WO2012091109A1

WO2012091109A1 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: WO2012091109A1
Application number: PCT/JP2011/080446
Authority: WO
Inventors: 徳俊三木; 耕平後藤; 雅章片山; 保坂　和義
Original assignee: 日産化学工業株式会社
Priority date: 2010-12-28
Filing date: 2011-12-28
Publication date: 2012-07-05
Also published as: KR101856274B1; CN103415805A; CN103415805B; JP5874646B2; TW201242991A; TWI545147B; KR20140002723A; JPWO2012091109A1

Abstract

Provided is a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film wherein burrs and cuts associated with rubbing do not easily occur and there is little reduction in a voltage holding ratio even after light irradiation for a long time. The liquid crystal aligning agent contains a component (A) and a component (B), listed below. Component (A): An amine compound having one primary amino group and a hydroxyl group in a molecule and wherein the primary amino group and the hydroxyl group are bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Compound (B): At least one type of polymer selected from a group comprising a polyamide precursor and a polyamide.

Description

Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film and a liquid crystal display element using the same.

Liquid crystal display elements are now widely used as display devices that are thin and light. Usually, in this liquid crystal display element, a liquid crystal alignment film is used to determine the alignment state of the liquid crystal. Further, except for some vertical alignment type liquid crystal display elements and the like, most of the liquid crystal alignment films are produced by performing some alignment treatment on the surface of the polymer film formed on the electrode substrate.

As a method for orienting a polymer film, a method generally used at present is a method of performing a so-called rubbing process in which the surface of the polymer film is rubbed with a cloth made of rayon or the like under pressure. . A method of using a liquid crystal alignment treatment agent containing a specific thermally crosslinkable compound together with at least one polymer of polyamic acid or polyimide for the scraping of the polymer film accompanying such rubbing treatment (for example, A method for improving rubbing resistance by using a curing agent, such as a method using a liquid crystal aligning agent containing an epoxy group-containing compound (see, for example, Patent Document 2) has been proposed. .

Japanese Unexamined Patent Publication No. 9-185065 Japanese Unexamined Patent Publication No. 9-146100

Recently, for the purpose of shortening the manufacturing process time of the liquid crystal display element, the rubbing treatment is performed under strong rubbing conditions in a short time. Therefore, compared to the conventional case, there is a problem in that the polymer film scraped off due to the rubbing treatment and many scratches accompanying the rubbing treatment occur. These abnormalities are considered to be one of the causes that deteriorate the characteristics of the liquid crystal display element and further cause the yield to decrease.

Also, with the recent improvement in performance of liquid crystal display elements, liquid crystal display elements are used for large-screen, high-definition liquid crystal televisions and in-vehicle applications such as car navigation systems and meter panels. In such applications, in order to obtain high luminance, a backlight with a large calorific value may be used. For this reason, the liquid crystal alignment film is required to have high reliability from another point of view, that is, high stability against light from the backlight. In particular, when the voltage holding ratio, which is one of the electrical characteristics of the liquid crystal display element, is reduced by light irradiation from the backlight, the burn-in defect (hereinafter referred to as line burn-in) which is one of the display defects of the liquid crystal display element. The liquid crystal display element with high reliability cannot be obtained. Therefore, in the liquid crystal alignment film, in addition to good initial characteristics, for example, it is required that the voltage holding ratio does not easily decrease even after being exposed to light irradiation for a long time.

Therefore, an object of the present invention is to provide a liquid crystal alignment film having the above characteristics. That is, the object of the present invention is that the polymer film is less likely to be scraped or damaged due to the rubbing process during the manufacturing process of the liquid crystal display element. An object of the present invention is to provide a liquid crystal alignment film in which a decrease in voltage holding ratio is suppressed even when exposed to irradiation.

Also, an object of the present invention is to provide a liquid crystal alignment treatment agent that can provide the above-mentioned liquid crystal alignment film, and a liquid crystal display element obtained by using this liquid crystal alignment treatment agent.

As a result of intensive studies, the present inventors have found that a liquid crystal aligning agent containing an amine compound having a specific structure is extremely effective for achieving the above object, and has completed the present invention. .

That is, the present invention has the following gist.
(1) Liquid crystal aligning agent containing the following component (A) and component (B).
Component (A): An amine having one primary amino group and a hydroxyl group in the molecule, and the primary amino group and the hydroxyl group are bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Compound.
Component (B): at least one polymer selected from the group consisting of polyimide precursors and polyimides.
(2) The liquid-crystal aligning agent as described in said (1) whose amine compound of a component (A) is a compound shown by following formula [1].

(In the formula [1], X ₁ is an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and X ₂ is a single bond, —O—, —NH—, —CO—, — COO—, —OCO—, —NH—, —N (CH ₃ ) —, —NHCO—, —N (CH ₃ ) CO—, —CONH—, —CON (CH ₃ ) —, —S— or —SO ₂ , X ₃ is a single bond, a benzene ring or a cyclohexane ring, X ₄ is a single bond, —O—, —CO—, —COO—, —OCO—, —NH—, —N (CH ₃ ) —, —NHCO—, —N (CH ₃ ) CO—, —CONH—, —CON (CH ₃ ) —, —S— or —SO ₂ —, wherein X ₅ is a single bond, an aliphatic hydrocarbon group Or an organic group having a non-aromatic cyclic hydrocarbon group, and n is an integer of 1 to 5.
(3) The above (2), wherein X ₁ of the formula [1] which is the amine compound of the component (A) is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexane ring or a bicyclohexyl ring. Liquid crystal alignment treatment agent.
(4) The liquid crystal aligning agent according to the above (2) or (3), wherein X ₂ of the formula [1] which is the amine compound of the component (A) is a single bond, —O— or —OCO—.
(5) The liquid crystal aligning agent according to any one of (2) to (4) above, wherein X _{3 of} formula [1] which is the amine compound of component (A) is a single bond or a benzene ring.
(6) Any one of the above (2) to (5), wherein X ₄ of the formula [1] which is the amine compound of component (A) is a single bond, —O—, —NH— or —CONH—. The liquid crystal aligning agent of description.
(7) X ₅ of the formula [1] which is an amine compound of component (A) is a single bond, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclohexane ring. The liquid-crystal aligning agent in any one of said (6).
(8) The component (B) is at least one heavy selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic dianhydride and a polyimide obtained by dehydrating and ring-closing the polyamic acid. The liquid crystal aligning agent according to any one of (1) to (7), which is a coalescence.
(9) The liquid-crystal aligning agent as described in said (8) whose diamine component is a diamine compound which has a side chain shown by following formula [2].

(In the formula [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—. Y ₂ is a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15), Y ₃ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15) ), —O—, —CH ₂ O—, —COO— or —OCO—, wherein Y ₄ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms Alternatively, it may be substituted with a fluorine atom, or has a steroid skeleton having 12 to 25 carbon atoms A divalent organic group selected from organic groups, Y ₅ is a cyclic group selected from benzene ring, the group consisting of cyclohexane ring and heterocyclic cyclohexane, any hydrogen atoms on these cyclic groups, 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, n is an integer of 0 to 4, Y ₆ is 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 group having 1 to 18 carbon atoms An alkoxyl group).
(10) The liquid-crystal aligning agent as described in said (8) whose diamine component is a diamine compound shown by following formula [2a].

(In Formula [2a], Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n have the same significance as defined in Formula [2], and m is an integer of 1 to 4. .)
(11) The liquid crystal aligning agent according to (9) or (10), wherein the diamine compound of the formula [2a] is contained in an amount of 5 to 80 mol% in the diamine component.
(12) The liquid crystal according to any one of (8) to (11) above, wherein the polymer of component (B) is a polymer using a tetracarboxylic dianhydride represented by the following formula [3]: Alignment treatment agent.

