JPWO2013115387A1 - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

In addition to the initial characteristics, a liquid crystal alignment treatment agent that can suppress a decrease in voltage holding ratio even when exposed to light irradiation for a long time, and can obtain a liquid crystal alignment film in which the charge accumulated by a DC voltage is quickly relaxed I will provide a. Liquid crystal aligning agent containing the following component (A) and component (B). Component (A): It has a nitrogen-containing aromatic heterocycle and a hydroxyl group or a C1-C3 alkoxyl group in the molecule, and the hydroxyl group or C1-C3 alkoxyl group is an aliphatic hydrocarbon group or A compound bonded to a non-aromatic cyclic hydrocarbon group. Component (B): at least one polymer selected from the group consisting of polyimide precursors and polyimides obtained by imidizing polyimide precursors.

Description

  The present invention relates to a liquid crystal aligning agent used for forming a liquid crystal aligning film, and a liquid crystal display element having a liquid crystal aligning film obtained from the liquid crystal aligning agent.

Currently, as a liquid crystal alignment film of a liquid crystal display element, a so-called polyimide liquid crystal alignment film obtained by applying and baking a liquid crystal alignment treatment agent mainly composed of a polyimide precursor such as polyamic acid or a soluble polyimide solution is mainly used. ing.
The liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal. However, as liquid crystal display elements become higher in definition, liquid crystal alignment films used for liquid crystal display elements also have a high voltage holding ratio and direct current voltage from the viewpoint of suppressing contrast reduction and reducing afterimage phenomenon of liquid crystal display elements. Characteristics such as a small amount of accumulated charge when a voltage is applied and a rapid relaxation of charges accumulated by a DC voltage are becoming increasingly important.

In the formation of a polyimide-based liquid crystal alignment film, a liquid crystal alignment containing a tertiary amine having a specific structure in addition to a polyamic acid or an imide group-containing polyamic acid, assuming that the time until the afterimage generated by the DC voltage disappears is short. Those using a treating agent (see, for example, Patent Document 1), those using a liquid crystal alignment treating agent containing a soluble polyimide using a specific diamine having a pyridine skeleton or the like as a raw material (see, for example, Patent Document 2) are known. ing.
In addition to polyamic acid and a polymer obtained by imidizing the polyamic acid, one carboxylic acid in the molecule is assumed to have a high voltage holding ratio and a short time until an afterimage generated by a direct current voltage disappears. Liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing a group, a compound containing one carboxylic anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (For example, refer to Patent Document 3) is known.

Japanese Unexamined Patent Publication No. 9-316200 Japanese Unexamined Patent Publication No. 10-104633 Japanese Unexamined Patent Publication No. 8-76128

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. Therefore, the liquid crystal alignment film is required to have high reliability from another viewpoint, that is, high stability against light from the backlight. Therefore, not only the initial characteristics of the electrical characteristics of the liquid crystal alignment film, that is, the relaxation characteristics of the charges accumulated by the voltage holding ratio and the direct current voltage are good, for example, after being exposed to backlight light for a long time. Even if it exists, it is calculated | required to maintain a favorable characteristic. When the relaxation characteristics of the stored charge due to the voltage holding ratio and the direct current voltage are greatly reduced, display defects of the liquid crystal display element, line burn-in and surface burn-in are likely to occur, and a highly reliable liquid crystal display element is obtained I can't. Therefore, in the liquid crystal alignment film, in addition to good initial characteristics, for example, even after being exposed to light irradiation for a long time, the voltage holding ratio is difficult to decrease and charges are accumulated by a DC voltage. It is required to be difficult to do.
The object of the present invention has been made in view of the above circumstances, and in addition to the initial characteristics, even when exposed to light irradiation for a long time, it suppresses a decrease in voltage holding ratio and further accumulates with a DC voltage. A liquid crystal alignment treatment agent capable of obtaining a liquid crystal alignment film with fast charge relaxation, and a highly reliable liquid crystal having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent and capable of withstanding long-term use in harsh usage environments It is to provide a display element.

As a result of intensive studies, the present inventors have found that a liquid crystal aligning agent containing a compound having a specific structure is extremely effective for achieving the above object, and 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): It has a nitrogen-containing aromatic heterocyclic ring and a hydroxyl group or a C1-C3 alkoxyl group in the molecule, and the hydroxyl group or the C1-C3 alkoxyl group is an aliphatic hydrocarbon group. Or a compound bonded to a non-aromatic cyclic hydrocarbon group.
Component (B): At least one polymer selected from the group consisting of polyimide precursors and polyimides obtained by imidizing polyimide precursors.

（式［１］中、Ｘ_１は脂肪族炭化水素基又は非芳香族環式炭化水素基を有する２価の有機基であり、Ｘ_２は窒素含有芳香族複素環であり、Ｒ_１は水素原子又は炭素数１〜３のアルキル基である。）
（３）前記成分（Ａ）の化合物が、下記式［１ａ］で示される化合物である上記（１）に記載の液晶配向処理剤。

（式［１ａ］中、Ｘ_３は炭素数１〜２０の脂肪族炭化水素基又は炭素数１〜２０の非芳香族環式炭化水素基であり、Ｘ_４は単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−又は−Ｏ（ＣＨ_２）_ｍ−（ｍは１〜５の整数である）であり、Ｘ_５は窒素含有芳香族複素環であり、Ｒ_２は水素原子又は炭素数１〜３のアルキル基である。）(2) The liquid-crystal aligning agent as described in said (1) whose compound of the said component (A) is a compound shown by following formula [1].

(In the formula [1], X ₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, X ₂ is a nitrogen-containing aromatic heterocyclic ring, and R ₁ is hydrogen. It is an atom or an alkyl group having 1 to 3 carbon atoms.)
(3) The liquid-crystal aligning agent as described in said (1) whose compound of the said component (A) is a compound shown by following formula [1a].

(In the formula [1a], X ₃ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic cyclic hydrocarbon group having 1 to 20 carbon atoms, and X ₄ is a single bond, —O—, — _{NH -, - N (CH 3} ) -, - CONH -, - NHCO -, - COO -, - OCO -, - CON (CH 3) -, - N (CH 3) CO- or -O _(CH 2) _m— (m is an integer of 1 to 5), X ₅ is a nitrogen-containing aromatic heterocyclic ring, and R ₂ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(4) Liquid crystal aligning agent as described in said (3) whose X < ₃ > is a C1-C10 linear alkyl group, a C1-C10 branched alkyl group, or a cyclohexane ring in Formula [1a]. .
(5) In the formula [1a], X ₄ is a single bond, —O—, —NH—, —CONH—, —NHCO—, —COO—, —OCO— or —O (CH ₂ ) _m — (m is The liquid crystal aligning agent according to (3) or (4) above, which is an integer of 1 to 5.
(6) The liquid-crystal aligning agent in any one of said (3)-(5) whose X < ₅ > is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring in Formula [1a].
(7) The liquid-crystal aligning agent in any one of said (3)-(6) whose R < ₂ > is a hydrogen atom or a methyl group in Formula [1a].
(8) The component (B) is at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic acid component and a polyimide obtained by dehydrating and ring-closing the polyamic acid. The liquid-crystal aligning agent in any one of said (1)-(7).

（式［２］中、Ｙ_１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又は−Ｎ（ＣＨ_３）ＣＯ−である。Ｙ_２は単結合又は−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）である。Ｙ_３は単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１０の整数である）、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又は−Ｎ（ＣＨ_３）ＣＯ−である。Ｙ^４はベンゼン環、シクロヘキサン環及び複素環から選ばれる２価の環状基、又はステロイド骨格を有する炭素数１２〜２５の２価の有機基を示し、前記環状基上の任意の水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよい。Ｙ^５はベンゼン環、シクロヘキサン環及び複素環から選ばれる２価の環状基を示し、これらの環状基上の任意の水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよく、ｎは０〜４の整数を示す。Ｙ^６は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基を示す。）(9) The liquid-crystal aligning agent as described in said (8) whose said diamine component is a diamine compound which has a side chain shown by following formula [2].

(Wherein [2], _{Y 1} is a single _{bond, - (CH 2) a -} (a is an integer of 1~15), - O -, - NH -, - N (CH 3) -, - CONH —, —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO— 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 10), —O—, —NH—, — _{N (CH 3) -, -} CONH -, - NHCO -, - CH 2 O -, - COO -, - OCO -, - CON (CH 3) - or -N _(CH 3) a CO- .Y ⁴ Represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, Arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms. Or Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has 1 to 3 carbon atoms. An alkyl group of 1 to 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, and n is 0 to 4 Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. )

（式［２ａ］中、Ｙ_１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又は−Ｎ（ＣＨ_３）ＣＯ−である。Ｙ_２は単結合又は−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）である。Ｙ_３は単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１０の整数である）、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又は−Ｎ（ＣＨ_３）ＣＯ−である。Ｙ^４はベンゼン環、シクロヘキサン環及び複素環から選ばれる２価の環状基、又はステロイド骨格を有する炭素数１２〜２５の２価の有機基を示し、前記環状基上の任意の水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよい。Ｙ^５はベンゼン環、シクロヘキサン環及び複素環から選ばれる２価の環状基を示し、これらの環状基上の任意の水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよく、ｎは０〜４の整数を示す。Ｙ^６は炭素数１〜１８のアルキル基、炭素数１〜１８のフッ素含有アルキル基、炭素数１〜１８のアルコキシル基又は炭素数１〜１８のフッ素含有アルコキシル基を示す。ｍは１〜４の整数である。）(10) The liquid-crystal aligning agent as described in said (9) whose diamine compound which has a side chain of Formula [2] is a diamine compound shown by following formula [2a].

