JP2006268038A - Liquid crystal alignment film forming varnish and liquid crystal display element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alignment layer which has no hygroscopicity, and excellent light resistance. <P>SOLUTION: An alignment layer is prepared by using a varnish for formation of a liquid crystal alignment layer containing a polymer and a solvent, which is obtained by reacting a silsesquioxane derivative shown by a formula (1-1). All Rs in the formula (1-1) are non-substitute phenyl, cyclo pentyl, cyclo hexyl, or t-butyl, and Y<SP>1</SP>is a group shown by any of formulas (a-1) to (a-6), and R<SP>a</SP>is vinyl, allyl or stilyl, and X<SP>11</SP>, X<SP>12</SP>, X<SP>13</SP>, X<SP>14</SP>and X<SP>15</SP>are the alkyl or non-substitute phenyl where the number of carbons is 1 to 4. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a varnish for forming a liquid crystal alignment film and a liquid crystal display device having an alignment film formed using the varnish.

As a liquid crystal device used as a light modulation means mounted on a projection display device such as a liquid crystal projector or a direct view display device mounted on a mobile phone or the like, for example, a liquid crystal layer is provided between a pair of substrates arranged opposite to each other. An electrode for applying a voltage to the liquid crystal layer is formed on the liquid crystal layer side of these substrates. In such a liquid crystal device, an alignment film for controlling the alignment of liquid crystal molecules when no voltage is applied is formed on the outermost surface of the pair of substrates on the liquid crystal layer side. The display is performed based on the change in the arrangement of the liquid crystal molecules.

Conventionally, as the alignment film as described above, the surface of an organic film made of polyimide or the like rubbed in a predetermined direction with a cloth or the like is widely used because of its excellent liquid crystal alignment ability (liquid crystal alignment control function). Yes. However, for example, when mounted on a projection display device or the like irradiated with light having a high light intensity of about ² to 10 lm / mm ² , the alignment film is gradually decomposed by light and heat, and after long-term use, The liquid crystal alignment control function deteriorates and the display quality deteriorates, for example, the liquid crystal molecules when no voltage is applied cannot be arranged at a desired pretilt angle. This problem is particularly noticeable when an organic polyimide film having an imide bond that is easily decomposed by light or heat is used. When mounted on a projection display device, the liquid crystal device is known to be exposed to a temperature of about 50 to 70 ° C.

In order to solve this problem, a liquid crystal device that uses an inorganic alignment film made of an inorganic material such as silicon oxide as the alignment film and aligns liquid crystal molecules by the surface shape effect of the inorganic alignment film has been proposed. This inorganic alignment film is formed by an oblique vapor deposition method in which a substrate is fixed at a certain angle, an inorganic material is vapor-deposited from one direction, and columnar structures arranged at a predetermined angle with respect to the substrate are grown. The inorganic alignment film formed in this way is superior in light resistance and heat resistance compared to an organic film such as polyimide, and can improve the durability of the liquid crystal device.

However, since an inorganic alignment film made of an inorganic material such as silicon oxide has a hygroscopic property, moisture may enter the liquid crystal device, which may cause corrosion of metal wiring in the liquid crystal device and deterioration of the drive circuit. In the above, according to the study of the present inventors, it was found that the organic / inorganic alignment film using polysilsesquioxane has no hygroscopicity and excellent light resistance.

The object of the present invention is to provide a technique capable of eliminating the drawbacks of the prior art. That is, an object of the present invention is to provide an alignment film having no hygroscopic property and excellent light resistance.

The present inventor has intensively studied to solve the above problems. As a result, by using a varnish for forming a liquid crystal alignment film containing a polymer and a solvent obtained by using a silsesquioxane derivative as shown below, a liquid crystal alignment film having no hygroscopic property and excellent light resistance can be obtained. As a result, the present invention was completed.

式（１−１）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルであり、Ｙ¹は式（ａ−１）で示される基である。Ｒ^aがビニル、アリルまたはスチリルであって、Ｘ¹¹が炭素数１〜４のアルキルまたは非置換のフェニルである。

式（２−１）において、Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルであり、Ｘ²¹の少なくとも２つは水素であり、Ｘ²¹の残りはＲ¹である。

式（３−１）において、Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルであり、Ｌは単結合、−Ｏ−、−ＣＨ₂−、−（ＣＨ₂）₂−、−（ＣＨ₂）₃−、−（ＣＨ₂）₄−、１，４−フェニレン、４，４’−ジフェニレン、４，４’−オキシ−１，１’−ジフェニレン、または式（ｃ）で示される基である。そして式（ｃ）において、Ｒ²はＲ¹と同様に定義される基であり、ｍは１〜３０の整数である。

式（４−１）におけるすべてのＲは、非置換のフェニル、シクロペンチル、シクロヘキシル、ｔ−ブチル、ｉｓｏ−ブチル、又はトリフルオロプロピルであり、Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルあり。Ｘ³¹の少なくとも２つは水素であって、その残りはＲ¹である。

式（５−１）におけるすべてのＲは、非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルである。Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルである。Ｘ³¹の少なくとも２つは水素であって、その残りはＲ¹である。

式（６−１）において、Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルである。

式（７−１）において、Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルである。
（２）Ｒが非置換のフェニルである、（１）の液晶配向膜形成用ワニス。
（３）式（１−２）で示されるシルセスキオキサン誘導体を、式（８−２）で示される化合物と反応させて得られる重合体および溶剤を含有する液晶配向膜形成用ワニス。

（４）Ｒが非置換のフェニルである、（３）の液晶配向膜形成用ワニス。
（５）式（１−３）で示されるシルセスキオキサン誘導体を、カルボン酸もしくはエポキシドと反応させて得られる重合体および溶剤を含有する液晶配向膜形成用ワニス。

式（１−３）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルであり、Ｙ³は式（ａ−３）で示される基である。Ｒ⁴は炭素数１〜２０の２価の有機基であり、Ｘ¹³は炭素数１〜４のアルキルまたは非置換のフェニルである。（６）Ｒが非置換のフェニルである、（５）の液晶配向膜形成用ワニス。
（７）式（１−４）で示されるシルセスキオキサン誘導体を、ジアミンと反応させて得られる重合体および溶剤を含有する液晶配向膜形成用ワニス。

式（１−４）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルであり、Ｙ⁴は式（ａ−４）または（ｂ−１）で示される基である。Ｒ⁴は炭素数１〜２０の２価の有機基であり、Ｘ¹⁴は炭素数１〜４のアルキルまたは非置換のフェニルである。Ｒ⁵は単結合または炭素数１〜２０の２価の有機基であり、Ｘ¹⁴は炭素数１〜４のアルキルまたは非置換のフェニルである。
（８）ジアミンのうち少なくとも１種類以上が式（９−１）で示されるシルセスキオキサ
ン誘導体である、（７）の液晶配向膜形成用ワニス

式（９−１）において、すべてのＲ⁶は炭素数１〜２０のアルキル、炭素数２〜２０のアルケニルまたは炭素数６〜２０のアリールであり、任意の−ＣＨ₂−は酸素で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよい。Ｒ⁷は単結合または炭素数１〜１５の２価の有機基、Ｒ⁸は炭素数１〜１５の３価の有機基である。
（９）Ｒが非置換のフェニルである、（７）または（８）の液晶配向膜形成用ワニス。
（１０）式（１−３）で示されるシルセスキオキサン誘導体を、式（１−４）で示されるシルセスキオキサン誘導体と反応させて得られる重合体および溶剤を含有する液晶配向膜形成用ワニス。

式（１−３）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルであり、Ｙ³は式（ａ−３）で示される基である。Ｒ⁴は炭素数１〜２０の２価の有機基であり、Ｘ¹³は炭素数１〜４のアルキルまたは非置換のフェニルである。

式（１−４）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルであり、Ｙ⁴は式（ａ−４）または（ｂ−１）で示される基である。Ｒ⁴は炭素数１〜２０の２価の有機基であり、Ｘ¹⁴は炭素数１〜４のアルキルまたは非置換のフェニルである。Ｒ⁵は単結合または炭素数１〜２０の２価の有機基であり、Ｘ¹⁴は炭素数１〜４のアルキルまたは非置換のフェニルである。
（１１）Ｒが非置換のフェニルである、（１０）の液晶配向膜形成用ワニス。
（１２）式（１−４）で示されるシルセスキオキサン誘導体を、式（１−５）で示されるシルセスキオキサン誘導体と反応させて得られる重合体および溶剤を含有する液晶配向膜形成用ワニス。

式（１−４）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルであり、Ｙ⁴は式（ａ−４）または（ｂ−１）で示される基である。Ｒ⁴は炭素数１〜２０の２価の有機基であり、Ｘ¹⁴は炭素数１〜４のアルキルまたは非置換のフェニルである。Ｒ⁵は単結合または炭素数１〜２０の２価の有機基であり、Ｘ¹⁴は炭素数１〜４のアルキルまたは非置換のフェニルである。

式（１−５）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルであり、Ｙ⁵は式（ａ−５）で示される基である。Ｒ⁴は炭素数１〜２０の２価の有機基であり、Ｘ¹⁵は炭素数１〜４のアルキルまたは非置換のフェニルである。
（１３）Ｒが非置換のフェニルである、（１２）の液晶配向膜形成用ワニス。
（１４）式（１−４）で示されるシルセスキオキサン誘導体を、式（９−１）で示されるシルセスキオキサン誘導体と反応させて得られる重合体および溶剤を含有する液晶配向膜形成用ワニス。

式（１−４）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルであり、Ｙ⁴は式（ａ−４）または（ｂ−１）で示される基である。Ｒ⁴は炭素数１〜２０の２価の有機基であり、Ｘ¹⁴は炭素数１〜４のアルキルまたは非置換のフェニルである。Ｒ⁵は単結合または炭素数１〜２０の２価の有機基であり、Ｘ¹⁴は炭素数１〜４のアルキルまたは非置換のフェニルである。

