JP4552489B2 - Liquid crystal alignment film forming varnish, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

  The present invention relates to a composition for forming a liquid crystal alignment film. And it is related with the liquid crystal aligning film obtained from this composition, and the liquid crystal display element containing this aligning film. This composition is characterized by containing a polymer obtained using a tetracarboxylic dianhydride having a silsesquioxane skeleton as a raw material. “Silsesquioxane” is a class name indicating a compound in which each silicon atom is bonded to three oxygen atoms, and each oxygen atom is bonded to two silicon atoms. A “silsesquioxane skeleton” is used as a generic term for silsesquioxane structures and silsesquioxane-like structures in which a part thereof is deformed.

  Among liquid crystal display elements, display elements using nematic liquid crystals are the mainstream. Examples thereof include a TN liquid crystal display element twisted by 90 °, an STN liquid crystal display element twisted by 180 ° or more, a so-called TFT liquid crystal display device using a thin film transistor, and the like. Furthermore, in recent years, horizontal electric field type in-plane switching (hereinafter referred to as IPS) type liquid crystal display elements with improved visual characteristics, vertical alignment (Vertical Alignment, hereinafter) , VA.) Type liquid crystal display element, which has an extremely fast response speed and a relatively wide viewing angle, and is optically compensated birefringence (OCB). ) Type liquid crystal display elements have been proposed.

  In these liquid crystal display elements, it is important to align the major axis direction of the liquid crystal molecules uniformly. As industrially representative methods for uniformly aligning liquid crystal molecules, the following rubbing methods are known. That is, this is a method in which an alignment film made of an organic film is provided on the surface of the substrate, the surface is rubbed in a certain direction with a cloth such as cotton, nylon, polyester, and the liquid crystal molecules are aligned in the rubbing direction. This rubbing method is industrially mainstream because stable uniform orientation can be obtained relatively easily and the productivity is excellent. As materials for the alignment film, polymers such as polyvinyl alcohol, polyoxyethylene, polyamide, polyimide, and polyamideimide are known. From the viewpoint of stability and durability that can withstand industrial mass production, polyimides that are excellent in chemical stability and thermal stability are most often used.

  An alignment treatment method for rubbing the alignment film is an industrially useful method because it is simple and excellent in productivity. However, as the liquid crystal display elements are used in various fields, the performance enhancement of the liquid crystal display elements has been promoted, and various problems have been pointed out accordingly. For example, there are problems such that scratches on the surface of the alignment film caused by rubbing appear as alignment defects, or the alignment film is scraped off by rubbing, and the shavings become display defects. Such a defect caused by rubbing becomes defective if even one of them exists on the screen, and is one of the major factors for a decrease in yield with the recent increase in screen size. Therefore, rub resistance more severe than before is required. In recent years, attempts have been made to sinter the varnish for forming a liquid crystal alignment film at a low temperature of less than 200 ° C. using a plastic film instead of the conventional glass substrate in order to reduce the manufacturing cost or reduce the weight (patents). (See Reference 1, Patent Reference 2, etc.). However, especially when polyamic acid, which is a precursor of polyimide, is applied onto a substrate and baked at low temperature, polyamic acid does not undergo sufficient dehydration (imidation), and damage to the alignment film due to insufficient mechanical strength of polyimide. Such problems are becoming more serious.

  Examples of problems with the alignment film related to the rubbing method are that the mechanical strength is insufficient and the friction due to rubbing cannot be dealt with, and the adhesiveness with the glass substrate and the like is insufficient and the film is peeled off. is there. These problems can be attributed to the fact that the conventional organic polymer that is the main component of the alignment film contains many carbon atoms. Therefore, development of an alignment film in which these are improved is desired. The lack of mechanical strength can be improved to some extent by changing the molecular structure of the alignment film. However, since the electrical characteristics of the alignment film and the pretilt angle of the liquid crystal tend to change by changing the structure, it is difficult to improve the mechanical strength. The adhesion to the glass substrate can be improved to some extent by using a silane coupling agent. However, the silane coupling agent is easily hydrolyzed, and there is a problem in storage stability as an alignment film forming varnish. On the other hand, when it is used excessively to prevent peeling, there is a problem that the performance of the liquid crystal display element is lowered.

JP-A 61-205924 JP-A-1-239525

  An object of the present invention is to form an alignment film having mechanical strength that can cope with rubbing friction, excellent adhesion to a glass substrate, and excellent storage stability. It is to provide a varnish for use. Furthermore, it is also an object of the present invention to provide an alignment film obtained by using this varnish and a liquid crystal display element including the alignment film.

  As a result of intensive studies to solve these problems, the present inventors have incorporated a polymer having a silsesquioxane skeleton in the main chain into the varnish for forming a liquid crystal alignment film in order to solve the above problems. Knew that it was effective. That is, the liquid crystal alignment film obtained from this varnish has high mechanical strength and excellent adhesion to the glass substrate, and thus has high resistance to rubbing. Furthermore, this alignment film is excellent in storage stability. Since the silsesquioxane skeleton in the polymer used in the present invention is a highly crosslinked product itself, there is no site where hydrolysis occurs. Therefore, the storage stability is much better than the varnish for forming a liquid crystal alignment film using a silane coupling agent in order to improve the adhesion to the glass substrate. Further, a highly reliable liquid crystal alignment film that does not adversely affect the display performance of the liquid crystal display element can be formed.

First, terms and symbols used in the present invention will be described. The term “arbitrary” indicates that not only the position but also the number is arbitrary. For example, when it is expressed that any —CH ₂ — in alkyl may be replaced by —O— or —CH═CH—, a plurality of —CH ₂ — may be replaced by different groups. Examples of such cases are alkyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, and alkenyloxyalkyl. In the present invention, it is preferable that two consecutive —CH ₂ — are replaced by —O— or —S— to become —O—O—, —O—S— or —S—S—. Absent. Alkyl and alkylene are used to include both straight and branched groups unless otherwise specified. For example, butyl may be any of n-butyl, 2-methylpropyl and 1,1-dimethylethyl. Halogen means fluorine, chlorine or bromine.

ここに、Ｒ^１は独立して水素、炭素数１〜４５のアルキル、置換基を有してもよいアリール、または置換基を有してもよいアリールとアルキレンとで構成されるアリールアルキルであり；炭素数１〜４５のアルキルにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−、シクロアルキレンまたはシクロアルケニレンで置き換えられてもよく、そして任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく；アリールアルキルのアルキレンにおいて、任意の水素はフッ素で置き換えられてもよく、任意の−ＣＨ_２−は−Ｏ−またはシクロアルキレンで置き換えられてもよく、そして任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく；
Ｑ^１は水素、ハロゲン、炭素数１〜１０のアルキル、フェニル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘキセニル、または少なくとも１つの水素がハロゲンもしくは炭素数１〜５のアルキルで置き換えられたフェニルであり；炭素数１〜１０のアルキルおよびフェニルの置換基である炭素数１〜５のアルキルのそれぞれにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよく；
そして、Ｑ^２は式（２）で表される基である：

ここに、Ａ^１、Ａ^２、Ａ^３およびＡ^４は独立して１，４−シクロヘキシレンまたは１，４−フェニレンであり；これらの環において任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、そして任意の−ＣＨ＝は−Ｎ＝で置き換えられてもよく；１，４−シクロヘキシレンにおいては隣り合わない２つの炭素が架橋されてもよく；そして、すべての環における任意の水素はハロゲン、−ＣＮ、−ＮＯ_２または炭素数１〜５のアルキルで置き換えられてもよく；環の置換基である炭素数１〜５のアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよく；
Ｚ^０は炭素数１〜１０のアルキレンであり、このアルキレン中の任意の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよく；
Ｚ^１、Ｚ^２およびＺ^３は、独立して単結合、−Ｏ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＯＣＯ−または炭素数１〜１０のアルキレンであり；この炭素数１〜１０のアルキレンにおいて、任意の−ＣＨ_２−は−Ｏ−、−Ｓ−、−ＮＨ−、−ＳｉＲ^２ _２−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；
Ｚ^４は単結合または炭素数１〜１０のアルキレンであり；この炭素数１〜１０のアルキレンにおいて、任意の−ＣＨ_２−は−Ｏ−、−ＮＨ−、−ＳｉＲ^２ _２−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はフッ素で置き換えられてもよく；Ｓｉに結合するＲ^２は、炭素数１〜１０のアルキル、フェニル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘキセニル、または少なくとも１つの水素がハロゲンもしくは炭素数１〜５のアルキルで置き換えられたフェニルであり；この炭素数１〜１０のアルキルおよびフェニルの置換基である炭素数１〜５のアルキルのそれぞれにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよく；
ｋは０または１であり、ｌ、ｍ、ｎおよびｐは独立して０、１、２または３であり；
そして、Ｙは２−オキサプロパン−１，３−ジオイルを有する基である。 The present invention has the following configuration.
[1] Liquid crystal alignment film forming varnish containing a polymer obtained by using the compound represented by formula (1):

Here, R ¹ is independently hydrogen, alkyl having 1 to 45 carbon atoms, aryl optionally having substituent (s), or arylalkyl composed of aryl optionally having substituent (s) and alkylene. In the alkyl having 1 to 45 carbon atoms, any hydrogen may be replaced by fluorine, any —CH ₂ — may be replaced by —O—, cycloalkylene or cycloalkenylene, and any — ( CH ₂ ) ₂ — may be replaced by —CH═CH—; in the arylalkyl alkylene, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O— or cycloalkylene. It may be replaced, and any - _{(CH 2) 2} - may be replaced by -CH = CH-;
Q ¹ is hydrogen, halogen, alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons. Yes; In each of alkyl having 1 to 10 carbons and alkyl having 1 to 5 carbons which is a substituent of phenyl, any —CH ₂ — may be replaced by —O—, and any — (CH _{2 2} ) may be replaced with —CH═CH— or —C≡C— and any hydrogen may be replaced with a halogen;
Q ² is a group represented by the formula (2):

Where A ¹ , A ² , A ³ and A ⁴ are independently 1,4-cyclohexylene or 1,4-phenylene; in these rings any —CH ₂ — is replaced by —O—. And any —CH═ may be replaced by —N═; in 1,4-cyclohexylene, two non-adjacent carbons may be bridged; and any ring in any ring Hydrogen may be replaced by halogen, —CN, —NO ₂ or alkyl having 1 to 5 carbons; in the alkyl having 1 to 5 carbons which is a ring substituent, any —CH ₂ — is —O—. Any — (CH ₂ ) ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen may be replaced with halogen;
Z ⁰ is alkylene having 1 to 10 carbons, and any —CH ₂ — in the alkylene may be replaced by —O—, —COO— or —OCO—;
Z ¹ , Z ² and Z ³ are each independently a single bond, —O—, —CH═CH—, —C≡C—, —COO—, —OCO— or alkylene having 1 to 10 carbons; In the alkylene having 1 to 10 carbon atoms, arbitrary —CH ₂ — may be replaced by —O—, —S—, —NH—, —SiR ² ₂ —, —COO— or —OCO—. — (CH ₂ ) ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen may be replaced with fluorine;
Z ⁴ is a single bond or alkylene having 1 to 10 carbons; in the alkylene having 1 to 10 carbons, any —CH ₂ — may be —O—, —NH—, —SiR ² ₂ —, —COO—. Or —OCO— may be replaced, any — (CH ₂ ) ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen may be replaced with fluorine. Well; R ² bonded to Si is alkyl of 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or at least one hydrogen is replaced by halogen or alkyl of 1 to 5 carbons Each of the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl. -CH ₂ - may be replaced by -O-, arbitrary - _{(CH 2) 2} - may be replaced by -CH = CH- or -C≡C-, and in any hydrogen halide May be replaced;
k is 0 or 1, and l, m, n and p are independently 0, 1, 2 or 3;
Y is a group having 2-oxapropane-1,3-dioyl.

[2] R ¹ is independently hydrogen, alkyl having 1 to 30 carbon atoms, phenyl which may have a substituent, phenylalkyl which is composed of phenyl and alkylene which may have a substituent, or naphthyl. In alkyl having 1 to 30 carbons, any hydrogen may be replaced by fluorine, any —CH ₂ — may be replaced by —O—, cycloalkylene, or cycloalkenylene, and any — (CH ₂ ) ₂ — may be replaced by —CH═CH—; in the optionally substituted phenyl, any hydrogen may be replaced by halogen or alkyl having 1 to 10 carbons. In the alkyl having 1 to 10 carbon atoms which is a substituent of this phenyl, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O— or phenyl; It may be replaced by Ren, and any - _{(CH 2) 2} - may be replaced by -CH = CH-; and, in the alkylene phenylalkyl, the number of carbon atoms is 1 to 12, optionally In which hydrogen may be replaced with fluorine, any —CH ₂ — may be replaced with —O— or cycloalkylene, and any — (CH ₂ ) ₂ — may be replaced with —CH═CH—. The varnish as described in the item [1].

