JP6083382B2 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

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

  Liquid crystal display elements used for liquid crystal televisions, liquid crystal displays, and the like are currently widely used as thin and lightweight display devices. As a liquid crystal alignment film for aligning liquid crystals, a so-called polyimide-based polyimide film is applied by applying a liquid crystal alignment treatment agent mainly composed of a polyimide precursor such as polyamic acid (also referred to as polyamic acid) or a solution of soluble polyimide to a glass substrate or the like, and baking it. The liquid crystal alignment film is mainly used.

  As liquid crystal display elements are further increased in size and definition, liquid crystal alignment films have excellent liquid crystal alignment properties and liquid crystal molecules with respect to the substrate surface due to demands such as reduction of contrast reduction and afterimage phenomenon. In addition to stable expression and control of orientation tilt angle (pretilt angle), high voltage holding ratio, suppression of afterimages generated by AC drive, low residual charge when DC voltage is applied, residual charge accumulated by DC voltage Characteristics such as fast relaxation are becoming increasingly important. Polyimide precursors and soluble polyimides such as polyamic acid, which are components of the liquid crystal alignment treatment agent, are generally synthesized by the reaction of a tetracarboxylic acid derivative such as tetracarboxylic dianhydride and a diamine component. The structures of the carboxylic acid derivative and the diamine component are variously selected in order to satisfy the various characteristics of the liquid crystal alignment film described above.

  For example, for the above-described pretilt angle characteristics of the liquid crystal, a method of using a liquid crystal alignment treatment agent made of a soluble polyimide produced by using a diamine having a side chain as a part of a raw material has been proposed. In this method, since the pretilt angle can be controlled according to the use ratio of the diamine having a side chain, it is relatively easy to obtain the target pretilt angle, which is useful as a means for increasing the pretilt angle (for example, Patent Documents). 1).

  However, a liquid crystal alignment film made of only such soluble polyimide is inferior in residual charge characteristics. Therefore, in order to achieve both the pretilt angle characteristic and the residual charge characteristic, a liquid crystal aligning agent in which the soluble polyimide is mixed with polyamic acid has been proposed (see Patent Document 2). Moreover, the liquid-crystal aligning agent containing two specific types of polyimide is also proposed (patent document 3).

JP-A-5-043688 JP-A-8-220541 International Publication No. 2008/062877 Pamphlet

  However, in the liquid crystal alignment treatment agents of these documents, the uniformity of the coating film is low when the liquid crystal alignment treatment agent is applied, that is, polymer aggregates are generated at the edge of the coating surface (both whitening and aggregation). Say).

  An object of the present invention is to solve the above-mentioned problems of the prior art, which can provide a liquid crystal alignment film that gives a high pretilt angle to the liquid crystal and has a small accumulated charge, and does not cause whitening / aggregation. An object of the present invention is to provide a liquid crystal alignment treatment agent, a liquid crystal alignment film and a liquid crystal display element excellent in coating film uniformity.

  As a result of diligent research, the present inventor has found that a liquid crystal aligning agent containing two types of specific polymers having side chains having a specific structure and defining the relative amount of the side chains and a crosslinkable compound having a specific structure. The inventors have found that the present invention is extremely effective for achieving the above object, and have completed the present invention.

That is, the present invention has the following gist.
1. The liquid crystal aligning agent characterized by containing the following specific polymer (A), specific polymer (B), and specific crosslinkable compound (C).
Specific polymer (A): At least one polymer selected from the group consisting of a polyimide precursor and a polyimide using a diamine compound having a side chain represented by the formula [1] as a part of the raw material.
Specific polymer (B): A diamine compound having a side chain represented by the formula [1] is used as a part of the raw material, and a diamine compound having a side chain represented by the formula [1] in all diamine components of the raw material. At least one heavy selected from the group consisting of a polyimide precursor and a polyimide having a proportion lower than the proportion of the diamine compound having a side chain represented by the formula [1] in the total diamine component of the raw material of the specific polymer (A). Coalescence.
Specific crosslinkable compound (C): crosslinkable compound having at least two substituents selected from the group consisting of epoxy group, isocyanate group, oxetane group and cyclocarbonate group, hydroxyl group, hydroxyalkyl group and carbon number A crosslinkable compound having at least two substituents selected from the group consisting of 1 to 6 alkoxyalkyl groups, or a crosslinkable compound having two or more polymerizable unsaturated bonds.

（式［１］中、Ｘ_１は単結合、−（ＣＨ_２）_ａ−（ａは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−または−ＯＣＯ−であり、Ｘ_２は単結合または−（ＣＨ_２）_ｂ−（ｂは１〜１５の整数である）であり、Ｘ_３は単結合、−（ＣＨ_２）_ｃ−（ｃは１〜１５の整数である）、−Ｏ−、−ＣＨ_２Ｏ−、−ＣＯＯ−または−ＯＣＯ−であり、Ｘ_４はベンゼン環、シクロへキサン環および複素環よりなる群から選ばれる２価の環状基、または、ステロイド骨格を有する炭素数１２〜２５の２価の有機基であり、前記環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、Ｘ_５はベンゼン環、シクロへキサン環および複素環よりなる群から選ばれる２価の環状基であり、これらの環状基上の任意の水素原子が、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシル基、炭素数１〜３のフッ素含有アルキル基、炭素数１〜３のフッ素含有アルコキシル基またはフッ素原子で置換されていてもよく、ｎは０〜４の整数であり、Ｘ_６は炭素数１〜１８の直鎖状若しくは分岐状アルキル基、炭素数１〜１８の直鎖状若しくは分岐状フッ素含有アルキル基、炭素数１〜１８の直鎖状若しくは分岐状アルコキシル基、または、炭素数１〜１８の直鎖状若しくは分岐状フッ素含有アルコキシル基であり、特定重合体（Ａ）の原料のジアミン化合物が有する式［１］で示される側鎖と、特定重合体（Ｂ）の原料のジアミン化合物が有する式［１］で示される側鎖は同じであっても異なっていても良い。）

(In the formula [1], X ₁ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. X ₂ is a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15), X ₃ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15) -O-, -CH ₂ O-, -COO- or -OCO-, and X ₄ is a divalent cyclic group selected from the group consisting of 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, and any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or a carbon number 1 to 3 fluorine-containing alkyl groups, 1 to 3 fluorine-containing alkoxyl groups or substituted with fluorine atoms Even if well, X ₅ is a divalent cyclic group selected from benzene ring, the group consisting of cyclohexane ring and heterocyclic cyclohexane, any hydrogen atoms on these cyclic groups, having 1 to 3 carbon atoms An alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, and n is 0 to 4 X ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 18 carbon atoms, or a linear or branched group having 1 to 18 carbon atoms. A side chain represented by the formula [1] of the diamine compound as a raw material of the specific polymer (A), which is a linear alkoxyl group or a linear or branched fluorine-containing alkoxyl group having 1 to 18 carbon atoms, and a specific Raw material of polymer (B) The side chain of the formula [1] with the diamine compound may be different and the same.)

2. When the ratio of the diamine compound having a side chain represented by the formula [1] in the total diamine component of the raw material of the specific polymer (A) is 1, the formula in the total diamine component of the raw material of the specific polymer (B) The liquid crystal aligning agent according to 1, wherein the ratio of the diamine compound having a side chain represented by [1] is 0.3 or more and less than 1.0.

3. A diamine compound having a side chain represented by the formula [1] which is a raw material of the specific polymer (A) and a diamine compound having a side chain represented by the formula [1] which are a raw material of the specific polymer (B), respectively. 3. The liquid crystal aligning agent according to 1 or 2, which is a diamine compound represented by the following formula [1a].

（式［１ａ］中、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４、Ｘ_５、Ｘ_６、ｎは、式［１］におけるＸ_１、Ｘ_２、Ｘ_３、Ｘ_４、Ｘ_５、Ｘ_６、ｎと同じであり、ｍは１〜４の整数であり、特定重合体(Ａ)の原料である式［１ａ］で示されるジアミン化合物と、特定重合体（Ｂ）の原料である式［１ａ］で示されるジアミン化合物は同じであっても異なっていても良い。）

(In Formula [1a], X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , and n are X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ in Formula [1]. , N, m is an integer of 1 to 4, and the diamine compound represented by the formula [1a] which is a raw material of the specific polymer (A) and the formula [B] which is a raw material of the specific polymer (B) The diamine compounds represented by 1a] may be the same or different.)

4). 4. At least one of the specific polymer (A) and the specific polymer (B) uses a diamine compound represented by the following formula [2] as a raw material diamine component, Liquid crystal alignment treatment agent.