式（９−１）において、すべてのＲ⁶は炭素数１〜２０のアルキル、炭素数２〜２０のアルケニルまたは炭素数６〜２０のアリールであり、任意の−ＣＨ₂−は酸素で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよい。Ｒ⁷は単結合または炭素数１〜１５の２価の有機基、Ｒ⁸は炭素数１〜１５の３価の有機基である。
（１５）Ｒ⁶がフルオロアルキルまたはフルオロアリールである（１４）の液晶配向膜形
成用ワニス。
（１６）Ｒ⁶がトリフルオロメチル、３，３，３−トリフルオロプロピル、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル、トリデカフルオロ−１，１，２，２−テトラヒドロオクチル、ヘプタデカフルオロ−１，１，２，２−テトラヒドロデシル、パーフルオロ−１Ｈ，１Ｈ，２Ｈ，２Ｈ−ドデシル、パーフルオロ−１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラデシル、ペンタフルオロフェニル及び４−フルオロフェニルの何れかである（１４）の液晶配向膜形成用ワニス。
（１７）Ｒ⁸がベンゼントリイルまたはトリフルオロベンゼントリイルである（１４）の液晶配向膜形成用ワニス。
（１８）Ｒが非置換のフェニルである、（１４）の液晶配向膜形成用ワニス。
（１９）Ｒが非置換のフェニルで、Ｒ⁶がフルオロアルキルまたはフルオロアリールである（１４）の液晶配向膜形成用ワニス。
（２０）Ｒが非置換のフェニルで、Ｒ⁶がトリフルオロメチル、３，３，３−トリフルオロプロピル、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル、トリデカフルオロ−１，１，２，２−テトラヒドロオクチル、ヘプタデカフルオロ−１，１，２，２−テトラヒドロデシル、パーフルオロ−１Ｈ，１Ｈ，２Ｈ，２Ｈ−ドデシル、パーフルオロ−１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラデシル、ペンタフルオロフェニル及び４−フルオロフェニルの何れかである（１３）の液晶配向膜形成用ワニス。
（２１）Ｒが非置換のフェニルで、Ｒ⁸がベンゼントリイルまたはトリフルオロベンゼントリイルである（１４）の液晶配向膜形成用ワニス。
（２２）（１）〜（２１）のいずれかの液晶配向膜形成用ワニスを用いて形成される配向膜を有することを特徴とする液晶表示素子。 That is, the present invention has the following configuration.
(1) A silsesquioxane derivative represented by the formula (1-1) is represented by a compound represented by the formula (2-1), a compound represented by the formula (3-1), and a formula (4-1). A compound obtained by reacting with at least one selected from the group consisting of a compound, a compound represented by formula (5-1), a compound represented by formula (6-1), and a compound represented by formula (7-1) A liquid crystal alignment film-forming varnish containing a coalescence and a solvent.

All R in Formula (1-1) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ¹ is a group represented by Formula (a-1). R ^a is vinyl, allyl or styryl, and X ¹¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.

In formula (2-1), R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl, at least two of X ²¹ are hydrogen, and the remainder of X ²¹ is R ¹ .

In Formula (3-1), R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl, and L is a single bond, —O—, —CH ₂ —, — (CH ₂ ) ₂ —, — ( CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, 1,4-phenylene, 4,4′-diphenylene, 4,4′-oxy-1,1′-diphenylene, or a group represented by formula (c) It is. In the formula (c), R ² is a group defined similarly to R ^1, and m is an integer of 1-30.

All R in the formula (4-1) are unsubstituted phenyl, cyclopentyl, cyclohexyl, t-butyl, iso-butyl, or trifluoropropyl, and R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted. With phenyl. At least two of X ³¹ are hydrogen and the rest are R ¹ .

All R in the formula (5-1) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl. R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. At least two of X ³¹ are hydrogen and the rest are R ¹ .

In the formula (6-1), R ¹ is alkyl having 1 to 4 carbons or unsubstituted phenyl.

In the formula (7-1), R ¹ is alkyl having 1 to 4 carbons or unsubstituted phenyl.
(2) The varnish for forming a liquid crystal alignment film according to (1), wherein R is unsubstituted phenyl.
(3) A varnish for forming a liquid crystal alignment film, comprising a polymer obtained by reacting a silsesquioxane derivative represented by formula (1-2) with a compound represented by formula (8-2) and a solvent.

(4) The varnish for forming a liquid crystal alignment film according to (3), wherein R is unsubstituted phenyl.
(5) A varnish for forming a liquid crystal alignment film comprising a polymer obtained by reacting a silsesquioxane derivative represented by the formula (1-3) with a carboxylic acid or an epoxide and a solvent.

All R in Formula (1-3) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ³ is a group represented by Formula (a-3). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹³ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. (6) The varnish for forming a liquid crystal alignment film according to (5), wherein R is unsubstituted phenyl.
(7) A varnish for forming a liquid crystal alignment film, comprising a polymer obtained by reacting a silsesquioxane derivative represented by the formula (1-4) with a diamine and a solvent.

All R in Formula (1-4) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ⁴ is a group represented by Formula (a-4) or (b-1). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. R ⁵ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is an alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.
(8) The varnish for forming a liquid crystal alignment film according to (7), wherein at least one of the diamines is a silsesquioxane derivative represented by the formula (9-1):

In the formula (9-1), all R ⁶ are alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons or aryl having 6 to 20 carbons, and any —CH ₂ — is replaced by oxygen. Any hydrogen may be replaced by halogen. R ⁷ is a single bond or a divalent organic group having 1 to 15 carbon atoms, and R ⁸ is a trivalent organic group having 1 to 15 carbon atoms.
(9) The varnish for forming a liquid crystal alignment film according to (7) or (8), wherein R is unsubstituted phenyl.
(10) Formation of a liquid crystal alignment film containing a polymer obtained by reacting a silsesquioxane derivative represented by formula (1-3) with a silsesquioxane derivative represented by formula (1-4) and a solvent For varnish.

All R in Formula (1-3) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ³ is a group represented by Formula (a-3). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹³ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.

All R in Formula (1-4) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ⁴ is a group represented by Formula (a-4) or (b-1). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. R ⁵ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is an alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.
(11) The varnish for forming a liquid crystal alignment film according to (10), wherein R is unsubstituted phenyl.
(12) Formation of a liquid crystal alignment film containing a polymer and a solvent obtained by reacting a silsesquioxane derivative represented by the formula (1-4) with a silsesquioxane derivative represented by the formula (1-5) For varnish.

All R in Formula (1-4) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ⁴ is a group represented by Formula (a-4) or (b-1). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. R ⁵ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is an alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.

All R in Formula (1-5) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ⁵ is a group represented by Formula (a-5). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹⁵ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.
(13) The varnish for forming a liquid crystal alignment film according to (12), wherein R is unsubstituted phenyl.
(14) Formation of liquid crystal alignment film containing a polymer obtained by reacting a silsesquioxane derivative represented by formula (1-4) with a silsesquioxane derivative represented by formula (9-1) and a solvent For varnish.

All R in Formula (1-4) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ⁴ is a group represented by Formula (a-4) or (b-1). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. R ⁵ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is an alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.

In the formula (9-1), all R ⁶ are alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons or aryl having 6 to 20 carbons, and any —CH ₂ — is replaced by oxygen. Any hydrogen may be replaced by halogen. R ⁷ is a single bond or a divalent organic group having 1 to 15 carbon atoms, and R ⁸ is a trivalent organic group having 1 to 15 carbon atoms.
(15) The varnish for forming a liquid crystal alignment film according to (14), wherein R ⁶ is fluoroalkyl or fluoroaryl.
(16) R ⁶ is trifluoromethyl, 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, perfluoro-1H, 1H, 2H, 2H-tetradecyl, pentafluoro (14) The varnish for forming a liquid crystal alignment film according to any one of phenyl and 4-fluorophenyl.
(17) The varnish for forming a liquid crystal alignment film according to (14), wherein R ⁸ is benzenetriyl or trifluorobenzenetriyl.
(18) The varnish for forming a liquid crystal alignment film according to (14), wherein R is unsubstituted phenyl.
(19) The varnish for forming a liquid crystal alignment film according to (14), wherein R is unsubstituted phenyl and R ⁶ is fluoroalkyl or fluoroaryl.
(20) R is unsubstituted phenyl, R ⁶ is trifluoromethyl, 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, perfluoro-1H, 1H, The varnish for forming a liquid crystal alignment film according to (13), which is any one of 2H, 2H-tetradecyl, pentafluorophenyl, and 4-fluorophenyl.
(21) The varnish for forming a liquid crystal alignment film according to (14), wherein R is unsubstituted phenyl and R ⁸ is benzenetriyl or trifluorobenzenetriyl.
(22) A liquid crystal display element comprising an alignment film formed using the liquid crystal alignment film forming varnish according to any one of (1) to (21).

Since the organic / inorganic alignment film using the polysilsesquioxane of the present invention has no hygroscopic property and excellent light resistance, it can be used effectively in an environment exposed to strong light such as a liquid crystal projector.

  In the following description, “silsesquioxane” may be represented by the symbol “PSQ”. Therefore, “silsesquioxane derivative” is expressed as “PSQ derivative”. A PSQ derivative represented by the formula (1-1) may be referred to as a compound (1-1). A compound represented by the formula (2-1) may be referred to as a compound (2-1). PSQ derivatives and compounds represented by other formulas may be simplified in the same manner. Hereinafter, the present invention will be described in more detail.

  In any case, the alkyl in the present invention may be a linear group, a branched group, or a part or all of a cyclic group. Specific examples of the divalent organic group include methylene, ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl and benzenediyl (phenylene).

Furthermore, difluoromethylene, tetrafluoroethanediyl, hexafluoropropanediyl, octafluorobutanediyl, perfluoropentanediyl, perfluorohexanediyl, perfluoroheptanediyl, hexafluorocyclobutanediyl, perfluoro, in which hydrogen atoms are substituted with fluorine Examples thereof include divalent groups such as cyclopentanediyl, perfluorocyclohexanediyl, and fluorobenzenediyl (fluorophenylene).