(In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms).
(13) The liquid crystal aligning agent according to the above (12), wherein the tetracarboxylic dianhydride has a structure represented by the following formulas [3a] to [3j].

(In the formula [3a], Z ₂ to Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, which may be the same or different. In the formula [3g], Z ₆ and Z ₇ Are hydrogen atoms or methyl groups, which may be the same or different.
(14) The liquid crystal aligning agent according to any one of (1) to (13) above, wherein the polymer of component (B) is a polyimide obtained by dehydrating and ring-closing polyamic acid.
(15) The liquid crystal aligning agent according to any one of (1) to (14), wherein the component (A) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (B).
(16) The liquid crystal aligning agent according to any one of (1) to (15), wherein the liquid crystal aligning agent contains 5% by mass to 60% by mass of a poor solvent.
(17) A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of (1) to (16).
(18) A liquid crystal display device having the liquid crystal alignment film according to (17).
(19) 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. The liquid crystal alignment film according to (17), which is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.
(20) A liquid crystal display device having the liquid crystal alignment film according to (19).
(21) A liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (17), which is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.
(22) A liquid crystal display device having the liquid crystal alignment film according to (21).

By using the liquid crystal alignment treatment agent of the present invention, the polymer film is less likely to be scraped or scratched due to the rubbing process during the manufacturing process of the liquid crystal display element, and further, it can be irradiated with light for a long time. Even when exposed, a liquid crystal alignment film in which a decrease in voltage holding ratio is suppressed can be obtained. 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.

The present invention is a liquid crystal aligning agent containing the following component (A) and component (B), a liquid crystal aligning film obtained using the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal aligning film. is there.
Component (A): An amine having one primary amino group and a hydroxyl group in the molecule, and the primary amino group and the hydroxyl group are bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Compound (hereinafter sometimes referred to as a specific amine compound).
Component (B): at least one polymer selected from the group consisting of a polyimide precursor and a polyimide (hereinafter sometimes referred to as a specific polymer).

In the liquid crystal aligning agent of the present invention, the primary amino group in the specific amine compound forms a salt with the carboxyl group in the specific polymer, or relative to the carboxyl group or carboxy ester group in the specific polymer, It is considered that the amide bond is accompanied by elimination of water or alcohol, or that the imide group in the specific polymer undergoes a binding reaction involving ring opening of the imide group. Furthermore, it is considered that the primary amino group that forms a salt with the carboxyl group in the specific polymer forms an amide bond due to elimination of water in the baking step in producing the liquid crystal alignment film. As a result, although the liquid crystal aligning agent of the present invention is a simple means of mixing in an organic solvent, the specific amine compound and the specific polymer are efficiently bonded in the liquid crystal alignment film obtained therefrom. I think.

In addition, the hydroxyl group in the specific amine compound is heated by an esterification reaction accompanied by elimination of water or alcohol with respect to a carboxyl group or a carboxy ester group in the specific polymer, or water generated by hydroxyl groups in the specific amine compound. It is known that an etherification reaction involving the elimination of Therefore, as described above, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has a specific amine compound bonded to a specific polymer. The curing process of the sealing agent when producing the liquid crystal display element, that is, the baking process causes a cross-linking reaction between the polymers, the physical stability is improved, and the resistance to heat and light is high. Become.

Furthermore, in the present invention, since the specific amine compound that causes the crosslinking reaction is bonded to the specific polymer, the characteristics of the liquid crystal display element are deteriorated due to remaining unreacted components that occur when the crosslinking compound is added. There is no problem.

Therefore, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is less scraped from the polymer coating film due to the rubbing process during the manufacturing process of the liquid crystal display element than the liquid crystal alignment film containing no specific amine compound. And scratches associated with the rubbing process are less likely to occur, and further, even when exposed to light irradiation for a long time, a decrease in voltage holding ratio can be suppressed.

Since this specific amine compound has only one primary amino group contained in the molecule, problems such as polymer precipitation and gelation occur when preparing the liquid crystal aligning agent or during storage of the liquid crystal aligning agent. The possibility can also be avoided.
<Specific amine compound>
The specific amine compound of the present invention has one primary amino group and a hydroxyl group in the molecule, and the primary amino group and the hydroxyl group are bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. It is an amine compound.

More specifically, it is an amine compound represented by the following formula [1].

In the formula [1], X ₁ represents an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group so that the primary amino group contained in the specific amine compound can easily form a salt or bond with the specific polymer. It is an organic group.

Specific examples of the aliphatic hydrocarbon group include a linear alkyl group, a branched alkyl group, or a hydrocarbon group having an unsaturated bond. Of these, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable. More preferred is a linear or branched alkyl group having 1 to 15 carbon atoms, and further preferred is a linear or branched alkyl group having 1 to 10 carbon atoms.

Specific examples of the non-aromatic cyclic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, Cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicyclohexyl ring, bicyclo Examples include heptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like. Of these, a ring having 3 to 20 carbon atoms is preferable. A ring having 3 to 15 carbon atoms is more preferable, and a non-aromatic cyclic hydrocarbon group having a ring having 6 to 12 carbon atoms is still more preferable. Specifically, it is a cyclohexane ring or a bicyclohexyl ring, and particularly preferably a cyclohexane ring.

In the formula [1], X ₂ represents a single bond, —O—, —CO—, —COO—, —OCO—, —NH—, —N (CH ₃ ) —, —NHCO—, —N (CH ₃ ). CO—, —CONH—, —CON (CH ₃ ) —, —S— or —SO ₂ —. Of these, a single bond, —O—, —NH—, —COO—, —OCO—, —CONH— or —NHCO— is preferable. More preferred is a single bond, —O—, —NH—, —OCO— or —NHCO—, and particularly preferred is a single bond, —O— or —OCO—.
In the formula [1], X ₃ is a single bond, a benzene ring or a cyclohexane ring. More preferably, it is a single bond or a benzene ring.
In the formula [1], X ₄ represents a single bond, —O—, —CO—, —COO—, —OCO—, —NH—, —N (CH ₃ ) —, —NHCO—, —N (CH ₃ ). CO—, —CONH—, —CON (CH ₃ ) —, —S— or —SO ₂ —. Of these, a single bond, —O—, —NH—, —COO—, —OCO—, —CONH— or —NHCO— is preferable. More preferred is a single bond, —O—, —NH—, —OCO— or —CONH—, and particularly preferred is a single bond, —O—, —NH— or —CONH—.

In the formula [1], X ₅ is an organic group having a single bond, an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Specific examples of the aliphatic hydrocarbon group and the non-aromatic cyclic hydrocarbon group include those described above. Of these, a single bond, a linear or branched alkyl group having 1 to 20 carbon atoms, or a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms is preferable. More preferably, they are a single bond, a linear or branched alkyl group having 1 to 15 carbon atoms, or a non-aromatic cyclic hydrocarbon group having 3 to 15 carbon atoms. More preferably, they are a single bond, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexane ring or a bicyclohexyl ring, and particularly preferably a single bond, a linear chain having 1 to 10 carbon atoms. Or it is a branched alkyl group or a cyclohexane ring.
In the formula [1], n is an integer of 1 to 5. Among these, an integer of 1 to 4 is preferable. More preferably, it is an integer of 1 to 3.
Preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and n in the formula [1] are as shown in Tables 1 to 14.

<Specific polymer>
The specific polymer of the present invention is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide, and the polyimide precursor has a structure represented by the following formula [A].

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

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

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

(In the formula [D], R ₁ , R ₂ and n are as defined in the formula [A]).
In the formula [A] and the formula [D], R ₁ and R ₂ may each be one type, or may be a combination of different types having different R ₁ and R ₂ as repeating units. .

