KR20040099129A - Varnishes for producing alignment layers for liquid crystals, alignment layers for liquid crystals and liquid crystal display devices - Google Patents

Abstract

PURPOSE: A liquid crystal aligning agent varnish, an alignment layer formed by using the varnish and an LCD device containing the alignment layer are provided, to improve the mechanical strength of an alignment layer, the adhesion to a substrate and storage stability and to prevent the damage due to rubbing. CONSTITUTION: The liquid crystal aligning agent varnish comprises a polymer obtained by using a compound represented by the formula 1, wherein R1s are independently H, a C1-C45 alkyl group, an aryl group capable of having a substituent, or an arylalkyl group comprising an aryl group capable of having a substituent and an alkylene group; Q1 is H, a halogen atom, a C1-C10 alkyl group, a phenyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, or a phenyl whose at least one hydrogen atom is substituted with a halogen atom or a C1-C5 alkyl group; and Q2 is a group represented by the formula 2. In the formula 2, A1 to A4 are independently a 1,4-cyclohexylene group or a 1,4-phenylene group; Z0 is a C1-C10 alkylene group; Z1 to Z3 are independently a single bond, -O-, -CH=CH-, a triple bond of C-C, -COO-, -OCO- or a C1-C10 alkylene group; Z4 is a single bond or a C1-C10 alkylene group; k is 0 or 1; l, m, n and p are independently an integer of 0-3; and Y is a group having a 2-oxapropane-1,3-dioyl group.

Description

Varnish, liquid crystal aligning film, and liquid crystal display element for forming a liquid crystal aligning film TECHNICAL FIELD [0001] The ALIGNMENT LAYERS FOR LIQUID CRYSTALS AND LIQUID CRYSTAL DISPLAY DEVICES

The present invention relates to a composition for forming a liquid crystal alignment film. This invention also relates to the liquid crystal aligning film obtained from this composition, and the liquid crystal display element containing this alignment film. This composition is characterized by containing a polymer obtained by using tetracarboxylic dianhydride having a silsesquioxanes skeleton as a raw material. In addition, although "silsesquioxane" is the name of the class which shows the compound in which each silicon atom couple | bonds with three oxygen atoms, and each oxygen atom couple | bonds with two silicon atoms, in the present invention, a silsesquioxane structure and a part thereof are used. As the generic name of the modified silsesquioxane like structure, the "silseschioxane skeleton" is used.

In liquid crystal display elements, display elements using nematic liquid crystals are mainstream. Examples thereof include TN type liquid crystal display elements twisted at 90 degrees, STN type liquid crystal display elements twisted at least 180 degrees, and so-called TFT type liquid crystal display elements using thin film transistors. In recent years, in-plane switching (hereinafter referred to as IPS) type liquid crystal display device having a transverse electric field method having improved visual characteristics, and a vertical alignment using a vertical alignment state are referred to as VA. Optically Compensate Birefringence (hereinafter referred to as OCB) type liquid crystal display device and the like, which are characterized by a very fast response speed and a relatively wide viewing angle, have been proposed.

In these liquid crystal display elements, it is important to orient the long axis direction of the liquid crystal molecules uniformly. As an industrially representative method for uniformly aligning liquid crystal molecules, the following rubbing method is known. That is, it is a method of providing the alignment film which consists of an organic film on the surface of a board | substrate, rubbing the surface with cloth, such as cotton, nylon, and polyester in a fixed direction, and orienting a liquid crystal molecule in the rubbing direction. This rubbing method is industrially mainstream because stable uniform orientation is obtained relatively easily, and also excellent productivity. As the material of the alignment film, for example, polymers such as polyvinyl alcohol, polyoxyethylene, polyamide, polyimide, and polyamidoimide are known. In terms of stability and durability that can be adapted to industrial mass production, polyimides having excellent chemical stability and thermal stability are most used.