In these hydrocarbon groups, the position of the bonding group is arbitrary. For example, ethanediyl includes both 1,2-ethanediyl and 1,1-ethanediyl. Benzenediyl includes cases of 1,4-benzenediyl, 1,3-benzenediyl, and 1,2-benzenediyl. Further, any —CH ₂ — of these hydrocarbons may be substituted with oxygen, an ester bond, an amide bond or a carbonyl group. In such a case, when two or more oxygen atoms are continuous, it is not preferable because it is chemically unstable. When the compound (1-1) is used, a polymer having at least two Si—H groups as a reaction partner can be selected to obtain a polymer using a hydrosilylation reaction. In order to make the chemical structure of the obtained polymer linear without branching, it is preferable to select a compound having two Si—H groups as the reaction partner of the compound (1-1). By selecting a silsesquioxane derivative or a compound having a siloxane as such a compound, a polymer having excellent heat resistance and weather resistance can be obtained.

The 1st aspect of the polymer contained in the varnish for liquid crystal aligning film formation of this invention is the compound shown by Formula (2-1), Formula (2-1), Formula (1-1), Formula (1-1), 3-1), compound represented by formula (4-1), compound represented by formula (5-1), compound represented by formula (6-1), represented by formula (7-1) A polymer obtained by reacting with at least one of the above compounds. A polymer (polymer 1) can be obtained by subjecting these compounds to hydrosilylation polymerization using a solvent and a catalyst.

式（１−１）において、すべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルであり、特に好ましくは非置換のフェニルである。Ｙ¹は式（ａ−１）で示される基であり、Ｒ^aがビニル、アリルまたはスチリルであって、Ｘ¹¹が炭素数１〜４のアルキルまたは非置換のフェニルである。
本発明で用いる化合物（１−１）は、国際公開第03/024870号パンフレットに記載されている方法により製造することができる。
化合物（１−１）として具体的には、後述の合成例１、２で示す化合物が挙げられるが、これらには限定されない。

In the formula (1-1), all R are unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and particularly preferably unsubstituted phenyl. Y ¹ is a group represented by the formula (a-1), R ^a is vinyl, allyl or styryl, and X ¹¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.
The compound (1-1) used in the present invention can be produced by the method described in International Publication No. 03/024870 pamphlet.
Specific examples of the compound (1-1) include compounds shown in Synthesis Examples 1 and 2 described later, but are not limited thereto.

式（２−１）において、Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルであり、Ｘ²¹の少なくとも２つは水素であり、Ｘ²¹の残りはＲ¹である。

In formula (2-1), R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl, at least two of X ²¹ are hydrogen, and the remainder of X ²¹ is R ¹ .

式（３−１）において、Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルであり、Ｌは単結合、−Ｏ−、−ＣＨ₂−、−（ＣＨ₂）₂−、−（ＣＨ₂）₃−、−（ＣＨ₂）₄−、１，４−フェニレン、４，４’−ジフェニレン、４，４’−オキシ−１，１’−ジフェニレン、または式（ｃ）で示される基である、そして式（ｃ）において、Ｒ²はＲ¹と同様に定義される基であり、ｍは１〜３０の整数である。

In Formula (3-1), R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl, and L is a single bond, —O—, —CH ₂ —, — (CH ₂ ) ₂ —, — ( CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, 1,4-phenylene, 4,4′-diphenylene, 4,4′-oxy-1,1′-diphenylene, or a group represented by formula (c) In the formula (c), R ² is a group defined similarly to R ^1, and m is an integer of 1-30.

式（４−１）におけるすべてのＲは、非置換のフェニル、シクロペンチル、シクロヘキシル、ｔ−ブチル、ｉｓｏ−ブチル、又はトリフルオロプロピルであり、Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルであり、Ｘ³¹の少なくとも２つは水素であって、その残りはＲ¹である。
化合物（４−１）は特開2005-015738号公報に記載されている方法を参照して製造することができる。
化合物（４−１）として具体的には、後述の合成例１、２で示す化合物が挙げられるが、これらには限定されない。

All R in the formula (4-1) are unsubstituted phenyl, cyclopentyl, cyclohexyl, t-butyl, iso-butyl, or trifluoropropyl, and R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted. Phenyl, at least two of X ³¹ are hydrogen and the rest are R ¹ .
Compound (4-1) can be produced with reference to the method described in JP-A-2005-015738.
Specific examples of the compound (4-1) include compounds shown in Synthesis Examples 1 and 2 described later, but are not limited thereto.

式（５−１）におけるすべてのＲは、非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルである。Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルである。Ｘ³¹の少なくとも２つは水素であって、その残りはＲ¹である。
化合物（５−１）は、国際公開第2004/024741号パンフレットに記載されている方法を参照して製造することができる。
化合物（５−１）として具体的には、後述の合成例１で示す化合物が挙げられるが、これには限定されない。

All R in the formula (5-1) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl. R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. At least two of X ³¹ are hydrogen and the rest are R ¹ .
Compound (5-1) can be produced with reference to the method described in International Publication No. 2004/024741 pamphlet.
Specific examples of the compound (5-1) include, but are not limited to, compounds shown in Synthesis Example 1 described later.

式（６−１）において、Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルである。
化合物（６−１）として具体的には、後述の合成例２で示す化合物が挙げられるが、これには限定されない。

In the formula (6-1), R ¹ is alkyl having 1 to 4 carbons or unsubstituted phenyl.
Specific examples of the compound (6-1) include, but are not limited to, compounds shown in Synthesis Example 2 described later.

式（７−１）において、Ｒ¹は炭素数１〜４のアルキルまたは非置換のフェニルである。

In the formula (7-1), R ¹ is alkyl having 1 to 4 carbons or unsubstituted phenyl.

The above compounds can also be obtained from Hybrid Plastics.

  The solvent used for hydrosilylation polymerization is not particularly limited as long as it does not inhibit the progress of the reaction. Preferred solvents are hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran (THF) and dioxane, methylene chloride and tetrachloride. Halogenated hydrocarbon solvents such as carbon and ester solvents such as ethyl acetate. These solvents may be used alone or in combination. Of these solvents, aromatic hydrocarbon solvents, and toluene is most preferred. A solvent is not necessarily required, but when used, a preferred ratio of the compound of the present invention to the solvent is 0.05 to 80% by weight based on the weight of the solvent. A more desirable ratio is 30 to 70% by weight. The proportion depends on the purpose.

Hydrosilylation polymerization may be carried out at room temperature. Heating may be performed to promote polymerization. It may be cooled to control exothermic or undesirable polymerization due to polymerization. In the hydrosilylation polymerization, a catalyst can be used as necessary. By adding a hydrosilylation catalyst, the polymerization can proceed more easily. Examples of preferred hydrosilylation catalysts are Karstedt catalyst, Spier catalyst, hexachloroplatinic acid and the like, which are generally well known catalysts. Since these hydrosilylation catalysts have high reactivity, the reaction can proceed sufficiently if added in a small amount. The amount used is 10 ⁻⁹ to 1 mol% in terms of the ratio of the transition metal contained in the catalyst to the hydrosilyl group. A preferable addition ratio is 10 ⁻⁷ to 10 ⁻³ mol%. 10 ⁻⁹ mol% is the lower limit of the addition ratio required to allow the polymerization to proceed and be completed within an acceptable time. In consideration of keeping the manufacturing cost low, this ratio is preferably 1 mol% or less.

The molecular weight of the polymer obtained by hydrosilylation polymerization is preferably 3000 to 200,000. If it is 3000 or less, it will be hard to melt | dissolve in a solvent, and if it is 200,000 or more, it will gelatinize easily. More preferably, the molecular weight is 3000-20000. In the coating solution in the present invention, two or more kinds of polymers having different molecular weights may be mixed and used.

In the second aspect of the polymer contained in the varnish for forming a liquid crystal alignment film of the present invention, the silsesquioxane derivative represented by the formula (1-2) is reacted with the compound represented by the formula (8-2). It is a polymer obtained. A polymer (polymer 2) can be obtained by subjecting these compounds to a dehydration condensation reaction using a solvent and a catalyst.

式（１−２）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルであり、特に好ましくは非置換のフェニルである。Ｙ²は式（ａ−２）で示される基である。Ｘ¹²が炭素数１〜４のアルキルまたは非置換のフェニルである。
化合物（１−２）は、国際公開第03/024870号パンフレットに記載されている方法により製造することができる。
化合物（１−２）として具体的には、後述の合成例４で示す化合物が挙げられるが、これには限定されない。

All R in the formula (1-2) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and particularly preferably unsubstituted phenyl. Y ² is a group represented by the formula (a-2). X ¹² is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.
Compound (1-2) can be produced by the method described in International Publication No. 03/024870 pamphlet.
Specific examples of the compound (1-2) include, but are not limited to, compounds shown in Synthesis Example 4 described later.

式（８−２）におけるＲ¹は炭素数１〜４のアルキルまたは非置換のフェニル、Ｒ³はフェニル、ナフタレン、又はアントラセンである。
化合物（８−２）として具体的には、後述の合成例４で示す１，４−ビス（ヒドロキシジメチルシリル）ベンゼンが挙げられるが、これには限定されない。

In the formula (8-2), R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl, and R ³ is phenyl, naphthalene, or anthracene.
Specific examples of the compound (8-2) include 1,4-bis (hydroxydimethylsilyl) benzene shown in Synthesis Example 4 described later, but are not limited thereto.

Solvents used in the dehydration condensation reaction are ether solvents such as diethyl ether and diisopropyl ether, and ester solvents such as ethyl acetate, propyl acetate, and butyl acetate, which easily dissolve the compound (1-2) and the compound (8-2). And hydrocarbon solvents such as hexane and heptane, which easily dissolve the polymer, aromatic hydrocarbon solvents such as benzene, toluene and xylene, and halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride. It is preferred to use. However, it is not limited to this as long as both can be dissolved. A preferred ratio of the compound of the present invention to the solvent is 1% by weight to 80% by weight based on the weight of the solvent. A more desirable ratio is 20 to 50% by weight.

Examples of the catalyst used in the dehydration condensation reaction include triethylamine, tributylamine, diisopropylamine, N, N-diethylhexylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5. 4.0] undeca7-ene, amines such as 2,5-diazabicyclo [2.2.1] heptane, tetramethylguanidinium-2-ethylhexoate, and the like. The catalyst concentration is 0.01 to 10.0% with respect to the substrate. Preferably it is 0.1 to 1.0%.

The dehydration condensation reaction can proceed by azeotropic dehydration.