(In Formula [2a], Y ₁ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —NH—, —N (CH ₃ ) —, —CONH. —, —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO— 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 10), —O—, —NH—, — _{N (CH 3) -, -} CONH -, - NHCO -, - CH 2 O -, - COO -, - OCO -, - CON (CH 3) - or -N _(CH 3) a CO- .Y ⁴ Represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton. Arbitrary hydrogen atoms on the cyclic group include 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, and a fluorine-containing alkoxyl group having 1 to 3 carbon atoms. Or Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has 1 to 3 carbon atoms. An alkyl group of 1 to 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, and n is 0 to 4 Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. m is 1 4 is an integer.)

（式［３］中、Ｚ_１は炭素数４〜１３の４価の有機基であり、かつ炭素数４〜１０の非芳香族環状炭化水素基を含有する。）(11) The liquid crystal alignment according to the above (9) or (10), wherein the diamine compound having a side chain of the formula [2] or the diamine compound represented by the formula [2a] is 5 to 80 mol% in the diamine component. Processing agent.
(12) The liquid crystal aligning agent according to any one of (8) to (11), wherein the tetracarboxylic acid component is 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 10 carbon atoms.)

（式［３ａ］中、Ｚ_２〜Ｚ_５は水素原子、メチル基、塩素原子又はベンゼン環であり、それぞれ、同じであっても異なってもよい。式［３ｇ］中、Ｚ_６及びＺ_７は水素原子又はメチル基であり、それぞれ同じであっても異なってもよい。）(13) _{Z 1} is a liquid crystal alignment treating agent according to (12) is a structure represented by the following formula [3a] ~ formula [3j].

(In formula [3a], Z _{2 to} Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In 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), wherein the polymer of the component (B) is a polyimide obtained by dehydrating and ring-closing polyamic acid.
(15) The liquid-crystal aligning agent in any one of said (1)-(14) whose component (A) is 0.1-20 mass parts with respect to 100 mass parts of said (B) component.
(16) The liquid-crystal aligning agent in any one of said (1)-(15) containing a 5-60 mass% poor solvent with respect to whole quantity (100 mass%) of a liquid-crystal aligning agent.
(17) A liquid crystal alignment film obtained using the liquid crystal aligning agent according to any one of (1) to (16).
(18) A liquid crystal display device comprising the liquid crystal alignment film according to (17).

(19) A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal alignment film according to (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 comprising the liquid crystal alignment film according to (19).
(21) A liquid crystal alignment film comprising 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 comprising the liquid crystal alignment film according to (21).

  By using the liquid crystal aligning agent of the present invention, in addition to the initial characteristics, even when exposed to light irradiation for a long time, the decrease in the voltage holding ratio is suppressed, and further, the charge accumulated by the DC voltage is quickly relaxed. A liquid crystal alignment film can be obtained. Furthermore, a highly reliable liquid crystal display element that can withstand long-term use in a harsh use environment can be provided.

The present invention is described in detail below.
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): It has a nitrogen-containing aromatic heterocyclic ring and a hydroxyl group or a C1-C3 alkoxyl group in the molecule, and the hydroxyl group or the C1-C3 alkoxyl group is an aliphatic hydrocarbon group. Alternatively, a compound (also referred to as a specific compound) bonded to a non-aromatic cyclic hydrocarbon group.
Component (B): at least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor (also referred to as a polymer).

In the liquid crystal alignment treatment agent of the present invention, the nitrogen-containing aromatic heterocycle in the specific compound functions as an electron hopping site (site for giving and receiving) due to its conjugated structure, thus promoting charge transfer in the liquid crystal alignment film. To do.
In addition, when a liquid crystal alignment film is formed, the nitrogen-containing aromatic heterocycle and the carboxyl group in the polymer are bound by an electrostatic interaction such as salt formation or hydrogen bonding, so that it is identified from the carboxyl group in the polymer. Charge transfer occurs between nitrogen-containing aromatic heterocycles in the compound.
Furthermore, the hydroxyl group or the C1-C3 alkoxyl group in the specific compound is subjected to an esterification reaction accompanied by elimination of water or alcohol with respect to the carboxyl group or carboxy ester group in the polymer due to heat. It is known that an etherification reaction accompanied by elimination of water or alcohol by a hydroxyl group or an alkoxyl group having 1 to 3 carbon atoms in a compound occurs.

In addition, as described above, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has a static state in which the nitrogen-containing aromatic heterocycle in the specific compound and the carboxyl group in the polymer form a salt or hydrogen bond. Since they are connected by electrical interaction, a cross-linking reaction between polymers occurs in the baking process when forming the liquid crystal alignment film and the curing process of the sealing agent when manufacturing the liquid crystal display element, Stability is improved, and furthermore, resistance to heat and light is high.
In addition, in the present invention, since the specific compound that causes the crosslinking reaction is bonded to the polymer, problems such as deterioration of liquid crystal display element characteristics due to remaining unreacted components that occur when the crosslinking compound is added. Does not occur.

<Specific compounds>
The specific compound contained in the liquid crystal aligning agent of the present invention has a nitrogen-containing aromatic heterocyclic ring and a hydroxyl group (also referred to as a hydroxyl group) or an alkoxyl group having 1 to 3 carbon atoms in the molecule, and the hydroxyl group is fatty. Compound bonded to an aromatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.
More specifically, it is a compound represented by the following formula [1].

In Formula [1], X ₁ is an aliphatic hydrocarbon group or a non-aromatic cyclic carbonization so that a hydroxyl group or an alkoxyl group having 1 to 3 carbon atoms contained in the specific compound can easily react with the specific polymer. It is a divalent organic group having a hydrogen 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. Especially, a C1-C20 linear alkyl group or a C1-C20 branched alkyl group is preferable. More preferably, it is a linear alkyl group having 1 to 15 carbon atoms or a branched alkyl group having 1 to 15 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms or 1 carbon atom. -10 branched alkyl groups.

  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. Among these, as the non-aromatic cyclic hydrocarbon group, a ring having 3 to 20 carbon atoms is preferable. A ring having 3 to 15 carbon atoms is more preferable, and 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 addition, —CH ₂ — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the hydroxyl group or the alkoxyl group having 1 to 3 carbon atoms contained in X ₁ is —O—, — NH—, —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —S—, —S (O) ₂ —, —CF ₂ —, —C (CF ₃ ) ₂ —, — _{C (CH 3) 2 -,} - Si (CH 3) 2 -, - O-Si (CH 3) 2 -, - Si (CH 3) 2 -O -, - O-Si (CH 3) 2 O- , May be substituted with a cyclic hydrocarbon group and a heterocyclic ring. Moreover, the hydrogen atom couple | bonded with arbitrary carbon atoms is a C1-C10 linear alkyl group, a C1-C10 branched alkyl group, a C1-C10 cyclic hydrocarbon group, carbon It may be replaced with a fluorine-containing alkyl group, a heterocyclic ring, a fluorine atom or a hydroxyl group of formulas 1-5.

Specific examples of the cyclic hydrocarbon group include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, 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, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like.
Specific examples of the heterocyclic ring include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, Pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. Can be mentioned.

式［１−Ｃ］中、Ａ_１は炭素数１〜５の直鎖状アルキル基又は炭素数１〜５の分岐状アルキル基である。
具体的には、ピロール環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、ピリジン環、ピリミジン環、キノリン環、ピラゾリン環、イソキノリン環、カルバゾール環、プリン環、チアジアゾール環、ピリダジン環、ピラゾリン環、トリアジン環、ピラゾリジン環、トリアゾール環、ピラジン環、ベンズイミダゾール環、ベンゾイミダゾール環、チノリン環、フェナントロリン環、インドール環、キノキサリン環、ベンゾチアゾール環、フェノチアジン環、オキサジアゾール環、アクリジン環などを挙げることができる。In the formula [1], X ₂ is a nitrogen-containing aromatic heterocyclic ring, and at least one structure selected from the group consisting of the following formulas [1-A], [1-B] and [1-C]. Is an aromatic heterocyclic ring containing

In formula [1-C], A ₁ is a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms.
Specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, List triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. Can do.

In formula [1], X ₂ is preferably pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring. , Pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, tinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring Or acridine ring, more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, A riazole ring, a pyrazine ring, a benzimidazole ring, and a benzimidazole ring. More preferred are a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, and a benzimidazole ring, and particularly preferred are a pyrrole ring, An imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring.
In the formula [1], R ₁ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or 1 or 2 carbon atoms, particularly preferably a hydrogen atom or methyl.
In formula [1], n is an integer of 1-4.