（式［２］中、Ｙ_１は−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−または−Ｎ（ＣＨ_３）ＣＯ−であり、Ｙ_２は単結合、２価の炭素数１〜２０の脂肪族炭化水素基、非芳香族環式炭化水素基または芳香族炭化水素基であり、Ｙ_３は単結合、−Ｏ−、−ＮＨ−、−Ｎ（ＣＨ_３）−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮ（ＣＨ_３）−、−Ｎ（ＣＨ_３）ＣＯ−または−Ｏ（ＣＨ_２）_ｉ−（ｉは１〜５の整数である）であり、Ｙ_４は１価の窒素含有芳香族複素環であり、ｈは１〜４の整数である。）

(Wherein [2], _{Y 1} is _{-O -, - NH -, -} N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCO -, - CON (CH 3) — Or —N (CH ₃ ) CO—, Y ₂ is a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group. , Y ₃ represents a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ) —, —N ( CH ₃ ) CO— or —O (CH ₂ ) _i — (i is an integer of 1 to 5), Y ₄ is a monovalent nitrogen-containing aromatic heterocyclic ring, and h is an integer of 1 to 4. .)

5. 5. The specific polymer (A) and the specific polymer (B) each using a tetracarboxylic dianhydride represented by the following formula [3] as a part of a raw material, Liquid crystal alignment treatment agent.

（式［３］中、Ｚ_１は炭素数４〜６の非芳香族環状炭化水素基を含有する炭素数４〜１３の４価の有機基である。）

(Wherein [3], _{Z 1} is a tetravalent organic group having 4 to 13 carbon atoms which contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms.)

6). Z ₁ is a liquid crystal alignment treating agent according to 5, characterized in that the structure represented by the following formula [3a] ~ formula [3j].

（式［３ａ］中、Ｚ_２〜Ｚ_５は水素原子、メチル基、塩素原子またはベンゼン環であり、それぞれ、同じであっても異なってもよく、式［３ｇ］中、Ｚ_６およびＺ_７は水素原子またはメチル基であり、それぞれ、同じであっても異なってもよい。）

(In the formula [3a], Z _{2 to} Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [3g], Z ₆ and Z ₇ Are hydrogen atoms or methyl groups, which may be the same or different.

7). The specific crosslinkable compound (C) is selected from the group consisting of a crosslinkable compound having an oxetane group, a crosslinkable compound having a cyclocarbonate group, or a hydroxyl group, a hydroxyalkyl group, and an alkoxyalkyl group having 1 to 6 carbon atoms. The liquid crystal aligning agent according to any one of 1 to 6, which is a crosslinkable compound which is benzene or a phenolic compound having at least one substituent.

8). The liquid crystal aligning agent according to any one of 1 to 7, wherein the specific polymer (A) and the specific polymer (B) are polyamic acids.

9. The liquid crystal aligning agent according to any one of 1 to 7, wherein the specific polymer (A) and the specific polymer (B) are polyimides obtained by dehydrating and ring-closing polyamic acid.

10. Any one of 1 to 9, wherein the specific crosslinkable compound (C) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the specific polymer (A) and the specific polymer (B). A liquid crystal alignment treatment agent according to claim 1.

11. The liquid-crystal aligning agent in any one of 1-10 characterized by containing 11.5-60 mass% poor solvent.

12. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of 12.1 to 11.

13. 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 13. The liquid crystal alignment film according to 12, which is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage therebetween.

14. A liquid crystal display element comprising the liquid crystal alignment film according to item 12.12 or 13.

  By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film which gives a high pretilt angle to the liquid crystal and has a small accumulated charge when used as a liquid crystal display element. Furthermore, the liquid crystal aligning agent of this invention is suppressed in whitening and aggregation and is excellent in the coating film uniformity of the liquid crystal alignment film. Further, by using this liquid crystal alignment film, it is possible to provide a liquid crystal display element having a high pretilt angle and a small accumulated charge.

The present invention is described in detail below.
This invention is a liquid-crystal aligning agent containing a specific polymer (A), a specific polymer (B), and a specific crosslinkable compound (C). The liquid crystal alignment treatment agent is a coating liquid for forming a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction. Each component of the liquid crystal aligning agent of this invention is demonstrated below.

<Specific polymer (A) and specific polymer (B)>
A specific polymer (A) and a specific polymer (B) are polyimide precursors, such as a polyamic acid and a polyamic acid ester, and a polyimide. That is, the specific polymer (A) and the specific polymer (B) may be at least one selected from the group consisting of a polyimide precursor and a polyimide, respectively, and the combination is not particularly limited. For example, the specific polymer (A) may be a polyimide and the specific polymer (B) may be a polyimide precursor, or the specific polymer (A) and the specific polymer (B) may both be a polyimide precursor. Also, a combination in which both the specific polymer (A) and the specific polymer (B) are polyimides may be used. The polyimide precursor is obtained by polymerizing at least one tetracarboxylic acid component selected from tetracarboxylic acid and derivatives thereof and a diamine component. And the specific polymer (A) and specific polymer (B) used by this invention are synthesize | combined using the diamine compound which has the structure shown by said Formula [1] as a side chain as this diamine component which is a raw material. It is a polymer.

In the formula [1], as described above, X ₁ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or -OCO-. Among these, a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, or —COO— is preferable because they are easily synthesized. More preferably, a single _{bond, - (CH 2) a -} (a is an integer of 1 to _{10), - O -, - CH} 2 O- or -COO-.

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

In Formula [1], X ₃ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. . Among these, a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO— is preferable because they are easily synthesized. More preferably, they are a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 10), —O—, —CH ₂ O—, —COO— or —OCO—.

In the formula [1], X ₄ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton. . Arbitrary hydrogen atoms on these cyclic groups 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 atom having 1 to 3 carbon atoms. It may be substituted with a contained alkoxyl group or a fluorine atom. Among these, a divalent organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton is preferable.

In the formula [1], X ₅ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring. Arbitrary hydrogen atoms on these cyclic groups 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 atom having 1 to 3 carbon atoms. It may be substituted with a contained alkoxyl group or a fluorine atom.

  In formula [1], n is an integer of 0-4. Preferably, it is an integer of 0-2.

In the formula [1], X ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 18 carbon atoms, or a linear chain having 1 to 18 carbon atoms. Or it is a branched alkoxyl group or a C1-C18 linear or branched fluorine-containing alkoxyl group. Among them, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxyl group having 1 to 18 carbon atoms, Alternatively, a linear or branched fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, they are a C1-C12 linear or branched alkyl group or a C1-C12 linear or branched alkoxyl group. More preferably, they are a C1-C9 linear or branched alkyl group or a C1-C9 linear or branched alkoxyl group.

Preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and n in the formula [1] are as shown in Tables 1 to 42.

Examples of the diamine compound having a side chain represented by the above formula [1] include a diamine compound represented by the above formula [1a]. In the formula [1a], m is an integer of 1 to 4, preferably 1. Further, _X 1 in the formula _{[1a], X 2, X} 3, X 4, X 5, preferred groups of _{X 6} and _{n, X 1, X 2, X} 3 in the formula _{[1], X 4,} It is the same as X ₅ , X ₆ and n, and preferred combinations are as shown in Table 1 to Table 42, as in Formula [1].

Moreover, the bonding position of the _two amino groups (—NH ₂ ) in the formula [1a] is not limited. Specifically, with respect to the linking group (X ₁ ) of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring Position or 3, 5 positions. Among these, from the viewpoint of reactivity when synthesizing the polymer, the 2,4 position, the 2,5 position, or the 3,5 position is preferable. Considering the ease in synthesizing the diamine compound, the positions 2, 4 or 2, 5 are more preferable.

  More specifically, the formula [1a] is a structure represented by, for example, the following formulas [1-1] to [1-31].

（式［１−１］〜式［１−３］中、Ｒ_１は−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯＯＣＨ_２−または−ＣＨ_２ＯＣＯ−であり、Ｒ_２は炭素数１〜２２の直鎖状若しくは分岐状アルキル基、炭素数１〜２２の直鎖状若しくは分岐状アルコキシル基、炭素数１〜２２の直鎖状若しくは分岐状フッ素含有アルキル基、または、フッ素含有アルコキシル基である。）

(In Formula [1-1] to Formula [1-3], 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 fluorine Containing alkoxyl groups.)

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

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

（式［１−７］および式［１−８］中、Ｒ_５は−ＣＯＯ−、−ＯＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＨ_２−または−Ｏ−であり、Ｒ_６はフッ素基、シアノ基、トリフルオロメタン基、ニトロ基、アゾ基、ホルミル基、アセチル基、アセトキシ基または水酸基である。）

(In Formula [1-7] and Formula [1-8], R ₅ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, — CH ₂ — or —O—, and R ₆ represents 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［１−９］および式［１−１０］中、Ｒ_７は炭素数３〜１２の直鎖状また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 [1-9] and [1-10], 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.)