As the diamine component, it is preferable to use a diamine compound having a side chain represented by the following formula [2] (hereinafter also referred to as a specific side chain structure).

In the formula [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—. . Among these, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O— or —COO— is preferable because the side chain structure can be easily synthesized. More preferably, it is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 10), —O—, —CH ₂ O— or —COO—.

In the formula [2], Y ₂ is 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 the formula [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—. . Among these, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO— is preferable because they are easily synthesized. More preferably, they are a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O—, —COO— or —OCO—.

In the formula [2], Y ₄ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms Group, 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. Y ₄ is 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.

In the formula [2], Y ₅ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl having 1 to 3 carbon atoms. Group, 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.

In the formula [2], n is an integer of 0 to 4. Preferably, it is an integer of 0-2.

In the formula [2], Y ₆ is 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. . Of these, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
Preferred combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n in the formula [2] are as shown in Table 15 to Table 56.

As a method for introducing a specific side chain structure into the polymer of the present invention, a diamine compound represented by the following formula [2a] (hereinafter sometimes referred to as a specific diamine compound) is preferably used as a part of the raw material. .

Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n in the formula [2a] have the same meaning as defined in the formula [2], and m is an integer of 1 to 4. )
Further, the preferred combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n in the above formula [2a] are as shown in Table 15 to Table 56, as in the formula [2]. It is.
In the formula [2a], m is an integer of 1 to 4. Preferably, it is an integer of 1.

More specifically, the structure is represented by the following formulas [2-1] to [2-32].

(In Formula [2-1] and Formula [2-2], R ₁ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or —CH ₂ OCO—, and R ₂ represents An alkyl group having 1 to 22 carbon atoms, an alkoxyl group, a fluorine-containing alkyl group, or a fluorine-containing alkoxyl group).

(In the formulas [2-3] to [2-5], R ₃ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ — or — CH ₂ —, wherein R ₄ is an alkyl group having 1 to 22 carbon atoms, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxyl group).

(In the formulas [2-6] and [2-7], R ₅ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, — CH ₂ — or —O—, wherein R ₆ is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group).

(In Formula [2-8] and Formula [2-9], R ₇ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. ).

(In the formulas [2-10] and [2-11], R ₈ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. ).

(In the formula [2-12], A ₄ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ represents a 1,4-cyclohexylene group or a 1,4-phenylene group. A ₂ is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A ₃ ), and A ₁ is an oxygen atom or —COO— * (where “*” Is a bond with (CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.

In the present invention, other diamine compounds other than the specific diamine compound (hereinafter sometimes referred to as other diamine compounds) can be used as the diamine component as long as the effects of the present invention are not impaired. Specific examples are given below.
p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 , 6-diaminoresorcinol, 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'-diph Fluoro-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'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3 '-Sulphonyldianiline, bis (4-aminophenyl) silane, bis (3-amino Nophenyl) 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-methyl (3 3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8- Diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3 -Aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4aminophenyl) butane, 1,4-bis ( 3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) ben 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-amino) Benzyl) 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-phenylene Bis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3 -Ami Phenyl) 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) bi (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-aminophenoxy) diphenylsulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2 '-Bis (3-amino-4-methylphenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-amino) Phenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4 -Aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) Nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane, 4- (aminomethyl) aniline, 3- (aminomethyl) aniline, 4- (2-aminoethyl) aniline or Aromatic diamines such as 3- (2-aminoethylaniline); bis (4-aminocyclohexyl) methane or bis (4-amino-3-methyl) Cyclohexyl) alicyclic diamines such as methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 An aliphatic diamine such as diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane;

In addition, a diamine compound having an alkyl group or a fluorine-containing alkyl group in the diamine side chain can be used as long as the effects of the present invention are not impaired.
Specifically, diamines represented by the following formulas [DA1] to [DA12] can be exemplified.

(Wherein [DA1] ~ formula [DA5], _{A 1} is an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms).

(In the formulas [DA6] to [DA11], A ₂ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or —NH—, A ₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

(In the formula [DA12], p is an integer of 1 to 10).

In addition, diamine compounds represented by the following formulas [DA13] to [DA20] can also be used as long as the effects of the present invention are not impaired.

(In the formula [DA17], m is an integer of 0 to 3, and in the formula [DA20], n is an integer of 1 to 5).

Furthermore, as long as the effects of the present invention are not impaired, a diamine compound having a carboxyl group in the molecule represented by the following formulas [DA21] to [DA24] can also be used.

(In the formula [DA21], m ₁ is an integer of 1 to 4, and in the formula [DA22], A ₄ is a single bond, —CH ₂ —, —C ₂ H ₄ —, —C (CH ₃ ) ₂ —. , —CF ₂ —, —C (CF ₃ ) —, —O—, —CO—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO—, each of m ₂ and m ₃ is an integer of 0 to 4 and m ₂ + m ₃ Is an integer of 1 to 4, and in formula [DA23], m ₄ and m ₅ are each an integer of 1 to 5, and in formula [DA24], A ₅ is a linear or branched alkyl having 1 to 5 carbon atoms. a group, _{m 6} is an integer of 1 to 5, wherein [DA25], _{a 6} represents a single _{_{_{bond, -CH 2 -, - C 2}}} H 4 -, - C (C _{_{_{_{3) 2 -, - CF 2}}}} -, - C (CF 3) -, - O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O —, —OCH ₂ —, —COO—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO—, and m ₇ is an integer of 1 to 4.

The above-mentioned specific diamine compound and other diamine compounds may be used alone or in combination of two or more depending on the properties such as liquid crystal orientation, voltage holding ratio and accumulated charge when the liquid crystal alignment film is used. .

In order to obtain the specific polymer of the present invention, a tetracarboxylic dianhydride represented by the following formula [3] (hereinafter sometimes referred to as a specific tetracarboxylic dianhydride) is used as part of the raw material. It is preferable.

In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms.

Specifically, the structure is represented by the following formula [3a] to formula [3j].

In the formula [3a], Z ₂ to Z ₅ are groups selected from 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, and may be the same or different.
In the formula [3], particularly preferred structure of Z ₁ is the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] or the formula because of the polymerization reactivity and the ease of synthesis. [3 g].

In the present invention, other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride (hereinafter also referred to as other tetracarboxylic dianhydrides) are used as long as the effects of the present invention are not impaired. be able to. Other tetracarboxylic dianhydrides include the following tetracarboxylic acid dianhydrides.

Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 -Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis ( 3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2 , 2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bi (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxy) Phenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.
The above-mentioned specific tetracarboxylic dianhydride and other tetracarboxylic dianhydrides may be used alone or in combination of two or more depending on properties such as liquid crystal alignment, voltage holding ratio and accumulated charge when used as a liquid crystal alignment film. It can also be used by mixing.

The specific polymer of the present invention is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide, and the polyimide precursor is a structure represented by the formula [A].

In the present invention, the method for synthesizing the specific polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid. Specifically, a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and 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 esterifying a carboxylic acid group and a diamine component, 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.
Furthermore, in order to obtain a polyimide, the method of imidating the said polyamic acid or polyamic-acid alkylester to make a polyimide is used.

The liquid crystal alignment film obtained using the specific polymer of the present invention can increase the pretilt angle of the liquid crystal as the content ratio of the specific diamine compound in the diamine component increases. For the purpose of enhancing this property, it is preferable that 5 mol% or more and 80 mol% or less of the diamine component is the specific diamine compound. Especially, it is preferable that 5 mol% or more and 60 mol% or less of a diamine component are specific diamine compounds from the viewpoint of the applicability | paintability of a liquid-crystal aligning agent, and the electrical property as a liquid crystal aligning film.