The molar ratio of the reaction of the compound (1-2) and the compound (8-2) is such that the ratio of the compound (1-2) is 10 mol% to 80 mol%. Preferably they are 50 mol%-75 mol%.

The molecular weight of the polymer obtained by the dehydration condensation reaction is preferably 3000 to 1,000,000.

A third aspect of the polymer contained in the varnish for forming a liquid crystal alignment film of the present invention is a polymer obtained by reacting a silsesquioxane derivative represented by the formula (1-3) with a carboxylic acid or an epoxide. is there. A polymer (polymer 3) can be obtained by reacting a silsesquioxane derivative represented by the formula (1-3) with one or more of carboxylic acid and epoxide in an organic solvent.

式（１−３）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、又はｔ−ブチルであり、特に好ましくは非置換のフェニルである。Ｙ³は式（ａ−３）で示される基である。Ｒ⁴は炭素数１〜２０の２価の有機基であり、Ｘ¹³は炭素数１〜４のアルキルまたは非置換のフェニルである。
化合物（１−３）は、国際公開第03/024870号パンフレットに記載されている方法により製造することができる。
化合物（１−３）として具体的には、後述の合成例３で示す化合物が挙げられるが、これには限定されない。

All R in the formula (1-3) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and particularly preferably unsubstituted phenyl. Y ³ is a group represented by the formula (a-3). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹³ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.
Compound (1-3) can be produced by the method described in International Publication No. 03/024870 pamphlet.
Specific examples of the compound (1-3) include, but are not limited to, compounds shown in Synthesis Example 3 described later.

The carboxylic acid used is a polyvalent carboxylic acid selected from tetracarboxylic acids or dicarboxylic acids. The term “tetracarboxylic acid” is used as a general term including tetracarboxylic acid, ester of tetracarboxylic acid, acid anhydride and acid halide. Dicarboxylic acids are similarly defined terms.

Tetracarboxylic acids may belong to any group of aliphatic, alicyclic and aromatic groups. These may contain siloxane groups or may be optically active. Some tetracarboxylic dianhydrides have isomers, but a mixture containing them may also be used. Two or more tetracarboxylic dianhydrides may be used in combination. When two or more tetracarboxylic dianhydrides are used, two or more may be selected from the same type, or at least one may be selected from different types. In addition, although the tetracarboxylic dianhydride used for this invention is illustrated below, it is not limited to the following exemplary compound.

Examples of the aliphatic tetracarboxylic dianhydride are ethanetetracarboxylic dianhydride and butanetetracarboxylic dianhydride. Examples of alicyclic tetracarboxylic dianhydrides include cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, bicycloheptane tetracarboxylic dianhydride, bicyclooctane tetracarboxylic dianhydride, bicyclo [2.2.2] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclohexane-1,2,5,6-tetracarboxylic dianhydride, 3, 4- Dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, 3,3′-bicyclohexyl-1,1 ′, 2,2′-tetracarboxylic dianhydride, 2,3 , 5-tricarboxycyclopentylacetic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 1,3,3 , 4,5,9b-Hexahydro-5-tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 3,5,6-tricarboxynorbornane 2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, and tetracyclo [6.2.11, 3.02,7] dodecane-4,5,9,10-tetra Carboxylic dianhydride. Furthermore, the acid dianhydride shown by the following structural formula can be mentioned. In these compounds, any hydrogen may be replaced with lower alkyl such as methyl and ethyl.

Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, naphthalene dianhydride (2,3,6,7 -Naphthalene anhydride etc.), 3,3'-4,4'-diphenylmethanetetracarboxylic dianhydride, 3,3'-4,4'-diphenylethanetetracarboxylic dianhydride, 3,3'- 4,4'-diphenylpropanetetracarboxylic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′- Bis (3,4-dicarboxyfe Noxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenylmethyl) diphenylmethane dianhydride, 4,4′-bis (3,4-dicarboxyphenylmethyl) diphenylethane dianhydride 4,4′-bis (3,4-dicarboxyphenylmethyl) diphenylpropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylmethane dianhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diphenylethane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoropropylene Dendiphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylsulfine oxide dianhydride, p-pheny Len-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, and Bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride.

The dicarboxylic acids may belong to any group of aliphatic, alicyclic and aromatic groups. These may contain siloxane groups or may be optically active. Some dicarboxylic acids have isomers, but a mixture containing them may also be used. Two or more dicarboxylic acids may be used in combination. When two or more dicarboxylic acids are used, two or more may be selected from the same type, or at least one may be selected from different types. In addition, although the dicarboxylic acid used for this invention is illustrated below, it is not limited to the following exemplary compound.

Examples of aliphatic dicarboxylic acids are malonic acid, succinic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethyl Glutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid.

Examples of alicyclic dicarboxylic acids are 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutane. Dicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4- Dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3- Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4- (2-norvol Dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo [2.2.2] octane-1,4-dicarboxylic acid, bicyclo [2.2.2] octane-2,3-dicarboxylic acid, 2, 5-dioxo-1,4-bicyclo [2.2.2] octanedicarboxylic acid, 1,3-adamantane dicarboxylic acid, 4,8-dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro [3. 3] Heptanedicarboxylic acid, 1,3-adamantanediacetic acid, and camphoric acid.

Examples of aromatic dicarboxylic acids are o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethyl Terephthalic acid, tetramethyl terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1, 4-anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4 "-terphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid 4,4′-diphenylethanedicarboxylic acid, 4,4′-diphenylpro Dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-tolane Dicarboxylic acid, 4,4′-carbonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 4,4′-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3′-p-phenylenedipropionic acid 4-carboxycinnamic acid, p-phenylene diacrylic acid, 3,3 ′-(4,4 ′-(methylenedi-p-phenylene)) dipropionic acid, 4,4 ′-(4,4 ′-(oxydi) -P-phenylene)) dipropionic acid, 4,4 '-(4,4'-(oxydi-p-phenylene)) dibutyric acid, (isopropylidenedi-p-phenylenedioxy) dibutyric acid, and bis (p - Ruboxyphenyl) dimethylsilane.

Examples of dicarboxylic acids containing heterocycles are 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, , 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 3,5-pyridinedicarboxylic acid.

Epoxides may belong to any group of aliphatic, alicyclic and aromatic, and these may contain siloxane groups or may be optically active. Some epoxides have isomers, but a mixture containing them may be used. Two or more epoxides may be used in combination. When two or more epoxides are used, two or more may be selected from the same type, or at least one may be selected from different types.

The 4th aspect of the polymer contained in the varnish for liquid crystal aligning film formation of this invention is a polymer obtained by making the silsesquioxane derivative shown by Formula (1-4) react with diamine. A polymer (polymer 4) can be obtained by reacting compound (1-4) and diamine in an organic solvent.

式（１−４）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、ｔ−ブチルであり、特に好ましくは非置換のフェニルである。Ｙ⁴は式（ａ−４）または（ｂ−１）で示される基である。Ｒ⁴は炭素数１〜２０の２価の有機基であり、Ｘ¹⁴は炭素数１〜４のアルキルまたは非置換のフェニルである。Ｒ⁵は単結合または炭素数１〜２０の２価の有機基である。
化合物（１−４）は、国際公開第03/024870号パンフレットに記載されている方法により製造することができる。
化合物（１−４）として具体的には、後述の合成例３，５で示す化合物が挙げられるが、これらには限定されない。

All R in the formula (1-4) are unsubstituted phenyl, cyclopentyl, cyclohexyl and t-butyl, and particularly preferably unsubstituted phenyl. Y ⁴ is a group represented by the formula (a-4) or (b-1). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. R ⁵ is a single bond or a divalent organic group having 1 to 20 carbon atoms.
Compound (1-4) can be produced by the method described in International Publication No. 03/024870 pamphlet.
Specific examples of the compound (1-4) include compounds shown in Synthesis Examples 3 and 5 described later, but are not limited thereto.

The diamine may belong to any group of aliphatic, alicyclic, and aromatic, and these may contain siloxane groups or silsesquioxanes or may be optically active. Good. Examples of aliphatic diamines are ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, and hexamethylene diamine. In these alkylene diamines, a diamine having a structure in which any —CH ₂ — is replaced by —O— may be used. Some diamines have isomers, but a mixture containing them may also be used. Two or more diamines may be used in combination. And when using two or more diamines, two or more may be selected from the same type, or at least one may be selected from different types. The diamine used in the present invention is exemplified below, but is not limited to the following exemplified compounds.

Examples of alicyclic diamines include 1,4-diaminodicyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4,4′-diaminodicyclohexylmethane, bis ( 2-Methyl-4-aminocyclohexyl) methane, isophoronediamine, 2,5-bis (aminomethyl) -bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) -bicyclo [2.2. 1] heptane, 2,3-diaminobicyclo [2.2.1] heptane, 2,5-diaminobicyclo [2.2.1] heptane, 2,6-diaminobicyclo [2.2.1] heptane, 2 , 7-diaminobicyclo [2.2.1] heptane, 2,3-diamino-7-azabicyclo [2.2.1] heptane, 2,5-diamino-7-azabicyclo [2.2.1] heptane, 2,6-diamino-7-azabicyclo [2.2.1] heptane, 2,3-diamino-7-thiabicyclo [2.2.1] heptane, 2,5-diamino -7-thiabicyclo [2.2.1] heptane, 2,6-diamino-7-thiabicyclo [2.2.1] heptane, 2,3-diaminobicyclo [2.2.2] octane, 2,5- Diaminobicyclo [2.2.2] octane, 2,6-diaminobicyclo [2.2.2] octane, 2,5-diaminobicyclo [2.2.2] octane-7-ene, 2,5-diamino -7-azabicyclo [2.2.2] octane, 2,5-diamino-7-oxabicyclo [2.2.2] octane, 2,5-diamino-7-thiabicyclo [2.2.2] octane, 2,6-diaminobicyclo [3.2 1] Octane, 2,6-diaminoazabicyclo [3.2.1] octane, 2,6-diaminooxabicyclo [3.2.1] octane, 2,6-diaminothiabicyclo [3.2.1] Octane, 2,6-diaminobicyclo [3.2.2] nonane, 2,6-diaminobicyclo [3.2.2] nonane-8-ene, 2,6-diamino-8-azabicyclo [3.2. 2] nonane, 2,6-diamino-8-oxabicyclo [3.2.2] nonane, and 2,6-diamino-8-thiabicyclo [3.2.2] nonane.