[3] R ¹ is independently alkyl having 1 to 8 carbon atoms, phenyl optionally having substituent (s), and arbitrary hydrogen may be replaced with fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy. Phenylalkyl composed of phenyl and alkylene, or naphthyl; in alkyl having 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — represents —O—, cycloalkylene Or may be replaced with cycloalkenylene, and any — (CH ₂ ) ₂ — may be replaced with —CH═CH—; in the optionally substituted phenyl, any hydrogen is halogen or May be substituted with alkyl having 1 to 10 carbon atoms; in the alkyl having 1 to 10 carbon atoms which is a substituent of this phenyl, any hydrogen is substituted with fluorine. It may be replaced, and arbitrary -CH ₂ - may be replaced by -O-; the alkylene phenylalkyl, the number of carbon atoms is 1 to 8, arbitrary -CH ₂ - -O- Or may be replaced by cycloalkylene and any — (CH ₂ ) ₂ — may be replaced by —CH═CH—;
And Q ¹ is hydrogen, halogen, phenyl, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms. In the alkyl having 1 to 10 carbon atoms, arbitrary — (CH ₂ ) ₂ — may be replaced by —CH═CH—, and arbitrary hydrogen may be replaced by halogen; phenyl substituent The varnish according to item [1], wherein in the alkyl having 1 to 5 carbon atoms, optional —CH ₂ — may be replaced with —O—, and optional hydrogen may be replaced with halogen.

[4] R ¹ is independently alkyl having 1 to 8 carbon atoms, phenyl optionally having substituent (s), and arbitrary hydrogen may be replaced with fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy. Phenylalkyl composed of phenyl and alkylene, or naphthyl; in alkyl having 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — represents —O—, cycloalkylene Or may be replaced with cycloalkenylene, and any — (CH ₂ ) ₂ — may be replaced with —CH═CH—; in the optionally substituted phenyl, any hydrogen is halogen or May be replaced by alkyl having 1 to 10 carbons; in this alkyl having 1 to 10 carbons, any hydrogen may be replaced by fluorine; It may be replaced by -O- - arbitrary -CH ₂ Te; in phenylalkyl alkylene, the carbon number of 1 to 8, arbitrary -CH ₂ - replaced by -O- or cycloalkylene And any — (CH ₂ ) ₂ — may be replaced by —CH═CH—;
Q ¹ is hydrogen, halogen, alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons; In alkyl having 1 to 10 carbon atoms, optional — (CH ₂ ) ₂ — may be replaced by —CH═CH—, and optional hydrogen may be replaced by halogen; a phenyl substituent In C 1-5 alkyl, any —CH ₂ — may be replaced with —O— and any hydrogen may be replaced with halogen;
A ¹ , A ² , A ³ and A ⁴ are each independently a single bond, 1,4-cyclohexylene, 1,4-phenylene, bicyclo [3.1.0] cyclohexane-3,6-diyl, bicyclo [2.2.2] cyclooctane-1,4-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6- Diyl, 1,4-cyclohexylene in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons, or 1,4-in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons The varnish according to item [1], which is phenylene.

[5] R ¹ is phenyl in which arbitrary hydrogen may be replaced with halogen or alkyl having 1 to 10 carbons; in this alkyl having 1 to 10 carbons, arbitrary hydrogen may be replaced with fluorine , And any —CH ₂ — may be replaced by —O—;
Q ¹ is hydrogen, halogen, alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons; In alkyl having 1 to 10 carbon atoms, optional — (CH ₂ ) ₂ — may be replaced by —CH═CH—, and optional hydrogen may be replaced by fluorine; a phenyl substituent In alkyl having 1 to 5 carbon atoms, optional —CH ₂ — may be replaced by —O—, and optional hydrogen may be replaced by fluorine;
A ¹ , A ² , A ³ and A ⁴ are each independently a single bond, 1,4-cyclohexylene, 1,4-phenylene, bicyclo [3.1.0] cyclohexane-3,6-diyl, bicyclo [2 2.2] cyclooctane-1,4-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, 1,4-cyclohexylene in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms, or 1,4-phenylene in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms Yes;
Z ⁰ is alkylene having 1 to 8 carbon atoms in which arbitrary —CH ₂ — may be replaced by —O—;
Z ¹ , Z ² and Z ³ are each independently a single bond, —O—, —CH═CH—, —C≡C—, —COO—, —OCO— or alkylene having 1 to 10 carbons; In the alkylene having 1 to 10 carbon atoms, arbitrary —CH ₂ — may be replaced by —O—, —NH—, —COO— or —OCO—, and arbitrary — (CH ₂ ) ₂ — represents —CH ═CH— or —C≡C— and any hydrogen may be replaced with fluorine;
Z ⁴ is a single bond or alkylene having 1 to 10 carbon atoms; any —CH ₂ — in the alkylene having 1 to 10 carbon atoms is —O—, —COO—, —OCO— or —SiR ² _2. The varnish according to item [1], which may be replaced by-.

[6] R ¹ is phenyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons; in the alkyl having 1 to 5 carbons which is a substituent of phenyl, any —CH _2- may be replaced with -O- and any hydrogen may be replaced with halogen;
Q ¹ is hydrogen, halogen, alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons; In alkyl having 1 to 10 carbon atoms, optional — (CH ₂ ) ₂ — may be replaced by —CH═CH—, and optional hydrogen may be replaced by fluorine; a phenyl substituent In alkyl having 1 to 5 carbon atoms, optional —CH ₂ — may be replaced by —O—, and optional hydrogen may be replaced by fluorine;
And the varnish as described in the item [1], wherein Q ² is a group represented by any one of the following formulas (1-1) to (1-89):
In the following formulas, Z ⁰ , Z ¹ , Z ² , Z ³ and Z ⁴ have the same meaning as these symbols in formula (2). And groups representing 1,4-cyclohexylene, 1,4-phenylene and pyridine-2,5-diyl are used as representatives of the groups described in the right column, respectively:

    [7] The varnish according to item [1], wherein the polymer is a polyamic acid.

    [8] The varnish according to item [1], wherein the polymer is polyimide.

    [9] The varnish according to item [1], wherein the polymer is polyamideimide.

    [10] The varnish according to item [1], wherein the polymer is polyester.

    [11] The varnish according to item [1], wherein the polymer is at least one selected from the group consisting of polyamic acid, polyimide, polyamideimide, and polyester.

    [12] The polymer is at least one selected from the group consisting of polyamic acid, polyimide, polyamideimide and polyester, and further contains a polymer obtained without using the compound represented by formula (1). ] Varnish.

    [13] The varnish according to item [12], wherein the polymer obtained without using the compound represented by formula (1) is at least one selected from the group consisting of polyamic acid, polyimide, polyamideimide, and polyester. .

    [14] An alignment film formed using the varnish described in any one of [1] to [13].

    [15] Use of the varnish in the liquid crystal display element according to any one of [1] to [13].

    [16] A liquid crystal display device comprising the alignment film according to the item [14].

  The liquid crystal alignment film produced from the varnish of the present invention has a mechanical strength that can cope with friction caused by rubbing, particularly has excellent adhesion to a substrate with a transparent electrode, and also has excellent storage stability. . Further, such a liquid crystal alignment film can prevent streaks and scratches on the alignment film surface due to the rubbing operation, and thus can improve the voltage holding ratio which is one of the liquid crystal cell characteristics. That is, by using a polymer obtained using an acid dianhydride having a silsesquioxane skeleton as a component of a varnish for forming a liquid crystal alignment film, a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display An element, an IPS liquid crystal display element, a VA liquid crystal display element, an OCB liquid crystal display element, a ferroelectric liquid crystal display element, an antiferroelectric liquid crystal display element, or the like can be improved to a higher performance display element.

The present invention is described in detail below.
First, the compound represented by Formula (1) used by this invention is demonstrated. Below, the compound represented by Formula (1) may be described as a compound (1). Similarly, compounds represented by other formulas may be expressed in a simplified manner.

  The silsesquioxane skeleton contained in the formula (1) is a modification of a cage-type octasilsesquioxane. When a structure in which three oxygen atoms are bonded to one silicon atom is a T structure, and a structure in which two oxygen atoms are bonded to one silicon atom is a D structure, in the formula (1) The silsesquioxane skeleton can be said to have a T8D2 structure.

In Formula (1), R ¹ is independently hydrogen, alkyl having 1 to 45 carbon atoms, aryl optionally having substituent (s), or aryl composed of aryl optionally having substituent (s) and alkylene. Alkyl. This definition means that the eight R ¹ are independently selected from the group consisting of hydrogen, multiple alkyls, multiple aryls and multiple arylalkyls. Examples of the case where eight R ¹ are composed of different groups are composed of two or more alkyls, composed of two or more aryls, or composed of two or more arylalkyls , Composed of hydrogen and at least one aryl, composed of at least one alkyl and at least one aryl, composed of at least one alkyl and at least one arylalkyl, and at least one This is a case of being composed of one aryl and at least one arylalkyl. Combinations other than these examples may be used. And it is preferable that all R < ¹ > is the same one group.

When R ¹ is alkyl, the carbon number is 1 to 45. A preferable carbon number is 1-30. A more preferable carbon number is 1-8. The optional hydrogen may be replaced with fluorine, the optional —CH ₂ — may be replaced with —O—, cycloalkylene or cycloalkenylene, and the optional — (CH ₂ ) ₂ — is — It may be replaced with CH = CH-. Preferred examples of alkyl include unsubstituted alkyl having 1 to 30 carbons, alkoxyalkyl having 2 to 29 carbons, and a group in which one —CH ₂ — is substituted with cycloalkylene in alkyl having 1 to 8 carbons, In the alkenyl having 2 to 20 carbon atoms, the alkenyloxyalkyl having 2 to 20 carbon atoms, the alkyloxyalkenyl having 2 to 20 carbon atoms, and the alkyl having 1 to 8 carbon atoms, one —CH ₂ — is replaced by cycloalkenylene. Groups, and groups in which any hydrogen in these groups is replaced by fluorine. The preferable carbon number of cycloalkylene and cycloalkenylene is 3-8.

  Examples of unsubstituted alkyl having 1 to 30 carbon atoms are methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 1,1,2-trimethyl. Propyl, heptyl, octyl, 2,4,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, and triacontyl.

  Examples of fluorinated alkyls having 1 to 30 carbon atoms are 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1 , 1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl and perfluoro-1H, 1H, 2H, 2H-tetradecyl It is.

  Examples of C2-C29 alkoxyalkyl are 3-methoxypropyl, methoxyethoxyundecyl and 3-heptafluoroisopropoxypropyl.

Examples of the group in which one —CH ₂ — in C 1-8 alkyl is replaced by cycloalkylene are cyclohexylmethyl, adamantaneethyl, cyclopentyl, cyclohexyl, 2-bicycloheptyl, and cyclooctyl. Cyclohexyl is an example in which methyl —CH ₂ — is replaced by cyclohexylene. Cyclohexylmethyl is an example in which —CH ₂ — in ethyl is replaced by cyclohexylene.

Examples of C 2-20 alkenyl are vinyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl, 10-undecenyl, and 21-docosenyl.
An example of an alkenyloxyalkyl having 2 to 20 carbon atoms is allyloxyundecyl.

Examples of groups in which one —CH ₂ — is replaced by cycloalkenylene in alkyl having 1 to 8 carbon atoms are 2- (3-cyclohexenyl) ethyl, 5- (bicycloheptenyl) ethyl, and 2-cyclopentenyl. , 3-cyclohexenyl, 5-norbornen-2-yl, and 4-cyclooctenyl.

Preferred examples when R ¹ in formula (1) is aryl which may have a substituent include phenyl, naphthyl, and phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 10 carbons. It is. Preferred examples of halogen are fluorine, chlorine and bromine. In the alkyl having 1 to 10 carbon atoms, any hydrogen may be replaced with fluorine, any —CH ₂ — may be replaced with —O— or phenylene, and any — (CH ₂ ) ₂ -may be replaced by -CH = CH-. That is, preferred examples in the case where R ¹ is aryl which may have a substituent include phenyl, naphthyl, alkylphenyl, alkyloxyphenyl, alkenylphenyl, and any —CH ₂ — in the alkyl having 1 to 10 carbon atoms. And phenyl having as a substituent a group in which is substituted with phenylene, and a group in which at least one hydrogen is replaced with a halogen in these groups. In the present invention, when simply referred to as phenyl without particular notice, it means unsubstituted phenyl. The same applies to naphthyl.