（式［１−１１］および式［１−１２］中、Ｒ_８は炭素数３〜１２の直鎖状また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 [1-11] and [1-12], 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［１−１３］中、Ａ_１６はフッ素原子で置換されていてもよい炭素数３〜２０の直鎖状または分岐状アルキル基であり、Ａ_１５は１，４−シクロへキシレン基または１，４−フェニレン基であり、Ａ_１４は酸素原子または−ＣＯＯ−＊（ただし、「＊」を付した結合手がＡ_１５と結合する）であり、Ａ_１３は酸素原子または−ＣＯＯ−＊（ただし、「＊」を付した結合手が（ＣＨ_２）ａ_２）と結合する）である。また、ａ_１は０または１の整数であり、ａ_２は２〜１０の整数であり、ａ_３は０または１の整数である。）

(In the formula [1-13], A ₁₆ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₁₅ is a 1,4-cyclohexylene group or A ₁₄ is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A ₁₅ ), and A ₁₃ is an oxygen atom or —COO— *. (However, the 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. )

  The diamine compound having a side chain represented by the above formula [1] used as a raw material for the specific polymer (A) has a side chain represented by the above formula [1] used as a raw material for the specific polymer (B). It may be the same as or different from the diamine compound. Furthermore, one type or a mixture of two or more types can be used according to desired characteristics such as liquid crystal alignment properties, voltage holding ratio, and accumulated charge when a liquid crystal alignment film is formed.

  The diamine compound having a side chain represented by the above formula [1] used as a raw material for the specific polymer (A) has three or more long-chain alkyl groups or ring structures (saturated or unsaturated cyclic hydrocarbon groups). It is preferable that it is a diamine compound having a more hydrophobic group in the side chain, specifically, the above formula [1-9], formula [1-10], formula [1-11], formula [1-12], Formula [1-22], Formula [1-23], Formula [1-24], Formula [1-25], Formula [1-26], Formula [1-27], Formula [1] 1-28], Formula [1-29], Formula [1-30], and Formula [1-31] are preferable. Among them, the above formula [1-9], formula [1-10], formula [1-11], formula [1-12], formula [1-22], formula [1-23], formula [1] −24], Formula [1-25], Formula [1-28], and Formula [1-29] are preferable. Particularly preferred are the above formula [1-9], formula [1-10], formula [1-11] and formula [1-12].

  In addition, the diamine compound represented by the above formula [1] used as a raw material for the specific polymer (B) is preferably a diamine having a highly hydrophilic side chain group such as two or less ring structures. Specifically, the above formula [1-1], formula [1-2], formula [1-3], formula [1-4], formula [1-5], formula [1-6], formula [1-6] 1-7] and formula [1-8] are preferable.

  In the present invention, the specific polymer (B) is such that the ratio of the diamine compound having a side chain represented by the formula [1] in the total diamine component of the raw material is the total of the raw material of the specific polymer (A). It needs to be less than the proportion of the diamine compound having a side chain represented by the formula [1] in the diamine component. In other words, the ratio of the diamine compound having the side chain represented by the above formula [1] to the total amount of the diamine component of the raw material of the specific polymer (B) is the above formula [the total amount of the diamine component of the raw material of the specific polymer (A) [ The ratio of the diamine compound having a side chain represented by 1] must be smaller.

  The ratio of the diamine compound having a side chain represented by the above formula [1] with respect to the total amount of the diamine component that is a raw material of the specific polymer (A) or the specific polymer (B) is greater than that of the specific polymer (A) as described above. Is not particularly limited except that the specific polymer (B) needs to be small. For example, in the specific polymer (A), the raw material diamine component may be only the diamine compound represented by the above formula [1]. . Of course, the diamine component which is a raw material of the specific polymer (A) or the specific polymer (B) is a diamine compound other than the diamine compound having a side chain represented by the above formula [1], as long as the effects of the present invention are not impaired. Although a diamine compound may be included, a liquid crystal alignment film capable of giving a high pretilt angle to the liquid crystal is obtained as the proportion of the diamine compound having a side chain represented by the formula [1] increases. For the purpose of enhancing the pretilt angle characteristics, the specific polymer (A) and the specific polymer (B) each have 5 to 80 mol% of the total amount of the diamine component as a raw material having a side chain represented by the above formula [1]. A diamine compound is preferred. Especially, from a viewpoint of the applicability | paintability of a liquid-crystal aligning agent, and the electrical property as a liquid-crystal aligning film, 5-60 mol% of diamine component whole quantity is a diamine compound which has a side chain shown by the said Formula [1]. preferable. However, the amount of the diamine compound having a side chain represented by the formula [1] in the total diamine component of the raw material of the specific polymer (A) and the formula [1 in the total diamine component of the raw material of the specific polymer (B) ] Is too large, that is, the amount of the side chain having the structure represented by the formula [1] in the specific polymer (A) and the specific polymer (B). If the difference from the amount of the side chain having the structure represented by the formula [1] is too large, the specific polymer (A) or the specific polymer (B) may be aggregated. It is preferable that the difference in the amount of side chains is as small as possible while satisfying the conditions. Specifically, when the ratio of the diamine compound having the side chain represented by the formula [1] in the total diamine component of the specific polymer (A) is 1, preferably the raw material of the specific polymer (B) The ratio of the diamine compound having a side chain represented by the formula [1] in all diamine components is 0.3 or more and less than 1.0, and more preferably 0.6 or more and less than 1.0. In the present specification, unless otherwise specified, the “ratio” is based on the number of moles.

As other diamine compounds other than the diamine compound having a side chain represented by the above formula [1] that can be used as a diamine component of the raw material of the specific polymer (A) or the specific polymer (B), a heterocyclic ring-containing diamine Compounds. As the heterocyclic-containing diamine compound, it is preferable to use a diamine compound represented by the above formula [2]. In the above formula [2],-(-Y ₁ -Y ₂ -Y ₃ -Y ₄ ) _h indicates that there are h substituents -Y ₁ -Y ₂ -Y ₃ -Y ₄ , and each is the same But it can be different.

In Formula [2], Y ₁ represents —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —OCO—, —CON (CH ₃ ) —. Or a divalent organic group selected from —N (CH ₃ ) CO—. Among them, -O -, - NH -, - CONH -, - NHCO -, - CON (CH 3) -, - CH 2 O- or -OCO- are preferred because it is easy to synthesize the diamine compound. Particularly preferred is —O—, —NH—, —CONH—, —NHCO—, —CON (CH ₃ ) — or —CH ₂ O—.

Wherein [2], Y ₂ is a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group.

  The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond. A linear or branched alkyl group having 1 to 10 carbon atoms or an alkyl group having an unsaturated bond having 1 to 10 carbon atoms is preferable.

  Specific examples of the non-aromatic 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. Decane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring , Norbornene ring, adamantane ring and the like.

  Specific examples of the aromatic hydrocarbon group include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, and phenalene ring.

Preferred Y ₂ in the formula [2] is a single bond, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkyl group having an unsaturated bond having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclo A pentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring, more preferably a single bond or a straight chain having 1 to 10 carbon atoms Or a branched alkyl group, an alkyl group having an unsaturated bond having 1 to 10 carbon atoms, a cyclohexane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a fluorene ring or an anthracene ring, more preferably a single bond, A linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexane ring, A benzene ring or a naphthalene ring, particularly preferably a single bond, a linear or branched alkyl group having 1 to 5 carbon atoms, or a benzene ring.

In Formula [2], Y ₃ represents a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ). -, - a (i is an integer of 1 to 5), preferably a single _{bond, -O - - N (CH 3} ) CO- or _{-O (CH 2) i, -} NH -, - CONH- , —NHCO—, —COO—, —OCO—, or —O (CH ₂ ) _i — (i is an integer of 1 to 5), more preferably a single bond, —O—, —NH—, —CONH—, —NHCO—, —COO—, —OCO— or —O (CH ₂ ) _i — (i is an integer of 1 to 5), and more preferably a single bond, —O—, — CONH -, - NHCO -, - COO -, - OCO- or -O _(CH 2) _i - a (i is an integer of 1 to 5).

In formula [2], Y ₄ is a monovalent nitrogen-containing aromatic heterocycle, and for example, at least 1 selected from the following formula [2-A], formula [2-B] or formula [2-C]: It is an aromatic heterocycle containing individual structures.

（式［２−Ｃ］中、Ａ_１７は炭素数１〜５の直鎖状または分岐状アルキル基である。）

(In the formula [2-C], A ₁₇ is a linear or 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 [2], Y ₄ 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 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 or a benzimidazole ring, and particularly preferred are a pyrrole ring, An imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring;

Y ₃ is preferably bonded to a substituent that is not adjacent to Formula [2-A], Formula [2-B], and Formula [2-C] contained in Y ₄ .

Preferred combinations of Y ₁ , Y ₂ , Y ₃ and Y _{4 in} the formula [2] are as shown in Table 43 to Table 48.

  Among them, [1-7], [1-9], [1-12], [1-14], [1-17], [1-19], [1-19] in [Table 43 to Table 48] above. 22], [1-24], [1-27], [1-29], [1-52], [1-54], [1-124], [1-126], [1-148] , [1-150], [1-172] and [1-173] are preferable.

