGME (20.4 g) was added to the polyimide powder (17) (1.30 g) obtained by the synthesis method of Synthesis Example 17, and the mixture was stirred at 70 ° C. for 24 hours. Since the polyimide powder remained undissolved in the solution, the solution was further stirred at 70 ° C. for 12 hours, but the polyimide powder could not be completely dissolved.

  Therefore, the composition (33) and the liquid crystal aligning agent (33) could not be produced.

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

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

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

* 5: Pinholes associated with foreign matter were observed.
* 6: The polyimide powder was not completely dissolved, and the composition and the liquid crystal aligning agent could not be adjusted.
* 7: 25 or more alignment defects were confirmed.
* 8: 11 to 24 alignment defects were confirmed.
* 9: 5 to 10 alignment defects were confirmed.

  As can be seen from the above results, the composition of the example of the present invention has a uniform coating property that does not generate pinholes due to repellency or foreign matter when applied to the substrate, compared to the composition of the comparative example. showed that. Specifically, a comparison with a composition using the same polyimide precursor or solvent-soluble polyimide, that is, comparison between Example 1 and Comparative Example 1 or Comparative Example 2, Example 2 and Comparative Example 3 or Comparison with Comparative Example 4, Comparison between Example 3 and Comparative Example 6, and Comparison between Example 5 and Comparative Example 7 or Comparative Example 8. Furthermore, in the Example using the specific polar solvent which is (B) component of this invention, generation | occurrence | production of the pinhole accompanying a foreign material was able to be suppressed. Specifically, it is a comparison between Example 2 and Comparative Example 5 and a comparison between Example 5 and Comparative Example 9.

  Moreover, the same result was obtained also with the liquid crystal aligning film obtained from the liquid-crystal aligning agent using the composition of this invention. Specifically, a comparison with a composition using the same polyimide precursor or solvent-soluble polyimide, that is, comparison between Example 1 and Comparative Example 1 or Comparative Example 2, Example 2 and Comparative Example 3 or Comparison with Comparative Example 4, Comparison between Example 3 and Comparative Example 6, and Comparison between Example 5 and Comparative Example 7 or Comparative Example 8. Furthermore, the comparison between Example 2 and Comparative Example 5 and the comparison between Example 5 and Comparative Example 9 are shown. In particular, even in the case of a liquid crystal alignment treatment agent using a polyimide precursor or a solvent-soluble polyimide obtained by using a diamine compound having a side chain as a diamine component, a pinhole is not generated in the same manner as described above. The coating property was shown.

  Further, in the evaluation of the liquid crystal alignment property of the liquid crystal cell, the liquid crystal cell obtained from the liquid crystal alignment treatment agent using the composition of the present invention is the liquid crystal cell obtained from the liquid crystal alignment treatment agent using the composition of the comparative example. Compared with, no alignment defects due to pinholes were observed, and uniform liquid crystal alignment was obtained. Specifically, a comparison with a liquid crystal aligning agent using the same polyimide precursor or solvent-soluble polyimide, that is, comparison between Example 1 and Comparative Example 1 or Comparative Example 2, Example 2 and Comparative Example 3 is a comparison with 3 or Comparative Example 4, a comparison with Example 3 and Comparative Example 6, and a comparison with Example 5 and Comparative Example 7 or Comparative Example 8. Furthermore, the comparison between Example 2 and Comparative Example 5 and the comparison between Example 5 and Comparative Example 9 are shown.

  In addition, in the evaluation of the voltage holding ratio, the liquid crystal cell obtained from the liquid crystal aligning agent using the composition of the present invention is compared with the liquid crystal cell obtained from the liquid crystal aligning agent using the composition of the comparative example. Showed a high value. Specifically, a comparison with a liquid crystal aligning agent using the same polyimide precursor or solvent-soluble polyimide, that is, a comparison between Example 2 and Comparative Example 3, and a comparison between Example 3 and Comparative Example 6. And a comparison between Example 5 and Comparative Example 7.

  When the composition of the present invention is applied to a substrate, it is possible to obtain a resin film exhibiting a uniform coating property that does not generate pinholes accompanying repellency or foreign matter. Moreover, the same result can be obtained also with the liquid-crystal aligning agent using the composition of this invention.

  In addition, the liquid crystal alignment treatment agent of the present invention can provide a liquid crystal cell in which alignment defects due to pinholes accompanying repelling and foreign matters do not occur. In particular, the same result can be obtained even with a liquid crystal alignment treatment agent using a polyimide precursor or a solvent-soluble polyimide obtained by using a diamine compound having a side chain as a diamine component.