  Examples of halogenated phenyl are pentafluorophenyl, 4-chlorophenyl, and 4-bromophenyl.

  Examples of alkylphenyl are 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-butylphenyl, 4-pentylphenyl, 4-heptylphenyl, 4-octylphenyl, 4-nonylphenyl, 4-decylphenyl. 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 4- (1-methylethyl) phenyl, 4- (1,1-dimethylethyl) phenyl, 4- (2-ethylhexyl) phenyl and 2,4,6-tris (1-methylethyl) phenyl.

  Examples of alkyloxyphenyl are 4-methoxyphenyl, 4-ethoxyphenyl, 4-propoxyphenyl, 4-butoxyphenyl, 4-pentyloxyphenyl, 4-heptyloxyphenyl, 4-decyloxyphenyl, 4-octadecyloxyphenyl 4- (1-methylethoxy) phenyl, 4- (2-methylpropoxy) phenyl, and 4- (1,1-dimethylethoxy) phenyl.

  Examples of alkenylphenyl are 4-vinylphenyl, 4- (1-methylvinyl) phenyl, and 4- (3-butenyl) phenyl.

Examples of phenyl having as a substituent a group in which at least one —CH ₂ — in C 1-10 alkyl is replaced by phenylene include 4- (2-phenylvinyl) phenyl, 4-phenyloxyphenyl, 3- Phenylmethylphenyl, biphenyl, and terphenyl. 4- (2-Phenylvinyl) phenyl in the propyl group of propylphenyl, one —CH ₂ — was replaced with phenylene and the remaining — (CH ₂ ) ₂ — was replaced with —CH═CH—. It is an example.

  Examples of groups in which a part of hydrogen in phenyl is replaced by halogen and another hydrogen is replaced by alkyl, alkyloxy or alkenyl are 3-chloro-4-methylphenyl, 2,5-dichloro-4- Methylphenyl, 3,5-dichloro-4-methylphenyl, 2,3,5-trichloro-4-methylphenyl, 2,3,6-trichloro-4-methylphenyl, 3-bromo-4-methylphenyl, 2 , 5-dibromo-4-methylphenyl, 3,5-dibromo-4-methylphenyl, 2,3-difluoro-4-methylphenyl, 3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl, 3,5-dibromo-4-methoxyphenyl, 2,3-difluoro-4-methoxyphenyl, 2,3-difluoro-4-ethoxyphenyl Le, 2,3-difluoro-4-propoxy-phenyl, and 4-vinyl 2,3,5,6-tetrafluorophenyl.

Next, examples of the case R ¹ in the formula (1) is an arylalkyl composed of the aryl and the alkylene may have a substituent. In the arylalkyl alkylene, any hydrogen may be replaced with fluorine, any —CH ₂ — may be replaced with —O— or cycloalkylene, and any — (CH ₂ ) ₂ — is — It may be replaced with CH = CH-. A preferred example of arylalkyl is phenylalkyl composed of optionally substituted phenyl and alkylene. At this time, the preferable carbon number of alkylene is 1-12, and a more preferable carbon number is 1-8.

  Examples of phenylalkyl composed of unsubstituted phenyl and alkylene are phenylmethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, 11-phenylundecyl. 1-phenylethyl, 2-phenylpropyl, 1-methyl-2-phenylethyl, 1-phenylpropyl, 3-phenylbutyl, 1-methyl-3-phenylpropyl, 2-phenylbutyl, 2-methyl-2- Phenylpropyl, and 1-phenylhexyl.

Preferred examples of the substituent for phenyl are halogen and alkyl having 1 to 10 carbons. In the alkyl having 1 to 10 carbon atoms, any hydrogen may be replaced by fluorine, any —CH ₂ — may be replaced by —O—, cycloalkylene or phenylene, and any — (CH ₂ ) ₂ — may be replaced by —CH═CH—. Examples of phenylalkyl in which at least one hydrogen of phenyl is replaced by fluorine are 4-fluorophenylmethyl, 2,3,4,5,6-pentafluorophenylmethyl, 2- (2,3,4,5, 6-pentafluorophenyl) ethyl, 3- (2,3,4,5,6-pentafluorophenyl) propyl, 2- (2-fluorophenyl) propyl, and 2- (4-fluorophenyl) propyl.

  Examples of phenylalkyl in which at least one hydrogen of phenyl is replaced by chlorine are 4-chlorophenylmethyl, 2-chlorophenylmethyl, 2,6-dichlorophenylmethyl, 2,4-dichlorophenylmethyl, 2,3,6-trichlorophenyl Methyl, 2,4,6-trichlorophenylmethyl, 2,4,5-trichlorophenylmethyl, 2,3,4,6-tetrachlorophenylmethyl, 2,3,4,5,6-pentachlorophenylmethyl, 2- (2-chlorophenyl) ethyl, 2- (4-chlorophenyl) ethyl, 2- (2,4,5-chlorophenyl) ethyl, 2- (2,3,6-chlorophenyl) ethyl, 3- (3-chlorophenyl) propyl , 3- (4-chlorophenyl) propyl, 3- (2,4,5-trichlorophenyl) propi 3- (2,3,6-trichlorophenyl) propyl, 4- (2-chlorophenyl) butyl, 4- (3-chlorophenyl) butyl, 4- (4-chlorophenyl) butyl, 4- (2,3,6) -Trichlorophenyl) butyl, 4- (2,4,5-trichlorophenyl) butyl, 1- (3-chlorophenyl) ethyl, 1- (4-chlorophenyl) ethyl, 2- (4-chlorophenyl) propyl, 2- ( 2-chlorophenyl) propyl and 1- (4-chlorophenyl) butyl.

  Examples of phenylalkyl in which at least one hydrogen of phenyl is replaced by bromine are 2-bromophenylmethyl, 4-bromophenylmethyl, 2,4-dibromophenylmethyl, 2,4,6-tribromophenylmethyl, 2 , 3,4,5-tetrabromophenylmethyl, 2,3,4,5,6-pentabromophenylmethyl, 2- (4-bromophenyl) ethyl, 3- (4-bromophenyl) propyl, 3- ( 3-bromophenyl) propyl, 4- (4-bromophenyl) butyl, 1- (4-bromophenyl) ethyl, 2- (2-bromophenyl) propyl, and 2- (4-bromophenyl) propyl.

  Examples of phenylalkyl in which at least one hydrogen of phenyl is replaced by alkyl having 1 to 10 carbon atoms include 2-methylphenylmethyl, 3-methylphenylmethyl, 4-methylphenylmethyl, 4-decylphenylmethyl, (3 , 5-dimethylphenylmethyl, 2- (4-methylphenyl) ethyl, 2- (3-methylphenyl) ethyl, 2- (2,5dimethylphenyl) ethyl, 2- (4-ethylphenyl) ethyl, 2- (3-ethylphenyl) ethyl, 1- (4-methylphenyl) ethyl, 1- (3-methylphenyl) ethyl, 1- (2-methylphenyl) ethyl, 2- (4-methylphenyl) propyl, 2- (2-methylphenyl) propyl, 2- (4-ethylphenyl) propyl, 2- (2-ethylphenyl) propyl, 2- (2,3 Dimethylphenyl) propyl, 2- (2,5-dimethylphenyl) propyl, 2- (3,5-dimethylphenyl) propyl, 2- (2,4-dimethylphenyl) propyl, 2- (3,4-dimethylphenyl) ) Propyl, 2- (2,5-dimethylphenyl) butyl, 4- (1-methylethyl) phenylmethyl, 2- (4- (1,1-dimethylethyl) phenyl) ethyl, 2- (4- (1 -Methylethyl) phenyl) propyl and 2- (3- (1-methylethyl) phenyl) propyl.

  An example in which at least one hydrogen of phenyl is phenylalkyl substituted with alkyl having 1 to 10 carbon atoms, and hydrogen in the alkyl is substituted with fluorine is 3-trifluoromethylphenylmethyl, 2- (4-trifluoromethylphenyl) ethyl, 2- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexylphenyl) ethyl, 2- (4-heptadecafluorooctylphenyl) ethyl, 1- (3-trifluoromethylphenyl) ethyl, 1- (4-trifluoromethylphenyl) ethyl, 1- (4-nonafluorobutylphenyl) ethyl, 1- (4-tridecafluorohexylphenyl) ethyl, 1- ( 4-heptadecafluorooctylphenyl) ethyl, 2- (4-nonafluorobutylphenol) L) propyl, 1-methyl-1- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexylphenyl) propyl, 1-methyl-1- (4-tridecafluorohexylphenyl) ethyl, 2- (4-heptadecafluorooctylphenyl) propyl and 1-methyl-1- (4-heptadecafluorooctylphenyl) ethyl.

An example in which at least one hydrogen of phenyl is phenylalkyl substituted with alkyl having 1 to 10 carbon atoms, and —CH ₂ — in the alkyl is substituted with —CH═CH— is 2- ( 4-vinylphenyl) ethyl, 1- (4-vinylphenyl) ethyl, and 1- (2- (2-propenyl) phenyl) ethyl.

An example in which at least one hydrogen of phenyl is phenylalkyl in which alkyl having 1 to 10 carbon atoms is replaced, and —CH ₂ — in the alkyl is replaced by —O— is, for example, 4-methoxyphenylmethyl 3-methoxyphenylmethyl, 4-ethoxyphenylmethyl, 2- (4-methoxyphenyl) ethyl, 3- (4-methoxyphenyl) propyl, 3- (2-methoxyphenyl) propyl, 3- (3,4- Dimethoxyphenyl) propyl, 11- (4-methoxyphenyl) undecyl, 1- (4-methoxyphenyl) ethyl, (3-methoxymethylphenyl) ethyl, and 3- (2-nonadecafluorodecenyloxyphenyl) propyl It is.

An example in which at least one hydrogen of phenyl is phenylalkyl substituted with alkyl having 1 to 10 carbon atoms, and one of —CH ₂ — in the alkyl is substituted with cycloalkylene is another — Examples including the case where CH ₂ — is replaced by —O— are cyclopentylphenylmethyl, cyclopentyloxyphenylmethyl, cyclohexylphenylmethyl, cyclohexylphenylethyl, cyclohexylphenylpropyl, and cyclohexyloxyphenylmethyl.

An example in which at least one hydrogen of phenyl is phenylalkyl substituted with alkyl having 1 to 10 carbon atoms, and one of —CH ₂ — in the alkyl is substituted with phenylene, is another —CH 2 ₂ - when the illustrated, including when they are replaced by -O-, 2- (4-phenoxyphenyl) ethyl, 2- (4-phenoxyphenyl) propyl, 2- (2-phenoxyphenyl) propyl, 4- biphenylene Rylmethyl, 3-biphenylylethyl, 4-biphenylylethyl, 4-biphenylylpropyl, 2- (2-biphenylyl) propyl, and 2- (4-biphenylyl) propyl.

  Examples of phenylalkyl in which at least two hydrogens of phenyl are replaced by different groups are 3- (2,5-dimethoxy-3,4,6-trimethylphenyl) propyl, 3-chloro-2-methylphenylmethyl, 4 -Chloro-2-methylphenylmethyl, 5-chloro-2-methylphenylmethyl, 6-chloro-2-methylphenylmethyl, 2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmethyl, 2 , 3-dichloro-4-methylphenylmethyl, 2,5-dichloro-4-methylphenylmethyl, 3,5-dichloro-4-methylphenylmethyl, 2,3,5-trichloro-4-methylphenylmethyl, 2, , 3,5,6-tetrachloro-4-methylphenylmethyl, 2,3,4,6-tetrachloro-5-methylphenylmethyl 2,3,4,5-tetrachloro-6-methylphenylmethyl, 4-chloro-3,5-dimethylphenylmethyl, 2-chloro-3,5-dimethylphenylmethyl, 2,4-dichloro-3, 5-dimethylphenylmethyl, 2,6-dichloro-3,5-dimethylphenylmethyl, 2,4,6-trichloro-3,5-dimethylphenylmethyl, 3-bromo-2-methylphenylmethyl, 4-bromo- 2-methylphenylmethyl, 5-bromo-2-methylphenylmethyl, 6-bromo-2-methylphenylmethyl, 3-bromo-4-methylphenylmethyl, 2,3-dibromo-4-methylphenylmethyl, 2, 3,5-tribromo-4-methylphenylmethyl, 2,3,5,6-tetrabromo-4-methylphenylmethyl, and 11- (3-chloro -4-methoxyphenyl) undecyl.

  A more preferable example of phenyl constituting phenylalkyl is unsubstituted phenyl and phenyl having at least one of fluorine, alkyl having 1 to 4 carbon atoms, vinyl and methoxy as a substituent.