Examples of aromatic diamines are 2,2-bis (4-aminophenyl) propane, 2,6-diaminopyridine, bis- (4-aminophenyl) diethylsilane, bis- (4-aminophenyl) diphenylsilane, bis -(4-aminophenyl) ethylphosphine oxide, bis- (4-aminophenyl) -N-butylamine, N, N-bis- (4-aminophenyl) -N-methylamine, N- (3-aminophenyl) -4-aminobenzamide, 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 2,2-bis (3-aminophenyl) propane, 1,3 -Bis (3-aminophenyl) propane, 3,3'-diaminodiphenyl sulfide, 2,3,5,6-tetramethyl-p-phenyl Nylenediamine, 2,5-dimethyl-p-phenylenediamine, p-xylenediamine, m-xylenediamine, p-xylylenediamine, m-xylylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 1 , 2-bis (3-diaminophenyl) ethane, 1,1-bis (3-diaminophenyl) ethane, 4,4′-diaminodiphenylhexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1 , 5-diaminonaphthalene, 2,6-diaminonaphthalene, bis (4- (4-aminophenoxy) ) Phenyl) methane, 1,1-bis (4- (4-aminophenoxy) phenyl) ethane, 1,2-bis (4- (4-aminophenoxy) phenyl) ethane, 1,1-bis [4- ( 4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis (4- (4-aminophenoxy) phenyl) butane, 4,4′- Bis (4-aminophenoxy) diphenyl ketone, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfide, 1,3-bis (4- (4-amino) Phenoxy) phenyl) benzene, 1,4-bis (4- (4-aminophenoxy) phenyl) benzene, 4,4′-bis (4- (4-aminophenoxy) phenyl) bifu Nyl, 1,2-bis (4- (4-aminophenoxy) phenyl) cyclohexane, 1,3-bis (4- (4-aminophenoxy) phenyl) cyclohexane, 1,4-bis (4- (4-amino) Phenoxy) phenyl) cyclohexane, bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (2-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (3-Aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (3-carbamoyl-4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis- (3-sulfamoyl-4-amino) Phenyl) hexafluoropropane, 2,2-bis- (3-carboxy-4-aminophenyl) hexaful Oropropane, 2,2-bis (4- (3-sulfamoyl-4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (3-carboxy-4-aminophenoxy) phenyl) hexafluoropropane, 1,3-bis (2,2- {4- (4-aminophenoxy) phenyl} hexafluoroisopropyl) benzene, 2,4-bis (β-amino-t-butyl) toluene, bis (p-β-methyl) -Γ-aminopentyl) benzene, bis (p-1,1-dimethyl-5-aminopentyl) benzene, bis (p-β-amino-t-butylphenyl) ether, bis (4-aminobenzyloxy) Methane, bis (4-aminobenzyloxy) ethane, bis (4-aminobenzyloxy) propane, bis (4-aminobenzyloxy) silane Hexane, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4,4′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminobiphenyl, 3,3′-dimethylbenzidine, 1,3-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, bis (4-amino-3-methylphenyl) methane, bis (4 -Amino-2-methylphenyl) methane, 1,2-bis (4-amino-3-methylphenyl) ethane, 1,3-bis (4-amino-3-methylphenyl) propane, 1,2-bis ( 4-amino-2-methylphenyl) ethane, 1,3-bis (4-amino-2-methylphenyl) propane, 1,4-bis (4-aminophenyl) Nyl) benzene, 1,4-bis ((4-aminophenyl) methyl) benzene, 1,4-bis ((3-aminophenyl) methyl) benzene, 1,4-bis ((4-aminophenyl) ethyl) Benzene, 1,4-bis ((3-aminophenyl) ethyl) benzene, 1,4-bis ((4-amino-3-methyl-phenyl) methyl) benzene, 1,4-bis ((4-amino- 3-methyl-phenyl) ethyl) benzene, 4,4 ′-(4-aminophenyl) biphenyl, bis-((4- (4-aminophenylmethyl) phenyl) methane, bis-((4- (4-amino Phenylmethyl) phenyl) ethane, bis-((4- (3-aminophenylmethyl) phenyl) methane, bis-((4- (3-aminophenylmethyl) phenyl) ethane, 2,2-bis- ((4- (4-aminophenylmethyl) phenyl) propane, and 2,2-bis-((4- (3-aminophenylmethyl) phenyl) propane).

The fifth aspect of the polymer contained in the liquid crystal alignment film-forming varnish of the present invention is the silsesquioxane derivative represented by the formula (1-4), the silsesquioxane derivative represented by the formula (1-4). It is a polymer obtained by reacting with a derivative. A polymer (polymer 5) can be obtained by reacting compound (1-3) and compound (1-4) in an organic solvent.

A sixth aspect of the polymer contained in the varnish for forming a liquid crystal alignment film of the present invention is the silsesquioxane derivative represented by the formula (1-5), the silsesquioxane derivative represented by the formula (1-4). It is a polymer obtained by reacting with a derivative. A polymer (polymer 6) can be obtained by reacting compound (1-4) and compound (1-5) in an organic solvent.

式（１−５）におけるすべてのＲは非置換のフェニル、シクロペンチル、シクロヘキシル、またはｔ−ブチルであり、特に好ましくは非置換のフェニルである。Ｙ⁵は式（ａ−５）で示される基である。Ｘ¹⁵は炭素数１〜４のアルキルまたは非置換のフェニルである。Ｒ⁴は炭素数１〜２０の２価の有機基であり、
化合物（１−５）は、国際公開第03/024870号パンフレットに記載されている方法により製造することができる。
化合物（１−５）として具体的には、後述の合成例５で示す化合物が挙げられるが、これには限定されない。

All R in formula (1-5) are unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and particularly preferably unsubstituted phenyl. Y ⁵ is a group represented by the formula (a-5). X ¹⁵ is alkyl having 1 to 4 carbons or unsubstituted phenyl. R ⁴ is a divalent organic group having 1 to 20 carbon atoms,
Compound (1-5) can be produced by the method described in International Publication No. 03/024870 pamphlet.
Specific examples of the compound (1-5) include the compounds shown in Synthesis Example 5 described later, but are not limited thereto.

In a seventh embodiment of the polymer contained in the liquid crystal alignment film-forming varnish of the present invention, the silsesquioxane derivative represented by the formula (1-4) is converted into a silsesquioxane represented by the formula (9-1). It is a polymer obtained by reacting with a derivative. A polymer (polymer 7) can be obtained by reacting compound (1-4) and compound (9-1) in an organic solvent.

式（９−１）において、すべてのＲ⁶は炭素数１〜２０のアルキル、炭素数２〜２０のアルケニルまたは炭素数６〜２０のアリールであり、任意の−ＣＨ₂−は酸素で置き換えられてもよく、任意の水素はハロゲンで置き換えられてもよい。好ましくはフルオロアルキルまたはフルオロアリールであり、より好ましくはトリフルオロメチル、３，３，３−トリフルオロプロピル、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル、ト
リデカフルオロ−１，１，２，２−テトラヒドロオクチル、ヘプタデカフルオロ−１，１，２，２−テトラヒドロデシル、パーフルオロ−１Ｈ，１Ｈ，２Ｈ，２Ｈ−ドデシル、パーフルオロ−１Ｈ，１Ｈ，２Ｈ，２Ｈ−テトラデシル、ペンタフルオロフェニル及び４−フルオロフェニルの何れかである。
Ｒ⁷は単結合または炭素数１〜１５の２価の有機基である。
Ｒ⁸は炭素数１〜１５の３価の有機基であり、好ましくはベンゼントリイルまたはトリフルオロベンゼントリイルである。
なお、式（９−１）の化合物は、通常の有機化学的手法で容易に合成することによって得ることができる。すなわち、市販の不完全縮合型シルセスキオキサン誘導体（ａ）を、適当な官能基を持つトリクロロシラン誘導体で閉環する（ｂ）。この化合物（ｂ）にアミノ基へ誘導可能な官能基（具体的にはニトロ基等）を２つ有する任意の有機基を反応させ（ｃ）、得られた（ｃ）をアミノ基へ変換することで合成するのが最も一般的である。式（９−１）の化合物においてＲ⁷がエステル結合の場合の合成例を以下に示す。

In the formula (9-1), all R ⁶ are alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons or aryl having 6 to 20 carbons, and any —CH ₂ — is replaced by oxygen. Any hydrogen may be replaced by halogen. Preferably it is fluoroalkyl or fluoroaryl, more preferably trifluoromethyl, 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, tri Decafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl, perfluoro-1H, 1H, 2H , 2H-tetradecyl, pentafluorophenyl and 4-fluorophenyl.
R ⁷ is a single bond or a divalent organic group having 1 to 15 carbon atoms.
R ⁸ is a trivalent organic group having 1 to 15 carbon atoms, preferably benzenetriyl or trifluorobenzenetriyl.
In addition, the compound of Formula (9-1) can be obtained by easily synthesizing by a normal organic chemical method. That is, the commercially available incompletely condensed silsesquioxane derivative (a) is closed with a trichlorosilane derivative having an appropriate functional group (b). This compound (b) is reacted with an arbitrary organic group having two functional groups derivable to amino groups (specifically, nitro groups, etc.) (c), and the obtained (c) is converted into an amino group. Is the most common. Synthesis examples in the case where R ⁷ is an ester bond in the compound of the formula (9-1) are shown below.

式中のＲ⁶およびＲ⁸は前記と同じであり、Ｒは炭素数１〜１４の２価の有機基である。

R ⁶ and R ⁸ in the formula are the same as described above, and R is a divalent organic group having 1 to 14 carbon atoms.

In the reaction for synthesizing the polymers 3 to 7, the solvent used is not particularly limited as long as it can dissolve the monomer and the polymer without inhibiting the polymerization reaction. Specific examples include toluene, xylene, mesitylene, cyclopentanone, cyclohexanone, N-methyl-2-pyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl. Examples include sulfoxide, hexamethylphosphoric triamide, sulfolane, γ-butyrolactone, tetrahydrofuran, dioxane, dichloromethane, chloroform, and 1,2-dichloroethane. Cyclohexanone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide and tetrahydrofuran are preferred. These solvents may be used alone or in combination.