式［１ａ］中、Ｘ_３は炭素数１〜２０の脂肪族炭化水素基又は炭素数１〜２０の非芳香族環式炭化水素基である。
炭素数１〜２０の脂肪族炭化水素基の具体例としては、炭素数１〜２０の直鎖状アルキル基、炭素数１〜２０の分岐状アルキル基又は炭素数１〜２０の不飽和結合を有する炭化水素基等を挙げることができる。なかでも、炭素数が１〜２０の直鎖状アルキル基又は炭素数が１〜２０の分岐状アルキル基が好ましい。より好ましくは炭素数が１〜１５の直鎖状アルキル基又は炭素数が１〜１５の分岐状アルキル基であり、さらに好ましくは炭素数が１〜１０の直鎖状アルキル基又は炭素数が１〜１０の分岐状アルキル基である。A more specific structure of the specific compound of the present invention is a compound represented by the following formula [1a].

In the formula [1a], X ₃ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic cyclic hydrocarbon group having 1 to 20 carbon atoms.
Specific examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, or an unsaturated bond having 1 to 20 carbon atoms. The hydrocarbon group etc. which it has can be mentioned. Especially, a C1-C20 linear alkyl group or a C1-C20 branched alkyl group is preferable. More preferably, it is a linear alkyl group having 1 to 15 carbon atoms or a branched alkyl group having 1 to 15 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms or 1 carbon atom. -10 branched alkyl groups.

  Specific examples of the non-aromatic cyclic hydrocarbon group having 1 to 20 carbon atoms include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, and 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, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like can be mentioned. Especially, as a C1-C20 non-aromatic cyclic hydrocarbon group, the ring which consists of C3-C20 is preferable. A ring having 3 to 15 carbon atoms is more preferable, and a ring having 6 to 12 carbon atoms is still more preferable. Specifically, a cyclohexane ring and a bicyclohexyl ring are preferable, and a cyclohexane ring is particularly preferable.

In the formula [1a], X ₄ represents a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ). - is - (m is an integer of 1 to 5) - _{N (CH} 3) CO- or -O _{(CH 2)} m. Among them, a single bond, —O—, —NH—, —CONH—, —NHCO—, —COO—, —OCO— or —O (CH ₂ ) _m — (m is an integer of 1 to 5). preferable.
In the formula [1a], X ₅ is a nitrogen-containing aromatic heterocycle, and at least one structure selected from the group consisting of the above-described formula [1-A], formula [1-B] and [1-C]. Is an aromatic heterocyclic ring containing
Specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, List triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. Can do.

In formula [1a], preferred X ₅ is a pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring. , Pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, tinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring Or an acridine ring, more preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyrazoline ring, a carbazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, A triazole ring, a pyrazine ring, a benzimidazole ring or a benzimidazole ring. More preferred are a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, and a benzimidazole ring, and particularly preferred are a pyrrole ring, An imidazole ring, a pyrazole ring, a pyridine ring, and a pyrimidine ring.

Wherein [1a], _{X 4} is formula included in _{X 5} [1-A], it is preferably bonded in the formula [1-B], or a carbon atom not adjacent to each other with the formula [1-C].
In the formula [1a], R ₂ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among these, a hydrogen atom, an alkyl group having 1 or 2 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is most preferable.
In formula [1a], n is an integer of 1-4. Among these, an integer of 1 or 2 is preferable.
Preferred combinations of X ₃ , X ₄ , X ₅ and R _{2 in} the formula [1a] are as shown in Tables 1 to 32.

More specifically, it is a compound represented by the following formula [M1] to formula [M154].

Especially, Formula [M16], Formula [M17], Formula [M19], Formula [M20], Formula [M35], Formula [M36], Formula [M52], Formula [M60], Formula [M62], Formula [ M68] to formula [M71], formula [M117] to formula [M120], formula [M127], formula [M134], formula [M135] or formula [M139] are preferable. More preferably, Formula [M16], Formula [M17], Formula [M20], Formula [M35], Formula [M36], Formula [M62], Formula [M119], Formula [M134], Formula [M135] or Formula [M139]. More preferable is the formula [M20], the formula [M35], the formula [M36], the formula [M62], the formula [M119], the formula [M135], or the formula [M139].
Said specific compound can be used 1 type or in mixture of 2 or more types.

<Specific side chain structure>
The polymer contained in the liquid crystal alignment treatment agent of the present invention, that is, selected from the group consisting of a polyimide precursor obtained by reaction of a diamine component and a tetracarboxylic acid component and a polyimide obtained by dehydrating and ring-closing the polyimide precursor The at least one kind is preferably a polymer (also referred to as a specific polymer) containing a side chain (also referred to as a specific side chain structure) represented by the following formula [2]. This specific side chain structure is a divalent organic group having 12 to 25 carbon atoms having a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring in the side chain portion, or a steroid skeleton. Thereby, the stability with respect to the heat | fever and ultraviolet irradiation of a side chain site | part improves. Therefore, the pretilt angle is stable against heat and light. In addition, it is possible to suppress a decrease in the pretilt angle associated with the decomposition of the side chain component due to heat or ultraviolet irradiation. Furthermore, it is possible to suppress a decrease in voltage holding ratio accompanying the decomposition of the side chain component due to heat or ultraviolet irradiation.

式［２］中、Ｙ_１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又は−Ｎ（ＣＨ_３）ＣＯ−である。なかでも、単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−又は−ＣＯＯ−は、側鎖構造を合成しやすいので好ましい。より好ましくは、単結合、−（ＣＨ_２）_ａ−（ａは１〜１０の整数である）、−Ｏ−、−ＣＯＮＨ−、−ＣＨ_２Ｏ−又は−ＣＯＯ−である。さらに好ましくは、単結合、−（ＣＨ_２）_ａ−（ａは１〜１０の整数である）、−Ｏ−、−ＣＨ_２Ｏ−又は−ＣＯＯ−である。

In Formula [2], Y ₁ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —NH—, —N (CH ₃ ) —, —CONH—. , —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO—. Among them, a single _{bond, - (CH 2) a -} (a is an integer of 1~15), - O -, - CONH -, - CH 2 O- or -COO- synthesizes a side chain structure It is preferable because it is easy. More preferably, a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CONH -, - CH 2 O- or -COO- in which. More preferably, a single _{bond, - (CH 2) a -} (a is an integer of 1 to _{10), - O -, - CH} 2 O- or -COO- in which.

Wherein _{[2], Y} 2 is a single bond or a _{(CH 2)} b - a (b is an integer of 1 to 15). Among these, a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 10) is preferable.
In Formula [2], Y ₃ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —NH—, —N (CH ₃ ) —, —CONH—. , —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO—. 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 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, on the cyclic group. Arbitrary hydrogen atom is substituted with a C1-C3 alkyl group, a C1-C3 alkoxyl group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom May be. Among 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 divalent cyclic group selected from 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. Of these, a benzene ring or a cyclohexane ring is preferable.
In formula [2], n is an integer of 0-4. Preferably, it is an integer of 0-2.
Wherein [2], _{Y 6} is an alkyl group, a fluorine-containing alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxyl group having 1 to 18 alkoxyl group or a carbon of 1 to 18 carbon atoms having 1 to 18 carbon atoms . Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are a C1-C12 alkyl group or a C1-C12 alkoxyl group. More preferably, they are a C1-C9 alkyl group or a C1-C9 alkoxyl group.

Preferred combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n in the formula [2] are those described in Items 13 to 34 of International Publication No. WO2011 / 132751 (published 2011.10.27). The same combinations as (2-1) to (2-629) listed in Tables 6 to 47 are mentioned. In each table of International Publication, _Y 1 to Y ₆ in the present invention is shown as Y1 to Y6, Y1 to _Y6, shall read Y 1 to Y _6.

式［２ａ］中のＹ_１、Ｙ_２、Ｙ_３、Ｙ_４、Ｙ_５、及びＹ_６は、式［２］中の各基と同意義であり、ｎについても同様である。また、好ましい範囲についても式［２］中の各基と同様である。
さらに、式［２ａ］におけるＹ_１、Ｙ_２、Ｙ_３、Ｙ_４、Ｙ_５、Ｙ_６及びｎの好ましい組み合わせについても、式［２］の好ましい組み合わせと同様である。
式［２ａ］中、ｍは、１〜４の整数である。好ましくは、１の整数である。<Specific side chain diamine compound>
As a method for introducing the specific side chain structure into the specific polymer of the present invention, that is, the polymer having the specific side chain structure represented by the formula [2], a diamine compound represented by the following formula [2a] (specific side It is preferable to use a chain diamine compound) as a part of the raw material.

Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , and Y ₆ in the formula [2a] have the same meaning as each group in the formula [2], and the same applies to n. The preferred range is also the same as each group in formula [2].
Furthermore, the preferable combination of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n in the formula [2a] is the same as the preferable combination of the formula [2].
In formula [2a], m is an integer of 1-4. Preferably, it is an integer of 1.

（式［２−１］〜式［２−３］中、Ｒ_１は−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−又は−ＣＨ_２ＯＣＯ−であり、Ｒ_２は炭素数１〜２２の直鎖状又は分岐状アルキル基、炭素数１〜２２の直鎖状又は分岐状アルコキシル基、炭素数１〜２２の直鎖状又は分岐状フッ素含有アルキル基、又は炭素数１〜２２の直鎖状又は分岐状フッ素含有アルコキシル基である。）Specifically, it is a compound having a structure represented by, for example, the following formulas [2-1] to [2-32].