  In the formula [2], h is an integer of 1 to 4, preferably an integer of 1 to 3 from the viewpoint of reactivity with tetracarboxylic dianhydride.

  When both the specific polymer (A) and the specific polymer (B) use a heterocyclic ring-containing diamine compound as a raw material, the heterocyclic ring-containing diamine compound used as the raw material of the specific polymer (A) is a specific polymer (B ) May be the same as or different from the heterocyclic-containing diamine compound used as a starting material. Furthermore, one type or a mixture of two or more types can be used according to desired properties such as liquid crystal alignment properties, voltage holding ratio, and accumulated charge when a liquid crystal alignment film is formed.

  As the proportion of the heterocyclic ring-containing diamine compound increases, a liquid crystal alignment film with improved relaxation characteristics of charges accumulated by a DC voltage, that is, a liquid crystal alignment film having a small accumulated charge can be obtained. For the purpose of enhancing the relaxation property of the accumulated charge, the heterocycle-containing diamine compound is preferably 0.01 to 99 mol with respect to 1 mol of the diamine compound having a side chain represented by the formula [1]. . More preferably, it is 0.1-50 mol, More preferably, it is 0.2-20 mol, Most preferably, it is 0.2-10 mol.

  Other diamine compounds other than the diamine compound having a side chain represented by the above formula [1] include p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, and 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′-dihydro Si-4,4′-diaminobiphenyl, 3,3′-dicarboxy-4,4′-diaminobiphenyl, 3,3′-difluoro-4,4′-biphenyl, 3,3′-trifluoromethyl-4 , 4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3 '-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'- Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodi Phenyl ether, 4,4′-sulfonyldianiline, 3,3′-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, Dimethyl-bis (3-aminophenyl) silane, 4,4′-thiodianiline, 3,3′-thiodianiline, 4,4′-diaminodiphenylamine, 3,3′-diaminodiphenylamine, 3,4′-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 (4amino) Enyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 4,4 '-[1,4-phenylenebis (methylene)] dianiline, 4,4'-[1,3-phenylenebis (methylene)] dianiline, 3,4 ' -[1,4-phenylenebis (methylene)] dianiline, 3,4 '-[1,3-phenylenebis (methylene)] dianiline, 3,3'-[1,4-phenylenebis (methylene)] dia Phosphorus, 3,3 ′-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone ], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4 -Phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-amino Phenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-aminobenzamide), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1,4- Phenylene) bis (3-aminobenzamide), N, N ′-(1,3-phenylene) bis (3-aminobenzamide), N, N′-bis (4-aminophenyl) terephthalamide, N, N′— Bis (3-aminophenyl) terephthalamide, N, N′-bis (4-aminophenyl) isophthalamide, N, N′-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) ) Anthracene, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- ( -Aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3 -Amino-4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino) -4-methylphenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4 -Bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-amino Phenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3 -Aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-amino Phenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane, 4- (aminomethyl) aniline, 3- (amino) Aromatic diamines such as nomethyl) aniline, 4- (2-aminoethyl) aniline or 3- (2-aminoethylaniline), bis (4-aminocyclohexyl) methane or bis (4-amino-3-methylcyclohexyl) methane Alicyclic diamine such as 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, Examples include aliphatic diamines such as 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, or 1,12-diaminododecane.

  Moreover, the diamine compound which has an alkyl group or a fluorine-containing alkyl group in a side chain can be used as other diamine compounds other than the diamine compound which has a side chain shown by the said Formula [1]. Specifically, diamines represented by the following formulas [DA-1] to [DA-12] can be exemplified.

（式［ＤＡ−１］〜式［ＤＡ−５］中、Ａ_１は炭素数１〜２２の直鎖状若しくは分岐状アルキル基または炭素数１〜２２の直鎖状若しくは分岐状フッ素含有アルキル基である。）

(In Formula [DA-1] to Formula [DA-5], 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［ＤＡ−６］〜式［ＤＡ−１１］中、Ａ_２は−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＨ_２−、−Ｏ−、−ＣＯ−または−ＮＨ−を示し、Ａ_３は炭素数１〜２２の直鎖状若しくは分岐状アルキル基または炭素数１〜２２の直鎖状若しくは分岐状フッ素含有アルキル基を示す。）

(In Formula [DA-6] to Formula [DA-11], A ₂ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO— or —NH. And 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［ＤＡ−１２］中、ｐは１〜１０の整数である。）

(In Formula [DA-12], p is an integer of 1 to 10.)

  Moreover, the diamine compound shown by the following formula [DA-13]-a formula [DA-20] can also be used as other diamine compounds other than the diamine compound which has a side chain shown by the said Formula [1].

（式［ＤＡ−１７］中、ｋは０〜３の整数であり、式［ＤＡ−２０］中、ｌは１〜５の整数である。）

(In formula [DA-17], k is an integer of 0-3, and in formula [DA-20], l is an integer of 1-5.)

  Furthermore, as other diamine compounds other than the diamine compound having a side chain represented by the above formula [1], a diamine having a carboxyl group in the molecule represented by the following formula [DA-21] to formula [DA-25] Compounds can also be used.

（式［ＤＡ−２１］中、ｍ_１は１〜４の整数であり、式［ＤＡ−２２］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）−または−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ_２およびｍ_３はそれぞれ０〜４の整数であり、かつｍ_２＋ｍ_３は１〜４の整数であり、式［ＤＡ−２３］中、ｍ_４およびｍ_５はそれぞれ１〜５の整数であり、式［ＤＡ−２４］中、Ａ_５は炭素数１〜５の直鎖状または分岐状アルキル基であり、ｍ_６は、１〜５の整数であり、式［ＤＡ−２５］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）−または−Ｎ（ＣＨ_３）ＣＯ−であり、ｍ_７は、１〜４の整数である。）

(In Formula [DA-21], m ₁ is an integer of ₁ to 4, and in Formula [DA-22], 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, and in formula [DA-23], m ₄ and m ₅ are each an integer of 1 to 5, and in formula [DA-24], A ₅ has 1 carbon atom. A linear or branched alkyl group of ˜5, m ₆ is an integer of 1 to 5, and in the formula [DA-25], 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 1 to 4 (It is an integer.)

  Furthermore, as other diamine compounds other than the diamine compound having a side chain represented by the above formula [1], diamine compounds represented by the following formulas [DA-26] and [DA-27] 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.

  In the present invention, the method for synthesizing the specific polymer (A) or the specific polymer (B) is particularly limited except that the diamine compound having a side chain represented by the above formula [1] is part of the raw material. Not. 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. In order to obtain the polyamic acid alkyl ester, a method of converting the carboxyl group of the polyamic acid into an ester is used. Furthermore, in order to obtain a polyimide, a method may be used in which the polyamic acid or the polyamic acid alkyl ester is imidized to form a polyimide.

  As the tetracarboxylic acid component which is a raw material for obtaining the specific polymer (A) or the specific polymer (B) of the present invention, it is preferable to use a tetracarboxylic dianhydride represented by the above formula [3].

In the formula [3], particularly preferred structure of Z ₁ is the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] or the formula because of the polymerization reactivity and the ease of synthesis. [3 g]. Among these, the formula [3a], the formula [3e], the formula [3f], or the formula [3g] is preferable.

  Further, the ratio of the tetracarboxylic dianhydride represented by the above formula [3] with respect to the total amount of the tetracarboxylic acid component which is the raw material of the specific polymer (A) or the specific polymer (B) is not particularly limited. The tetracarboxylic acid component represented by formula (3) may be only the tetracarboxylic dianhydride represented by the above formula [3]. Of course, the tetracarboxylic acid component that is the raw material of the specific polymer (A) or the specific polymer (B) is not a tetracarboxylic dianhydride represented by the above formula [3] unless the effects of the present invention are impaired. These tetracarboxylic acids and tetracarboxylic acid derivatives may be included. In that case, it is preferable that 1 mol% or more of the total amount of the tetracarboxylic acid component is the tetracarboxylic dianhydride represented by the above formula [3], more preferably 5 mol% or more, and still more preferably 10 mol%. That's it.

  Other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the above formula [3] include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6 -Naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic 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, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4- Dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic Acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

  The tetracarboxylic dianhydride represented by the above formula [3] and other tetracarboxylic acids and tetracarboxylic acid derivatives have desired properties such as liquid crystal alignment, voltage holding ratio, and accumulated charge when used as a liquid crystal alignment film. Depending on the situation, one kind or a mixture of two or more kinds may be used.

  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 include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ- Butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, Ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol Nobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol Methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane , N-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, pyruvate Ethyl, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-metho Shipuropion acid, 3-methoxy propionic acid propyl, 3-methoxy propionic acid butyl, and the like diglyme or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use the said solvent in the range which the produced | generated polyimide precursor does not precipitate. Moreover, since the water | moisture content in an organic solvent inhibits a polymerization reaction, and also causes the produced polyimide precursor to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent.