Furthermore, if necessary, a solvent having a low surface tension may be used in combination for the purpose of improving coating properties. Specific examples include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether (such as ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (diethylene glycol monoethyl ether). -Tell etc.), ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether (eg propylene glycol monobutyl ether), dialkyl malonate (malonic acid) Diethyl and the like). Many of these solvents are poor solvents with respect to the previous good solvent. Therefore, it is preferable to add such an amount that the dissolved component does not precipitate.

A varnish for forming a liquid crystal alignment film can be obtained by dissolving any of the above polymers in a solvent.
The solvent used in the coating solution in the present invention is not particularly limited as long as it is a solvent capable of dissolving the polymer. Specific examples include toluene, xylene, mesitylene, cyclopentanone, cyclohexanone, N-methyl-2-pyrrolidone, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, dimethyl. Sulfoxide, hexamethylphosphoric triamide, sulfolane, γ-butyrolactone, tetrahydrofuran, dioxane, dichloromethane, chloroform, 1,2-dichloroethane, alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl Ether (such as ethylene glycol monobutyl ether), diethylene glycol monoalkyl ether (such as diethylene glycol monoethyl ether), ethylene glycol monoalkyl ether The Feniruasete -, tri ethylene glycol - monoalkyl et - ether, propylene glycol - monoalkyl et - ether (propylene glycol - monobutyl - ether, etc.), may be mentioned dialkyl malonate (diethyl malonate, etc.). Cyclohexanone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetrahydrofuran, and propylene glycol monomethyl ether acetate are preferable. These solvents may be used alone or in combination.

The polymer concentration of the varnish for forming a liquid crystal alignment film in the present invention is not particularly limited, but is preferably 0.5% by weight to 50% by weight.

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-methacryloylpropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane and the like. Silicone oils such as polydimethylsiloxane and polydiphenylsiloxane may be blended.

The mixing ratio of the coupling agent or silicone oil to the liquid crystal alignment film forming varnish is not particularly limited. A preferable blending ratio is 0.01 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the total amount of the polymer components contained in the varnish of the present invention. However, this range is a general standard when a silane coupling agent or the like 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, a nonionic surfactant, and the like, and these can be used as long as the properties of the alignment film are not impaired.

The alignment film is formed by a step of applying a liquid crystal alignment film forming varnish onto a substrate and a subsequent baking step. As the substrate, a glass substrate, a plastic substrate, a film substrate, or the like can be used. As a coating method, a spinner method, a printing method, a dipping method, a dropping method, or the like is generally known. These methods are similarly applicable in the present invention. Moreover, as a method of baking the liquid crystal alignment film forming varnish, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are equally applicable in the present invention. Moreover, it is preferable to perform a heat processing process under the temperature of about 80-300 degreeC generally. In particular, when a plastic substrate is used, it is preferably performed at a low temperature of about 120 to 160 ° C. in consideration of the heat resistant temperature of the substrate.

A substrate on which an alignment film is formed using the varnish of the present invention and a substrate on which an alignment film that is the same as or different from this substrate is disposed oppositely, and a liquid crystal is sandwiched therebetween to form a liquid crystal sandwich substrate. Using this liquid crystal holding substrate, a liquid crystal display element having the liquid crystal holding substrate can be obtained by a known method. The operation mode of the liquid crystal display element may be a TN type, STN type, IPS type, VA type, OCB type, ferroelectric type, or antiferroelectric type. The varnish of the present invention can be used as long as the liquid crystal display element is used by controlling the alignment of the liquid crystal molecules by the alignment film and changing the alignment state of the liquid crystal molecules.

When the alignment film of the present invention is used for the production of a TN-type, STN-type, IPS-type, or OCB-type liquid crystal display element, the liquid crystal composition having a positive dielectric anisotropy used together is not particularly limited. A liquid crystal composition having a positive rate anisotropy can be used. Examples of preferable liquid crystal compositions include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent 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. (EP 8852272A1), JP-A-9-302346 (EP 806466A1), JP-A-8-199168 (EP 722998A1), JP-A-9-235552, JP-A-9-255958, JP-A-9-241463. (EP 885271A1), JP-A-10-204016 (EP 844229A1), JP-A-10-204436, JP-A-10-231482, JP-A-2000-087040, JP-A-2001-48822, etc. It is disclosed.

Further, when the alignment film of the present invention is used for the production of a VA type liquid crystal display element, the liquid crystal composition having a negative dielectric anisotropy used together is not particularly limited, and various dielectric anisotropies are negative. A liquid crystal composition can be used. Examples of preferred liquid crystal compositions include JP-A-57-141432, JP-A-2-4725, JP-A-4-224858, JP-A-8-40953, JP-A-8-104869, Japanese Laid-Open Patent Publication No. 10-168076, Japanese Laid-Open Patent Publication No. 10-168453, Japanese Laid-Open Patent Publication No. 10-236989, Japanese Laid-Open Patent Publication No. 10-236990, Japanese Laid-Open Patent Publication No. 10-236992, Japanese Laid-Open Patent Publication No. 10-236993, Japanese Laid-open Patent Publication No. -236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076 JP, 10-237448 (EP967261), JP 10-287874. 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 It is disclosed in Japanese Patent Application Laid-Open No. 2001-072626 and Japanese Patent Application Laid-Open No. 2001-192657.

  The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

(Synthesis Example 1)
Compound (1) 170.0 g (141.0 mM), Compound (2) 51.9 g (46.9 mM), Compound (3) were added to a 2 L four-necked flask equipped with a thermometer, condenser, stirrer and oil bath. ) 45.9 g (35.3 mM) and 1071 g of toluene were added, and the mixture was heated and stirred at 80 ° C. under a nitrogen seal. When the reaction solution reached 80 ° C., 100 μl of karsted catalyst was added and stirred at the same temperature for 2 hours. After completion of the stirring, the oil bath was replaced with an ice bath, and the reaction solution was cooled to 10 ° C. or lower. The reaction solution was transferred to an eggplant type flask, and the toluene solvent was removed with an evaporator. Thereafter, it was further dried at 40 ° C. and 0.4 kPa for 8 hours to obtain 265.0 g of a white solid. The molecular weight of the obtained solid was weight average molecular weight (Mw): 3200. The molecular weight here is a value measured under the following conditions in a GPC apparatus: JASCO GULLIVER 1500 (intelligent differential refractometer RI-1530) manufactured by JASCO Corporation. Column: Tosoh columns G4000HXL, G3000HXL, G2500HXL and G2000HXL are used in this order, column temperature: 40 ° C., developing solvent: THF, flow rate: 1 ml / min, standard substance: polystyrene with known molecular weight the same).

(Synthesis Example 2)
Compound (1) 170.3 g (141.2 mM), Compound (2) 51.3 g (46.4 mM), Compound (4) were added to a 2 L four-necked flask equipped with a thermometer, condenser, stirrer and oil bath. ) 11.6 g (35.3 mM) and 932.8 g of toluene were added and heated and stirred at 80 ° C. under a nitrogen seal. When the reaction solution reached 80 ° C., 100 μl of karsted catalyst was added and stirred at the same temperature for 3 hours. After completion of the stirring, the oil bath was replaced with an ice bath, and the reaction solution was cooled to 10 ° C. or lower. The reaction solution was transferred to an eggplant type flask, and the toluene solvent was removed with an evaporator. Then, it was further dried at 40 ° C. and 0.4 kPa for 8 hours to obtain 233.0 g of a white solid. The molecular weight of the obtained solid was Mw: 14600.

(Synthesis Example 3)
Compound (6) 0.50 g, N, N-dimethylacetamide 0.75 g, cyclohexanone 0.75 g were put into a 10 ml three-necked flask equipped with a thermometer, a magnetic stirrer, and a stirrer chip, and at room temperature under a nitrogen seal. The compound (6) was dissolved by stirring. Next, 0.50 g of the compound (7) was added, and the mixture was stirred as it was at room temperature for 4 hours to obtain a very light yellow transparent polyamic acid solution.

(Synthesis Example 4)
Compound (6) 0.82g, N, N-dimethylacetamide 0.75g, cyclohexanone 0.75g was placed in a 10ml three-necked flask equipped with a thermometer, magnetic stirrer and stirrer tip at room temperature under nitrogen seal. The compound (6) was dissolved by stirring. Next, 0.18 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was added, and the mixture was stirred as it was at room temperature for 4 hours to obtain a very pale yellow transparent polyamic acid solution.

(Synthesis Example 5)
A 10 ml three-necked flask equipped with a thermometer, magnetic stirrer, and stirrer tip was charged with 0.12 g of 4,4′-diaminodiphenyl ether, 0.75 g of N, N-dimethylacetamide, and 0.75 g of cyclohexanone, and sealed with nitrogen. The mixture was stirred at room temperature to dissolve 4,4′-diaminodiphenyl ether. Next, 0.88 g of compound (7) was added, and the mixture was stirred as it was at room temperature for 4 hours to obtain a very light yellow transparent polyamic acid solution.

(Synthesis Example 6)
In a 10 ml three-necked flask equipped with a thermometer, a magnetic stirrer, and a stirrer chip, 0.05 g of 4,4′-diaminodiphenyl ether, 0.27 g of compound (9), 0.75 g of N, N-dimethylacetamide, cyclohexanone 0 .75 g was added and stirred at room temperature under a nitrogen seal to dissolve 4,4′-diaminodiphenyl ether and compound (9). Next, 0.68 g of compound (7) was added, and the mixture was stirred as it was at room temperature for 4 hours to obtain a very light yellow transparent polyamic acid solution.