Examples of phenylalkyl in which —CH ₂ — of alkylene constituting phenylalkyl is replaced by —O— or / and cycloalkylene are 3-phenoxypropyl, phenylcyclohexyl, and phenoxycyclohexyl. Examples of phenylalkyl in which — (CH ₂ ) ₂ — of alkylene constituting phenylalkyl is replaced by —CH═CH— are 1-phenylvinyl, 2-phenylvinyl, 3-phenyl-2-propenyl, 4- Phenyl-4-pentenyl.

Examples of phenylalkyl in which the hydrogen of phenyl is replaced by fluorine or methyl and the — (CH ₂ ) ₂ — of alkylene is replaced by —CH═CH— are 4-fluorophenylvinyl, 2,3-difluorophenylvinyl 2,3,4,5,6-pentafluorophenylvinyl, and 4-methylphenylvinyl.

Among the above examples relating to R ^1, preferred examples are phenyl alkyl composed of alkyl having 1 to 8 carbon atoms, phenyl, naphthyl, phenyl having a substituent, or phenyl and alkylene which may have a substituent. is there. More preferred examples are phenyl, naphthyl, phenyl having a substituent, or phenylalkyl composed of an optionally substituted phenyl and alkylene. In the alkyl having 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, any —CH ₂ — may be replaced by —O—, cycloalkylene or cycloalkenylene, and any — (CH ₂ ) ₂ — may be replaced by —CH═CH—. Examples of substituted phenyl are phenyl in which at least one hydrogen has been replaced by halogen, methyl or methoxy. In phenylalkyl composed of phenyl and alkylene which may have a substituent, any hydrogen of phenyl may be replaced with fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy. In the phenylalkyl alkylene, the carbon number is 1 to 8, any —CH ₂ — may be replaced by —O— or cycloalkylene, and any — (CH ₂ ) ₂ — is — It may be replaced with CH = CH-. In these groups, when phenyl has a plurality of substituents, these substituents may be the same group or different groups. And it is preferable that all R < ¹ > in Formula (1) is the same group selected from these preferable examples of R < ¹ >.

More specific examples of R ¹ are phenyl, phenyl halide, phenyl having at least one methyl, methoxyphenyl, naphthyl, phenylmethyl, phenylethyl, phenylbutyl, 2-phenylpropyl, 1-methyl-2- Phenylethyl, pentafluorophenylpropyl, 4-ethylphenylethyl, 3-ethylphenylethyl, 4- (1,1-dimethylethyl) phenylethyl, 4-vinylphenylethyl, 1- (4-vinylphenyl) ethyl, 4 -Methoxyphenylpropyl and phenoxypropyl. Of these examples, phenyl is most preferred.

In Formula (1), Q ¹ is hydrogen, halogen, alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or at least one hydrogen is halogen or alkyl having 1 to 5 carbons Is replaced by phenyl. In each of the alkyl having 1 to 10 carbons and the alkyl having 1 to 5 carbons which is a substituent of phenyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced with —CH═CH— or —C≡C— and any hydrogen may be replaced with a halogen.

Preferred examples of Q ¹ are hydrogen, chlorine, alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons. It is. At this time, in the alkyl having 1 to 10 carbon atoms, arbitrary — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and arbitrary hydrogen may be replaced with fluorine. Then, in the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, arbitrary -CH 2 _- may be replaced by -O-, arbitrary hydrogen may be replaced by fluorine.

More preferred examples of Q ¹ are hydrogen, chlorine, —CF ₃ , —OCF ₃ , methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy , Methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, 2-fluoroethyl, 3-fluoropropyl, vinyl, 1-propenyl, 2-propenyl , Allyl, 3-butenyl, 3-pentenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.

ここに、Ａ^１、Ａ^２、Ａ^３およびＡ^４は、独立して１，４−シクロヘキシレンまたは１，４−フェニレンである。これらの環において任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−ＣＨ＝は−Ｎ＝で置き換えられてもよい。１，４−シクロヘキシレンにおいては、隣り合わない２つの炭素が架橋されていてもよい。そして、すべての環における任意の水素はハロゲン、−ＣＮ、−ＮＯ_２または炭素数１〜５のアルキルで置き換えられてもよい。環の置換基である炭素数１〜５のアルキルにおいて、任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲンで置き換えられてもよい。 In the formula (1), Q ² is a group represented by the formula (2).

Here, A ¹ , A ² , A ³ and A ⁴ are independently 1,4-cyclohexylene or 1,4-phenylene. In these rings, arbitrary —CH ₂ — may be replaced by —O—, and arbitrary —CH═ may be replaced by —N═. In 1,4-cyclohexylene, two carbons that are not adjacent to each other may be cross-linked. Any hydrogen in all rings may be replaced with halogen, —CN, —NO _2, or alkyl having 1 to 5 carbon atoms. In the alkyl having 1 to 5 carbon atoms as the ring substituent, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) ₂ — represents —CH═CH— or —C ≡C— may be replaced, and any hydrogen may be replaced with a halogen.

Preferred examples of A ^{1 to} A ⁴ include 1,4-cyclohexylene, 1,4-phenylene, bicyclo [3.1.0] cyclohexane-3,6-diyl, bicyclo [2.2.2] cyclooctane- 1,4-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, at least one hydrogen is fluorine or carbon 1,4-cyclohexylene substituted with alkyl having 1 to 5 and 1,4-phenylene in which at least one hydrogen is replaced with fluorine, chlorine or alkyl having 1 to 5 carbons.

More preferred examples of A ^{1 to} A ⁴ are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by fluorine or methyl. , And 1,4-phenylene in which at least one hydrogen is replaced by fluorine, chlorine, methyl, ethyl or propyl. Besides these, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, and pyridazine-3,6-diyl are also preferred. More preferable examples of A ^{1 to} A ⁴ include 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro- 1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2-methyl-1,4- Phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 3-methyl-1,4-phenylene, 3-ethyl-1,4-phenylene, and 3-propyl-1,4 -Phenylene.

Z ⁰ , Z ¹ , Z ² , Z ³ and Z ⁴ in the formula (2) are linking groups. Z ⁰ is alkylene having 1 to 10 carbons. Then, arbitrary _-CH 2 - in this alkylene, -O -, - COO- or may be replaced by -OCO-. A preferred example of Z ⁰ is alkylene having 1 to 8 carbons in which any —CH ₂ — may be replaced by —O—. In order to bond a large group to Si, a Grignard reaction or a hydrosilylation reaction is usually used. When utilizing a hydrosilylation reaction, a large group is bonded to Si via —C ₂ H ₄ —. That is, a preferable example of Z ⁰ in the formula (2) is (Si) —C ₂ H ₄ — (CH ₂ ) _f —, (Si) —C ₂ H when the bonding point to Si is represented by (Si). _{4 - (CH 2) f -O} -, (Si) -C 2 H 4 -O- (CH 2) h -, and _{(Si) -C 2 H 4 -CH} 2 -O- (CH 2) h - It is. In these formulas, f is an integer of 0 to 5, and h is an integer of 1 to 4. At this time, k in Formula (2) is 1. When using the Grignard reaction, k in formula (2) is zero. The case where k is 1 and Z ⁰ is methylene is also an example utilizing the Grignard reaction. In addition, when it is not necessary to consider hydrolysis, you may make Si-Cl group and the big group which has a hydroxyl group at the terminal react. At this time, Z ⁰ is —O—.

Z ¹ , Z ² and Z ³ in formula (2) are each independently a single bond, —O—, —CH═CH—, —C≡C—, —COO—, —OCO—, or C 1-10. Of alkylene. In the alkylene having 1 to 10 carbon atoms, arbitrary —CH ₂ — may be replaced by —O—, —S—, —NH—, —SiR ² ₂ —, —COO—, or —OCO—. , Any — (CH ₂ ) ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen may be replaced with fluorine. A plurality of consecutive —CH ₂ — may be replaced with —SiR ² ₂ O—, —OSiR ² ₂ —, or —OSiR ² ₂ O—. R ² is alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons. In each of the alkyl having 1 to 10 carbons and the alkyl having 1 to 5 carbons which is a substituent of phenyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced with —CH═CH— or —C≡C— and any hydrogen may be replaced with a halogen.

Preferred examples of Z ^{1 to} Z ³ are a single bond, —O—, —CH═CH—, —C≡C—, —COO—, —OCO—, and alkylene having 1 to 10 carbon atoms. In the alkylene, any —CH ₂ — may be replaced by —O—, —NH—, —COO—, or —OCO—, and any — (CH ₂ ) ₂ — represents —CH═ CH— or —C≡C— may be replaced, and any hydrogen may be replaced with fluorine.

More preferable examples of Z ^{1 to} Z ³ include a single bond, —O—, —CH═CH—, —C≡C—, —COO—, —OCO—, alkylene having 1 to 4 carbon atoms, —CF ₂ CF _{2 -, - CH 2 O -} , - OCH 2 -, - CF 2 O-, and -OCF ₂ - is.

Z ⁴ in the formula (2) is a single bond or alkylene having 1 to 10 carbon atoms. In the alkylene having 1 to 10 carbon atoms, arbitrary —CH ₂ — may be replaced by —O—, —NH—, —SiR ² ₂ —, —COO—, or —OCO—, and any — (CH ₂ ) ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen may be replaced with fluorine. R ² is alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons. In each of the alkyl having 1 to 10 carbons and the alkyl having 1 to 5 carbons which is a substituent of phenyl, any —CH ₂ — may be replaced by —O—, and any — (CH ₂ ) _2- may be replaced with —CH═CH— or —C≡C— and any hydrogen may be replaced with a halogen.

Preferred examples of Z ⁴ are a single bond and alkylene having 1 to 10 carbon atoms in which any —CH ₂ — may be replaced by —O—, —COO—, —OCO— or —SiR ² ₂ —. . In this case, preferred examples of R ² are alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl or phenyl.

More preferable examples of Z ⁴ include a single bond, alkylene having 1 to 4 carbon atoms, oxyalkylene having 1 to 4 carbon atoms, —Si (Me) ₂ — (CH ₂ ) ₃ —, —Si (Ph) ₂ — ( CH _{2) 3} -, and _{-Si (Me) 2 -O-Si} (Me) 2 - (CH 2) 3 - is. Here, Me is methyl and Ph is phenyl.

Y in Formula (2) is a group having 2-oxapropane-1,3-dioyl. 2-oxapropane-1,3-dioyl is the following divalent group. This group is an acid anhydride group. That is, compound (1) is tetracarboxylic dianhydride.

The groups shown below are examples of groups having 2-oxapropane-1,3-dioyl.

The example which further actualized Formula (2) is shown next. In the following formulas, Z ⁰ , Z ¹ , Z ² , Z ³ and Z ⁴ have the same meaning as those symbols in formula (2). The groups representing 1,4-cyclohexylene, 1,4-phenylene and pyridine-2,5-diyl are each used as a representative group described in the right column.

  Of the above formulas, Formula (1-1) to Formula (1-42) and Formula (1-46) to Formula (1-86) are more preferable, and Formula (1-1) to Formula (1-31) are more preferable. ) And formulas (1-46) to (1-75) are more preferable.

Next, the manufacturing method of the compound (1) used by this invention is demonstrated. Compound (1) can be produced as shown in Scheme 1 using the compound represented by formula (1m) as a starting material.
<Scheme 1>

That is, in the presence of a basic compound such as triethylamine, a compound represented by the formula (1m) and a dichlorosilane derivative represented by the formula (3) are reacted in an organic solvent to represent the formula (1-a). Can be obtained. In the above scheme, R ¹ , Q ¹ and Q ² have the same meaning as those symbols in formula (1), respectively, and M is a monovalent alkali metal ion. The compound (1m) can be produced by hydrolyzing and polycondensing the silane compound R ¹ SiA ₃ in the presence or absence of an organic solvent in the presence of a monovalent alkali metal hydroxide and water. . A is a hydrolyzable group, preferably chlorine and alkoxy having 1 to 4 carbon atoms. Examples of monovalent alkali metal hydroxides are lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide. Of these, sodium hydroxide and potassium hydroxide are preferred. The amount of monovalent alkali metal hydroxide used is 0.3 to 1.5 in terms of a molar ratio to the silane compound. A more preferred molar ratio is 0.4 to 0.8. And the quantity of the water to add is 1.0-1.5 in the molar ratio with respect to a silane compound. A more preferred molar ratio is 1.1 to 1.3. A preferable example of the organic solvent is a linear, branched or cyclic monohydric alcohol. Alcohols are presumed to contribute to structure control during the condensation process.