  When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is dispersed or dissolved in the organic solvent as it is. And a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent, a method of alternately adding a tetracarboxylic acid component and a diamine component, and the like. 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. It is good also as a specific polymer (A) and a specific polymer (B) by carrying out a mixing reaction. Although the polymerization temperature in that case can select the arbitrary temperature of -20 degreeC-150 degreeC, Preferably it is the range of -5 degreeC-100 degreeC. The reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight specific polymer (A) or specific polymer (B), and if the concentration is too high, The viscosity becomes too high and uniform stirring becomes difficult. Therefore, the concentration of the total amount of the diamine component and the tetracarboxylic acid component is preferably 1 to 50% by mass, more preferably 5 to 30% by mass in the reaction solution. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

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

  The specific polymer (A) and the specific polymer (B) polymerized in this way are, for example, a polyimide precursor that is a polymer having a repeating unit represented by the following formula [a].

（式［ａ］中、Ｒ_１１は、４価の有機基であり、Ｒ_１２は、原料のジアミン成分に由来する２価の有機基であり、Ａ_１１およびＡ_１２は、水素原子または炭素数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、ｊは正の整数を示す。）

(In the formula [a], R ₁₁ is a tetravalent organic group, R ₁₂ is a divalent organic group derived from the diamine component of the raw material, and A ₁₁ and A ₁₂ are a hydrogen atom or a carbon number. 1 to 8 alkyl groups, which may be the same or different, and j represents a positive integer.)

In the above formula [a], each of R ₁₁ and R ₁₂ may be one type and a polymer having the same repeating unit, or R ₁₁ and R ₁₂ may be a plurality of types and a polymer having a repeating unit having a different structure. But you can.

In the above formula [a], R ₁₁ is a group derived from a tetracarboxylic acid component represented by the following formula [c] as a raw material, and R ₁₂ is a diamine component represented by the following formula [b] as a raw material. Is a group derived from For example, if R ₁₂ is a diamine-derived group having a side chain represented by the above formula [1], the main chain of the polyimide precursor, that is, the polyamic acid skeleton, is directly or via an appropriate bonding group. A polymer in which the structure represented by [1] is bonded as a side chain.

（式［ｂ］および式［ｃ］中、Ｒ_１１およびＲ_１２は、式［ａ］で定義したものと同じである。）

(In formula [b] and formula [c], R ₁₁ and R ₁₂ are the same as defined in formula [a].)

  The following formula [d] is used because it can be obtained relatively easily by using a diamine component represented by the above formula [b] and a tetracarboxylic dianhydride component represented by the above formula [c] as raw materials. ] The polyamic acid which consists of structural formula of the repeating unit shown by this, or the polyimide which imidated this polyamic acid is preferable.

（式［ｄ］中、Ｒ_１１、Ｒ_１２およびｊは、式［ａ］で定義したものと同じである。）

(In the formula [d], R ₁₁ , R ₁₂ and j are the same as those defined in the formula [a].)

  The specific polymer (A) or the specific polymer (B) may be a polyimide obtained by dehydrating and ring-closing the polyimide precursor. Such a polyimide is useful as a polymer for obtaining a liquid crystal alignment film.

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

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

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

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

  The dehydration ring closure rate (imidation rate) of the amic acid group of the polyimide used as the specific polymer (A) does not necessarily need to be 100%, and can be arbitrarily selected in the range of 0% to 100% according to the application and purpose. However, from the viewpoint of better vertical alignment, 20% to 80% is preferable, and 40% to 60% is more preferable.

  Similarly, the imidation ratio of the polyimide used as the specific polymer (B) is not necessarily 100%, and can be arbitrarily selected within the range of 0% to 100%. From the viewpoint of further suppressing precipitation, the imidization rate of the specific polymer (B) is preferably equal to or greater than the imidization rate of the specific polymer (A) when the specific polymer (A) also uses polyimide. The amount of the diamine compound having a side chain represented by the formula [1] in the total diamine component of the raw material of the specific polymer (A) and the formula [1] in the total diamine component of the raw material of the specific polymer (B) The larger the difference in the amount of the diamine compound having a side chain represented by formula (1), that is, the amount of the side chain represented by the formula [1] in the specific polymer (A) and the formula [B] 1] The greater the difference from the side chain amount Body (A) and it is preferable that a large difference in the imidation rate of the specific polymer (B).

  Although the blending ratio of the specific polymer (A) and the specific polymer (B) in the liquid crystal aligning agent of the present invention is not particularly limited, for example, the specific polymer (A) with respect to 100 parts by mass of the specific polymer (A) It is preferable to contain 40 to 400 parts by mass of B).

  In addition, the molecular weight of the specific polymer (A) or the specific polymer (B) is determined by considering the strength of the polymer film obtained therefrom, workability when forming the polymer film, and uniformity of the polymer film. The weight average molecular weight measured by the (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Specific crosslinkable compound (C)>
The specific crosslinkable compound (C) contained in the liquid crystal aligning agent of the present invention has a crosslinkability having at least two substituents selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group. A crosslinkable compound having two or more substituents selected from the group consisting of a compound, a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 6 carbon atoms, or two having a polymerizable unsaturated bond This is the crosslinkable compound.

  Examples of the two or more crosslinkable compounds 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-xylene. Diamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxy) Propoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobi Phenyl, triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3 -Epoxypropoxy) phenyl) ethyl) phenyl) propane or 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2 , 3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like. Of these, bisphenolacetone glycidyl ether, tetraglycidylaminodiphenylene, and tetraglycidyl-1,3-bis (aminoethyl) cyclohexane are preferable.

  Examples of the crosslinkable compound having two or more oxetane groups include a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

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

（式［４−１］中ｎ１は１〜３の整数であり、式［４−７］中ｎ２は１〜３の整数であり、式［４−８］中ｎ３は１〜３の整数であり、式［４−９］中ｎ４は１〜１００の整数であり、式［４−１１］中ｎ５は１〜１０の整数である。）

(In formula [4-1], n1 is an integer of 1 to 3, in formula [4-7], n2 is an integer of 1 to 3, and in formula [4-8], n3 is an integer of 1 to 3. Yes, n4 in the formula [4-9] is an integer of 1 to 100, and n5 in the formula [4-11] is an integer of 1 to 10.)

  Among these, the above formula [4-2], formula [4-4], formula [4-10], and formula [4-11] are preferable.

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

  Specific examples include crosslinkable compounds represented by the following formulas [5-1] to [5-37].

（式［５−２４］中、ｎ６は１〜５の整数であり、式［５−２５］中、ｎ７は１〜５の整数であり、式［５−３６］中、ｎ８は１〜１００の整数であり、式［５−３７］中、ｎ９は１〜１０の整数である。）

(In Formula [5-24], n6 is an integer of 1-5, In Formula [5-25], n7 is an integer of 1-5, and in Formula [5-36], n8 is 1-100. (In formula [5-37], n9 is an integer of 1 to 10.)

  Furthermore, examples of the specific crosslinkable compound (C) include polysiloxanes having at least one structure represented by the following formulas [5-38] to [5-40].

（式［５−３８］〜式［５−４０］中、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４およびＲ_２５は、それぞれ独立して、式［５］で示される構造、水素原子、水酸基、炭素数１〜１０のアルキル基、アルコキシル基、脂肪族環または芳香族環であり、少なくとも１つは式［５］で示される構造である。）

(In formula [5-38] to formula [5-40], R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are each independently a structure represented by formula [5], a hydrogen atom, 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].

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

（式［５−４１］中、Ｒ_２６は上記式［５］で示されるシクロカーボネート基であり、式［５−４２］中、ｎ１０は１〜１０の整数である。）

(In the formula [5-41], R ₂₆ is a cyclocarbonate group represented by the above formula [5]. In the formula [5-42], n10 is an integer of 1 to 10.)

  Among them, as the crosslinkable compound having two or more cyclocarbonate groups, the above formula [5-1], formula [5-2], formula [5-3], formula [5-5], formula [5- 12], [5-20], [5-41] and [5-42] are preferable.

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

  Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring. Eight-substituted MW-30 (from 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 etoxy Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 Cyanamide). Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174. Of these, Cymel 303 and Cymel 1141 are preferable.

  Further, as a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group, benzene having a hydroxyl group, a hydroxyalkyl group or an alkoxyl group, a hydroxyl group, a hydroxyalkyl group Examples of the benzene having a hydroxyl group, a hydroxyalkyl group or an alkoxyl group, or a phenolic compound including a phenolic compound having a group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1, Examples include 2,4-tris (isopropoxymethyl) benzene, 1,4-bis (sec-butoxymethyl) benzene, and 2,6-dihydroxymethyl-p-tert-butylphenol.

  More specifically, it is a crosslinkable compound represented by the following formula [6-1] to formula [6-48].