In order to obtain the specific polymer of the present invention, it is preferable to use a specific tetracarboxylic dianhydride as the tetracarboxylic acid component. In that case, it is preferable that 1 mol% or more of a tetracarboxylic acid component is a specific tetracarboxylic dianhydride, More preferably, it is 5 mol% or more, More preferably, it is 10 mol% or more. Further, 100 mol% of the tetracarboxylic acid component may be a specific tetracarboxylic dianhydride.

The reaction between the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent. The organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Specific examples are given below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, isopropyl alcohol, Methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene Glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether , Propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether , 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n -Pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, 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, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since the water | moisture content in an organic solvent inhibits a polymerization reaction, and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is dispersed or dissolved in the organic solvent as it is. And a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent, a method of alternately adding a tetracarboxylic acid component and a diamine component, etc. Any of these methods may be used. In addition, when reacting using a plurality of diamine components or tetracarboxylic acid components, they may be reacted in a premixed state, individually or sequentially, or further individually reacted low molecular weight substances. May be mixed and reacted to form a specific polymer. In this case, the polymerization temperature can be selected from -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a specific polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. It becomes difficult. Therefore, it is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by 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 acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
The polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the above polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.
In the polyimide of the present invention, the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and 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 a method is preferably performed while removing water generated by the imidization reaction from the system.

The catalytic 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 ° C to 250 ° C, preferably 0 ° C to 180 ° C. it can. The amount of the basic catalyst is 0.5 mol times to 30 mol times, preferably 2 mol times to 20 mol times of the amic acid groups, and the amount of the acid anhydride is 1 mol times to 50 mols of the amic acid groups. Double, preferably 3 to 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is easy. 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, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, 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. In addition, when the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further improved.

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 obtained polymer film, workability at the time of forming the polymer film, and uniformity of the polymer film. The molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Liquid crystal aligning agent>
The liquid-crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a coating liquid containing the specific amine compound, the polymer component containing a specific polymer, and an organic solvent.

The content of the specific amine compound in the liquid crystal alignment treatment agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the specific polymer, and the desired crosslinking reaction proceeds. The amount is more preferably 0.1 to 100 parts by mass in order to exhibit film curability and not to deteriorate the alignment of the liquid crystal. More preferred is 1 to 50 parts by weight, and particularly preferred is 0.1 to 20 parts by weight.

The polymer component in the liquid crystal aligning agent of the present invention may all be a specific polymer used in the present invention, and other polymers may be mixed with the specific polymer of the present invention. . At that time, the content of the other polymer in the polymer component is 0.5 to 15% by mass, preferably 1 to 10% by mass. Other polymers include polyimide precursors or polyimides obtained from a diamine component that does not contain a specific diamine compound and a tetracarboxylic acid component that does not contain a specific tetracarboxylic dianhydride. Furthermore, a polyimide precursor and a polymer other than polyimide, specifically, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide and the like can be mentioned.

The organic solvent in the liquid crystal aligning agent of the present invention preferably has an organic solvent content of 70% by mass to 99% by mass from the viewpoint of forming a uniform polymer film by coating. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film. The organic solvent in that case will not be specifically limited if it is an organic solvent in which the specific polymer mentioned above is dissolved. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, Dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, Examples thereof include ethylene carbonate, propylene carbonate, diglyme and 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.

The liquid crystal aligning agent of the present invention has at least one selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group or an oxetane group, and a hydroxyl group and an alkoxyl group, as long as the effects of the present invention are not impaired. In addition to the crosslinkable compound having a substituent, a crosslinkable compound having a polymerizable unsaturated bond can also be introduced.

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- Epoxypropoxy) phenyl) ethyl) phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2, And 3-epoxypropoxyphenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol.

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 [4a] to formula [4k].

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 and / or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, Examples include glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, and ethylene urea-formaldehyde resin. Specifically, a melamine derivative in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group or both, a benzoguanamine derivative, glycoluril, or the like can be used. The melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring. Eight-substituted MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.), 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 eth Cymethylated 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, methoxymethylolated glycoluril such as Powderlink 1174, and the like.

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

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 and glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meta ) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (me ) 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, diglycidyl ester phthalate di (meth) acrylate, neopentyl glycol dihydroxypivalate Crosslinkable compounds having two polymerizable unsaturated groups in the molecule such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropylene (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl ( Examples thereof include crosslinkable compounds having one polymerizable unsaturated group in the molecule, such as (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester, and N-methylol (meth) acrylamide. .

In addition, a compound represented by the following formula [5] can also be used.

(In Formula [5], E ₁ is a group selected from a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring and a phenanthrene ring, and E ₂ is the following: A group selected from the formula [5a] and the formula [5b], and n is 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 contained in the liquid crystal aligning agent of this invention may be one type, and may be combined two or more types.

The content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 parts by mass to 150 parts by mass with respect to 100 parts by mass of the polymer component. In order to exhibit the effect and not to deteriorate the orientation of the liquid crystal, the amount is more preferably 0.1 to 100 parts by weight, and particularly 1 to 50 parts by weight.

Nitrogen-containing heterocyclic amine compounds represented by the following formulas [M1] to [M156] are used as compounds that promote charge transfer in the liquid crystal alignment film and promote charge release of a liquid crystal cell using the liquid crystal alignment film. It is preferable to add to the liquid crystal aligning agent. This amine compound may be added directly to the solution of the specific polymer, but it is 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 an appropriate solvent. It is preferable to do. The solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer described above.

Unless the effect of this invention is impaired, the liquid-crystal aligning agent of this invention is the organic solvent (henceforth a poor solvent) which improves the uniformity of the film thickness of a polymer film at the time of apply | coating a liquid-crystal aligning agent, and surface smoothness. Or a compound may be used. Furthermore, a compound that improves the adhesion between the liquid crystal alignment film and the substrate can also be used.

Specific examples of the poor solvent that improves the uniformity of the film thickness and the surface smoothness include the following.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, n-hexane, n-pentane, n-octane, diethyl 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, 3-methoxy Ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy- 2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether Low surface tension such as ru-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactyl isoamyl ester An organic solvent is mentioned.

These poor solvents may be used alone or in combination. When the above poor solvent is used, the content is preferably 5% by mass to 80% by mass, and more preferably 5% by mass to 60% by mass with respect to the total organic solvent contained in the liquid crystal aligning agent.

Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like. The ratio of these surfactants to be used is preferably 0.01 parts by weight to 2 parts by weight, more preferably 0.01 parts by weight to 100 parts by weight of the polymer component contained in the liquid crystal aligning agent. 1 part by mass.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
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, N, N, N ′ , N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane and the like.

When using a compound that improves the adhesion to the substrate, it is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. Is 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.

The liquid crystal aligning agent of the present invention includes the above-mentioned crosslinkable compound, poor solvent, compound for improving film thickness uniformity and surface smoothness, and compound for improving adhesion to the substrate. As long as the effect is not impaired, a dielectric material or conductive material for changing the electrical characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film may be added.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment or light irradiation. Moreover, in the case of vertical alignment use 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 aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet method are generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method spray method, and the like, and these may be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied on the substrate, the solvent can be evaporated at 50 ° C. to 300 ° C., preferably 80 ° C. to 250 ° C. by a heating means such as a hot plate to form a polymer film. If the thickness of the polymer 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 between 10 nm and 100 nm. When the liquid crystal is aligned horizontally or tilted, the polymer film after baking 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 above-described method 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 the liquid crystal under reduced pressure, or a method of sealing the substrate by bonding the substrate after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed.

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 above liquid crystal display element controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, 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 liquid crystal molecules can be controlled by polymerizing.

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 of bonding the other substrate and injecting liquid crystal under reduced pressure, or a method in which a liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed, and then the substrate is bonded to perform sealing. .