Compound (1) can also be obtained by utilizing a hydrosilylation reaction as shown in Scheme 2.
<Scheme 2>

That is, first, the compound (1m) and the dichlorosilane derivative represented by the formula (3a) are reacted to obtain a compound (1-H). Next, in the presence of a platinum catalyst, this can be reacted with a terminal alkenyl compound represented by formula (3b) to obtain compound (1-b). In this scheme, R ¹ , Q ¹ , M and Y are as defined above, and Q ³ is a residue obtained by removing Z ⁰ and Y from formula (2). The above scheme is an example in the case where Z ⁰ in Formula (2) is —CH ₂ CH ₂ —.

The next example is a method utilizing the Grignard reaction.
<Scheme 3>

スキーム４における記号の意味は前記の通りである。前記の化合物（１−Ｃｌ）と末端に水酸基を有する化合物（３ｅ）との脱ＨＣｌ反応により、化合物（１−ｄ）を得ることができる。 In Scheme 3, X is halogen, and the meanings of other symbols are as described above. First, the compound (1m) is reacted with a trichlorosilane derivative represented by the formula (3c) to obtain a compound (1-Cl). And compound (1-c) can be obtained by Grignard reaction of this compound (1-Cl) and compound (3d).
Compound (1) can also be produced according to Scheme 4.
<Scheme 4>

The meanings of the symbols in Scheme 4 are as described above. A compound (1-d) can be obtained by deHCl reaction of the compound (1-Cl) with a compound (3e) having a hydroxyl group at the terminal.

  The linking group in formula (2) can be generated by a normal chemical method. For example, the method described in JP-A-2002-371026, pages 11 to 14 (pages 14 to 17 of EP1245660A2) can be referred to. Even when an appropriate method is not described in this publication, a method suitable for the purpose can be searched from a reference book generally sold. Examples of such books include Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Wiley & Sons, Inc., Organic Reactions ( Organic Reactions, John Wiley & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Course (Maruzen).

By applying the above scheme and the method for producing a linking group, a very large number of compounds (1) can be produced. Specific examples of the compound (1) are shown in Tables 1 to 11. These are examples relating to Z ⁰ , Q ³ and Y in formula (1-e). That is, in the formula (1), R ¹ is phenyl (Ph) and Q ¹ is methyl (Me), and the compound (1) used in the present invention is not limited to these examples.

<Table 1>

<Table 2>

<Table 3>

<Table 4>

<Table 5>

<Table 6>

<Table 7>

<Table 8>

<Table 9>

<Table 10>

<Table 11>

Next, the varnish for forming a liquid crystal alignment film of the present invention will be described.
In the following description, the liquid crystal alignment film-forming varnish of the present invention may be referred to as the varnish of the present invention. The varnish of the present invention contains a polymer obtained by reacting a compound (1) having two acid anhydride groups with a compound having at least two functional groups that react with an acid anhydride group. The functional group that reacts with the acid anhydride is a group having active hydrogen. Examples thereof include an amino group, a carboxyl group, a sulfonic acid group, a hydroxy group, a hydroxyphenyl group, an amide group, a hydrazino group, a hydrazinocarbonyl group, and a mercapto group. Preferred examples of the polymer contained in the varnish of the present invention include polyamic acid obtained by reacting compound (1) with diamine, soluble polyimide obtained by dehydration reaction of this polyamic acid, compound (1) and dicarboxylic acids. Polyamideimide obtained by reacting the mixture with diamine, and polyester obtained by reacting compound (1) with diol. Dicarboxylic acids mean dicarboxylic acids or their derivatives. Examples of dicarboxylic acid derivatives are dicarboxylic acid anhydrides, dicarboxylic acid dihalides and dicarboxylic acid diesters.

  When the above polyamic acid, soluble polyimide, polyamideimide or polyester is produced, a tetracarboxylic dianhydride other than the compound (1) (hereinafter referred to as other TCDA) may be used in combination. In that case, the preferable usage-amount of a compound (1) is 0.001 mol% or more in the ratio on the basis of the total amount of tetracarboxylic dianhydride. Although not added to the examples of the present specification, it has been confirmed by experiments that the effect of the compound (1) is recognized even at such a very small ratio. A preferable range of this ratio is 0.01 to 75 mol%, and a more preferable range is 0.01 to 50 mol%. A more preferred range is 0.1 to 50 mol%, and a particularly preferred range is 0.1 to 20 mol%. By using the compound (1) at this ratio, it is possible to form a liquid crystal alignment film in which a balance is maintained in rubbing resistance, liquid crystal alignment properties and display quality.

  The diamine or diol is selected as the minimum condition for reacting with the compound (1). The other TCDA or dicarboxylic acid used in combination with the compound (1) is only selected by reaction with such a diamine or diol, and there is no other limitation. Two or more compounds (1), other TCDAs, dicarboxylic acids, diamines and diols may be used.

  Specific examples of other TCDA and diamine include 5 to 9 pages of WO98 / 31725A1 pamphlet, 15 to 31 pages of WO99 / 33902A1 pamphlet, 16 to 35 pages of WO99 / 33923A1 pamphlet, 17 to 36 pages of WO99 / 34252A1 pamphlet, It is described in pages 15 to 39 of the WO01 / 00732A1 pamphlet. Specific examples of the dicarboxylic acid are described in part on pages 9 to 27 of the WO01 / 14457A1 pamphlet. These compounds and dicarboxylic acid derivatives can be arbitrarily selected and used.

Other preferred examples of TCDA are shown below.

  Some of the other TCDAs described above have structural isomers. Such a compound may be a single substance or a mixture of a plurality of isomers.

Next, the preferable example of diamine is shown. In the following examples, R is hydrogen or alkyl having 1 to 10 carbons. In this alkyl, any —CH ₂ — may be replaced with —O—, any — (CH ₂ ) ₂ — may be replaced with —CH═CH— or —C≡C—, and Any hydrogen may be replaced with fluorine.

上記の式において、ｎは１〜２０の整数である。

In said formula, n is an integer of 1-20.

Diamines having a silsesquioxane skeleton can also be mentioned as examples of diamines. A preferred example of a diamine having a silsesquioxane skeleton is a compound represented by formula (4).

式（５）におけるＺ^０、Ｚ^１〜Ｚ^３、Ｚ^４、Ａ^１〜Ａ^４、ｋ、ｌ、ｍ、ｎおよびｐは、式（２）におけるこれらの記号とそれぞれ同様に定義される基である。 In the formula (4), R ¹ and Q ¹ are groups defined in the same manner as those symbols in the formula (1), and Q ⁴ is a group represented by the formula (5).

Z ⁰ , Z ^{1 to} Z ³ , Z ⁴ , A ^{1 to} A ⁴ , k, l, m, n, and p in the formula (5) are groups defined similarly to these symbols in the formula (2), respectively. It is.

式（６）において、Ｒ^３およびＲ^４は独立して炭素数１〜４のアルキルまたはフェニルである。Ｒ^５は炭素数１〜１０のアルキレンであり、このアルキレン中の任意の−ＣＨ_２−は−Ｏ−またはフェニレンで置き換えられてもよい。このフェニレンの任意の水素は、炭素数１〜４のアルキルで置き換えられてもよい。そして、ｑは１〜１０の整数である。 Siloxane-based diamines having a siloxane bond can also be mentioned as examples of diamines. A preferred example of the siloxane-based diamine is a compound represented by the formula (6).

In the formula (6), R ³ and R ⁴ are independently alkyl having 1 to 4 carbons or phenyl. R ⁵ is alkylene having 1 to 10 carbon atoms, and any —CH ₂ — in the alkylene may be replaced by —O— or phenylene. Any hydrogen in the phenylene may be replaced with alkyl having 1 to 4 carbon atoms. And q is an integer of 1-10.

Preferred examples of NH ₂ —R ⁵ — in formula (6) include NH ₂ — (CH ₂ ) ₃ —, NH ₂ —C ₂ H ₄ O (CH ₂ ) ₂ —, NH ₂ —C ₂ H ₄ O ( _{CH 2) 3 -, NH 2} - (CH 2) 3 O (CH 2) 2 -, NH 2 - (CH 2) 3 O (CH 2) 3 -, NH 2 - (CH 2) 4 O (CH 2 _{) 2 -, NH 2 - (} CH 2) 4 O (CH 2) 3 -, NH 2 - (CH 2) 5 O (CH 2) 2 -, NH 2 - (CH 2) 5 O (CH 2) 3 _{-, NH 2 - (CH 2} ) 6 O (CH 2) 3 -, NH 2 - (CH 2) 6 O (CH 2) 2 -, NH 2 -Ph-C 2 H 4 -, NH 2 -Ph- _{O (CH 2) 2 -,} NH 2 -Ph-O (CH 2) 3 -, NH 2 -CH 2 -Ph-O (CH 2) 2 -, NH _{2 -CH 2 -Ph-O (CH} 2) 3 -, NH 2 -Ph-CH 2 O (CH 2) 2 -, NH 2 -Ph-CH 2 O (CH 2) 3 -, NH 2 -Ph- _{C 2 H 4 O (CH 2} ) 2 -, NH 2 -Ph-C 2 H 4 O (CH 2) 3 -, NH 2 -Ph (CH 3) -O (CH 2) 2 -, and NH ₂ - Ph (CH ₃ ) —O (CH ₂ ) ₃ —. In these examples, Ph is phenylene and Ph (CH ₃ ) is methylphenylene.

  Examples of diamines may further include diamines having a steroid skeleton side chain. Examples of steroid skeletons are cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, erygosteryl, estril, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl, melatranyl, methyltestosteryl, noretisteryl, pregnnonyl, β-sitosteryl, Stigmasteryl, testosteryl, and acetic acid cholesterol esters.

  Examples of diols are aliphatic diols, alicyclic diols and aromatic diols, with aliphatic diols being most preferred. And next preferred is an alicyclic diol. Examples of aliphatic diols are ethylene glycol, 1,2-propanediol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polybutylene glycol.

  Examples of alicyclic diols are 1,3-bis (hydroxymethyl) -cyclohexane, 1,4-bis (hydroxymethyl) -cyclohexane, 1,2-bis (hydroxymethyl) -decahydronaphthalene, 1,3- Bis (hydroxymethyl) -decahydronaphthalene, 1,4-bis (hydroxymethyl) -decahydronaphthalene, 1,5-bis (hydroxymethyl) -decahydronaphthalene, 1,6-bis (hydroxymethyl) -decahydro Naphthalene, 2,7-bis (hydroxymethyl) -decahydronaphthalene, bis (hydroxymethyl) tetralin, bis (hydroxymethyl) norbornane, bis (hydroxymethyl) tricyclodecane, and bis (hydroxymethyl) pentacyclododecane . Alkylene oxide adducts of these diols can also be used.

  Examples of aromatic diols are hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylbenzophenone, 4,4 ′-(1-methylethylidene) bisphenol , Methylene bisphenol (bisphenol F), 4,4′-cyclohexylidene bisphenol (bisphenol Z), 4,4′-sulfonyl bisphenol (bisphenol S), and alkylene oxide adducts of these diols.

  The varnish of the present invention can contain other polymers as long as the effects of the present invention are not impaired. The other polymer is a polymer obtained without using the compound (1), and examples thereof include polyamic acid, polyimide, polyamide, polyamideimide, and polyester. A desirable ratio of the other polymer is 0.01 to 99.9% by weight based on the total amount of the polymer components contained in the varnish. A more preferable range of this ratio is 30 to 98% by weight, and a further preferable range is 50 to 96% by weight.

  In the following description, a polymer obtained by using compound (1), which is polyamic acid, soluble polyimide, polyamideimide or polyester, or a mixture of two or more thereof, means a polymer having a silsesquioxane skeleton. May be referred to as “SQ polymer”. The varnish of the present invention is a composition in a state where an SQ polymer and other components added as necessary are dissolved in a solvent. The other component is a component other than the SQ polymer, and means another polymer and / or an additive other than the polymer obtained without using the compound (1).

  When the compound (1) or the organic acid component containing the compound (1) is reacted with diamine or diol in a solvent, a solution of SQ polymer is obtained. Depending on the type of raw material selected, the SQ polymer can be any of polyamic acid, soluble polyimide, polyamideimide, polyester, and mixtures of two or more thereof. This solution itself may be used as the varnish of the present invention. The varnish of the present invention can also be obtained by mixing reaction liquids containing different types of SQ polymers. The reaction product may be separated from the reaction solution and dissolved in a solvent different from the reaction solvent to obtain a varnish. The simplest method for separating the reaction products is to distill off the solvent under reduced pressure. When a solvent having a high boiling point is used, a method of adding a poor solvent to precipitate the polymer component may be used in combination.