(Synthesis Example 7)
Compound (5) 5.00 g (4.22 mM), 1,4-bis (hydroxydimethylsilyl) benzene 0.95 g (4.22 mM), ethyl acetate 29.8 g, toluene 29.8 g in a 100 ml four-necked flask The mixture was heated and stirred at 50 ° C. under a nitrogen seal. When the liquid temperature reached 50 ° C., 0.059 g of catalyst (tetramethylguanidinium-2-ethylhexanoic acid) was added. After the catalyst was charged, azeotropic dehydration was performed for 16 hours. The reaction solution was cooled to room temperature and then filtered using a 1 μm PTFE membrane filter. The solvent was distilled off from the filtrate at room temperature under reduced pressure (0.4 kPa) to obtain 5.8 g of a white solid. The molecular weight of the obtained solid was Mw = 44700.

(Synthesis Example 8)
Into a 10 ml three-necked flask equipped with a thermometer, a magnetic stirrer, and a stirrer chip, 0.2 g of compound (8) and 1.8 g of dimethylacetamide were added and stirred under a nitrogen seal to dissolve compound (8). . Next, 0.21 g of compound (7) was added and stirred as it was.

4.01 g of the polymer obtained in Example 1 was dissolved in 6.00 g of propylene glycol monomethyl ether acetate, and this solution was filtered through a 0.2 μm PTFE filter. The resulting solution was designated as varnish 1.

4.00 g of the polymer obtained in Example 2 was dissolved in 7.01 g of propylene glycol monomethyl ether acetate, and this solution was filtered through a 0.2 μm PTFE filter. The resulting solution was named Varnish 2.

The polyamic acid solution obtained in Example 3 was filtered through a 0.2 μm PTFE filter. The resulting solution was designated as varnish 3.

The polyamic acid solution obtained in Example 4 was filtered through a 0.2 μm PTFE filter. The resulting solution was designated as varnish 4.

The polyamic acid solution obtained in Example 5 was filtered with a 0.2 μm PTFE filter. The resulting solution was designated as varnish 5.

The polyamic acid solution obtained in Example 6 was filtered through a 0.2 μm PTFE filter. The resulting solution was designated as varnish 6.

(Weather resistance test-1)
The varnishes 1 to 6 obtained in Examples 1 to 6 above and the polyamic acid varnish (comparative example 1) which is commercially available and does not contain a silsesquioxane derivative in the present invention are used as spinners on a glass substrate, respectively. And pre-baked at 80 ° C. for 3 minutes. Subsequently, it baked for 60 minutes at 230 degreeC, and formed the weathering test sample. The formed film had a thickness of 1 to 5 μm on the glass substrate.

(Weather resistance test-2)
The weather resistance test is performed using a xenon weatherometer (Ci65A type, manufactured by Atlas Co., Ltd.) according to JIS K 7350-2, with a black panel temperature of 83 ± 3 ° C., a relative humidity of 50%,
The accelerated weathering test was conducted without water spray. The appearance of the weather resistance test sample was visually observed after 250 hours and 500 hours. The results are shown in Table 1. Regarding the notation in the table, ◯: No film surface roughening or film thickness reduction, Δ: Either film surface roughening or film thickness reduction, x: Film surface roughness or film thickness reduction.

(Preparation of liquid crystal cell-1)
The polymer obtained in Synthesis Example 1 was diluted with an NMP-BC mixed solvent (weight ratio 1/1) and adjusted so that the concentration of the polymer component was 3% by weight. did. 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. Subsequently, it baked at 230 degreeC for 60 minute (s), the 60-nm-thick orientation film was formed, and the board | substrate which performed the orientation process by rubbing the whole surface was obtained. Prepare another sheet of the same substrate, sprinkle a 20 μm gap material on the alignment film surface of one substrate, and stack the other substrate so that the alignment film surfaces face each other. Then, an anti-parallel cell with a gap of 20 μm was produced.
The liquid crystal composition 1 shown below was poured into this cell, and the inlet was sealed with a photocuring agent. Next, a heat treatment was performed at 110 ° C. for 30 minutes to produce a homogeneously oriented cell. When this cell was sandwiched between two polarizing plates arranged in a crossed Nicol state and rotated inside, a uniform, clear light and darkness without alignment defects due to scratches generated on the alignment film by rubbing was observed. Were confirmed to be well oriented.

(Production of liquid crystal cell-2)
The polymer obtained in Synthesis Example 2 was diluted with an NMP-BC mixed solvent (weight ratio 1/1) and adjusted so that the concentration of the polymer component was 3% by weight. did. 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. Subsequently, it baked at 230 degreeC for 60 minute (s), the 60-nm-thick orientation film was formed, and the board | substrate which performed the orientation process by rubbing the whole surface was obtained. Prepare another sheet of the same substrate, sprinkle a 20 μm gap material on the alignment film surface of one substrate, and stack the other substrate so that the alignment film surfaces face each other. Then, an anti-parallel cell with a gap of 20 μm was produced.
The liquid crystal composition 1 shown below was poured into this cell, and the inlet was sealed with a photocuring agent. Next, a heat treatment was performed at 110 ° C. for 30 minutes to produce a homogeneously oriented cell. When this cell was sandwiched between two polarizing plates arranged in a crossed Nicol state and rotated inside, a uniform, clear light and darkness without alignment defects due to scratches generated on the alignment film by rubbing was observed. Were confirmed to be well oriented.

Hereafter, the manufacturing method of the compound used in order to manufacture the polymer contained in the varnish of this invention is illustrated as a reference example.

[Reference Example 1]
<Synthesis of Compound (3-1-1)>
In a reaction vessel having an internal volume of 50 liters equipped with a reflux condenser, a thermometer, and a stirring device, phenyltrimethoxysilane (6.54 kg), 2-propanol (26.3 liters), pure water (0.66 kg), and Sodium hydroxide (0.88 kg) was charged and sealed with dry nitrogen. The mixture was heated with stirring and reacted at reflux for 5 hours. After completion of the reaction, the heater was removed from the reaction vessel, and this vessel was left at room temperature for 15 hours to cool the reaction mixture. The supernatant was removed from the reaction mixture thus obtained by decantation. The white solid remaining in the reaction vessel was washed once with 2-propanol (9.87 kg). This was transferred to a stainless steel vat lined with a polytetrafluoroethylene sheet and dried for 24 hours at an internal temperature of 80 ° C. and a pressure of 6.7 × 10 ⁻⁴ MPa using a vacuum dryer. A white powdery compound (3-1-1) was obtained.

[Reference Example 2]
<Introduction of trimethylsilyl group into compound (3-1-1)>
A 50 ml four-necked flask equipped with a reflux condenser was charged with compound (3-1-1) (1.2 g), tetrahydrofuran (10 g), and triethylamine (1.6 g) and sealed with dry nitrogen. . While stirring with a magnetic stirrer, trimethylchlorosilane (2.2 g) was added dropwise over about 1 minute while maintaining the solution temperature at 15 to 20 ° C. After completion of the dropwise addition, stirring was continued at 15 ° C. for 3.5 hours. After completion of the reaction, the reaction product was washed with pure water and vacuum dried to obtain a white solid (1.2 g). This is designated as Compound (3-T).

[Reference Example 3]
<Synthesis of Compound (a)>
Into a three-necked flask having an internal volume of 300 ml equipped with a dropping funnel, a thermometer, and a reflux condenser, a compound (3-1-1) (11. 6 g), tetrahydrofuran (100 g) was charged, and sealed with dry nitrogen. While stirring with a magnetic stirrer, methyldichlorosilane (3.4 g) was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 hour. After completion of the reaction, 50 g of pure water was added to dissolve the generated sodium chloride and hydrolyze unreacted methyldichlorosilane. The reaction mixture thus obtained was transferred to a separatory funnel and separated into an organic layer and an aqueous layer. The obtained organic layer was washed with saturated brine, and then washed repeatedly with water until neutrality. The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure using a rotary evaporator. The obtained residue was washed with methanol and dried to obtain 6.9 g of a white powdery solid. The following analytical data suggested that this compound has a structure represented by the formula (a).
¹ H NMR (400 MHz, CDCl ₃ , TMS standard: δ = 0.0 ppm): 0.37 (s, 6H), 4.99 (s, 2H), 7.15-7.56 (m, 40H).
²⁹ Si NMR (79 MHz, CDCl ₃ , TMS standard: δ = 0.0 ppm): -32.78 (s, 2Si), -77.91 (s, 4Si),
-79.39 (t, 4Si).

[Reference Example 4]
<Production of Compound (1-3-7)>
Compound (1-3-7) was produced by the following route.

First stage: Preparation of allyl-p-nitrophenyl ether Potassium carbonate (49.7 g, 0) was added to a solution of p-nitrophenol (25.0 g, 0.18 mol) in N, N-dimethylformamide (250 ml) under a nitrogen atmosphere. .36 mol) was added and suspended, and 3-bromopropene (21.7 g, 0.18 mol) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours, water was added, and the mixture was extracted with diethyl ether. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography (elution solvent: toluene). Toluene was distilled off under reduced pressure, and then recrystallized from ethanol to obtain allyl-p-nitrophenyl ether (25.7 g).

Second stage: Production of compound (b) Under a nitrogen atmosphere, toluene (500 ml) was added to and suspended in compound (a) (50.0 g, 43.3 mmol), and a platinum-divinylsiloxane complex (3 wt% toluene solution, 25 μl). ) And heated to 90 ° C. To this, allyl-p-nitrophenyl ether (16.3 g, 91 mmol) was added dropwise over 5 minutes and heated at reflux for 2 hours. After cooling, toluene (100 ml) and water (300 ml) were added for extraction. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (elution solvent: toluene). Toluene was distilled off under reduced pressure, and then recrystallized from ethanol / ethyl acetate to obtain 18.7 g of compound (b).
¹ H-NMR (solvent: CDCl ₃ ): δ (ppm); 0.34 (s, 6H), 0.85-0.88 (t, 4H), 1.92-1.95 (m, 4H) 3.85-3.88 (t, 4H), 6.60-6.63 (d, 4H), 7.15-7.52 (m, 40H), 7.94-7.97 (d, 4H).
²⁹ Si-NMR (solvent: CDCl ₃ ): δ (ppm); −17.8 (d, 2 Si), −78.5 (s, 4 Si), −79.4 (t, 4 Si).