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, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled. When the polymerizable compound exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases, and the liquid crystal display The burn-in characteristic of the element is deteriorated.

After producing the liquid crystal cell, 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 disposing a liquid crystal alignment film containing a group and applying a voltage between the electrodes. Here, ultraviolet rays are suitable as the active energy ray.

In order to obtain a liquid crystal alignment film containing a polymerizable group that is polymerized by 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 this invention contains the specific amine compound which has the double bond site | part which reacts by irradiation of a heat | fever or an ultraviolet-ray, it can control the orientation of a liquid crystal molecule by at least one of an ultraviolet irradiation and a heating. it can. Examples of the double bond site include an acryl group, a methacryl group, a vinyl group, and a cinnamoyl group.

After the liquid crystal cell is produced, 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 following examples further illustrate the present invention in more detail, but are not to be construed as being limited to “synthesis of polyimide precursor and polyimide”.
(Tetracarboxylic dianhydride)
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride TCA: represented by the following formula Tetracarboxylic dianhydride TDA: tetracarboxylic dianhydride represented by the following formula

(Specific diamine compound)
PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene PBCH5DAB: 1,3-diamino-4- {4- [trans-4- (trans-4 -N-pentylcyclohexyl) cyclohexyl] phenoxy} benzene m-PBCH5DABz: 1,3-diamino-5- {4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxymethyl} benzene ColDAB -1: Specific diamine compound represented by the following formula ColDAB-2: Specific diamine compound represented by the following formula

(Other diamine compounds)
p-PDA: p-phenylenediamine m-PDA: m-phenylenediamine DBA: 3,5-diaminobenzoic acid AP18: 1,3-diamino-4-octadecyloxybenzene

(Specific amine compounds)
A-1: Aminoethanol A-2: 3-Amino-1-propanol

(Organic solvent)
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve (Measurement of molecular weight of polyimide precursor and polyimide)
The number average molecular weight and weight average molecular weight of the polyimide in the synthesis example are as follows: normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK), column (KD-803, KD-805) (manufactured by Shodex) Was measured as follows.
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additive, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol) / L, 10 ml / L of tetrahydrofuran (THF))
Flow rate: 1.0 ml / min Standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12, 000, 4,000, 1,000) (manufactured by Polymer Laboratory).

(Measurement of imidization rate)
The imidation ratio of polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder is put into an NMR 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 sonication. 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 by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of amic acid that appears near 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidization rate (%) = (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 Example 1>
CBDA (3.10 g, 15.8 mmol), PCH7DAB (3.01 g, 7.90 mmol), and p-PDA (0.85 g, 7.90 mmol) were mixed in NMP (20.9 g) at 40 ° C. Reaction was performed for 6 hours to obtain a polyamic acid solution (1) having a resin solid content concentration of 25.0% by mass. The number average molecular weight of this polyamic acid was 26,100, and the weight average molecular weight was 74,200.

<Synthesis Example 2>
BODA (5.31 g, 21.2 mmol), PCH7DAB (3.03 g, 7.96 mmol), and DBA (2.82 g, 18.6 mmol) were mixed in NMP (20.1 g) and at 80 ° C. for 5 hours. After the reaction, CBDA (1.04 g, 5.30 mmol) and NMP (16.5 g) were added, the mixture was reacted at 40 ° C. for 6 hours, and the polyamic acid solution (2) having a resin solid content concentration of 25.0 mass% Got. The number average molecular weight of this polyamic acid was 25,300, and the weight average molecular weight was 65,100.

<Synthesis Example 3>
After adding NMP to the polyamic acid solution (2) (20.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 2 and diluting to 6% by mass, acetic anhydride ( 2.50 g) and pyridine (1.90 g) were added and reacted at 80 ° C. for 4 hours. This reaction solution was poured into methanol (320 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (3). The imidation ratio of this polyimide was 58%, the number average molecular weight was 21,500, and the weight average molecular weight was 51,900.

<Synthesis Example 4>
BODA (5.36 g, 21.4 mmol), PBCH5DAB (4.05 g, 9.36 mmol), and DBA (2.65 g, 17.4 mmol) were mixed in NMP (21.6 g) and at 80 ° C. for 5 hours. After the reaction, CBDA (1.05 g, 5.35 mmol) and NMP (17.7 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 (20.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst, and Reacted for hours. This reaction solution was poured into methanol (400 ml), and the resulting precipitate was filtered off. 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 80%, the number average molecular weight was 19,600, and the weight average molecular weight was 49,100.

<Synthesis Example 5>
BODA (3.27 g, 13.1 mmol), m-PBCH5DABz (2.51 g, 5.61 mmol), and p-PDA (1.42 g, 13.1 mmol) were mixed in NMP (13.7 g) After reacting at 5 ° C. for 5 hours, CBDA (1.10 g, 5.61 mmol) and NMP (11.2 g) were added, and reacted at 40 ° C. for 6.5 hours. The resin solid content concentration was 25.0% by mass. A polyamic acid solution was obtained.
After adding NMP to the obtained polyamic acid solution (20.1 g) and diluting to 6% by mass, acetic anhydride (4.52 g) and pyridine (3.35 g) were added as an imidization catalyst, and Reacted for hours. This reaction solution was poured into methanol (430 ml), and the resulting precipitate was filtered off. 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 81%, the number average molecular weight was 20,200, and the weight average molecular weight was 50,300.

<Synthesis Example 6>
BODA (5.26 g, 21.0 mmol), ColDAB-1 (2.06 g, 3.94 mmol), and DBA (3.40 g, 22.3 mmol) were mixed in NMP (19.4 g) at 80 ° C. After reacting for 5 hours, CBDA (1.03 g, 5.25 mmol) and NMP (15.9 g) were added and reacted at 40 ° C. for 7 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%. Obtained.
After adding NMP to the obtained polyamic acid solution (20.2 g) and diluting to 6% by mass, acetic anhydride (2.55 g) and pyridine (1.92 g) were added as an imidization catalyst, Reacted for hours. This reaction solution was poured into methanol (310 ml), and the resulting precipitate was filtered off. 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 55%, the number average molecular weight was 17,200, and the weight average molecular weight was 45,900.

<Synthesis Example 7>
BODA (3.36 g, 13.4 mmol), ColDAB-2 (1.42 g, 2.88 mmol), and p-PDA (1.77 g, 16.3 mmol) were mixed in NMP (12.7 g) After reacting at 5 ° C. for 5 hours, CBDA (1.13 g, 5.76 mmol) and NMP (10.4 g) were added, reacted at 40 ° C. for 7 hours, and the polyamic acid having a resin solid content concentration of 25.0 mass% A solution was obtained.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (2.48 g) and pyridine (1.90 g) were added as an imidization catalyst, and Reacted for hours. This reaction solution was poured into methanol (330 ml), and the resulting precipitate was filtered off. 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 53%, the number average molecular weight was 15,600, and the weight average molecular weight was 44,200.

<Synthesis Example 8>
TCA (3.12 g, 13.9 mmol), PCH7DAB (1.59 g, 4.18 mmol), and m-PDA (1.05 g, 9.71 mmol) were mixed in NMP (17.3 g) at 40 ° C. The reaction was performed for 6 hours to obtain a polyamic acid solution (8) having a resin solid content concentration of 25.0% by mass. The number average molecular weight of this polyamic acid was 26,700, and the weight average molecular weight was 74,200.