  In producing the SQ polymer, a monoamino compound or a dicarboxylic anhydride may be used in combination in order to form a reaction terminal of the polymer. Examples of monoamino compounds are alkylamines, anilines, and cyclohexylamine, and examples of dicarboxylic acid anhydrides are maleic anhydride, phthalic anhydride, and nadic anhydride. In order to further improve the adhesion of the alignment film to the glass substrate, a silane-based or titanium-based coupling agent may be added to the varnish of the present invention. Examples of silane coupling agents are aminopropyltrimethoxysilane, aminopropyltriethoxysilane, vinyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane. Silicone oils such as polydimethylsiloxane and polydiphenylsiloxane may be used.

  The amount of the coupling agent or silicone oil used is 0.01 to 5% by weight based on the total amount of polymer in the varnish. A preferred range for this proportion is 0.1 to 3% by weight. However, this range is a general standard when a silane coupling agent is used, and is not characteristic of the present invention.

  In addition to the above coupling agent, other additives can be blended in the varnish of the present invention as necessary. For example, when it is desired to improve the coating property and the antistatic property, a surfactant corresponding to each purpose may be blended. Examples of the surfactant are an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant, and these can be used as long as the properties of the alignment film are not impaired.

  A preferred concentration of the polymer component in the varnish of the present invention is 0.1 to 40% by weight based on the total amount of varnish. If the density | concentration of a polymer component exists in this range, the varnish for liquid crystal aligning film formation which has suitable viscosity will be obtained. And since it is also easy to dilute this, it can adjust to an optimal film thickness. In the case of the spinner method or printing method, the concentration of the polymer component is usually 10% by weight or less in order to keep the film thickness good. In other coating methods, for example, dipping, the concentration may be further reduced. In the usual spinner method and printing method, the concentration of the polymer component is 0.1% by weight or more, preferably 0.5 to 10% by weight. However, depending on the application method of the varnish for forming a liquid crystal alignment film, it may be used at a dilute concentration.

  The conditions for selecting the solvent used in the varnish of the present invention are only to have the ability to dissolve the raw materials used in polymer production, the polymer obtained, and the like, and there are no other particular limitations. Therefore, it may be appropriately selected according to the purpose from a solvent usually used for producing polyamic acid, soluble polyimide, polyamideimide, polyester and the like, and a solvent usually used for using these polymers. Examples of these solvents are aprotic polar organic solvents which are the parent solvents for polyamic acids, soluble polyimides, polyamideimides and polyesters, such as N-methyl-2-pyrrolidone (NMP), dimethylimidazolidinone, N -Methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N, N-dimethylformamide (DMF), N, N-diethylformamide, diethylacetamide, and γ- A butyl lactone (GBL) can be mentioned. These solvents may be used as a mixture. In producing the polyester, more general solvents such as ethers and ketones can be used.

  Other solvents can be used in combination for the purpose of improving coating properties. Examples of such solvents are alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether (eg, ethylene glycol monobutyl ether (BC)), diethylene glycol monoalkyl ether (eg, diethylene glycol mono). Ethyl ether), ethylene glycol monoacetate, ethylene glycol monophenyl acetate, triethylene glycol monoalkyl ether, triethylene glycol monoacetate, propylene glycol monoalkyl ether (eg, propylene glycol monobutyl ether), dialkyl malonate (eg, malonic acid) Diethyl), propylene glycol monoacetate, dipropylene glycol monoalkyl ether (eg, dipropylene glycol) Monomethyl ether), and dipropylene glycol monoacetate. These solvents may be used as a mixture.

  The alignment film of the present invention can be effectively used in any liquid crystal display element. Even in a mode in which a strong rubbing operation is performed in order to obtain a strong alignment regulating force, the effect of the present invention that no rubbing scratches are generated and there is no alignment defect is noticeable. Examples of such modes are IPS mode, STN mode, TN mode, OCB mode, ferroelectric type, anti-ferroelectric type, and the like. In the VA mode, rubbing may be performed for the purpose of controlling how the liquid crystal molecules are tilted when a voltage is applied. In this mode as well, a remarkable effect is recognized.

  Although the manufacturing method of the alignment film of this invention is not specifically limited, Specifically, it can manufacture by the following procedure. The varnish of the present invention is applied to a glass substrate with a transparent electrode or a plastic substrate with a transparent electrode by a brush coating method, a dipping method, a spinner method, a spray method or a printing method. Next, the temperature of the substrate with electrodes is set to 50 to 150 ° C., preferably 80 to 120 ° C., and the solvent is evaporated. Then, in a glass substrate with a transparent electrode, a film is formed on the surface of the glass substrate by firing at a temperature of 150 to 400 ° C., preferably 180 to 280 ° C. In particular, when a plastic substrate is used, it is preferable to perform firing at a low temperature of about 120 to 160 ° C. in consideration of the heat resistant temperature of the substrate. The alignment film of the present invention can be obtained by rubbing the film surface in one direction using, for example, a cloth.

  If the substrate surface is treated with a silane coupling agent before applying the varnish of the present invention to a glass substrate with a transparent electrode or a plastic substrate, the adhesion between the alignment film formed on the substrate surface and the substrate can be improved. Further improve.

  The liquid crystal composition used in the liquid crystal display element of the present invention is not particularly limited. In the case of a liquid crystal display element such as a TN type, STN type, IPS type, or OCB type, a liquid crystal composition having a positive dielectric anisotropy is used. Preferred examples of this liquid crystal composition include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Application Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157828, Japanese Patent Laid-Open No. 8-231960, and Japanese Patent Laid-Open No. 9-241644. JP (EP885272A1), JP-A-9-302346 (EP806466A1), JP-A-8-199168 (EP722998A1), JP-A-9-235552, JP-A-9-255958, JP-A-9-241463. (EP882711A1), JP-A-10-204016 (EP844229A1), JP-A-10-204436, JP-A-10-231482, JP-A-2000-087040, JP-A-2001-48822, and the like. .

  When the liquid crystal alignment film of the present invention is used for manufacturing a VA liquid crystal display element, a liquid crystal composition having a negative dielectric anisotropy is used. Preferred examples of this liquid crystal composition are JP-A-57-141432, JP-A-2-4725, JP-A-4-224855, JP-A-8-40953, JP-A-8-104869, JP-A-10-10168076, JP-A-10-168453, JP-A-10-236989, JP-A-10-236990, JP-A-10-236992, JP-A-10-23993, JP-A-10-236993 JP-A-10-236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10- No. 237076, JP-A-10-237448 (EP967261), JP-A-10-287 74, JP-A-10-287875, JP-A-10-291945, JP-A-11-029581, JP-A-11-080049, JP-A-2000-256307, JP-A-2001-019965, JP-A-2001-072626, JP-A-2001-192657, and the like.

  The rubbing resistance of the alignment film can be evaluated by observing or measuring the ease of scratching (scratching) caused by rubbing and the mechanical properties from the formation of the scratch to the destruction of the alignment film. . That is, according to the experiments by the present inventors, rubbing while applying a load, the load when the scratches are scratched on the alignment film, or after the scratches are formed, the alignment film is destroyed. Sometimes the load is related to the rubbing resistance of the alignment film. Therefore, the rubbing resistance can be evaluated by comparing these values. At this time, for example, the alignment film (P1) formed from a polymer having a silsesquioxane skeleton has a load when a scratch is scratched on the alignment film (P1), and the alignment film is formed from a polymer not including a silsesquioxane skeleton. When the load when scratch scratching (P2) is W2, if these ratios (W1 / W2) are 1.05 or more, it may be considered that P1 has higher rubbing resistance than P2. .

Examples are described in detail below, but the present invention is not limited to these examples. All NMR data in the examples are values measured in deuterated chloroform. GPC was used for the measurement of molecular weight, polystyrene was used as a standard solution, and DMF was used as an eluent. The meanings of symbols used in the examples are as follows.
Ph: phenyl Me: methyl DDM: 4,4′-diaminodiphenylmethane DDEt: 4,4′-diaminodiphenylethane DDS: 4,4′-diaminodiphenyl sulfide DDS4: 1,4-bis (4-aminophenylthio) butane DDS5: 1,5-bis (4-aminophenylthio) pentane APM-CH: 1, 1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane DABD: 5- (4- (4 -(4-pentylcyclohexyl) cyclohexyl) phenylmethyl) -1,3-diaminobenzene CBDA: cyclobutanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride TPA-Cl: terephthalic acid dichloride THF: tetrahydrofuran NMP: N- Methyl-2-pyrrolidone BC: Butyl cellosolve IPA: isopropyl alcohol

<Evaluation method of liquid crystal display element>
Below, the evaluation method of the liquid crystal display element used in the Example is described. In addition, the various physical-property values described in the present Example are measured values at 25 ° C.
(1) Scraping due to rubbing When a voltage was applied to the liquid crystal display element to perform display, a portion that had a display defect was visually observed.
(2) Adhesive force of the liquid crystal alignment film to the substrate For measuring the adhesion force of the alignment film to the substrate, the peeling load (load at the beginning of peeling) of the alignment film was measured using a scanning scratch tester SST101 manufactured by Shimadzu Corporation. The value was used for evaluation. The peel load measurement conditions were a stylus curvature of 10 μm, a scratch speed of 20 μm / s, an amplitude of 100 μm, and a stylus pressing speed of 5 μm / s.
(3) Pretilt angle It was performed by the crystal rotation method. The measurement wavelength is 589 nm.
(4) Voltage holding ratio It measured based on the method as described in "Mizushima et al., 14th liquid crystal discussion meeting proceedings collection, p78". The voltage applied to the cell during measurement has a gate width of 69 μs, a wave height of ± 4.5 V, and a frequency of 30 Hz or 0.3 Hz.

[Example 1]
<Synthesis of acid dianhydride having a silsesquioxane skeleton>
Compound (b) was synthesized according to the following scheme.

Compound (a) is produced from compound (a-0) and methyldichlorosilane according to Scheme 2 above.

Under a nitrogen atmosphere, compound (a) (50.0 g; 43.3 mmol) was suspended in THF (150 ml), and platinum-divinylsiloxane complex (3.0 wt% toluene solution, 320 μl) was added thereto. Heated to 90 ° C. To this mixture, allyl succinic anhydride (14.5 g; 103.5 mmol) was added dropwise over 5 minutes, and then refluxed for 7 hours. After allowing to cool and distilling off the solvent under reduced pressure, methanol (150 ml) was added and the mixture was stirred at room temperature for 2 hours. The solid precipitated by adding methanol was collected by filtration, dissolved again in THF (150 ml), added with activated carbon (6 g), and stirred at room temperature for 2 hours. After the activated carbon was filtered off, the solvent was distilled off under reduced pressure to obtain compound (b) (55.9 g).
¹ H-NMR (solvent: CDCl ₃ ): δ (ppm); 0.32 (s, 6H), 0.70 to 0.79 (t, 4H), 1.32 to 1.42 (m, 6H) 1.74-1.80 (m, 2H), 1.89-1.99 (m, 2H), 2.24-2.37 (m, 2H), 2.51-2.60 (m, 2H), 7.15-7.56 (m, 40H).
²⁹ Si-NMR (solvent: CDCl ₃ ): δ (ppm); −18.1 (d, 2Si), −78.5 (s, 4Si), −79.4 to −79.8 (t, 4Si) .

[Example 2]
<Preparation of polyamic acid varnish (1)>
DDM (2.99 g; 1.51 × 10 ⁻² mol) and dehydrated NMP (54.0 g) are charged into a 200 ml four-necked flask and dissolved by stirring under a dry nitrogen stream to bring the solution temperature to 5 ° C. Lowered. To this, the compound (b) obtained in Example 1 (0.060 g; 4.18 × 10 ⁻⁵ mol) and CBDA (2.95 g; 1.50 × 10 ⁻² mol) were added and reacted for 30 hours. I let you. At this time, the temperature of the reaction system was not particularly controlled. Finally, BC (40.0 g) was added to synthesize a polyamic acid varnish having a polymer component concentration of 6.0% by weight. This is called varnish A1. In the examples of the present invention, the thickening reaction was allowed to proceed while checking the viscosity. Then, when the increase in viscosity decreased, BC was added to stop the progress of the thickening reaction. After adding BC, the viscosity of the varnish was adjusted by heating, and the heating operation was stopped when the viscosity reached 55 to 65 mPa · s. The viscosity was measured at 25 ° C. using an E-type viscometer. And the obtained varnish was preserve | saved at low temperature.

[Example 3]
<Preparation of polyamic acid varnish (2)>
The amounts of DDM, compound (b) and CBDA used were 2.76 g (1.39 × 10 ⁻² mol), 0.600 g (4.18 × 10 ⁻⁴ mol) and 2.65 g (1.35 ×), respectively. The polyamic acid varnish having a polymer component concentration of 6.0% by weight was obtained in exactly the same manner as in Example ² except that 10 ⁻² mol) was used. This is called varnish A2.