The orientation treatment method of rubbing the alignment film is an industrially useful method because of its simplicity and excellent productivity. However, as the liquid crystal display elements are used in various fields, the high performance of the liquid crystal display elements is promoted, and various problems are pointed out accordingly. For example, there are problems such as damage to the surface of the alignment film caused by rubbing as an orientation defect, shaping of the alignment film due to rubbing, and debris becoming a display defect. Such a defect due to rubbing becomes a defect if any one of them is present on the screen, and thus is one of the very large factors for yield reduction with the recent large screen. Therefore, more stringent rubbing resistance is required compared with the prior art. In recent years, an attempt has been made to bake varnish for forming a liquid crystal alignment film at a low temperature of less than 200 ° C by using a plastic film instead of a conventional glass substrate in order to lower the manufacturing cost or to reduce the weight (Japanese Patent Laid-Open No. 61-205924). See Japanese Patent Application Laid-Open No. 1 and Japanese Patent Laid-Open No. 1-239525). However, especially when polyamic acid, which is a precursor of polyimide, is applied onto a substrate and calcined at low temperature, dehydration ring closure (imidization) of polyamic acid does not proceed sufficiently, resulting in insufficient alignment of the alignment film due to insufficient mechanical strength of polyimide. Problems such as damage become more serious.

Problems of the alignment film related to the rubbing method are, for example, that the mechanical strength is insufficient, so that it cannot cope with friction due to rubbing, and that the adhesive film is peeled off due to lack of adhesion to a glass substrate or the like. These problems are considered to be attributable to the fact that the conventional organic polymer which is the main component of the alignment film contains many carbon atoms. Therefore, development of an alignment film having improved such a problem is required. The lack of mechanical strength can be improved to some extent by changing the molecular structure of the alignment film. However, it was difficult to improve the mechanical strength because the electrical characteristics of the alignment film and the pretilt angle of the liquid crystal tended to be changed by changing the structure. Adhesiveness with a glass substrate can be improved to some extent by using a silane coupling agent. However, the silane coupling agent tends to be hydrolyzed and has a problem in storage stability as a varnish for forming an alignment film. If it is used excessively for the prevention of peeling, there also existed a problem that the performance of a liquid crystal display element will be reversed.

The objective of this invention is providing the varnish for liquid crystal aligning film formation which has the mechanical strength which can cope with the friction by rubbing, and is excellent in adhesiveness with a glass substrate, and is excellent also in storage stability. Moreover, it is also the objective of this invention to provide the alignment film obtained using this varnish, and the liquid crystal display element containing this alignment film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the problem of the prior art, it turned out that it is effective to contain the polymer which has a silsesquioxane skeleton in a principal chain in the varnish for liquid crystal aligning film formation in order to solve the said problem. That is, since the liquid crystal aligning film obtained from this varnish has large mechanical strength and is excellent also in adhesiveness with respect to a glass substrate, it has high resistance to rubbing. This alignment film is also excellent in storage stability. Since the silsesquioxane skeleton in the polymer used by this invention is itself a highly crosslinked body, the site | part which hydrolysis generate | occur | produces does not exist. For this reason, in order to improve adhesiveness with respect to a glass substrate, storage stability is much better compared with the varnish for liquid crystal aligning film formation using a silane coupling agent. Moreover, a highly reliable liquid crystal aligning film which does not adversely affect the display performance of the liquid crystal display element or the like can be formed.

First, terms and symbols used in the present invention will be described. The term "any" refers to any number as well as position. For example, when expressing that arbitrary -CH ₂ -may be substituted by -O- or -CH = CH- in alkyl, some -CH ₂ -may respectively be substituted by a different group. Examples in this case are alkyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, and alkenyloxyalkyl. In the present invention, it is not preferable that two consecutive -CH ₂ -are replaced with -O- or -S- and become -O-0-, -OS- or -SS-. Alkyl and alkylene are used as including both a linear group and a branched group unless there is particular notice. For example, butyl may be any of n-butyl, 2-methylpropyl and 1,1-dimethylethyl. Halogen means fluorine, chlorine or bromine.

The present invention has the following configuration.

[1] A varnish for forming a liquid crystal alignment film containing a polymer obtained by using the compound represented by the following formula (1):

R ¹ is, independently, hydrogen, alkyl having 1 to 45 carbon atoms, aryl which may have a substituent, or arylalkyl consisting of aryl and alkylene which may have a substituent; In alkyl having 1 to 45 carbon atoms, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O-, cycloalkylene or cycloalkenylene, and optional-( CH ₂ ) ₂ -may be substituted with -CH = CH-; In alkylene of arylalkyl, arbitrary hydrogen may be substituted with fluorine, any -CH ₂ -may be substituted with -O- or cycloalkylene, and optional-(CH ₂ ) _2- May be substituted with -CH = CH-;