<Synthesis Example 9>
TCA (3.10 g, 13.8 mmol), PBCH5DAB (1.79 g, 4.14 mmol), and DBA (1.47 g, 9.66 mmol) were mixed in NMP (19.1 g) and at 40 ° C. for 6 hours. The reaction was performed 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 (20.0 g) and diluting to 6% by mass, acetic anhydride (2.46 g) and pyridine (1.96 g) were added as imidization catalysts, Reacted for hours. This reaction solution was poured into methanol (320 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (9). The imidation ratio of this polyimide was 54%, the number average molecular weight was 23,200, and the weight average molecular weight was 59,600.

<Synthesis Example 10>
TCA (3.08 g, 13.7 mmol), ColDAB-2 (1.35 g, 2.74 mmol), and m-PDA (1.19 g, 11.0 mmol) were mixed in NMP (16.9 g). The reaction was carried out at 0 ° C. for 8 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 (20.0 g) and diluting to 6% by mass, acetic anhydride (2.46 g) and pyridine (1.95 g) were added as imidization catalysts, Reacted for hours. This reaction solution was poured into methanol (320 ml), and the resulting precipitate was filtered off. 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 53%, the number average molecular weight was 21,100, and the weight average molecular weight was 53,900.

<Synthesis Example 11>
TDA (1.98 g, 6.59 mmol), PBCH5DAB (2.85 g, 6.59 mmol), and p-PDA (1.66 g, 15.4 mmol) were mixed in NMP (15.7 g) at 80 ° C. After reacting for 5 hours, CBDA (3.01 g, 15.3 mmol) and NMP (12.8 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%. Obtained.
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst, and Reacted for hours. This reaction solution was poured into methanol (450 ml), and the resulting precipitate was filtered off. 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 79%, the number average molecular weight was 19,100, and the weight average molecular weight was 48,500.

<Synthesis Example 12>
TDA (1.99 g, 6.64 mmol), m-PBCH5DABz (2.97 g, 6.65 mmol), and DBA (2.36 g, 15.5 mmol) were mixed in NMP (17.1 g) at 80 ° C. After reacting for 5 hours, CBDA (3.04 g, 15.5 mmol) and NMP (14.0 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%. Obtained.
After adding NMP to the obtained polyamic acid solution (20.5 g) and diluting to 6% by mass, acetic anhydride (4.46 g) and pyridine (3.32 g) were added as an imidization catalyst, and Reacted for hours. This reaction solution was poured into methanol (450 ml), and the resulting precipitate was filtered off. 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 80%, the number average molecular weight was 19,900, and the weight average molecular weight was 50,100.

<Synthesis Example 13>
BODA (5.61 g, 22.4 mmol), AP18 (3.17 g, 8.42 mmol), and DBA (2.99 g, 19.7 mmol) were mixed in NMP (21.2 g) and at 80 ° C. for 5 hours. After the reaction, CBDA (1.10 g, 5.61 mmol) and NMP (17.4 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 (20.0 g) and diluting to 6% by mass, acetic anhydride (2.54 g) and pyridine (1.95 g) were added as an imidization catalyst, The reaction was allowed for 5 hours. This reaction solution was poured into methanol (330 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (13). The imidation ratio of this polyimide was 60%, the number average molecular weight was 18,200, and the weight average molecular weight was 46,200.
The polyamic acid and polyimide of the present invention are shown in Table 57.

* 1: Polyamic acid.

“Production of Liquid Crystal Alignment Treatment Agent of the Present Invention”
In Examples 1 to 14 and Comparative Examples 1 to 4 described below, production examples of liquid crystal alignment treatment agents are described. Each liquid crystal alignment treatment agent is used for evaluation. Further, Table 58 and Table 59 show the liquid crystal aligning agents of the present invention.
“Preparation of liquid crystal alignment film”, “Evaluation of rubbing treatment resistance”, “Preparation of liquid crystal cell (ordinary cell)”, “Preparation of liquid crystal cell (PSA cell)” and “Evaluation of electrical characteristics” are as follows: is there. In addition, Tables 60 to 64 show the characteristics of the liquid crystal alignment treatment agents obtained in Examples 1 to 14 and Comparative Examples 1 to 4.
Table 60 and Table 61 show the evaluation of rubbing resistance, Table 62 and Table 63 show the evaluation of electrical characteristics using a normal cell, and Table 64 shows the evaluation results of electrical characteristics using a PSA cell.

"Production of liquid crystal alignment film"
The liquid crystal alignment treatment agent is spin-coated on the ITO surface of the substrate with 30 mm × 40 mm ITO electrode, and heat-treated at 80 ° C. for 5 minutes on a hot plate and at 220 ° C. for 30 minutes in a thermal circulation clean oven, A substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained.

"Evaluation of resistance to rubbing treatment"
Using the rayon cloth with a rubbing device having a roll diameter of 120 mm, the coating surface of the substrate with the liquid crystal alignment film obtained in the above-mentioned “Preparation of liquid crystal alignment film”, roll rotation speed 300 rpm, roll progression speed 20 mm / sec, And the rubbing process was carried out under the condition of the pushing amount of 0.4 mm. The surface of the liquid crystal alignment film in the vicinity of the center of the substrate after the rubbing treatment is randomly observed with a laser microscope set at a magnification of 100 times, and the rubbing scratches confirmed in the observation visual field range of about 6.5 mm square and The rubbing treatment resistance was evaluated from the average value of the rubbing scrap residue (attachment). The evaluation criteria were determined as follows.
(Evaluation criteria)
A: Less than 20 rubbing scratches and rubbing scraps
B: 20 to 40 rubbing scratches and rubbing scraps
C: 40-60 rubbing scratches and rubbing scraps
D: 60 or more rubbing scratches or rubbing scraps.

"Production of liquid crystal cell (normal cell)"
The liquid crystal alignment treatment agent is spin-coated on the ITO surface of the substrate with 30 mm × 40 mm ITO electrode, and heat-treated at 80 ° C. for 5 minutes on a hot plate and at 220 ° C. for 30 minutes in a thermal circulation clean oven, An ITO substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained. The coated 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 liquid crystal alignment film surface on the inside with a 6 μm spacer in between, and the periphery was adhered with a sealant to produce an empty cell. MLC-6608 (manufactured by Merck Japan) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).

About the liquid crystal cell obtained by the Example and the comparative example, the alignment uniformity of the liquid crystal was confirmed by polarizing microscope observation. In any of the liquid crystal cells, there was no shaving or poor alignment due to the rubbing treatment, and the liquid crystal was uniformly aligned.
"Production of liquid crystal cell (PSA cell)"
A liquid crystal alignment treatment agent is spin-coated on the ITO surface of a 10 mm × 10 mm ITO electrode substrate with a pattern spacing of 20 μm in the center and a 10 mm × 40 mm ITO electrode substrate in the center, and is heated on a hot plate at 80 ° C. for 5 minutes. Then, heat treatment was performed at 220 ° C. for 30 minutes in a heat circulation type clean oven to obtain a polyimide coating film having a thickness of 100 nm. The coating surface was washed with pure water, and then heat-treated at 100 ° C. for 15 minutes in a heat-circulating clean oven to obtain a substrate with a liquid crystal alignment film.

This substrate with a liquid crystal alignment film was combined with a 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 liquid crystal obtained by mixing 0.3% by mass of the polymerizable compound (1) represented by the following formula with respect to 100% by mass of MLC-6608 (manufactured by Merck Japan) was injected into this empty cell by a reduced pressure injection method. Thereafter, 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 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 cells obtained in the examples and comparative examples, the response speed of the liquid crystal cell after ultraviolet irradiation was faster than that of the liquid crystal cell before ultraviolet irradiation, confirming that the alignment direction of the liquid crystal was controlled. did.
In any liquid crystal cell, it was confirmed that the liquid crystal was uniformly aligned by observation with a polarizing microscope.