(In Formula [2-1] to Formula [2-3], R ₁ is —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or —CH ₂ OCO—, and R ₂ is A linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or the number of carbon atoms 1 to 22 linear or branched fluorine-containing alkoxyl groups.)

（式［２−４］〜式［２−６］中、Ｒ_３は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−又は−ＣＨ_２−であり、Ｒ_４は炭素数１〜２２の直鎖状又は分岐状アルキル基、炭素数１〜２２の直鎖状又は分岐状アルコキシル基、炭素数１〜２２の直鎖状又は分岐状フッ素含有アルキル基、又は炭素数１〜２２の直鎖状又は分岐状フッ素含有アルコキシル基である。）

(In the formulas [2-4] to [2-6], R ₃ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH _2. O—, —OCH ₂ — or —CH ₂ —, wherein R ₄ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, carbon number (It is a linear or branched fluorine-containing alkyl group having 1 to 22 or a linear or branched fluorine-containing alkoxyl group having 1 to 22 carbon atoms.)

（式［２−７］及び式［２−８］中、Ｒ_５は、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２−、−Ｏ−又は−ＮＨ−であり、Ｒ_６はフッ素基、シアノ基、トリフルオロメタン基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基又は水酸基である。）

(In Formula [2-7] and Formula [2-8], R ₅ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH _2. O—, —OCH ₂ —, —CH ₂ —, —O— or —NH—, wherein R ₆ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group. Or a hydroxyl group.)

（式［２−９］及び式［２−１０］中、Ｒ_７は炭素数３〜１２の直鎖状又は分岐状アルキル基であり、１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。）

（式［２−１１］及び式［２−１２］中、Ｒ_８は炭素数３〜１２の直鎖状又は分岐状アルキル基であり、１,４-シクロヘキシレンのシス−トランス異性は、それぞれトランス異性体である。）

(In the formulas [2-9] and [2-10], R ₇ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is Trans isomer.)

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

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

(In the formula [2-13], A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ is a 1,4-cyclohexylene group or 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— * (wherein , A bond marked with “*” binds to (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. )

上記の特定側鎖型ジアミン化合物は、液晶配向膜とした際の液晶配向性、電圧保持率、蓄積電荷などの特性に応じて、１種類又は２種類以上を混合して使用することもできる。

Said specific side chain type diamine compound can also be used 1 type or in mixture of 2 or more types according to characteristics, such as liquid crystal orientation at the time of setting it as a liquid crystal aligning film, a voltage holding ratio, and an accumulation charge.

<Other diamine compounds>
In the present invention, as long as the effects of the present invention are not impaired, other diamine compounds (also referred to as other diamine compounds) other than the specific side chain diamine compound can be used as the diamine component. 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 '-Sulfonyldianiline, 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) be Zen, 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 -A Nophenyl) 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) (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, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5 -Bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) ) Heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-amino) Phenoxy) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) ) Aromatic diamines such as undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane; bis (4-aminocyclohexyl) ) Alicyclic diamines such as methane, bis (4-amino-3-methylcyclohexyl) methane; 1,3-diaminopropane, 1,4-di Aminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane Aliphatic diamines such as 1,12-diaminododecane.

（式［ＤＡ１］〜式［ＤＡ５］中、Ａ_１は炭素数１〜２２の直鎖状又は分岐状アルキル基、又は炭素数１〜２２の直鎖状又は分岐状フッ素含有アルキル基である。）Moreover, unless the effect of this invention is impaired, the diamine compound shown by the following formula [DA1]-a formula [DA12] can be illustrated.

(In Formula [DA1] to Formula [DA5], A ₁ is a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms. )

（式［ＤＡ６］〜式［ＤＡ１１］中、Ａ_２は−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−又は−ＮＨ−であり、Ａ_３は炭素数１〜２２の直鎖状又は分岐状アルキル基、又は炭素数１〜２２の直鎖状又は分岐状フッ素含有アルキル基を示す。）

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

（式［ＤＡ１２］中、ｐは１〜１０の整数である。）

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

（式［ＤＡ１７］中、ｍは０〜３の整数であり、式［ＤＡ２０］中、ｎは１〜５の整数である。）In addition, diamine compounds represented by the following formulas [DA13] to [DA20] can 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.)

（式［ＤＡ２１］中、ｍ_１は１〜４の整数である。式［ＤＡ２２］中、Ａ_４は単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又は−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ_２及びｍ_３はそれぞれ０〜４の整数であり、かつｍ_２＋ｍ_３は１〜４の整数である。式［ＤＡ２３］中、ｍ_４及びｍ_５はそれぞれ１〜５の整数である。式［ＤＡ２４］中、Ａ_５は炭素数１〜５の直鎖状又は分岐状アルキル基であり、ｍ_６は１〜５の整数である。式［ＤＡ２５］中、Ａ_６は単結合、−ＣＨ_２−、−Ｃ_２Ｈ_４−、−Ｃ（ＣＨ_３）_２−、−ＣＦ_２−、−Ｃ（ＣＦ_３）−、−Ｏ−、−ＣＯ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又は−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ_７は１〜４の整数である。）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 formula [DA21], m ₁ is an integer of ₁ to 4. In 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) a CO-, _{m 2} and _{m 3} is an integer of 0 to 4, and _m 2 + _{m 3} Is an integer of 1 to 4. In the formula [DA23], m ₄ and m ₅ are each an integer of 1 to 5. In the formula [DA24], A ₅ is a linear or branched group having 1 to ₅ carbon atoms. And m ₆ is an integer of 1 to 5. In the formula [DA25], A ₆ 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—, and m ₇ is an integer of 1 to 4.

（式［ＤＡ２６］中、Ａ_１は−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−又は−Ｎ（ＣＨ_３）ＣＯ−であり、Ａ_２は単結合、炭素数１〜２０の脂肪族炭化水素基、非芳香族環式炭化水素基又は芳香族炭化水素基である。Ａ_３は単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−又は−Ｏ（ＣＨ_２）_ｍ−（ｍは１〜５の整数である）であり、Ａ_４は窒素含有芳香族複素環であり、ｎは１〜４の整数である。） Furthermore, a diamine compound represented by the following formula [DA26] can also be used as long as the effects of the present invention are not impaired.

(In the formula [DA26], A ₁ represents —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ). - or -N _(CH 3) a CO-, _{a 2} is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group .A ₃ Is a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ) —, —N (CH ₃ ). CO— or —O (CH ₂ ) _m — (m is an integer of 1 to 5), A ₄ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4.

上記のその他ジアミン化合物は、液晶配向膜とした際の液晶配向性、電圧保持率、蓄積電荷などの特性に応じて、１種類又は２種類以上を混合して使用することもできる。In addition, as long as the effects of the present invention are not impaired, a diamine compound having a steroid skeleton represented by the following formula [DA27] or [DA28] can also be used.

Said other diamine compound can also be used 1 type or in mixture of 2 or more types according to characteristics, such as liquid crystal orientation at the time of setting it as a liquid crystal aligning film, a voltage holding ratio, and an accumulation charge.

式［３］中、Ｚ_１は炭素数４〜１３の４価の有機基であり、かつ炭素数４〜１０の非芳香族環状炭化水素基を含有する。<Specific tetracarboxylic dianhydride>
In order to obtain the polymer of the present invention, it is preferable to use a tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic dianhydride) represented by the following formula [3] as a part of the raw material.

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 10 carbon atoms.

Z ₁ is specifically a tetravalent group represented by, for example, the following formulas [3a] to [3j].

In the formula [3a], Z _{2 to} Z ₅ are groups selected from a hydrogen atom, a methyl group, a chlorine atom and 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 from the viewpoint of polymerization reactivity and ease of synthesis. [3 g]. Especially, the structure of Formula [3a], Formula [3e], Formula [3f], or Formula [3g] is preferable.

<Other tetracarboxylic dianhydrides>
In the present invention, other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride (also referred to as other tetracarboxylic dianhydrides) can be used as long as the effects of the present invention are not impaired. Specific examples thereof are dianhydrides of the following compounds.
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, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid Examples include acids.
The above-mentioned specific tetracarboxylic dianhydride and other tetracarboxylic dianhydrides may be used alone or in combination of two or more depending on the properties such as liquid crystal alignment, voltage holding ratio and accumulated charge when the liquid crystal alignment film is used. It can also be used by mixing.

（式［Ａ］中、Ｒ_１は４価の有機基であり、Ｒ_２は２価の有機基であり、Ａ_１及びＡ_２は水素原子又は炭素数１〜８のアルキル基であり、それぞれ同じであっても異なってもよく、ｎは正の整数を示す。）<Polymer / Specific polymer>
The polymer contained in the liquid crystal aligning agent of the present invention is at least selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic acid component and a polyimide obtained by dehydrating and ring-closing the polyamic acid. One kind of polymer.
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, (It may be the same or different, and n represents a positive integer.)

（式［Ｂ］及び式［Ｃ］中、Ｒ_１及びＲ_２は式［Ａ］で定義したものと同意義である。）The above polymer can be obtained relatively simply by using a diamine component represented by the following formula [B] and a tetracarboxylic dianhydride represented by the following formula [C] as raw materials. A polyamic acid having a structural formula of a repeating unit represented by D] or a polyimide obtained by dehydrating and ring-closing the polyamic acid is preferable.