  Among them, the above formula [6-14], formula [6-15], formula [6-17], formula [6-20], formula [6-21], formula [6-25], formula [6- 26] is preferred.

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

  Moreover, the compound shown by following formula [7] can also be used as a crosslinkable compound which has a polymerizable unsaturated bond.

（式［７］中、Ｅ_１はシクロヘキサン環、ビシクロヘキサン環、ベンゼン環、ビフェニル環、ターフェニル環、ナフタレン環、フルオレン環、アントラセン環またはフェナントレン環から選ばれる基であり、Ｅ_２は下記の式［７ａ］または式［７ｂ］から選ばれる基であり、ｎ１１は１〜４の整数である。）

(In formula [7], E ₁ is a group selected from a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring, and E ₂ is It is a group selected from the formula [7a] or the formula [7b], and n11 is an integer of 1 to 4.)

  Said specific crosslinking | crosslinked compound (C) 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 rate, and an accumulation charge. .

  By using the liquid crystal aligning agent of the present invention containing such a specific polymer (A), a specific polymer (B) and a specific crosslinkable compound (C), a high pretilt angle is given to the liquid crystal and a liquid crystal display is provided. A liquid crystal alignment film having a small accumulated charge when used as an element can be obtained. Furthermore, the crystal orientation treatment agent of the present invention does not generate polymer aggregates at the end of the coating film surface, does not cause so-called whitening or aggregation, and is excellent in coating film uniformity.

  By configuring the present invention, specifically, a liquid crystal aligning agent containing a specific polymer (A), a specific polymer (B) and a specific crosslinkable compound (C), such a pretilt angle characteristic, The reason why the accumulated charge characteristics and the uniformity of the coating film can be obtained is not necessarily clear, but it is generally considered as follows.

  The ratio of the diamine compound having a side chain represented by the above formula [1] in the diamine component of the raw material of the specific polymer (B) contained in the liquid crystal aligning agent of the present invention is the raw material of the specific polymer (A). The ratio of the diamine compound having a side chain represented by the above formula [1] in the diamine component is lower. Therefore, in the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention, the ratio of the side chain that increases the resistance of the liquid crystal alignment film (that is, the density of the side chain) is when the specific polymer (A) is used alone. Therefore, it is considered that it is difficult to accumulate charges accumulated by the DC voltage.

  Here, in order to reduce the accumulated charge, it is conceivable to simply reduce the amount of the diamine compound having a side chain, but if the amount of the diamine compound having a side chain is reduced, there is a problem that the pretilt angle characteristic is deteriorated. Arise. In the present invention, the specific polymer (B) in which the proportion of the diamine compound having a side chain represented by the above formula [1] as a raw material is relatively small is used as the substrate of the liquid crystal alignment film. The specific polymer (A) located on the side and having a relatively large proportion of the diamine compound having the side chain represented by the above formula [1] as the raw material is located on the surface of the liquid crystal alignment film (that is, the surface in contact with the liquid crystal) Thus, it is presumed that a good pretilt angle could be expressed in the liquid crystal mainly by the specific polymer (A). And the specific polymer (B) in which the ratio of the diamine compound having the side chain represented by the above formula [1] of the raw material is relatively small is located on the substrate side of the liquid crystal alignment film (that is, the side not in contact with the liquid crystal). Therefore, the accumulated charge is considered to be low.

  In addition, the specific crosslinkable compound (C) contained in the liquid crystal aligning agent of the present invention contains the carboxyl group, carboxyl ester group and amino group in the specific polymer (A) and the specific polymer (B), heat and ultraviolet rays. The side chain structure represented by the above formula [1] is further enhanced by the action of the specific crosslinkable compound (C) by cross-linking the main chains of the specific polymer (A) and the specific polymer (B). By stabilizing, the liquid crystal alignment film is considered to exhibit a high and stable pretilt angle regardless of the type of liquid crystal.

  And since both the side chain of a specific polymer (A) and the side chain of a specific polymer (B) have a structure represented by Formula [1], a specific polymer (A) and a specific polymer ( It is considered that aggregation and precipitation due to the difference in the characteristics of B) can be suppressed and the coating film uniformity is excellent.

  In addition, both the specific polymer (A) and the specific polymer (B) have the effect that the pretilt angle characteristic, the accumulated charge characteristic, and the coating film uniformity of the liquid crystal alignment film are all good. The raw material is a diamine compound having a side chain represented by the above formula [1] having a structure of the above formula, that is, both the specific polymer (A) and the specific polymer (B) have a specific structure. This is an effect exhibited only when the structure represented by 1] is present as a side chain and the specific crosslinkable compound (C) is present.

  Content of the specific crosslinking | crosslinked compound (C) in the liquid-crystal aligning agent of this invention is 0.1-150 mass parts with respect to 100 mass parts which match | combined the specific polymer (A) and the specific polymer (B). Preferably, the amount is 0.1 to 100 parts by mass, particularly 1 to 100 parts by mass, in order that the crosslinking reaction proceeds and expresses desired properties such as a pretilt angle and does not lower the orientation of the liquid crystal. -50 mass parts.

<Other components of liquid crystal alignment treatment agent>
In the liquid crystal aligning agent of the present invention, the polymer component may be only the specific polymer (A) and the specific polymer (B), and the specific polymer (A) and the specific polymer (B) Other polymers may be mixed. In that case, with respect to the specific polymer (A) and the specific polymer (B), the content of other polymers is 0.5 to 15% by mass, preferably 1.0 to 10% by mass. . Other polymers other than that include a diamine component not containing a diamine compound having a side chain represented by the above formula [1] and a tetracarboxylic acid not containing a tetracarboxylic dianhydride represented by the above formula [3]. A polyimide precursor or polyimide obtained from a dianhydride component can be mentioned. Furthermore, a polyimide precursor and a polymer other than polyimide, specifically, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or the like can be given.

  Moreover, the liquid-crystal aligning agent of this invention may contain the organic solvent.

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

  In the liquid crystal alignment treatment agent of the present invention, the following formulas [M1] to [M155] are used as compounds that promote charge transfer in the liquid crystal alignment film and promote charge loss of a liquid crystal cell using the liquid crystal alignment film. It is preferable to add the nitrogen-containing heterocyclic amine compound shown by these. The amine compound may be added directly to a solution in which the specific polymer (A) and the specific polymer (B) are dissolved in the organic solvent or the like, but the concentration is 0.1 to 10% by mass with an appropriate solvent. Preferably, it is added after making the solution 1.0 to 7.0% by mass. The solvent for the nitrogen-containing heterocyclic amine compound is not particularly limited as long as it is an organic solvent that dissolves the specific polymer (A) and the specific polymer (B) described above.

  Unless the effect of this invention is impaired, the liquid-crystal aligning agent of this invention is an organic solvent (it is also called a poor solvent) which improves the uniformity of the film thickness of a polymer film at the time of apply | coating a liquid-crystal aligning agent, and surface smoothness. ) Or a compound may be contained. Furthermore, you may contain the compound etc. which improve the adhesiveness of a liquid crystal aligning film and a board | substrate.

  Specific examples of poor solvents that improve film thickness uniformity and surface smoothness include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol Tolu, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoacetate , Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl Ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclo Hexene, propyl ether, dihexyl ether, n-to Sun, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxypropionic acid Methyl, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2- Acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester or lactic acid Examples thereof include organic solvents having a low surface tension such as isoamyl ester.

  These poor solvents may be used alone or in combination. When using the above poor solvent, it is preferable that it is 5-80 mass% of the whole organic solvent contained in a liquid-crystal aligning agent, More preferably, it is 20-60 mass%.

  Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass) and the like. The use 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 the polymer component component contained in the liquid crystal aligning agent. It is.

  Examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound, such as 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-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-to Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether , Polyethylene glycol jig Sidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneo Pentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N , N-diglycidylaminomethyl) cyclohexane or N, N, N ′, N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane.

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

  In the liquid crystal alignment treatment agent of the present invention, in addition to the above poor solvent and compound, as long as the effects of the present invention are not impaired, the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film are changed. A dielectric material or conductive material may be added.

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

  The method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, an inkjet method, or the like is generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose. Since the liquid-crystal aligning agent of this invention is excellent in coating-film uniformity, whitening and aggregation are suppressed and the coating film formed by apply | coating this becomes a uniform film | membrane.

  After the liquid crystal aligning 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 heat circulation type oven or an IR (infrared) type oven. A combined coating (liquid crystal alignment film) can be formed. 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 polymer film after baking is treated by rubbing or irradiation with polarized ultraviolet rays.

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

  As a liquid crystal cell manufacturing method, a pair of substrates on which the 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 inner side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or a method of sealing the substrate by bonding the substrate after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed.

  As the liquid crystal, a positive liquid crystal having positive dielectric anisotropy or a negative liquid crystal having negative dielectric anisotropy is used.

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

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

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

  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 a spacer on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure to seal, or a method in which the substrate is attached and sealed after the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed.