"Evaluation of electrical characteristics"
A voltage of 1 V was applied to the liquid crystal cell obtained in the above-mentioned “Preparation of liquid crystal cell (normal cell)” and “Preparation of liquid crystal cell (PSA cell)” at a temperature of 80 ° C., and after 16.67 ms and The voltage after 50 ms was measured, and how much the voltage could be held was calculated as the voltage holding ratio (VHR). In addition, the measurement uses a voltage holding ratio measuring device (manufactured by Toyo Technica Co., Ltd., VHR-1), Voltage (applied voltage): ± 1 V, Pulse Width (applied pulse): 60 μs, and Frame Period (frame period): The setting was performed at 16.67 ms or 50 ms.
The liquid crystal cell for which the measurement of the voltage holding ratio was completed was irradiated with ultraviolet rays of 50 J / cm ^{2 in} terms of 365 nm, and then VHR was measured under the same conditions. The ultraviolet irradiation was performed using a desktop UV curing device (HCT3B28HEX-1) (SEN LIGHT CORPRATION).

<Example 1>
Polyamide acid solution (1) (10.0 g), NMP (5.67 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 1 and N-1 solution (1.50 g) of A-1 (A- 1 was mixed with 5 mass% NMP solution) and BCS (25.8 g), and the mixture was stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (1). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (1), evaluation of rubbing treatment resistance and evaluation of electric characteristics of normal cells and PSA cells were performed under the above-described conditions.

<Example 2>
Polyamide acid solution (2) (10.5 g), NMP (8.95 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 2 and N-1 solution (2.51 g) of A-1 (A- 1 was mixed with 5 mass% NMP solution) and BCS (22.0 g), and the mixture was stirred at 25 ° C. for 2.5 hours to obtain a liquid crystal aligning agent (2). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (2), evaluation of rubbing resistance and evaluation of electric characteristics of a normal cell were performed under the conditions described above.

<Example 3>
NMP (13.8 g) was added to the polyimide powder (3) (2.48 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, add N-1 solution of A-1 (1.49 g) (NMP solution with A-1 of 5.0% by mass), NMP (8.13 g), and BCS (19.2 g), and add to 50 ° C. For 10 hours to obtain a liquid crystal aligning agent (3). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (3), evaluation of rubbing treatment resistance and evaluation of electric characteristics of normal cells and PSA cells were performed under the above-described conditions.

<Example 4>
NMP (13.6 g) was added to the polyimide powder (3) (2.51 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, N-2 solution (2.51 g) of A-2 (NMP solution containing 5.0% by mass of A-2), NMP (8.00 g), and BCS (19.8 g) were added, and the mixture was heated to 50 ° C. For 12 hours to obtain a liquid crystal aligning agent (4). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (4), evaluation of rubbing resistance and evaluation of electric characteristics of a normal cell were performed under the conditions described above.

<Example 5>
NMP (13.3 g) was added to the polyimide powder (4) (2.50 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 ° C. for 24 hours. To this solution was added an NMP solution of A-1 (3.50 g) (NMP solution containing 5.0% by mass of A-1), NMP (7.77 g), and BCS (20.1 g). For 15 hours to obtain a liquid crystal aligning agent (5). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (5), evaluation of rubbing resistance and evaluation of electric characteristics of a normal cell were performed under the above-described conditions.

<Example 6>
NMP (13.5 g) was added to the polyimide powder (5) (2.55 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, N-2 solution (3.57 g) of A-2 (NMP solution containing 5.0% by mass of A-2), NMP (7.93 g), and BCS (20.5 g) were added, and the mixture was heated to 50 ° C. And stirred for 15 hours to obtain a liquid crystal aligning agent (6). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (6), evaluation of rubbing resistance and evaluation of electric characteristics of a normal cell were performed under the conditions described above.

<Example 7>
NMP (19.2 g) was added to the polyimide powder (6) (2.51 g) obtained in Synthesis Example 6 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, an NMP solution of A-1 (1.51 g) (NMP solution of 5.0% by mass of A-1), NMP (9.46 g), and BCS (12.9 g) were added, and the mixture was heated to 50 ° C. For 10 hours to obtain a liquid crystal aligning agent (7). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (7), evaluation of rubbing resistance and evaluation of electric characteristics of a normal cell were performed under the above-described conditions.

<Example 8>
NMP (15.3 g) was added to the polyimide powder (7) (2.50 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 ° C. for 24 hours. To this solution was added N-2 solution of A-2 (1.50 g) (NMP solution containing 5.0% by mass of A-2), NMP (8.97 g), and BCS (17.2 g), and the mixture was heated to 50 ° C. For 10 hours to obtain a liquid crystal aligning agent (8). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (8), evaluation of rubbing resistance and evaluation of electric characteristics of a normal cell were performed under the conditions described above.

<Example 9>
Polyamic acid solution (8) (11.0 g), NMP (4.00 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 8, NMP solution (2.50 g) of A-1 (A- NMP solution 1 of 5% by mass) and BCS (26.3 g) were mixed and stirred at 25 ° C. for 2.5 hours to obtain a liquid crystal aligning agent (9). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (9), evaluation of rubbing resistance and evaluation of electric characteristics of a normal cell were performed under the conditions described above.

<Example 10>
NMP (12.0 g) was added to the polyimide powder (9) (2.53 g) obtained in Synthesis Example 9, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, an NMP solution of A-1 (3.54 g) (NMP solution of A-1 of 5.0% by mass), NMP (7.00 g), and BCS (22.6 g) were added, and the mixture was heated to 50 ° C. For 15 hours to obtain a liquid crystal aligning agent (10). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (10), evaluation of rubbing resistance and evaluation of electric characteristics of a normal cell were performed under the conditions described above.

<Example 11>
NMP (15.4 g) was added to the polyimide powder (10) (2.46 g) obtained in Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. To this solution was added N-2 solution of A-2 (4.92 g) (NMP solution containing 5.0% by mass of A-2), NMP (9.00 g), and BCS (15.8 g), and the mixture was heated to 50 ° C. For 15 hours to obtain a liquid crystal aligning agent (11). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (11), evaluation of rubbing resistance and evaluation of electric characteristics of a normal cell were performed under the above-described conditions.

<Example 12>
NMP (13.6 g) was added to the polyimide powder (11) (2.50 g) obtained in Synthesis Example 11, and dissolved by stirring at 70 ° C. for 24 hours. To this solution was added an N-2 solution of A-2 (2.50 g) (NMP solution containing 5.0% by mass of A-2), NMP (7.98 g), and BCS (19.7 g), and the mixture was heated to 50 ° C. For 12 hours to obtain a liquid crystal aligning agent (12). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (12), evaluation of rubbing treatment resistance and evaluation of electric characteristics of a normal cell were performed under the conditions described above.

<Example 13>
NMP (13.6 g) was added to the polyimide powder (12) (2.43 g) obtained in Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, an NMP solution of A-1 (1.46 g) (NMP solution of 5.0% by mass of A-1), NMP (7.95 g), and BCS (18.8 g) were added, and the mixture was heated to 50 ° C. For 10 hours to obtain a liquid crystal aligning agent (13). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (13), evaluation of rubbing treatment resistance and evaluation of electric characteristics of a normal cell were performed under the conditions described above.

<Example 14>
NMP (13.6 g) was added to the polyimide powder (13) (2.50 g) obtained in Synthesis Example 13, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, an NMP solution of A-1 (2.50 g) (NMP solution containing 5.0% by mass of A-1), NMP (5.78 g), and BCS (19.7 g) were added, and the mixture was heated to 50 ° C. For 12 hours to obtain a liquid crystal aligning agent (14). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (14), evaluation of rubbing treatment resistance and evaluation of electric characteristics of a normal cell were performed under the conditions described above.