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

（式［Ｄ］中、Ｒ_１、Ｒ_２及びｎは式［Ａ］で定義したものと同意義である。）
式［Ａ］及び式［Ｄ］において、Ｒ_１及びＲ_２はそれぞれ１種類でもあっても、それぞれ異なったＲ_１及びＲ_２を有して繰り返し単位として、異なった複数種を組み合わせたものでもよい。

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

In the present invention, the method for synthesizing the 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 A method of polycondensation of a dihalide and a diamine component to obtain a polyamic acid is used.
Polyamide acid alkyl ester can be obtained by polycondensation of carboxylic acid group with dialkyl esterified tetracarboxylic acid and diamine component, tetracarboxylic acid dihalide with carboxylic acid group dialkylesterified and diamine component. The method or the method of converting the carboxyl group of a polyamic acid into ester is used.
In order to obtain polyimide, a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.

The specific polymer of the present invention is a polymer having a specific side chain structure represented by the above formula [2], and the liquid crystal alignment film obtained using the specific polymer is represented by the above formula [2] in the diamine component. As the content of the specific side chain structure increases, the pretilt angle of the liquid crystal can be increased. In that case, it is preferable to use the specific side chain type diamine compound shown by the said Formula [2a] for a diamine component. In order to enhance this property, it is preferable that 5 mol% or more and 80 mol% or less of the diamine component is the specific side chain type diamine compound. Especially, it is preferable that 5 mol% or more and 60 mol% or less of a diamine component are a specific side chain type diamine compound from the viewpoint of the applicability | paintability of a liquid crystal aligning agent, and the electrical property as a liquid crystal aligning film.
Moreover, in order to obtain the polymer of this invention, it is preferable to use the specific tetracarboxylic dianhydride shown by the said Formula [3] for a tetracarboxylic-acid component. In particular, it is preferable to use a tetracarboxylic dianhydride in which Z ₁ in the formula [3] is a structure represented by the above formulas [3a] to [3j]. 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 of the diamine component and the tetracarboxylic acid component is usually performed 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.
For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 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, as long as the produced | generated polyimide precursor does not precipitate, you may mix and use the said solvent. Moreover, since the water | moisture content in an organic solvent inhibits a polymerization reaction and also causes a hydrolysis of the produced | generated polyimide precursor, it is preferable to use what was dehydrated and dried.
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 polymer.

The polymerization temperature can be selected from an arbitrary temperature of -20 to 150 ° C, preferably in the range of -5 to 100 ° C.
The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, Preferably it is 1-50 mass%, More preferably, it is 5-30 mass%. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
In the polymerization reaction of the polyimide precursor, the ratio between the total number of moles of the diamine component and the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
The polyimide contained in the liquid crystal aligning agent of this invention is a polyimide obtained by ring-closing the said polyimide precursor, and is useful as a polymer for obtaining a liquid crystal aligning film.
In the polyimide, the ring closure 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 catalytic imidization in which a catalyst is added to the polyimide precursor solution.
The temperature when the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
The catalyst imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.

The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, 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 these, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

  When recovering the produced polyimide precursor or polyimide from the polyimide precursor or polyimide reaction solution, the reaction solution may be poured into a solvent and precipitated. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.

The polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. Examples of the solvent at this time include alcohols, ketones, 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 polymer contained in the liquid crystal aligning agent of the present invention is GPC (Gel Permeation Chromatography) in consideration of the strength of the resin film obtained therefrom, the workability when forming the resin film, and the uniformity of the resin film. The weight average molecular weight measured by the method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Liquid crystal alignment agent>
The liquid crystal aligning agent of this invention is a solution for forming a liquid crystal aligning film, and is a coating liquid for forming the resin film containing a specific compound, a polymer, and an organic solvent.
The content of the specific compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the polymer. Especially, 0.1-100 mass parts is more preferable in order that a crosslinking reaction will advance, the sclerosis | hardenability of a desired resin film may be expressed, and the orientation of a liquid crystal may not be reduced. More preferably, it is 1-50 mass parts, and 1-20 mass parts is especially preferable.

All the polymer components in the liquid crystal aligning agent of the present invention may all be specific polymers, or other polymers other than the specific polymers may be mixed. In that case, content of the other polymer other than that in a polymer is 0.5-15 mass%, Preferably it is 1-10 mass%.
Other polymers include polyimide precursors or polyimides that do not contain a specific side chain structure. Specific examples of the polymer other than the polyimide precursor and the polyimide include acrylic polymer, methacrylic polymer, polystyrene, and polyamide.
The organic solvent in the liquid crystal aligning agent of the present invention has an organic solvent content of 70 to 99 with respect to the total amount (100% by mass) of the liquid crystal aligning agent from the viewpoint of forming a uniform resin film by coating. It is preferable that it is mass%, and 80-99 mass% is more preferable. Content can be suitably changed with the film thickness of the target liquid crystal aligning film.

The organic solvent in that case will not be specifically limited if it is an organic solvent in which the polymer mentioned above is dissolved.
For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone , Cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like. Of these, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyllactone, and the like. These may be used alone or in combination.

  The liquid crystal alignment treatment agent of the present invention comprises a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group unless the effects of the present invention are impaired. A crosslinkable compound having at least one substituent selected from the group, a crosslinkable compound having a polymerizable unsaturated bond, and the like may be contained. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.

  Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, Liglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxy) Propoxy) phenyl) ethyl) phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3 -Epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

具体的には、国際公開公報ＷＯ２０１１／１３２７５１（２０１１．１０．２７公開）の５８頁〜５９頁に掲載される式［４ａ］〜式［４ｋ］で示される架橋性化合物が挙げられる。The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

Specific examples include crosslinkable compounds represented by the formulas [4a] to [4k] published on pages 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27).

具体的には、国際公開公報ＷＯ２０１２／０１４８９８（２０１２．２．２公開）の７６頁〜８２頁に掲載される式［５−１］〜式［５−４２］で示される架橋性化合物が挙げられる。The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

Specifically, the crosslinkable compounds represented by the formulas [5-1] to [5-42] described on pages 76 to 82 of International Publication No. WO2012 / 014898 (published on 2012.2.2) are listed. It is done.

（式［５−３８］〜式［５−４０］中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立して、式［５］で示される構造、水素原子、水酸基、炭素数１〜１０のアルキル基、アルコキシル基、脂肪族環又は芳香族環であり、少なくとも１つは式［５］で示される構造である。）Furthermore, the polysiloxane which has at least 1 type of structure shown by following formula [5-38]-formula [5-40] can also be mentioned.

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

（式［５−４２］中、ｎは１〜１０の整数である。） More specifically, compounds of the following formulas [5-41] and [5-42] are mentioned.

(In Formula [5-42], n is an integer of 1 to 10.)

  As the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group, for example, an amino resin having a hydroxyl group or an alkoxyl group, for example, 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, a benzoguanamine derivative, glycoluril, or the like in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used. The melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 or more and 6 or less methylol groups or alkoxymethyl groups per triazine ring.

As an example of such a melamine derivative or a benzoguanamine derivative, MX-750 in which an average of 3.7 methoxymethyl groups is substituted per one triazine ring in a commercially available product, and an average of 5. methoxymethyl groups per one triazine ring. 8-substituted MW-30 (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 ethoxy Mitylated 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 or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis ( sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.
More specifically, International Publication WO2011 / 132751. (2011.10.27), pages 62 to 66, and the crosslinkable compounds represented by the formulas [6-1] to [6-48].

  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 (meth) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) Acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl 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 ( A crosslinkable compound having one polymerizable unsaturated group in the molecule such as (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate ester, N-methylol (meth) acrylamide; Can be mentioned.

（式［７］中、Ｅ_１はシクロヘキサン環、ビシクロヘキサン環、ベンゼン環、ビフェニル環、ターフェニル環、ナフタレン環、フルオレン環、アントラセン環及びフェナントレン環からなる群から選ばれる基であり、Ｅ_２は下記式［７ａ］及び式［７ｂ］から選ばれる基であり、ｎは１〜４の整数である。）

上記化合物は架橋性化合物の一例であり、これらに限定されるものではない。また、本発明の液晶配向処理剤に含有される架橋性化合物は、１種類であってもよく、２種類以上組み合わせてもよい。In addition, a compound represented by the following formula [7] can also be contained.

(Wherein [7], E ₁ is a cyclohexane ring, bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, a group selected from the group consisting of an anthracene ring and phenanthrene ring, E ₂ Is a group selected from the following formula [7a] and formula [7b], 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.