[Example 4]
<Preparation of polyamic acid varnish (3)>
As raw materials, DDEt (1.07 g; 5.04 × 10 ⁻³ mol), APM-CH (2.75 g; 5.04 × 10 ⁻³ mol), compound (b) (0.06 g; 4.18 ×) ^10-5 mol) and PMDA (2.19 g; 1.00 × 10 ⁻² mol) were used in the same manner as in Example 2 to obtain a polyamic acid varnish. This is named Varnish B1.

[Example 5]
<Preparation of polyamic acid varnish (4)>
DDet 1.08 g (5.09 × 10 ⁻³ mol), APM-CH 2.77 g (5.09 × 10 ⁻³ mol), and compound (b) 0.600 g (4.18 × 10 ⁻⁴ mol). mol), and a polyamic acid varnish was obtained in the same manner as in Example 4 except that 2.13 g (9.77 × 10 ⁻³ mol) of PMDA was used. This is named Varnish B2.

[Example 6]
<Preparation of polyamic acid varnish (5)>
As raw materials, DABD (3.96 g; 9.14 × 10 ⁻³ mol), compound (b) (0.060 g; 4.18 × 10 ⁻⁵ mol) and PMDA (1.99 g; 9.10 × 10 ^{− A} polyamic acid varnish was obtained in the same manner as in Example 2 except that ³ mol) was used. This is called varnish C1.

[Example 7]
<Preparation of polyamic acid varnish (6)>
DABD 3.65 g (8.44 × 10 ⁻³ mol), Compound (b) 0.600 g (4.18 × 10 ⁻⁴ mol), and PMDA 1.75 g (8.02 × 10 ⁻³ mol) ) A polyamic acid varnish was obtained in the same manner as in Example 6 except that it was used. This is called varnish C2.

[Example 8]
<Preparation of methylated polyamideimide varnish (1)>
DDEt (1.08 g; 5.09 × 10 ⁻³ mol), APM-CH (2.78 g; 5.09 × 10 ⁻³ mol) and NMP (20 g) were charged into a 50 ml-3 necked flask and dried nitrogen It was dissolved by stirring under an air stream. Compound (b) (0.060 g; 4.18 × 10 ⁻⁵ mol) and PMDA (1.11 g; 5.07 × 10 ⁻³ mol) were added to this solution, and the mixture was stirred in a nitrogen stream for 1 hour. Next, TPA-Cl (1.03 g; 5.07 × 10 ⁻³ mol) was added, pyridine (1 ml) was further added, and the mixture was stirred for 2 hours. Then, acetic anhydride (20 ml) was added and reacted at 100 ° C. for 1 hour. After cooling the reaction solution, this was added to methanol (300 ml) to precipitate the product. The crude product was boiled and washed for about 30 minutes, twice with pure water (150 ml) and once with methanol (150 ml). The solid separated by filtration was vacuum-dried at 120 ° C. for 7 hours to obtain polyamideimide (4.8 g). The weight average molecular weight of this polymer was 110,000.

  The above polyamideimide (1.0 g) was placed in a three-necked flask and dissolved in NMP (20 ml). To this solution was added 60 wt% sodium hydride (94 mg; 2.3 mmol), and the mixture was stirred at room temperature for 3 hours. Methyl iodide (430 g; 3.0 mmol) was added thereto, and the mixture was further reacted at room temperature for 2 hours. Next, the reaction product was poured into pure water (300 ml) to precipitate a polymer, followed by filtration. This was boiled and washed twice with pure water (150 ml) for 30 minutes each, and then washed once with 50 ml of a pure water-IPA mixed solvent (weight ratio 1/1). The polymer separated by filtration was vacuum-dried at 120 ° C. for 8 hours to obtain the desired methylated polyamideimide (960 mg). This polymer is designated as PAI-1. The weight average molecular weight of PAI-1 was 43,000. The substitution rate from amide hydrogen to methyl group in PAI-1 was 97% as a result of determination from NMR measurement values. NMP and BC are used in the same manner as in Example 2, and a solution in which PAI-1 is dissolved is designated as varnish D1.

[Example 9]
<Preparation of methylated polyamideimide varnish (2)>
DDEt was 1.10 g (5.16 × 10 ⁻³ mol), APM-CH was 2.81 g (5.16 × 10 ⁻³ mol), and Compound (b) was 0.600 g (4.18 × 10 ⁻⁴ mol). mol), 1.08 g of ^{PMDA (4.95 × 10 -3 mol)} , and TPA-Cl) except for using 1.005g (4.95 × ¹⁰ -3 mol) and in the same manner as in example 8, Polyamideimide (4.8 g) was obtained. The weight average molecular weight of this polymer was 110,000. Next, in the same manner as in Example 8, methylation reaction of amide hydrogen was performed to obtain methylated polyamideimide (940 mg). This polymer is designated as PAI-2. The weight average molecular weight of PAI-2 was 43,000. The substitution rate from amide hydrogen to methyl group in PAI-2 was 97%. NMP and BC are used in the same manner as in Example 2, and a solution in which PAI-2 is dissolved is designated as varnish D2.

About the polymer in the varnish of Examples 2-9, the molar ratio of the compound (b) with respect to the whole quantity of the tetracarboxylic dianhydride in a raw material is shown in Table 12.
<Table 12>

[Comparative Examples 1-4]
Each varnish was obtained according to Examples 2, 4, 6 and 8, except that the compound (b) was not used and the amount of the raw material diamine was reduced by the amount of the compound (b). This is named Varnish A0, Varnish B0, Varnish C0, and Varnish D0. Varnishes A0, B0 and C0 are polyamic acid varnishes, and varnish D0 is a varnish of methylated polyamideimide.

[Examples 10 to 17]
<Preparation of mixed varnish containing varnish obtained using compound (b)>
Varnish A1 and varnish A0 were mixed such that the weight ratio of the polymer components contained in each was 1: 9 to obtain mixed varnishes A1 and A0. In exactly the same manner, from each of varnishes A2, B1, B2, C1, C2, D1 and D2 and varnish A0, mixed varnishes A2 / A0, B1 / A0, B2 / A0, C1 / A0, C2 / A0, D1 • A0 and D2 · A0 were obtained.

[Comparative Examples 5 to 7]
<Preparation of mixed varnish not containing varnish obtained using compound (1)>
Varnish B0 and varnish A0 were mixed such that the weight ratio of the polymer components contained in each was 1: 9 to obtain mixed varnish B0 · A0. In exactly the same manner, mixed varnishes C0 · A0 and D0 · A0 were obtained from each of varnishes C0 and D0 and varnish A0.

[Example 18]
Varnish A1 obtained in Example 2 was diluted with an NMP-BC mixed solvent (weight ratio 1/1) to adjust the concentration of the polymer component to 3% by weight. This diluted varnish was applied onto a substrate with a transparent electrode by a spinner and pre-baked at 80 ° C. for about 5 minutes. Next, the film was baked at 210 ° C. for 30 minutes to form an alignment film having a film thickness of 60 nm, and the surface was subjected to alignment treatment by rubbing. Prepare another same substrate, spray 20μm gap material on the alignment film surface of one substrate, and stack the other substrate with the alignment film surface facing each other, then seal with epoxy curing agent. Thus, an anti-parallel cell with a gap of 20 μm was prepared.

  The following liquid crystal composition A was injected into this cell, and the injection port was sealed with a photocuring agent. Next, heat treatment was performed at 110 ° C. for 30 minutes to produce a homogeneously aligned cell, and a liquid crystal display element for observing the alignment state was obtained. When this liquid crystal display element was sandwiched between two polarizing plates arranged in a crossed Nicol state and rotated in it, uniform and clear light and darkness without alignment defects was observed, and the liquid crystal molecules were aligned well by rubbing. It was confirmed that That is, it was determined that no scratches due to rubbing occurred on the alignment film in the cell. The pretilt angle of this liquid crystal display element was 1.2 degrees.

<Liquid crystal composition A>

Next, a liquid crystal display element for measuring voltage holding ratio was prepared in the same process except that the gap was set to 6.8 μm, and the voltage holding ratio was measured. As a result, the voltage holding ratios at 30 Hz and 0.3 Hz were 98.2% and 93.0%, respectively. No Vth unevenness was observed.
Next, baking was carried out under the same conditions as described above except that the film was applied on a substrate with a transparent electrode with a spinner so as to have a film thickness of 1 μm, thereby preparing a scratch test substrate. The adhesion of the liquid crystal alignment film to the substrate was measured on the substrate using a scanning scratch tester SST101. As a result, the peeling load was 0.113N.

[Examples 19 to 33]
According to the method of Example 18 except that the varnish shown in Table 13 was used instead of the varnish A1, a liquid crystal display element for observing the alignment state, a liquid crystal display element for measuring voltage holding ratio, and a scratch test substrate were prepared. Created for each varnish. The results of evaluation in the same manner as in Example 18 are shown in Table 13 together with the data of Example 18. In Examples 22, 23, 30 and 31, the liquid crystal composition B was used in place of the liquid crystal composition A.

<Liquid crystal composition B>

[Comparative Examples 8-14]
A liquid crystal display element for observing the alignment state, for measuring the voltage holding ratio, according to the method of Example 18 except that a varnish containing no polymer obtained by using compound (1) in place of varnish A1 was used. A liquid crystal display element and a scratch test substrate were prepared for each varnish. The results of evaluation in the same manner as in Example 18 are shown in Table 13. In Comparative Examples 10 and 13, the liquid crystal composition B was used in place of the liquid crystal composition A.

（注１）削り傷の有無の欄において、◎は配向膜面にラビングによる削り傷がなく、液晶の配向が良好であることを示し、×はラビング方向にスジ、傷が認められ、また液晶の配向に乱れが観察されたことを示す。
（注２）表示ムラの欄において、◎はＶｔｈムラが認められなかったことを示し、×はＶｔｈムラが観察されたことを示す。 <Table 13>

(Note 1) In the column of presence or absence of scratches, ◎ indicates that the alignment film surface is free of rubbing due to rubbing and the liquid crystal orientation is good, x indicates streaks and scratches in the rubbing direction, and the liquid crystal It shows that disorder was observed in the orientation.
(Note 2) In the display unevenness column, “◎” indicates that Vth unevenness was not recognized, and “x” indicates that Vth unevenness was observed.

[Example 34]
<Preparation of polyamic acid varnish (7)>
A polyamic acid varnish was prepared in the same manner as in Example 2 except that DDS (2.82 g), compound (b) (0.56 g), CBDA (1.20 g) and PMDA (1.42 g) were used as raw materials. Obtained. This is called varnish E1.

[Example 35]
<Preparation of polyamic acid varnish (8)>
A polyamic acid varnish was prepared in the same manner as in Example 2 except that DDS4 (3.32 g), compound (b) (0.47 g), CBDA (1.01 g) and PMDA (1.19 g) were used as raw materials. Obtained. This is called varnish F1.

[Example 36]
<Preparation of polyamic acid varnish (9)>
A polyamic acid varnish was prepared in the same manner as in Example 2 except that DDS5 (3.40 g), compound (b) (0.46 g), CBDA (0.98 g) and PMDA (1.16 g) were used as raw materials. Obtained. This is called varnish G1.

[Example 37]
<Preparation of polyamic acid varnish (10)>
A polyamic acid varnish was prepared in the same manner as in Example 2 except that DDet (2.80 g), compound (b) (0.56 g), CBDA (1.21 g) and PMDA (1.43 g) were used as raw materials. Obtained. This is called varnish H1.

Table 14 shows the molar ratio of the compound (b) to the total amount of tetracarboxylic dianhydride in the raw materials for the polymers in the varnishes of Examples 34 to 37.
<Table 14>

[Comparative Examples 15 to 18]
Each varnish was obtained according to Examples 34, 35, 36 and 37 except that the compound (b) was not used and the amount of the raw material diamine was reduced by the amount of the compound (b). This is named Varnish E0, Varnish F0, Varnish G0 and Varnish H0. Varnishes E0 to H0 are polyamic acid varnishes.

[Examples 38 to 45]
<Preparation of mixed varnish containing varnish obtained using compound (b)>
Varnish E1 and varnish A0 were mixed such that the weight ratio of the polymer components contained in each was 1: 9 to obtain mixed varnish E1 · A0. In exactly the same manner, mixed varnishes F1 · A0, G1 · A0 and H1 · A0 were obtained from varnishes F1, G1 and H1 and varnish A0. In exactly the same manner, mixed varnishes H1 · E0, H1 · F0, H1 · G0 and H1 · H0 were obtained from varnish H1 and each of varnishes E0, F0, G0 and H0.