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

  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.

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

  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 a spacer on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure to seal, or a method in which the substrate is attached and sealed after the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed.

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

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

  Hereinafter, an example will be described. In addition, this invention is limited to these and is not interpreted.

<Synthesis of Specific Polymer (A) and Specific Polymer (B)>
Abbreviations used below are as follows.
(Tetracarboxylic dianhydride)
A-1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride A-2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride A-3 : Pyromellitic dianhydride

(Diamine compound having a side chain represented by the above formula [1])
B-1: 1,3-Diamino-5- [4- {1- (trans-4-n-pentylcyclohexyl) -trans-4-cyclohexyl} phenoxymethyl] benzene B-2: 1,3 -Diamino-4- {4- (4-n-heptylcyclohexyl) phenoxy} benzene

(Other diamine compounds)
B-3: 1,4-phenylenediamine B-4: N- (3-picolyl) -3,5-diaminobenzamide B-5: 3,5-diaminobenzoic acid B-6: diaminodiphenylmethane

(Additive)
C-1: 3-aminopyridine

(Crosslinkable compound)
D-1: 2,2-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane

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

(Molecular weight measurement of polyamic acid and polyimide)
The molecular weights of the polyamic acid and the polyimide were measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Showa Denko KK and a column (KD-803, KD-805) manufactured by Shodex.
Column temperature: 50 ° C
Eluent: N, N′-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) is 30 mmol / L, Tetrahydrofuran (THF) 10ml / L)
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, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (manufactured by Polymer Laboratories) Molecular weight about 12,000, 4,000, 1,000).

(Measurement of imidization rate)
Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 by Kusano Kagaku Co., Ltd.) and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture). The solution was completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum. The imidation rate is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of amic acid that appears near 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.
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.

<Example 1>
A-2 (48.9 g, 19.5 mmol), B-1 (31.0 g, 6.89 mmol), B-3 (17.4 g, 16.0 mmol) were mixed in NMP (290 g), and 40 ° C. Then, A-1 (5.77 g, 2.94 mmol) and NMP (120 g) were added and reacted at 40 ° C. for 15 hours to obtain a polyamic acid solution (concentration: 20.0 mass%). . The number average molecular weight of this polyamic acid was 11,700, and the weight average molecular weight was 40,600.

  After adding NMP to this polyamic acid solution (485 g) and diluting to 6% by mass, acetic anhydride (66.2 g) and pyridine (34.2 g) were added as an imidization catalyst and reacted at 100 ° C. for 2.5 hours. It was. The reaction solution was poured into methanol (6010 g), and the generated precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (corresponding to the specific polymer (A)). The imidation ratio of this polyimide was 60%, the number average molecular weight was 10,900, and the weight average molecular weight was 38,900.

  NMP (18.8 g) was added to the polyimide powder (3.85 g) and dissolved by stirring at 70 ° C. for 30 hours, and then NMP, an NMP solution of C-1 and BCS were added, and the mixture was heated to 50 ° C. The polyimide solution (A) was prepared such that the polyimide was 6% by mass, C-1 was 0.5% by mass, NMP was 48.5% by mass, and BCS was 45% by mass.

<Example 2>
A-2 (236 g, 94.0 mmol), B-2 (84.5 g, 22.2 mmol), B-4 (53.7 g, 22.1 mmol), B-5 (101 g, 66.3 mmol) were mixed with NMP ( 1510 g), the mixture was reacted at 80 ° C. for 5 hours, A-1 (30.4 g, 15.5 mmol) and NMP (506 g) were added, and the mixture was reacted at 40 ° C. for 15 hours to obtain a polyamic acid solution (concentration) 20.0 mass%) was obtained. The number average molecular weight of this polyamic acid was 12,600, and the weight average molecular weight was 61,400.

  After adding NMP to this polyamic acid solution (600 g) and diluting to 6% by mass, acetic anhydride (268 g) and pyridine (41.6 g) were added as an imidization catalyst and reacted at 100 ° C. for 4 hours. The reaction solution was poured into methanol (8080 g), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (corresponding to the specific polymer (B)). The imidation ratio of this polyimide was 80%, the number average molecular weight was 10,900, and the weight average molecular weight was 38,900.

  NMP (18.8 g) was added to the polyimide powder (3.85 g) and dissolved by stirring at 70 ° C. for 30 hours, and then NMP, an NMP solution of C-1 and BCS were added, and the mixture was heated to 50 ° C. The polyimide solution (B) was prepared so that the polyimide was 6% by mass, C-1 was 0.3% by mass, NMP was 48.5% by mass, and BCS was 45% by mass.

<Example 3>
The polyimide solution (A) obtained in Example 1 and the polyimide solution (B) obtained in Example 2 were mixed at room temperature so that the polyimide solution (A) and the polyimide solution (B) were 20:80 by mass%. In addition, 3% by mass of D-1 was added to the polyimide and stirred, followed by pressure filtration with a membrane filter having a pore diameter of 1 μm to obtain a liquid crystal alignment treatment agent of Example 3.

<Example 4>
In the same manner as in Example 3, the polyimide solution (A) and the polyimide solution (B) were mixed at room temperature so that the polyimide solution (A) and the polyimide solution (B) were 40:60 by mass, and further D -1 was added to 3% by mass with respect to the polyimide and stirred, followed by pressure filtration with a membrane filter having a pore diameter of 1 μm to obtain a liquid crystal alignment treatment agent of Example 4.

<Example 5>
In the same manner as in Example 3, the polyimide solution (A) and the polyimide solution (B) are mixed at room temperature so that the polyimide solution (A) and the polyimide solution (B) are 70% by mass, and further D -1 was added in an amount of 3% by mass with respect to the polyimide, and the mixture was stirred and filtered under pressure with a membrane filter having a pore diameter of 1 μm to obtain a liquid crystal aligning agent of Example 5.

<Comparative Example 1>
3% by mass of D-1 with respect to polyimide is added to the polyimide solution (A) obtained in Example 1 and stirred, followed by pressure filtration with a membrane filter having a pore diameter of 1 μm, and the liquid crystal alignment treatment agent of Comparative Example 1 Got.

<Comparative example 2>
The polyimide solution (A) obtained in Example 1 and the polyimide solution (B) obtained in Example 2 were mixed at room temperature so that the polyimide solution (A) and the polyimide solution (B) were 20:80 by mass%. And pressure filtered through a membrane filter having a pore diameter of 1 μm to obtain a liquid crystal alignment treatment agent of Comparative Example 2.

<Comparative Example 3>
Referring to Patent Document 2, A-1 (19.6 g, 10 mmol), A-3 (20.1 g, 9.19 mmol), B-6 (39.7 g, 20 mmol) were mixed in NMP (450 g). And reacted at 23 ° C. for 4 hours to obtain a polyamic acid solution (concentration: 15.0% by mass). NMP and BCS were added to this solution, and a polyamic acid solution (C) was prepared so that the polyamic acid was 6% by mass, NMP was 49% by mass, and BCS was 45% by mass.

  The polyimide solution (A) and the polyamic acid solution (C) obtained in Example 1 were mixed at room temperature so that the polyimide solution (A) and the polyamic acid solution (C) were 20:80 by mass. Further, 3% by mass of D-1 was added to the total of polyimide and polyamic acid, and the mixture was stirred and pressure filtered through a membrane filter having a pore diameter of 1 μm to obtain a liquid crystal alignment treatment agent of Comparative Example 3.

  Table 49 shows the liquid crystal aligning agents obtained in the examples and comparative examples.

<Evaluation of residual DC>
A liquid crystal alignment treatment agent is spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C. for 5 minutes, and then baked in a hot air circulation oven at 230 ° C. for 30 minutes to form a film with a thickness of 100 nm. Thus, a substrate with a liquid crystal alignment film was obtained. Two substrates with this liquid crystal alignment film are prepared, a spacer of 4 μm is sprayed on the surface of one liquid crystal alignment film, a sealant is printed thereon, and the other substrate has a liquid crystal alignment film surface. After laminating so as to face each other, the sealing agent was cured to produce an empty cell. Liquid crystal MLC-2041 (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 vertically aligned liquid crystal cell. In addition, the said operation was performed using the liquid-crystal aligning agent of Examples 3-5 and Comparative Examples 1-3, respectively, and the vertical alignment liquid crystal cell was obtained.

  An AC voltage of 30 Hz, 13 Vpp, and a DC voltage of 1 V were applied to these liquid crystal cells, and the liquid crystal cells were driven at a temperature of 23 ° C. for 12 hours. Thereafter, flicker was evaluated, and the applied voltage at which the intensity was minimized was defined as residual DC. The evaluation results are shown in Table 50.