It is preferable that content of the crosslinkable compound in the liquid-crystal aligning agent of this invention is 0.1-150 mass parts with respect to 100 mass parts of all the polymer components. In order that the cross-linking reaction proceeds and the desired effect is exhibited and the orientation of the liquid crystal is not lowered, 0.1 to 100 parts by mass is more preferable with respect to 100 parts by mass of all polymer components, and 1 to 50 parts by mass. Part is most preferred.
Unless the effect of this invention is impaired, the liquid-crystal aligning agent of this invention is the organic solvent (it is also called a poor solvent) which improves the uniformity of the film thickness of a resin film at the time of apply | coating a liquid-crystal aligning agent, and surface smoothness. Alternatively, a compound can be used. Furthermore, a compound that improves the adhesion between the liquid crystal alignment film and the substrate can 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, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2- Etanji 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentane Diol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2 Heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- (methoxymethoxy) ethanol, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol hexyl ether, 2- (hexyloxy) ethanol, Furfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene group Cole monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, lactic acid Ethyl, 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, methyl lactate, ethyl lactate Ester, lactic n- propyl ester, lactate n- butyl ester, surface tension, such as lactic isoamyl ester is low organic solvent.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monobutyl ether are preferably used.
These poor solvents are preferably 1 to 80% by mass of the whole organic solvent contained in the liquid crystal aligning agent. Especially, 5-70 mass% is preferable. More preferred is 10 to 70% by mass.

Examples of the compound that improves the uniformity and surface smoothness of the resin coating 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 content ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components.

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.

When using the compound to adhere | attach with a board | substrate, it is preferable that the content is 0.1-30 mass parts with respect to 100 mass parts of all the polymer components, More preferably, it is 1-20 mass parts. is there. 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 alignment treatment agent of the present invention impairs the effects of the present invention in addition to the above-mentioned crosslinkable compound, poor solvent, compound that improves the uniformity and surface smoothness of the resin film, and compound that adheres to the substrate. If it is within the range, a dielectric or conductive material may be added for the purpose of changing the electrical characteristics such as dielectric constant and conductivity of the liquid crystal alignment film.

<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 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, screen printing, offset printing, flexographic printing, inkjet method, and the like are common. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.
After the liquid crystal alignment treatment agent is applied on the substrate, the solvent is evaporated at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, a thermal circulation oven, an IR (infrared) oven, etc. It can be a united 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 10 to 100 nm.
When the liquid crystal is aligned horizontally or tilted, the fired polymer film is treated by rubbing, irradiation with polarized ultraviolet rays, or the like.

The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
As a method for manufacturing a liquid crystal cell, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, a method of bonding the substrate after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacers are dispersed, and the like.

Furthermore, the liquid-crystal aligning agent of this invention has a liquid crystal layer between a pair of board | substrates provided with the electrode, The polymeric compound superposed | polymerized between at least one of an active energy ray and a heat | fever between a pair of board | substrates. And a liquid crystal display device manufactured 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 the electrodes. . Here, ultraviolet rays are suitable as the active energy ray. As a wavelength of the ultraviolet ray to be used, 300 to 400 nm is preferable, and 310 to 360 nm is more preferable.
In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

The liquid crystal display element controls a pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method.
In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound. The pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer.

The PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process.
That is, in the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the above-described method, a liquid crystal cell is prepared and polymerizable by at least one of ultraviolet irradiation and heating. The orientation of the liquid crystal molecules can be controlled by polymerizing the compound.
To give an example of manufacturing a PSA type liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded, the liquid crystal is injected under reduced pressure and sealed, the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed. .

In the liquid crystal, a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed. Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. In that case, it is preferable that content of a polymeric compound is 0.01-10 mass parts with respect to 100 mass parts of a liquid-crystal component, More preferably, it is 0.1-5 mass parts. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled. The seizure characteristics of the steel deteriorate.
After the liquid crystal cell is produced, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.

In addition, the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of 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. As a wavelength of an ultraviolet-ray, 300-400 nm is preferable and 310-360 nm is more preferable.
In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.
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 containing a coalescing component is exemplified.

Since the liquid crystal aligning agent of the present invention contains a specific compound having a double bond site that reacts by irradiation with heat or ultraviolet rays, the alignment of liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating. it can.
If an example of liquid crystal cell production is given, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is bonded and the liquid crystal is injected under reduced pressure and sealed, and a method in which the substrate is bonded and sealed after the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed.
After the liquid crystal cell is manufactured, the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
As described above, the liquid crystal display element manufactured using the liquid crystal aligning agent of the present invention has excellent reliability, and is suitable for a large-screen, high-definition liquid crystal television.

The present invention will be described in more detail with reference to the following examples, but should not be construed as being limited thereto.
The abbreviations of the compounds used in the examples are as follows.

(Specific tetracarboxylic dianhydride)
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride TCA: shown by the following formula Tetracarboxylic dianhydride TDA: tetracarboxylic dianhydride represented by the following formula

(Specific side chain diamine compounds)
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

（有機溶媒）
ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＢＣＳ：ブチルセロソルブ(Specific compound (component (A)))
A-1: Specific compound represented by the following formula A-2: Specific compound represented by the following formula

(Organic solvent)
NMP: N-methyl-2-pyrrolidone
BCS: Butyl cellosolve

(Measurement of molecular weight of polyimide precursor and polyimide)
It measured as follows using the normal temperature gel permeation chromatography (GPC) apparatus (GPC-101, Showa Denko Co., Ltd. product) and a column (KD-803, KD-805) (Shodex product).
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L (liter), phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, 10 ml / L of tetrahydrofuran (THF))
Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratory).

(Measurement of imidization rate)
Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 (Kusano Kagaku)) and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) Then, it was completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring machine (JNW-ECA500, manufactured by JEOL Datum). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
Imidation ratio (%) = (1−α · x / y) × 100
In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

<Synthesis Example 1>
CBDA (3.15 g, 16.1 mmol), PCH7DAB (3.06 g, 8.0 mmol), and p-PDA (0.87 g, 8.0 mmol) were mixed in NMP (21.2 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 23,600, and the weight average molecular weight was 71,200.

<Synthesis Example 2>
BODA (1.28 g, 5.1 mmol), PCH7DAB (1.16 g, 3.0 mmol), and DBA (1.09 g, 7.2 mmol) were mixed in NMP (7.5 g) and at 80 ° C. for 4 hours. After the reaction, CBDA (1.00 g, 5.1 mmol) and NMP (6.1 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 (15.0 g) and diluting to 6% by mass, acetic anhydride (1.89 g) and pyridine (1.45 g) were added as imidization catalysts, and The reaction was allowed for 5 hours. This reaction solution was poured into methanol (240 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 (2). The imidation ratio of this polyimide was 55%, the number average molecular weight was 20,200, and the weight average molecular weight was 58,200.

<Synthesis Example 3>
BODA (5.26 g, 21.0 mmol), PCH7DAB (5.00 g, 13.1 mmol), and DBA (2.00 g, 13.1 mmol) were mixed in NMP (21.9 g) and at 80 ° C. for 5 hours. After the reaction, CBDA (1.03 g, 5.3 mmol) and NMP (18.0 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%. .
After adding NMP to the obtained polyamic acid solution (20.2 g) and diluting to 6% by mass, acetic anhydride (4.47 g) and pyridine (3.27 g) were added as an imidization catalyst, Reacted for hours. This reaction solution was put into methanol (420 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (3). The imidation ratio of this polyimide was 77%, the number average molecular weight was 19,100, and the weight average molecular weight was 49,600.

<Synthesis Example 4>
BODA (3.27 g, 13.1 mmol), PBCH5DAB (2.83 g, 6.5 mmol), and DBA (1.85 g, 12.2 mmol) were mixed in NMP (14.9 g) and at 80 ° C. for 5 hours. After the reaction, CBDA (1.10 g, 5.6 mmol) and NMP (12.2 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%. .
After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.31 g) were added as imidization catalysts, and Reacted for hours. This reaction solution was poured into methanol (410 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 18,200, and the weight average molecular weight was 48,100.

<Synthesis Example 5>
BODA (3.04 g, 12.2 mmol), m-PBCH5DABz (2.32 g, 5.2 mmol), and m-PDA (1.31 g, 12.1 mmol) were mixed in NMP (12.7 g) and 80 After reacting at 5 ° C. for 5 hours, CBDA (1.02 g, 5.2 mmol) and NMP (10.4 g) were added, reacted at 40 ° C. for 6 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 (20.5 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 (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 19,900, and the weight average molecular weight was 49,900.

<Synthesis Example 6>
BODA (5.77 g, 23.1 mmol), ColDAB-1 (2.26 g, 4.3 mmol), and DBA (3.73 g, 24.5 mmol) were mixed in NMP (21.3 g) at 80 ° C. After reacting for 5 hours, CBDA (1.13 g, 5.8 mmol) and NMP (17.4 g) were added, and reacted at 40 ° C. for 6.5 hours. 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 (2.46 g) and pyridine (1.90 g) were added as imidization catalysts, 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 (6). The imidation ratio of this polyimide was 51%, the number average molecular weight was 17,600, and the weight average molecular weight was 46,200.

<Synthesis Example 7>
BODA (5.61 g, 22.4 mmol), ColDAB-2 (1.38 g, 2.8 mmol), and p-PDA (2.73 g, 25.2 mmol) were mixed in NMP (17.9 g) and 80 After reacting at 5 ° C. for 5 hours, CBDA (1.10 g, 5.6 mmol) and NMP (14.6 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 (20.0 g) and diluting to 6% by mass, acetic anhydride (2.50 g) and pyridine (1.90 g) were added as imidization catalysts, and 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 (7). The imidation ratio of this polyimide was 52%, the number average molecular weight was 16,900, and the weight average molecular weight was 46,200.