Q ¹ is hydrogen, halogen, alkyl of 1 to 10 carbon atoms, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which at least one hydrogen is substituted by halogen or alkyl of 1 to 5 carbon atoms Is; In each of alkyl having 1 to 5 carbon atoms which is a substituent of alkyl having 1 to 10 carbon atoms and phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary-(CH ₂ ) ₂ -is -CH May be substituted with = CH- or -C≡C-, and any hydrogen may be substituted with halogen; And Q ² is a group represented by the following formula (2):

Wherein A ¹ , A ² , A ³ and A ⁴ are independently 1,4-cyclohexylene or 1,4-phenylene; Arbitrary -CH ₂ -in these rings may be substituted with -O-, and arbitrary -CH = may be substituted with -N =; In 1,4-cyclohexylene two non-adjacent carbons may be crosslinked; Optional hydrogen in all rings may be substituted with halogen, —CN, —NO ₂ or alkyl of 1 to 5 carbon atoms; In the alkyl having 1 to 5 carbon atoms of the ring substituents, arbitrary -CH ₂ - may be substituted with -O-, arbitrary - (CH _{2) 2} - is -CH = CH- or -C≡C- May be substituted, and arbitrary hydrogen may be substituted with halogen;

Z ⁰ is alkylene having 1 to 10 carbon atoms, and any of -CH ₂ -in the alkylene may be substituted with -O-, -CO0-, or -OCO-;

Z ¹ , Z ² and Z ³ are independently a single bond, -O-, -CH = CH-, -C≡C, -CO0-, -OCO- or alkylene having 1 to 10 carbon atoms; In the alkylene having 1 to 10 carbon atoms, any -CH ₂ -may be substituted with -O-, -S-, -NH-, -SiR ² _2- , -COO-, or -OCO-, Any — (CH ₂ ) ₂ — may be substituted with —CH═CH— or —C≡C—, and any hydrogen may be substituted with fluorine;

Z ⁴ 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 substituted with -O-, -NH-, -SiR ² ₂ , -COO- or -OCO-, and arbitrary-(CH ₂ ) ₂ may be substituted with —CH═CH— or —C≡C—, and any hydrogen may be substituted with fluorine; R ² bonded to Si is alkyl having 1 to 10 carbon atoms, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or at least one hydrogen substituted with halogen or alkyl having 1 to 5 carbon atoms. Phenyl; In each of alkyl having 1 to 5 carbon atoms which is a substituent of the alkyl having 1 to 10 carbon atoms and phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary-(CH ₂ ) ₂ -is- CH = CH- or -C≡C- may be substituted, and any hydrogen may be substituted with halogen;

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 comprising phenyl and alkylene which may have a substituent, or naphthyl; In alkyl having 1 to 30 carbon atoms, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O-, cycloalkylene or cycloalkenylene, and arbitrary-( CH ₂ ) ₂ -may be substituted with -CH = CH-; In phenyl which may have a substituent, arbitrary hydrogen may be substituted by halogen or alkyl of 1 to 10 carbon atoms; In alkyl having 1 to 10 carbon atoms as a substituent of the phenyl, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O- or phenylene, and arbitrary-( CH ₂ ) ₂ -may be substituted with -CH = CH-; Then, in the alkylene group of the phenylalkyl, the carbon number is 1 to 12, and any hydrogen may be replaced by fluorine, arbitrary -CH ₂ - may be substituted with -O- or cycloalkylene , any - (CH _{2) 2} - is described in the varnish which may be substituted with -CH = CH-, [1] wherein.

[3] R ¹ is, independently, alkyl having 1 to 8 carbon atoms, phenyl which may have a substituent, phenyl and alkyl optionally having hydrogen substituted with fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy. Phenylalkyl or naphthyl consisting of ene; In alkyl having 1 to 8 carbon atoms, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O-, cycloalkylene or cycloalkenylene, and arbitrary-( CH ₂ ) ₂ -may be substituted with -CH = CH-; In phenyl which may have a substituent, arbitrary hydrogen may be substituted by halogen or alkyl of 1 to 10 carbon atoms; In alkyl having 1 to 10 carbon atoms which is a substituent of phenyl, arbitrary hydrogen may be substituted with fluorine, and optional -CH ₂ -may be substituted with -O-; In alkylene of phenylalkyl, the carbon number is 1 to 8, and optionally -CH ₂ -may be substituted with -O- or cycloalkylene, and optional-(CH ₂ ) ₂ -is -CH = May be substituted with CH-;

And Q ¹ is hydrogen, halogen, phenyl, alkyl of 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is substituted with halogen or alkyl of 1 to 5 carbon atoms; In the alkyl having 1 to 10 carbon atoms, any-(CH ₂ ) ₂ -may be substituted with -CH = CH-, and arbitrary hydrogen may be substituted with halogen; In the alkyl having 1 to 5 carbon atoms in the substituents of phenyl, any -CH ₂ - may be substituted with -O-, arbitrary hydrogen is described in the varnish which may be substituted by halogen, (1) wherein.