  Furthermore, the liquid-crystal aligning agent of this invention can express a high voltage holding rate even by baking at low temperature.

  The liquid crystal aligning agent of the present invention is a liquid crystal display element that switches between a liquid crystal transmission state (also referred to as a transparent state) and a scattering state, that is, a polymer dispersed liquid crystal (PDLC (Polymer Dispersed Liquid Crystal)). ) And polymer network liquid crystal (PNLC (Polymer Network Liquid Crystal)).

  In particular, it is useful for a reverse type element that is transparent when no voltage is applied and is in a scattering state when a voltage is applied. This reverse type element is a liquid crystal display for display using a glass substrate, or a plastic substrate such as PET (polyethylene terephthalate) or an acrylic substrate, and a light control for controlling transmission and blocking of light. This is useful for windows, light shutter elements, light control windows of vehicles such as cars, and back plates of transparent displays.

  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 (17)

It is a composition containing the following (A) component, (B) component, and (C) component , and the following (A) component is 55 mass%-99 mass% of the whole solvent contained in the said composition. The composition characterized by these.
Component (A): at least one solvent selected from the following formula [1a] or [1b].

(In formula [1a], X ¹ represents an alkyl group having 1 to 3 carbon atoms, and in formula [1b], X ² represents an alkyl group having 1 to 3 carbon atoms).
Component (B): at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone.
Component (C): At least one polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group with a tetracarboxylic dianhydride component. The composition according to claim 1 , wherein the diamine compound having a carboxyl group as the component (C) is a diamine compound having a structure represented by the following formula [2].

(In formula [2], a represents an integer of 0 to 4). The composition according to claim 2 , wherein the diamine compound having a carboxyl group as the component (C) is a diamine compound having a structure represented by the following formula [2a].

(In formula [2a], a represents an integer of 0 to 4, and n represents an integer of 1 to 4). The said diamine compound which has a carboxyl group is 20 mol%-100 mol% in all the diamine used for the said (C) component, The Claim 1 characterized by the above-mentioned. Composition. The diamine component of said (C) component contains the at least 1 sort (s) of diamine compound chosen from the structure shown by following formula [2b], It is any one of Claims 1-4 characterized by the above-mentioned. Composition.

(In the formula [2b], Y represents the structure of the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5] 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 amine 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 an alkyl group having 8 to 22 carbon atoms, and in formula [2b-4], Y ⁸ and Y ⁹ are each independently a hydrocarbon having 1 to 6 carbon atoms. A group of formula [2b During ^{5], Y 10} represents an alkyl group having 1 to 8 carbon atoms). The composition according to any one of claims 1 to 5 , wherein the tetracarboxylic dianhydride component of the component (C) is a compound represented by the following formula [3].

(In the formula [3], Z ¹ is a group having at least one 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. As component (D), 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether The composition according to any one of claims 1 to 6 , comprising at least one solvent selected from diethylene glycol isopropyl ether and diethylene glycol monobutyl ether. A resin film obtained from the composition according to any one of claims 1 to 7 . Liquid crystal alignment treating agent characterized in that it is obtained from a composition according to any one of claims 1 to 7. A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to claim 9 . A liquid crystal display element comprising the liquid crystal alignment film according to claim 10 . By using the liquid crystal alignment treating agent according to claim 9, the method of manufacturing a liquid crystal alignment film, characterized by producing a liquid crystal alignment film by an ink jet method. Method of manufacturing a liquid crystal display device characterized by manufacturing a liquid crystal display device using a liquid crystal alignment film produced by the production method of the liquid crystal alignment film of claim 12. 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 method of manufacturing a liquid crystal alignment film according to 請 Motomeko 12 through a step of polymerizing a voltage the polymerizable compound while applying you characterized in that it is used in a method of manufacturing a liquid crystal display element between. Method of fabricating a liquid crystal display device using a liquid crystal alignment film obtained by the production method of the liquid crystal alignment film according to claim 14, characterized in that to produce a liquid crystal display device. 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; method of manufacturing a liquid crystal alignment film according to 請 Motomeko 12 through a step of polymerizing the polymerizable group while applying a voltage you characterized in that it is used in a method of manufacturing a liquid crystal display element between. Method of fabricating a liquid crystal display device using a liquid crystal alignment film obtained by the production method of the liquid crystal alignment film according to claim 16, characterized in that to produce a liquid crystal display device.