<Synthesis Example 8>
BODA (5.87 g, 23.5 mmol), AP18 (3.31 g, 8.8 mmol), and m-PDA (2.22 g, 20.5 mmol) were mixed in NMP (20.7 g) at 80 ° C. After reacting for 4 hours, CBDA (1.15 g, 5.9 mmol) and NMP (14.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%. Obtained.
After adding NMP to the obtained polyamic acid solution (20.5 g) and diluting to 6% by mass, acetic anhydride (1.90 g) and pyridine (1.51 g) were added as imidization catalysts, and The reaction was allowed for 5 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 (8). The imidation ratio of this polyimide was 50%, the number average molecular weight was 21,200, and the weight average molecular weight was 59,200.

<Synthesis Example 9>
TCA (3.12 g, 13.9 mmol), PBCH5DAB (1.81 g, 4.2 mmol), and DBA (1.48 g, 9.7 mmol) were mixed in NMP (19.2 g) and 6 hours at 40 ° C. 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 (1.85 g) and pyridine (1.45 g) were added as an imidization catalyst, and the mixture was heated at 80 ° C. for 4 hours. Reacted. This reaction solution was poured into methanol (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 (9). The imidation ratio of this polyimide was 55%, the number average molecular weight was 20,800, and the weight average molecular weight was 55,900.

<Synthesis Example 10>
TDA (2.00 g, 6.7 mmol), PCH7DAB (4.17 g, 11.0 mmol), and DBA (1.67 g, 11.0 mmol) were mixed in NMP (17.9 g) and at 80 ° C. for 5 hours. After the reaction, CBDA (3.01 g, 15.3 mmol) and NMP (14.7 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 (4.52 g) and pyridine (3.31 g) were added as imidization catalysts, and Reacted for hours. This reaction solution was put into methanol (480 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (10). The imidation ratio of this polyimide was 80%, the number average molecular weight was 20,500, and the weight average molecular weight was 50,100.
Table 33 shows the polyamic acid and polyimide obtained in the synthesis example together with the composition of each component used in the synthesis and the imidization ratio.

＊１：ポリアミド酸。

* 1: Polyamic acid.

"Preparation of liquid crystal alignment treatment agent"
Examples 1 to 11 and Comparative Examples 1 to 3 are preparation examples of liquid crystal alignment treatment agents. The obtained liquid crystal aligning agent was used also for each characteristic evaluation.
Tables 34 and 35 collectively show the resin components and the specific compound (A) used for the preparation of each liquid crystal alignment treatment agent.
Using the liquid crystal alignment treatment agents obtained in Examples and Comparative Examples, “Preparation of liquid crystal alignment film”, “Preparation of liquid crystal cell (ordinary cell)”, “Preparation of liquid crystal cell (PSA cell)”, “Voltage holding ratio” Evaluation of "," Evaluation of relaxation of charge accumulated by DC voltage (also called evaluation of relaxation of residual charge) "and" Evaluation after light irradiation "were performed.
Each evaluation method is as follows.

"Formation 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.

"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 Ltd.) 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 orientation uniformity of the liquid crystal was confirmed by observation with a polarizing microscope. 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 was spin-coated on the ITO surface of a substrate with an ITO electrode of 10 mm × 10 mm with a pattern interval of 20 μm in the center and a substrate with an ITO electrode of 10 mm × 40 mm in the center, and then on a hot plate at 80 ° C. for 5 minutes. Heat treatment was performed at 220 ° C. for 30 minutes in a heat-circulating clean oven to obtain a polyimide coating film having a film 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 the liquid crystal alignment film surface inside, with a 6 μm spacer in between, and the periphery was adhered with a sealant to produce an empty cell. The polymerizable compound (1) represented by the following formula was added to MLC-6608 (manufactured by Merck Japan Ltd.) by a reduced pressure injection method into this empty cell, and 0% of the polymerizable compound was 100% by mass of MLC-6608. A liquid crystal cell was obtained by injecting liquid crystal mixed by 3% by mass and sealing the injection port.

While applying an AC voltage of 5 V to the obtained liquid crystal cell, using a metal halide lamp with an illuminance of 60 mW, the wavelength of 350 nm or less was cut, and ultraviolet irradiation of 20 J / cm ^{2 in} terms of 365 nm was performed, and the alignment direction of the liquid crystal A liquid crystal cell (PSA cell) was controlled. The temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.
The response speed of the liquid crystal before and after the ultraviolet irradiation of the liquid crystal cell was measured. As the response speed, T90 → T10 from 90% transmittance to 10% transmittance was measured. In the PSA cells obtained in Examples and Comparative Examples, the response speed of the liquid crystal cell after ultraviolet irradiation was faster than the response speed of the liquid crystal cell before ultraviolet irradiation, so the alignment direction of the liquid crystal was controlled. It was confirmed.
In any liquid crystal cell, it was confirmed that the liquid crystal was uniformly aligned by observation with a polarizing microscope.

"Evaluation of voltage holding ratio"
A voltage of 1 V was applied to the liquid crystal cell obtained in the above-mentioned “Preparation of liquid crystal cell (normal cell)” and “Preparation of liquid crystal cell (PSA cell)” at a temperature of 80 ° C., and after 16.67 ms. The voltage after 50 ms was measured, and how much the voltage could be held after each time was calculated as the voltage holding ratio.
The measurement was performed using a VHR-1 voltage holding ratio measuring device (manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ± 1 V, Pulse Width: 60 μs, Frame Period: 16.67 ms or 50 ms. In this evaluation, the larger the value, the better the voltage holding characteristic.

"Evaluation of relaxation of residual charge (V)"
A DC voltage of 10 V was applied to the liquid crystal cell after measuring the voltage holding ratio for 30 minutes and short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. The residual charges after 50 seconds and 1000 seconds were measured and confirmed.
The measurement was performed using a 6254 type liquid crystal physical property evaluation apparatus (manufactured by Toyo Technica). In this evaluation, the smaller the value, the better the residual charge relaxation characteristics.

"Evaluation after UV irradiation"
After the evaluation of the relaxation of the residual charge was completed, the liquid crystal cell was irradiated with UV of 50 J / cm ^{2 in} terms of 365 nm, and then the voltage holding ratio and the residual charge were measured under the same conditions as described above. In addition, ultraviolet irradiation was performed using the table-type UV curing device (HCT3B28HEX-1, manufactured by Senlite Co., Ltd. (SEN LIGHT CORPORATION)).

As an evaluation of the liquid crystal cell produced by the above method using the liquid crystal aligning agents obtained in Examples 1 to 11 and Comparative Examples 1 to 3, "Evaluation of voltage holding ratio", "Charge accumulated by DC voltage" The results of “Evaluation of relaxation (also referred to as relaxation of residual charge (V))” and “Evaluation after ultraviolet irradiation” are collectively shown in Tables 36 to 41.
Tables 36 and 37 show the evaluation results of the voltage holding ratio using the normal cell, and Table 38 shows the evaluation results of the voltage holding ratio using the PSA cell. Tables 39 and 40 show the evaluation results of residual charge relaxation using a normal cell, and Table 41 shows the evaluation results of residual charge relaxation using a PSA cell. The evaluation results after ultraviolet irradiation are also shown in each table.

<Example 1>
Polyamide acid solution (1) (10.0 g) having a solid content concentration of 25.0% by mass obtained in Synthesis Example 1 (10.0 g), NMP (5.7 g), NMP solution of A-1 (1.50 g) (A- NMP solution with 1 being 5.0% by mass) and BCS (25.8 g) were added and 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), production of cells and various evaluations were performed under the above-described conditions.

<Example 2>
NMP (10.9 g) was added to the polyimide powder (2) (2.45 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, add N-1 solution (2.45 g) of A-1 (NMP solution with A-1 of 5.0% by mass), NMP (6.0 g), and BCS (23.6 g). For 10 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), cell preparation and various evaluations were performed under the above-described conditions.

<Example 3>
NMP (13.5 g) was added to the polyimide powder (3) (2.40 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 (2.40 g) (NMP solution with A-1 of 5.0% by mass), NMP (7.2 g), and BCS (18.9 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), cell preparation and various evaluations were performed under the above-described conditions.

<Example 4>
NMP (12.9 g) was added to the polyimide powder (3) (2.45 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 (4.90 g) (NMP solution with A-1 of 5.0% by mass), NMP (7.0 g), and BCS (20.2 g), and add to 50 ° C. For 14 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), cell preparation and various evaluations were performed under the above-described conditions.

<Example 5>
NMP (13.5 g) was added to the polyimide powder (4) (2.41 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, add N-1 solution (2.41 g) of A-1 (NMP solution with A-1 of 5.0% by mass), NMP (7.3 g), and BCS (19.0 g), and For 10 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), cell preparation and various evaluations were performed under the above-described conditions.

<Example 6>
NMP (13.5 g) was added to the polyimide powder (5) (2.40 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, add N-2 solution (2.40 g) of A-2 (NMP solution with A-2 of 5.0% by mass), NMP (7.4 g), and BCS (18.9 g). For 11 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), a cell was prepared and various evaluations were performed under the above-described conditions.

<Example 7>
NMP (16.5 g) was added to the polyimide powder (6) (2.40 g) obtained in Synthesis Example 6, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, add N-1 solution of A-1 (1.44 g) (NMP solution with A-1 of 5.0% by mass), NMP (9.0 g), and BCS (14.4 g), and add to 50 ° C. For 9 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), cell preparation and various evaluations were performed under the above-described conditions.