Third stage: Preparation of compound (1-3-7) A mixture of compound (b) (10.0 g, 6.61 mmol), Pd / C (1 g), and THF (100 ml) was stirred at room temperature under a hydrogen atmosphere at room temperature. Stir for hours. After filtering off Pd / C, THF was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (elution solvent: ethyl acetate). Ethyl acetate was distilled off under reduced pressure to obtain 6.3 g of compound (1-3-7).
¹ H-NMR (solvent: CDCl ₃ ): δ (ppm); 0.31 (s, 6H), 0.83-0.87 (t, 4H), 1.82-1.87 (m, 4H) 3.71-3.74 (t, 4H), 6.51-6.57 (d, 8H), 7.14-7.95 (m, 40H).
²⁹ Si-NMR (solvent: CDCl ₃ ): δ (ppm); −17.5 (d, 2 Si), −78.6 (s, 4 Si), −79.6 (t, 4 Si).

[Reference Example 5]
<Production of Compound (1-1-4)>
Compound (1-1-4) was produced by the following route.

Under a nitrogen atmosphere, THF (150 ml) was added and suspended in compound (a) (50.0 g, 43.3 mmol), platinum-divinylsiloxane complex (3 wt% toluene solution, 320 μl) was added, and the mixture was heated to 90 ° C. To this was added allyl succinic anhydride (14.5 g, 103.5 mmol) dropwise over 5 minutes, and the mixture was heated at reflux for 7 hours. After allowing to cool, the solvent was distilled off under reduced pressure, methanol (150 ml) was added to the resulting residue, and the mixture was stirred at room temperature for 2 hours. The solid was collected by filtration, dissolved in THF (150 ml), activated carbon (6 g) was added, and the mixture was stirred at room temperature for 2 hours. After filtering off the activated carbon, THF was distilled off under reduced pressure to obtain 55.9 g of the compound (1-1-4).
¹ H-NMR (solvent: CDCl ₃ ): δ (ppm); 0.32 (s, 6H), 0.70-0.79 (t, 4H), 1.32-1.42 (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) 2H), 7.15-7.56 (m, 40H).
²⁹ Si-NMR (solvent: CDCl ₃ ): δ (ppm); −18.1 (d, 2Si), −7
8.5 (s, 4 Si), -79.4--79.8 (t, 4 Si).

[Reference Example 6]
<Production of Compound (1-1-5)>
Compound (1-1-5) was produced by the following route.

Under a nitrogen atmosphere, toluene (50 ml) was added to and suspended in compound (a) (5.0 g, 4.33 mmol), platinum-divinylsiloxane complex (3 wt% toluene solution, 30 μl) was added, and the mixture was heated to 90 ° C. To this, allyl glycidyl ether (1.04 g, 9.1 mmol) was added dropwise and heated at reflux for 3 hours. After allowing to cool, toluene (50 ml) and water (100 ml) were added for extraction. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. Toluene was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (elution solvent: toluene / ethyl acetate). After distilling off the solvent under reduced pressure, recrystallization from ethanol / ethyl acetate gave 1.6 g of compound (1-1-5).
¹ H-NMR (solvent: CDCl ₃ ): δ (ppm); 0.30 (s, 6H), 0.73-0.76 (t, 4H), 1.66-1.72 (m, 4H) 2.42-2.44 (m, 2H), 2.64-2.66 (m, 2H), 2.95-2.98 (m, 2H), 3.15-3.19 (m, 2H) 2H), 3.28-3.39 (m, 4H), 3.44-3.48 (m, 2H), 7.18-7.53 (m, 40H).
²⁹ Si-NMR (solvent: CDCl ₃ ): δ (ppm); −17.4 (s, 2 Si), −78.6 (s, 4 Si), −79.5—−79.6 (t, 4 Si) .

Claims (22)

A silsesquioxane derivative represented by the formula (1-1) is
Compound represented by formula (2-1), compound represented by formula (3-1), compound represented by formula (4-1), compound represented by formula (5-1), formula (6-1) And a polymer obtained by reacting with at least one selected from the group consisting of the compound represented by formula (7-1) and the compound represented by formula (7-1), and a varnish for forming a liquid crystal alignment film containing a solvent.

All R in Formula (1-1) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ¹ is a group represented by Formula (a-1). R ^a is vinyl, allyl or styryl, and X ¹¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.

In formula (2-1), R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl, at least two of X ²¹ are hydrogen, and the remainder of X ²¹ is R ¹ .

In Formula (3-1), R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl, and L is a single bond, —O—, —CH ₂ —, — (CH ₂ ) ₂ —, — ( _{CH 2) 3 -, - (} CH 2) 4 -,
1,4-phenylene, 4,4′-diphenylene, 4,4′-oxy-1,1′-diphenylene, or a group represented by the formula (c). In the formula (c), R ² is R ¹
And m is an integer of 1 to 30.

All R in the formula (4-1) are unsubstituted phenyl, cyclopentyl, cyclohexyl, t-butyl, iso-butyl, or trifluoropropyl, and R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted. Phenyl; at least two of X ³¹ are hydrogen and the remainder is R ¹ .

All R in the formula (5-1) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl. R ¹ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. At least two of X ³¹ are hydrogen and the rest are R ¹ .

In the formula (6-1), R ¹ is alkyl having 1 to 4 carbons or unsubstituted phenyl.

In the formula (7-1), R ¹ is alkyl having 1 to 4 carbons or unsubstituted phenyl. The varnish for forming a liquid crystal alignment film according to claim 1, wherein R is unsubstituted phenyl. A varnish for forming a liquid crystal alignment film, comprising a polymer obtained by reacting a silsesquioxane derivative represented by formula (1-2) with a compound represented by formula (8-2), and a solvent.

The varnish for forming a liquid crystal alignment film according to claim 3, wherein R is unsubstituted phenyl. A varnish for forming a liquid crystal alignment film, comprising a polymer obtained by reacting a silsesquioxane derivative represented by the formula (1-3) with a carboxylic acid or an epoxide and a solvent.

All R in Formula (1-3) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ³ is a group represented by Formula (a-3). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹³ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. The varnish for forming a liquid crystal alignment film according to claim 5, wherein R is unsubstituted phenyl. A varnish for forming a liquid crystal alignment film, comprising a polymer obtained by reacting a silsesquioxane derivative represented by the formula (1-4) with a diamine and a solvent.

All R in Formula (1-4) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ⁴ is a group represented by Formula (a-4) or (b-1). R ⁴
Is a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. R ⁵ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is an alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. The varnish for forming a liquid crystal alignment film according to claim 7, wherein at least one of the diamines is a silsesquioxane derivative represented by the formula (9-1).

In the formula (9-1), all R ⁶ are alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons or aryl having 6 to 20 carbons, and any —CH ₂ — is replaced by oxygen. Any hydrogen may be replaced by halogen. R ⁷ is a single bond or a divalent organic group having 1 to 15 carbon atoms, and R ⁸ is a trivalent organic group having 1 to 15 carbon atoms. The varnish for forming a liquid crystal alignment film according to claim 7 and 8, wherein R is unsubstituted phenyl. A varnish for forming a liquid crystal alignment film, comprising a polymer obtained by reacting a silsesquioxane derivative represented by formula (1-3) with a silsesquioxane derivative represented by formula (1-4) and a solvent.

All R in Formula (1-3) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ³ is a group represented by Formula (a-3). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹³ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.

All R in Formula (1-4) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ⁴ is a group represented by Formula (a-4) or (b-1). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. R ⁵ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is an alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. The varnish for forming a liquid crystal alignment film according to claim 10, wherein R is unsubstituted phenyl. A varnish for forming a liquid crystal alignment film, comprising a polymer obtained by reacting a silsesquioxane derivative represented by formula (1-4) with a silsesquioxane derivative represented by formula (1-5) and a solvent.

All R in Formula (1-4) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ⁴ is a group represented by Formula (a-4) or (b-1). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. R ⁵ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is an alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.

All R in Formula (1-5) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ⁵ is a group represented by Formula (a-5). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹⁵ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. The varnish for forming a liquid crystal alignment film according to claim 12, wherein R is unsubstituted phenyl. A varnish for forming a liquid crystal alignment film, comprising a polymer obtained by reacting a silsesquioxane derivative represented by formula (1-4) with a silsesquioxane derivative represented by formula (9-1) and a solvent.

All R in Formula (1-4) is unsubstituted phenyl, cyclopentyl, cyclohexyl, or t-butyl, and Y ⁴ is a group represented by Formula (a-4) or (b-1). R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is alkyl having 1 to 4 carbon atoms or unsubstituted phenyl. R ⁵ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and X ¹⁴ is an alkyl having 1 to 4 carbon atoms or unsubstituted phenyl.

In the formula (9-1), all R ⁶ are alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons or aryl having 6 to 20 carbons, and any —CH ₂ — is replaced by oxygen. Any hydrogen may be replaced by halogen. R ⁷ is a single bond or a divalent organic group having 1 to 15 carbon atoms, and R ⁸ is a trivalent organic group having 1 to 15 carbon atoms. The varnish for forming a liquid crystal alignment film according to claim 14, wherein R ⁶ is fluoroalkyl or fluoroaryl. R ⁶ is trifluoromethyl, 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, perfluoro-1H, 1H, 2H, 2H-tetradecyl, pentafluorophenyl and 4 The varnish for forming a liquid crystal alignment film according to claim 14, which is any one of -fluorophenyl. The varnish for forming a liquid crystal alignment film according to claim 14, wherein R ⁸ is benzenetriyl or trifluorobenzenetriyl. The varnish for forming a liquid crystal alignment film according to claim 14, wherein R is unsubstituted phenyl. R is unsubstituted phenyl, for forming a liquid crystal alignment film varnish of claim 14, wherein R ⁶ is fluoroalkyl or fluoroaryl. R is unsubstituted phenyl, R ⁶ is trifluoromethyl, 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, perfluoro-1H, 1H, 2H, 2H The varnish for forming a liquid crystal alignment film according to claim 14, which is any one of tetradecyl, pentafluorophenyl, and 4-fluorophenyl. R is unsubstituted phenyl, for forming a liquid crystal alignment film varnish of claim 14, wherein R ⁸ is benzenetriyl or trifluoroacetic benzenetriyl. A liquid crystal display element comprising an alignment film formed using the varnish for forming a liquid crystal alignment film according to any one of claims 1 to 21.