<Evaluation of pretilt angle>
A liquid crystal alignment treatment agent is spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 80 ° C. for 5 minutes, and then baked in a hot air circulation oven at 230 ° C. for 30 minutes to form a film with a thickness of 100 nm. Thus, a substrate with a liquid crystal alignment film was obtained. The substrate was rubbed with cotton at a roller rotation speed of 1000 rpm, a stage speed of 50 mm / sec, and a roller pressing pressure of 0.2 mm. In addition, two substrates are prepared, and a spacer of 4 μm is sprayed on the surface of one liquid crystal alignment film, and then a sealant is printed thereon, so that the liquid crystal alignment film surface faces the other substrate. Further, after laminating so that the rubbing direction was anti-parallel, the sealing agent was cured to produce an empty cell. Liquid crystal MLC-2041 (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 vertically aligned liquid crystal cell. In addition, the said operation was performed using the liquid-crystal aligning agent of Examples 3-5 and Comparative Examples 1-3, respectively, and the vertical alignment liquid crystal cell was obtained.

  The retardation of these liquid crystal cells was measured by the crystal rotation method, and the pretilt angle of the liquid crystal was calculated from the ordinary light refractive index and the extraordinary light refractive index of the liquid crystal. The pretilt angle was defined as the angle from the horizontal direction of the substrate in the plane composed of the normal direction of the substrate and the rubbing direction. The evaluation results are shown in Table 50.

<Evaluation of whitening and aggregation>
Each of the liquid crystal alignment treatment agents of Examples 3 to 5 and Comparative Examples 1 to 3 was spin-coated on a chromium substrate (a glass substrate on which chromium was vapor-deposited), and left for 10 minutes in an atmosphere at a temperature of 23 ° C. and a relative humidity of 60%. Then, it was visually observed whether the aggregate of the polymer has generate | occur | produced in the coating-film surface edge part. The evaluation results are shown in Table 51.

  As a result, in the liquid crystal cell using the liquid crystal aligning agent of Examples 3 to 5 containing the predetermined specific polymer (A), the specific polymer (B) and the crosslinkable compound (C), the pretilt angle is large, Moreover, residual DC was small. Furthermore, in the liquid crystal aligning agent of Examples 3-5, whitening and aggregation did not occur and the coating film uniformity was excellent.

  On the other hand, in Comparative Examples 1 to 3 that do not contain the predetermined specific polymer (A), specific polymer (B), and crosslinkable compound (C), the pretilt angle characteristics, the accumulated charge characteristics, and the coating film uniformity of the liquid crystal alignment treatment agent Not all of sex was excellent. Specifically, in the liquid crystal cell using the liquid crystal aligning agent of Comparative Examples 1 to 3, the residual DC was higher than that of Examples 3 to 5. Further, in the comparison between Example 3 and Comparative Example 2, the pretilt angle was small in the liquid crystal cell using the liquid crystal aligning agent of Comparative Example 2 that did not contain the specific crosslinkable compound (C). Furthermore, in the comparison between Example 3 and Comparative Example 3, whitening and aggregation occurred in the liquid crystal aligning agent of Comparative Example 3 that did not contain the specific polymer (B).

Claims (13)

The following specific polymer (A), specific polymer (B) and specific crosslinkable compound (C) are contained , and at least one of the specific polymer (A) and the specific polymer (B) is a raw material The liquid-crystal aligning agent characterized by using the diamine compound shown by following formula [2] as a diamine component .
Specific polymer (A): At least one polymer selected from the group consisting of a polyimide precursor and a polyimide using a diamine compound having a side chain represented by the formula [1] as a part of the raw material.
Specific polymer (B): A diamine compound having a side chain represented by the formula [1] is used as a part of the raw material, and a diamine compound having a side chain represented by the formula [1] in all diamine components of the raw material. At least one heavy selected from the group consisting of a polyimide precursor and a polyimide having a proportion lower than the proportion of the diamine compound having a side chain represented by the formula [1] in the total diamine component of the raw material of the specific polymer (A). Coalescence.
Specific crosslinkable compound (C): crosslinkable compound having at least two substituents selected from the group consisting of epoxy group, isocyanate group, oxetane group and cyclocarbonate group, hydroxyl group, hydroxyalkyl group and carbon number A crosslinkable compound having at least two substituents selected from the group consisting of 1 to 6 alkoxyalkyl groups, or a crosslinkable compound having two or more polymerizable unsaturated bonds.

(In the formula [1], X ₁ is a single bond, — (CH ₂ ) _a — (a is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. X ₂ is a single bond or — (CH ₂ ) _b — (b is an integer of 1 to 15), X ₃ is a single bond, — (CH ₂ ) _c — (c is an integer of 1 to 15) -O-, -CH ₂ O-, -COO- or -OCO-, and X ₄ is a divalent cyclic group selected from the group consisting of 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, and any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or a carbon number 1 to 3 fluorine-containing alkyl groups, 1 to 3 fluorine-containing alkoxyl groups or substituted with fluorine atoms Even if well, X ₅ is a divalent cyclic group selected from benzene ring, the group consisting of cyclohexane ring and heterocyclic cyclohexane, any hydrogen atoms on these cyclic groups, having 1 to 3 carbon atoms An alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom, and n is 0 to 4 X ₆ is a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 18 carbon atoms, or a linear or branched group having 1 to 18 carbon atoms. A side chain represented by the formula [1] of the diamine compound as a raw material of the specific polymer (A), which is a linear alkoxyl group or a linear or branched fluorine-containing alkoxyl group having 1 to 18 carbon atoms, and a specific Raw material of polymer (B) The side chain of the formula [1] with the diamine compound may be different and the same.)

(Wherein [2], _{Y 1} is _{-O -, - NH -, -} N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCO -, - CON (CH 3) — Or —N (CH ₃ ) CO—, Y ₂ is a single bond, a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group. , Y ₃ represents a single bond, —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH ₃ ) —, —N ( CH ₃ ) CO— or —O (CH ₂ ) _i — (i is an integer of 1 to 5), Y ₄ is a monovalent nitrogen-containing aromatic heterocyclic ring, and h is an integer of 1 to 4. .)   When the ratio of the diamine compound having a side chain represented by the formula [1] in the total diamine component of the raw material of the specific polymer (A) is 1, the formula in the total diamine component of the raw material of the specific polymer (B) The liquid crystal aligning agent according to claim 1, wherein the ratio of the diamine compound having a side chain represented by [1] is 0.3 or more and less than 1.0. A diamine compound having a side chain represented by the formula [1] which is a raw material of the specific polymer (A) and a diamine compound having a side chain represented by the formula [1] which are a raw material of the specific polymer (B), respectively. The liquid crystal aligning agent according to claim 1 or 2, which is a diamine compound represented by the following formula [1a].

(In Formula [1a], X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ , and n are X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ in Formula [1]. , N and m is an integer of 1 to 4, and the diamine compound represented by the formula [1a] which is a raw material of the specific polymer (A) and the formula [B] which is a raw material of the specific polymer (B) The diamine compounds represented by 1a] may be the same or different.) The specific polymer (A) and specific polymer (B), claim 1-3, characterized in that the tetracarboxylic dianhydride represented by the following formula [3] used in the part of the raw material The liquid crystal aligning agent according to one item.

(Wherein [3], _{Z 1} is a tetravalent organic group having 4 to 13 carbon atoms which contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms.) Z ₁ is a liquid crystal alignment treating agent according to claim 4, characterized in that the structure represented by the following formula [3a] ~ formula [3j].

(In the 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 the formula [3g], Z ₆ and Z ₇ Are hydrogen atoms or methyl groups, which may be the same or different. The specific crosslinkable compound (C) is selected from the group consisting of a crosslinkable compound having an oxetane group, a crosslinkable compound having a cyclocarbonate group, or a hydroxyl group, a hydroxyalkyl group, and an alkoxyalkyl group having 1 to 6 carbon atoms. It is a crosslinkable compound which is a benzene or phenolic compound having at least one kind of substituent, The liquid crystal aligning agent according to any one of claims 1 to 5 . The liquid crystal aligning agent according to any one of claims 1 to 6 , wherein the specific polymer (A) and the specific polymer (B) are polyamic acids. The specific polymer (A) and specific polymer (B), the liquid crystal alignment treating agent according to any one of claims 1 to 6, characterized in that a polyimide obtained by the polyamic acid was cyclodehydration. The total amount 100 parts by mass of the specific polymer (A) and specific polymer (B), claim 1-8, wherein the specific crosslinkable compound (C) is 0.1 parts by mass to 50 parts by mass Liquid crystal aligning agent as described in any one of these. Liquid crystal alignment treating agent according to any one of claims 1 to 9, characterized in that it contains 5 to 60% by weight of the poor solvent. Liquid crystal alignment film, characterized in that it is obtained by using the liquid crystal alignment treating agent according to any one of claims 1-10. A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the electrodes It is used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric compound, applying a voltage in between, The liquid crystal aligning film of Claim 11 characterized by the above-mentioned. A liquid crystal display element comprising the liquid crystal alignment film according to claim 11 .