<Example 8>
NMP (16.5 g) was added to the polyimide powder (7) (2.41 g) obtained in Synthesis Example 7 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, add N-2 solution of A-2 (1.45 g) (NMP solution with A-2 of 5.0% by mass), NMP (8.9 g), and BCS (14.5 g), and add to 50 ° C. For 9 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), a cell was prepared and various evaluations were performed under the above-described conditions.

<Example 9>
NMP (13.5 g) was added to the polyimide powder (8) (2.40 g) obtained in Synthesis Example 8, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, add N-1 solution of A-1 (2.40 g) (NMP solution with A-1 of 5.0% by mass), NMP (7.4 g), and BCS (18.9 g). For 10 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), cell preparation and various evaluations were performed under the above-described conditions.

<Example 10>
NMP (14.5 g) was added to the polyimide powder (9) (2.40 g) obtained in Synthesis Example 9 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, add N-2 solution (3.36 g) of A-2 (NMP solution containing 5.0% by mass of A-2), NMP (8.0 g), and BCS (17.1 g). For 12 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), cell preparation and various evaluations were performed under the above-described conditions.

<Example 11>
NMP (14.0 g) was added to the polyimide powder (10) (2.40 g) obtained in Synthesis Example 10 and dissolved by stirring at 70 ° C. for 24 hours. To this solution, NMP solution (4.80 g) of A-1 (NMP solution with A-1 of 5.0% by mass), NMP (7.6 g), and BCS (17.6 g) were added, and the mixture was heated to 50 ° C. For 14 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), production of cells and various evaluations were performed under the above-described conditions.

<Comparative Example 1>
Polyamide acid solution (1) (10.0 g), NMP (6.7 g), and BCS (25.1 g) with a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 1 were added, and at 25 ° C. It stirred for 2 hours and obtained the 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), cell preparation and various evaluations were performed under the above-described conditions.

<Comparative example 2>
NMP (11.8 g) was added to the polyimide powder (2) (2.41 g) obtained in Synthesis Example 2, and dissolved by stirring at 70 ° C. for 24 hours. NMP (6.4 g) and BCS (22.1 g) were added to this solution, and the mixture was stirred at 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), cell preparation and various evaluations were performed under the above-described conditions.

<Comparative Example 3>
NMP (14.3 g) was added to the polyimide powder (4) (2.40 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours. NMP (7.7g) and BCS (18.1g) were added to this solution, and it stirred at 50 degreeC for 10 hours, and obtained the 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), cell preparation and various evaluations were performed under the above-described conditions.

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 light (ultraviolet rays) for a longer time than the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example. Even after being exposed to (), the decrease in the voltage holding ratio is small and the accumulation of residual charges is small. The same result was obtained for both the normal cell and the PSA cell.
In Comparative Examples 1 to 3, which did not contain the specific amine compound, the decrease in the voltage holding ratio after being exposed to light (ultraviolet rays) for a long time was large, and the accumulation of residual charges was large.
Moreover, in the comparison with the comparative example which does not contain a specific amine compound and the example containing a specific amine compound with the same polyimide precursor or polyimide, in the Example containing a specific amine compound, it is light (ultraviolet rays) for a long time. Even after the exposure, the decrease in the voltage holding ratio was small and the relaxation of the residual charge was small.
Specifically, as shown in Table 36, Table 37, Table 39, and Table 40 in a normal cell, comparison between Example 1 and Comparative Example 1, comparison between Example 2 and Comparative Example 2, and implementation This is a comparison between Example 5 and Comparative Example 3. Further, as shown in Table 38 and Table 41 in the PSA cell, it is a comparison between Example 1 and Comparative Example 1, and a comparison between Example 2 and Comparative Example 2.

In addition to the initial characteristics, the liquid crystal alignment treatment agent of the present invention suppresses a decrease in the voltage holding ratio even when exposed to light irradiation for a long time, and further, the liquid crystal alignment film has a fast relaxation of charges accumulated by a DC voltage. The liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent reliability and is suitable for a large-screen, high-definition liquid crystal television and the like. It is useful as a TN element, an STN element, a TFT liquid crystal element, particularly a vertical alignment type liquid crystal display element.
Furthermore, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is useful also in the production of a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a liquid crystal display element.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2012-021830 filed on February 3, 2012 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (22)

The liquid crystal aligning agent characterized by containing the following component (A) and component (B).
Component (A): It has a nitrogen-containing aromatic heterocyclic ring and a hydroxyl group or a C1-C3 alkoxyl group in the molecule, and the hydroxyl group or the C1-C3 alkoxyl group is a divalent aliphatic. A compound bonded to a hydrocarbon group or a non-aromatic cyclic hydrocarbon group.
Component (B): At least one polymer selected from the group consisting of polyimide precursors and polyimides obtained by imidizing polyimide precursors. The liquid-crystal aligning agent of Claim 1 whose compound of the said component (A) is a compound shown by following formula [1].

(In the formula [1], X ₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, X ₂ is a nitrogen-containing aromatic heterocyclic ring, and R ₁ is hydrogen. It is an atom or an alkyl group having 1 to 3 carbon atoms.) The liquid-crystal aligning agent of Claim 1 whose compound of the said component (A) is a compound shown by following formula [1a].

(In the formula [1a], X ₃ is a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a non-aromatic cyclic hydrocarbon group having 1 to 20 carbon atoms, X ₄ is a single bond, —O _{-, - NH -, - N} (CH 3) -, - CONH -, - NHCO -, - COO -, - OCO -, - CON (CH 3) -, - N (CH 3) CO- or -O ( CH ₂ ) _m — (m is an integer of 1 to 5), X ₅ is a nitrogen-containing aromatic heterocyclic ring, and R ₂ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) The liquid crystal aligning agent according to claim 3, wherein, in the formula [1a], X ₃ is a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 1 to 10 carbon atoms, or a cyclohexane ring. In the formula [1a], X ₄ is a single bond, —O—, —NH—, —CONH—, —NHCO—, —COO—, —OCO— or —O (CH ₂ ) _m — (m is 1 to 5). The liquid-crystal aligning agent of Claim 3 or 4 which is an integer of these. In formula [1a], X < ₅ > is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring, The liquid-crystal aligning agent as described in any one of Claims 3-5. In formula [1a], R < ₂ > is a hydrogen atom or a methyl group, The liquid-crystal aligning agent as described in any one of Claims 3-6.   The component (B) is at least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine component and a tetracarboxylic acid component and a polyimide obtained by dehydrating and ring-closing the polyamic acid. Item 8. The liquid crystal aligning agent according to any one of Items 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].

(Wherein [2], _{Y 1} is a single _{bond, - (CH 2) a -} (a is an integer of 1~15), - O -, - NH -, - N (CH 3) -, - CONH —, —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO— 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 10), —O—, —NH—, — _{N (CH 3) -, -} CONH -, - NHCO -, - CH 2 O -, - COO -, - OCO -, - CON (CH 3) - or -N _(CH 3) a CO- .Y ⁴ Represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, Arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms. Or Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has 1 to 3 carbon atoms. An alkyl group of 1 to 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, and n is 0 to 4 Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. ) The liquid-crystal aligning agent of Claim 9 whose diamine compound which has a side chain of Formula [2] is a diamine compound shown by following formula [2a].

(In Formula [2a], Y ₁ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —NH—, —N (CH ₃ ) —, —CONH. —, —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — or —N (CH ₃ ) CO— 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 10), —O—, —NH—, — _{N (CH 3) -, -} CONH -, - NHCO -, - CH 2 O -, - COO -, - OCO -, - CON (CH 3) - or -N _(CH 3) a CO- .Y ⁴ Represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton. Arbitrary hydrogen atoms on the cyclic group include 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, and a fluorine-containing alkoxyl group having 1 to 3 carbon atoms. Or Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has 1 to 3 carbon atoms. An alkyl group of 1 to 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, and n is 0 to 4 Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. m is 1 4 is an integer.)   The liquid crystal aligning agent according to claim 9 or 10, wherein the diamine compound having a side chain of the formula [2] or the diamine compound represented by the formula [2a] is 5 to 80 mol% in the diamine component. The liquid crystal aligning agent according to any one of claims 8 to 11, wherein the tetracarboxylic acid component is 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 10 carbon atoms.) The liquid crystal aligning agent according to claim 12, wherein Z ₁ has a structure represented by the following formulas [3a] to [3j].

(In formula [3a], Z _{2 to} Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In 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 the component (B) is a polyimide obtained by dehydrating and ring-closing polyamic acid.   The liquid-crystal aligning agent as described in any one of Claims 1-14 whose said component (A) is 0.1-20 mass parts with respect to 100 mass parts of the said component (B).   The liquid-crystal aligning agent as described in any one of Claims 1-15 containing a 5-60 mass% poor solvent with respect to the whole quantity (100 mass%) of a liquid-crystal aligning agent.   The liquid crystal aligning film obtained using the liquid-crystal aligning agent as described in any one of Claims 1-16.   A liquid crystal display device comprising 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 device comprising the liquid crystal alignment film according to claim 19.   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 device comprising the liquid crystal alignment film according to claim 21.