[Examples 46 to 57]
According to the method of Example 18 except that the varnish shown in Table 15 was used instead of the varnish A1, a liquid crystal display element for observing the alignment state, a liquid crystal display element for measuring voltage holding ratio, and a scratch test substrate were prepared. Created for each varnish. The results of evaluation in the same manner as in Example 18 are shown in Table 15.

（注１）削り傷の有無の欄において、◎は配向膜面にラビングによる削り傷がなく、液晶の配向が良好であることを示す。
（注２）表示ムラの欄において、◎はＶｔｈムラが認められなかったことを示す。 <Table 15>

(Note 1) In the column of presence or absence of scratches, ◎ indicates that the alignment film surface has no scratches due to rubbing, and the alignment of the liquid crystal is good.
(Note 2) In the display unevenness column, ◎ indicates that Vth unevenness was not recognized.

  As is clear from Tables 13 and 15, in the liquid crystal display element having a pretilt angle of 1.0 to 89.3 degrees, the effect of the alignment film obtained using the varnish of the present invention on rubbing scratches and abrasions was confirmed. It was. TN type liquid crystal display element, STN type liquid crystal display element, TFT type liquid crystal display element, IPS type liquid crystal display element, VA type liquid crystal display element, OCB type liquid crystal display element, ferroelectric liquid crystal display element, antiferroelectric property This means that the effects of the present invention can be expected in various types of liquid crystal display elements such as liquid crystal display elements. And the liquid crystal aligning film of this invention did not have a rubbing damage | wound and shaving, but was able to improve the adhesive force to a board | substrate. As a result, the voltage holding ratio which is one of the characteristics of the liquid crystal display element can be improved.

Claims (16)

Liquid crystal alignment film forming varnish containing a polymer obtained by using the compound represented by the formula (1):

Here, R ¹ is independently hydrogen, alkyl having 1 to 45 carbon atoms, aryl optionally having substituent (s), or arylalkyl composed of aryl optionally having substituent (s) and alkylene. In the alkyl having 1 to 45 carbon atoms, any hydrogen may be replaced by fluorine, any —CH ₂ — may be replaced by —O—, cycloalkylene or cycloalkenylene, and any — ( CH ₂ ) ₂ — may be replaced by —CH═CH—; in the arylalkyl alkylene, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O— or cycloalkylene. It may be replaced, and any - _{(CH 2) 2} - may be replaced by -CH = CH-;
Q ¹ is hydrogen, halogen, alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons. Yes; In each of alkyl having 1 to 10 carbons and alkyl having 1 to 5 carbons which is a substituent of phenyl, any —CH ₂ — may be replaced by —O—, and any — (CH _{2 2} ) may be replaced with —CH═CH— or —C≡C— and any hydrogen may be replaced with a halogen;
Q ² is a group represented by the formula (2):

Where A ¹ , A ² , A ³ and A ⁴ are independently 1,4-cyclohexylene or 1,4-phenylene; in these rings any —CH ₂ — is replaced by —O—. And any —CH═ may be replaced by —N═; in 1,4-cyclohexylene, two non-adjacent carbons may be bridged; and any ring in any ring Hydrogen may be replaced by halogen, —CN, —NO ₂ or alkyl having 1 to 5 carbons; in the alkyl having 1 to 5 carbons which is a ring substituent, any —CH ₂ — is —O—. Any — (CH ₂ ) ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen may be replaced with halogen;
Z ⁰ is alkylene having 1 to 10 carbons, and any —CH ₂ — in the alkylene may be replaced by —O—, —COO— or —OCO—;
Z ¹ , Z ² and Z ³ are each independently a single bond, —O—, —CH═CH—, —C≡C—, —COO—, —OCO— or alkylene having 1 to 10 carbons; In the alkylene having 1 to 10 carbon atoms, arbitrary —CH ₂ — may be replaced by —O—, —S—, —NH—, —SiR ² ₂ —, —COO— or —OCO—. — (CH ₂ ) ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen may be replaced with fluorine;
Z ⁴ is a single bond or alkylene having 1 to 10 carbons; in the alkylene having 1 to 10 carbons, any —CH ₂ — may be —O—, —NH—, —SiR ² ₂ —, —COO—. Or —OCO— may be replaced, any — (CH ₂ ) ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen may be replaced with fluorine. Well; R ² bonded to Si is alkyl of 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or at least one hydrogen is replaced by halogen or alkyl of 1 to 5 carbons Each of the alkyl having 1 to 10 carbon atoms and the alkyl having 1 to 5 carbon atoms which is a substituent of phenyl. -CH ₂ - may be replaced by -O-, arbitrary - _{(CH 2) 2} - may be replaced by -CH = CH- or -C≡C-, and in any hydrogen halide May be replaced;
k is 0 or 1, and l, m, n and p are independently 0, 1, 2 or 3;
Y is a group having 2-oxapropane-1,3-dioyl. R ¹ is independently hydrogen, alkyl having 1 to 30 carbon atoms, phenyl which may have a substituent, phenylalkyl which is composed of an optionally substituted phenyl and alkylene, or naphthyl; In the alkyl having 1 to 30 carbon atoms, any hydrogen may be replaced by fluorine, any —CH ₂ — may be replaced by —O—, cycloalkylene or cycloalkenylene, and any — (CH ₂ ) ₂ — may be replaced by —CH═CH—; in the optionally substituted phenyl, any hydrogen may be replaced by halogen or alkyl having 1 to 10 carbons; in alkyl having 1 to 10 carbon atoms which is a substituent, arbitrary hydrogen may be replaced by fluorine and arbitrary -CH 2 _- -O- or phenylene May be replaced come, and any - _{(CH 2) 2} - may be replaced by -CH = CH-; and, in the alkylene phenylalkyl, the number of carbon atoms is 1 to 12, any Hydrogen may be replaced with fluorine, any —CH ₂ — may be replaced with —O— or cycloalkylene, and any — (CH ₂ ) ₂ — may be replaced with —CH═CH—. The varnish according to claim 1. R ¹ is independently alkyl having 1 to 8 carbon atoms, phenyl which may have a substituent, phenyl and alkylene in which arbitrary hydrogen may be replaced by fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy In the alkyl having 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, cycloalkylene, or cycloalkenylene. And any — (CH ₂ ) ₂ — may be replaced by —CH═CH—; in the optionally substituted phenyl, any hydrogen may be halogen or carbon number 1 In the alkyl having 1 to 10 carbon atoms which is a substituent of the phenyl, any hydrogen is replaced by fluorine. And any —CH ₂ — may be replaced by —O—; in the alkylene of phenylalkyl, the carbon number is 1-8, and optional —CH ₂ — is —O— or May be replaced by cycloalkylene and any — (CH ₂ ) ₂ — may be replaced by —CH═CH—;
And Q ¹ is hydrogen, halogen, phenyl, alkyl having 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms. In the alkyl having 1 to 10 carbon atoms, arbitrary — (CH ₂ ) ₂ — may be replaced by —CH═CH—, and arbitrary hydrogen may be replaced by halogen; phenyl substituent The varnish of claim 1, wherein in the alkyl having 1 to 5 carbon atoms, optional —CH ₂ — may be replaced with —O—, and optional hydrogen may be replaced with halogen. R ¹ is independently alkyl having 1 to 8 carbon atoms, phenyl which may have a substituent, phenyl and alkylene in which arbitrary hydrogen may be replaced by fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy In the alkyl having 1 to 8 carbon atoms, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be —O—, cycloalkylene, or cycloalkenylene. And any — (CH ₂ ) ₂ — may be replaced by —CH═CH—; in the optionally substituted phenyl, any hydrogen may be halogen or carbon number 1 -10 alkyl; in this C 1-10 alkyl, any hydrogen may be replaced by fluorine, and any —CH ₂ — may be replaced with —O—; in the alkylene of phenylalkyl, the carbon number thereof is 1-8, and any —CH ₂ — may be replaced with —O— or cycloalkylene. Well, and any — (CH ₂ ) ₂ — may be replaced by —CH═CH—;
Q ¹ is hydrogen, halogen, alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons; In alkyl having 1 to 10 carbon atoms, optional — (CH ₂ ) ₂ — may be replaced by —CH═CH—, and optional hydrogen may be replaced by halogen; a phenyl substituent In alkyl having 1 to 5 carbon atoms, optional —CH ₂ — may be replaced by —O—, and optional hydrogen may be replaced by halogen;
A ¹ , A ² , A ³ and A ⁴ are independently a single bond, 1,4-cyclohexylene, 1,4-phenylene, bicyclo [ 3.1.0] cyclohexane-3,6-diyl, bicyclo [2.2.2] octane-1,4-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6 Diyl, 1,4-cyclohexylene in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons, or 1,4-in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons The varnish of claim 1 which is phenylene. R ¹ is phenyl in which arbitrary hydrogen may be replaced by halogen or alkyl having 1 to 10 carbons; in this alkyl having 1 to 10 carbons, any hydrogen may be replaced by fluorine, and optional -CH ₂ - may be replaced by -O-;
Q ¹ is hydrogen, halogen, alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons; In alkyl having 1 to 10 carbon atoms, optional — (CH ₂ ) ₂ — may be replaced by —CH═CH—, and optional hydrogen may be replaced by fluorine; a phenyl substituent In alkyl having 1 to 5 carbon atoms, optional —CH ₂ — may be replaced by —O—, and optional hydrogen may be replaced by fluorine;
A ¹ , A ² , A ³ and A ⁴ are independently a single bond, 1,4-cyclohexylene, 1,4-phenylene, bicyclo [ 3.1.0] cyclohexane-3,6-diyl, bicyclo [ 2 2.2] cyclooctane-1,4-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, 1,4-cyclohexylene in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms, or 1,4-phenylene in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms Yes;
Z ⁰ is alkylene having 1 to 8 carbon atoms in which arbitrary —CH ₂ — may be replaced by —O—;
Z ¹ , Z ² and Z ³ are each independently a single bond, —O—, —CH═CH—, —C≡C—, —COO—, —OCO— or alkylene having 1 to 10 carbons; In the alkylene having 1 to 10 carbon atoms, arbitrary —CH ₂ — may be replaced by —O—, —NH—, —COO— or —OCO—, and arbitrary — (CH ₂ ) ₂ — represents —CH ═CH— or —C≡C— and any hydrogen may be replaced with fluorine;
Z ⁴ is a single bond or alkylene having 1 to 10 carbons; any —CH ₂ — in the alkylene having 1 to 10 carbons is —O—, —COO—, —OCO— or —SiR ² _2. The varnish of claim 1, which may be replaced by −.

R ¹ is phenyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbon atoms; in the alkyl having 1 to 5 carbon atoms that is a substituent of phenyl, any —CH ₂ — is -O- may be replaced, and any hydrogen may be replaced with a halogen;
Q ¹ is hydrogen, halogen, alkyl having 1 to 10 carbons, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons; In alkyl having 1 to 10 carbon atoms, optional — (CH ₂ ) ₂ — may be replaced by —CH═CH—, and optional hydrogen may be replaced by fluorine; a phenyl substituent In alkyl having 1 to 5 carbon atoms, optional —CH ₂ — may be replaced by —O—, and optional hydrogen may be replaced by fluorine;
Then, a ^{group Q 2} is represented by any one of formulas (1-1) to Formula (1-89) shown below, according to claim 1 varnish:
In the following formulas, Z ⁰ , Z ¹ , Z ² , Z ³ and Z ⁴ have the same meaning as these symbols in formula (2). And groups representing 1,4-cyclohexylene, 1,4-phenylene and pyridine-2,5-diyl are used as representatives of the groups described in the right column, respectively:

  The varnish of claim 1, wherein the polymer is a polyamic acid.   The varnish of claim 1, wherein the polymer is polyimide.   The varnish of claim 1, wherein the polymer is polyamideimide.   The varnish of claim 1, wherein the polymer is polyester.   The varnish according to claim 1, wherein the polymer is at least one selected from the group consisting of polyamic acid, polyimide, polyamideimide, and polyester.   The polymer is at least one selected from the group consisting of polyamic acid, polyimide, polyamideimide and polyester, and further contains a polymer obtained without using the compound represented by formula (1). Varnish.   The varnish according to claim 12, wherein the polymer obtained without using the compound represented by the formula (1) is at least one selected from the group consisting of polyamic acid, polyimide, polyamideimide and polyester.   The alignment film formed using the varnish of any one of Claims 1-13.   Use of the varnish according to any one of claims 1 to 13 in a liquid crystal display element.   A liquid crystal display element comprising the alignment film according to claim 14.