<Comparative Example 1>
The polyamic acid solution (1) (10.5 g), NMP (7.00 g), and BCS (26.3 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 1 were mixed, and the mixture was heated to 25 ° C. For 2 hours to obtain a liquid crystal aligning agent (15). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (15), evaluation of rubbing resistance and evaluation of electric characteristics of normal cells and PSA cells were performed under the above-described conditions.

<Comparative Example 2>
NMP (14.3 g) was added to the polyimide powder (3) (2.48 g) obtained in Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. NMP (8.41 g) and BCS (18.6 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours to obtain a liquid crystal aligning agent (16). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (16), evaluation of rubbing treatment resistance and evaluation of electric characteristics of normal cells and PSA cells were performed under the above-described conditions.

<Comparative Example 3>
NMP (14.5 g) was added to the polyimide powder (4) (2.50 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours. NMP (8.50 g) and BCS (18.8 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours to obtain a liquid crystal aligning agent (17). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (17), evaluation of rubbing treatment resistance and evaluation of electric characteristics of a normal cell were performed under the conditions described above.

<Comparative example 4>
NMP (13.2 g) was added to the polyimide powder (13) (2.51 g) obtained in Synthesis Example 13 and dissolved by stirring at 70 ° C. for 24 hours. NMP (7.75 g) and BCS (20.9 g) were added to this solution, and the mixture was stirred at 50 ° C. for 15 hours to obtain a liquid crystal aligning agent (18). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
Using the obtained liquid crystal aligning agent (18), evaluation of rubbing treatment resistance and evaluation of electric characteristics of a normal cell were performed under the conditions described above.

As can be seen from the above results, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example of the present invention is less rubbing scraped by rubbing than the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example. Further, the decrease in the voltage holding ratio was small even after being exposed to ultraviolet rays for a long time.
In Comparative Examples 1 to 4 which do not contain the specific amine compound, there were many rubbing scraps due to the rubbing treatment, and the decrease in the voltage holding ratio after being exposed to ultraviolet rays for a long time was also large.

In addition, in the comparison between the example including the specific amine compound and the comparative example not including the specific amine compound in the same polyimide precursor or polyimide, in the example including the specific amine compound, after being exposed to ultraviolet rays for a long time. Even so, the decrease in the voltage holding ratio was small. Specifically, the comparison between Example 1 and Comparative Example 1, the comparison between Example 3 and Example 4 and Comparative Example 2, the comparison between Example 5 and Comparative Example 3, and the comparison between Example 14 and Comparative Example 4 It is a comparison.

By using the liquid crystal alignment treatment agent of the present invention, the polymer film is less likely to be scraped or scratched due to the rubbing process during the manufacturing process of the liquid crystal display element, and further, it can be irradiated with light for a long time. Even if exposed, a liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio can be obtained. 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 is polymerized by 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.

The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2010-292723 filed on Dec. 28, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims

Liquid crystal aligning agent containing the following component (A) and component (B).
Component (A): An amine having one primary amino group and a hydroxyl group in the molecule, and the primary amino group and the hydroxyl group are bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Compound.
Component (B): at least one polymer selected from the group consisting of polyimide precursors and polyimides.
The liquid-crystal aligning agent of Claim 1 whose amine compound of a component (A) is a compound shown by following formula [1].

(In the formula [1], X 1 is an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and X 2 is a single bond, —O—, —NH—, —CO—, — COO—, —OCO—, —NH—, —N (CH 3 ) —, —NHCO—, —N (CH 3 ) CO—, —CONH—, —CON (CH 3 ) —, —S— or —SO 2 , X 3 is a single bond, a benzene ring or a cyclohexane ring, X 4 is a single bond, —O—, —CO—, —COO—, —OCO—, —NH—, —N (CH 3 ) —, —NHCO—, —N (CH 3 ) CO—, —CONH—, —CON (CH 3 ) —, —S— or —SO 2 —, wherein X 5 is a single bond, an aliphatic hydrocarbon group Or an organic group having a non-aromatic cyclic hydrocarbon group, and n is an integer of 1 to 5.
The liquid crystal alignment according to claim 2, wherein X 1 of the formula [1] which is an amine compound of the component (A) is a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexane ring or a bicyclohexyl ring. Processing agent.
4. The liquid crystal aligning agent according to claim 2, wherein X 2 of the formula [1], which is the amine compound of component (A), is a single bond, —O— or —OCO—.
The liquid crystal aligning agent according to any one of claims 2 to 4, wherein X 3 of the formula [1] which is the amine compound of the component (A) is a single bond or a benzene ring.
The liquid crystal according to any one of claims 2 to 5, wherein X 4 of the formula [1] which is the amine compound of the component (A) is a single bond, -O-, -NH- or -CONH-. Alignment treatment agent.
X 5 of formula [1] which is an amine compound of component (A) is a single bond, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclohexane ring. The liquid-crystal aligning agent as described in any one of Claims.
Component (B) is at least one polymer selected from the group consisting of polyamic acid obtained by reacting a diamine component with tetracarboxylic dianhydride and polyimide obtained by dehydrating and ring-closing the polyamic acid. The liquid crystal aligning agent according to any one of claims 1 to 7.
The liquid crystal aligning agent according to claim 8, wherein the diamine component is a diamine compound having a side chain represented by the following formula [2].

(In the formula [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—. Y 2 is a single bond or — (CH 2 ) b — (b is an integer of 1 to 15), Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15) ), —O—, —CH 2 O—, —COO— or —OCO—, wherein Y 4 is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms Alternatively, it may be substituted with a fluorine atom, or has a steroid skeleton having 12 to 25 carbon atoms A divalent organic group selected from organic groups, Y 5 is a cyclic group selected from benzene ring, the group consisting of cyclohexane ring and heterocyclic cyclohexane, any hydrogen atoms on these cyclic groups, 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, n is an integer of 0 to 4, Y 6 is 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 group having 1 to 18 carbon atoms An alkoxyl group).
The liquid-crystal aligning agent of Claim 8 whose diamine component is a diamine compound shown by following formula [2a].

(In Formula [2a], Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 and n have the same significance as defined in Formula [2], and m is an integer of 1 to 4. .)
The liquid crystal aligning agent according to claim 9 or 10, wherein the diamine compound of the formula [2a] is contained in the diamine component in an amount of 5 mol% to 80 mol%.
The liquid crystal aligning agent according to any one of claims 8 to 11, wherein the polymer of the component (B) is a polymer using a tetracarboxylic dianhydride represented by the following formula [3]. .

(In the formula [3], Z 1 is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms).
The liquid crystal aligning agent according to claim 12, wherein the tetracarboxylic dianhydride has a structure represented by the following formulas [3a] to [3j].

(In the formula [3a], Z 2 to Z 5 are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, which may be the same or different. In the formula [3g], Z 6 and Z 7 Are hydrogen atoms or methyl groups, which may be the same or different.
The liquid crystal aligning agent according to any one of claims 1 to 13, wherein the polymer of component (B) is a polyimide obtained by dehydrating and ring-closing polyamic acid.
The liquid crystal aligning agent according to any one of claims 1 to 14, wherein the component (A) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (B).
The liquid crystal aligning agent according to any one of claims 1 to 15, wherein the liquid crystal aligning agent contains 5% by mass to 60% by mass of a poor solvent.
A liquid crystal alignment film obtained using the liquid crystal alignment treatment agent according to any one of claims 1 to 16.
A liquid crystal display element having the liquid crystal alignment film according to claim 17.
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 The liquid crystal aligning film of Claim 17 used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric compound, applying a voltage in between.
A liquid crystal display element having the liquid crystal alignment film according to claim 19.
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; The liquid crystal alignment film according to claim 17, which is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable group while applying a voltage therebetween.
A liquid crystal display element having the liquid crystal alignment film according to claim 21.