[4] R ¹ is, independently, alkyl having 1 to 8 carbon atoms, phenyl which may have a substituent, phenyl and alkyl optionally having hydrogen substituted with fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy. Phenylalkyl or naphthyl consisting of ene; In alkyl having 1 to 8 carbon atoms, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O-, cycloalkylene or cycloalkenylene, and arbitrary-( CH ₂ ) ₂ -may be substituted with -CH = CH-; In phenyl which may have a substituent, arbitrary hydrogen may be substituted by halogen or alkyl of 1 to 10 carbon atoms; In the alkyl having 1 to 10 carbon atoms, arbitrary hydrogen may be substituted with fluorine, and optional -CH ₂ -may be substituted with -O-; In the alkylene group of phenylalkyl, the carbon number is 1 to 8, any -CH- may be substituted with -O- or cycloalkylene, any - (CH _{2) 2} - is -CH = CH May be substituted with-;

Q ¹ is hydrogen, halogen, alkyl of 1 to 10 carbon atoms, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl of 1 to 5 carbon atoms; In the alkyl having 1 to 10 carbon atoms, any-(CH ₂ ) ₂ -may be substituted with -CH = CH-, and arbitrary hydrogen may be substituted with halogen; In alkyl having 1 to 5 carbons which is a substituent of phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary hydrogen may be substituted with halogen;

And 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 substituted with halogen or alkyl having 1 to 5 carbon atoms, or 1, in which at least one hydrogen is substituted with halogen or alkyl having 1 to 5 carbon atoms, The varnish as described in [1] which is 4-phenylene.

[5] R ¹ is phenyl in which arbitrary hydrogen may be substituted with halogen or alkyl having 1 to 10 carbon atoms; In the alkyl having 1 to 10 carbon atoms, arbitrary hydrogen may be substituted with fluorine, and optional -CH ₂ -may be substituted with -O-;

Q ¹ is hydrogen, halogen, alkyl of 1 to 10 carbon atoms, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl of 1 to 5 carbon atoms; In the alkyl having 1 to 10 carbon atoms, any-(CH ₂ ) ₂ -may be substituted with -CH = CH-, and arbitrary hydrogen may be substituted with fluorine; In alkyl having 1 to 5 carbons which is a substituent of phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary hydrogen may be substituted with 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 with at least one hydrogen substituted with halogen or alkyl having 1 to 5 carbon atoms, or 1,4- with at least one hydrogen substituted with halogen or alkyl having 1 to 5 carbon atoms Phenylene;

Z ⁰ is alkylene having 1 to 8 carbon atoms in which any -CH ₂ -may be substituted with -O-;

Z ¹ , Z ² and Z ³ are independently a single bond, -O-, -CH = CH-, -C≡C-CO0-, -OCO- or alkylene having 1 to 10 carbon atoms; In the alkylene having 1 to 10 carbon atoms, arbitrary -CH ₂ -may be substituted with -O-, -NH-, -COO-, or -OCO-, and arbitrary-(CH ₂ ) ₂ -is May be substituted with —CH═CH— or —C 치환 C—, and any hydrogen may be substituted with fluorine;

And Z ⁴ is a single bond or alkylene having 1 to 10 carbon atoms; The varnish according to [1], wherein -CH ₂ -in the alkylene having 1 to 10 carbon atoms may be substituted with -O-, -COO-, -OCO-, or -SiR ² _2- .

[6] R ¹ is phenyl or phenyl in which at least one hydrogen is substituted with halogen or alkyl having 1 to 5 carbon atoms; In alkyl having 1 to 5 carbons which is a substituent of phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary hydrogen may be substituted with halogen;

Q ¹ is hydrogen, halogen, alkyl of 1 to 10 carbon atoms, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl of 1 to 5 carbon atoms; In the alkyl having 1 to 10 carbon atoms, any-(CH ₂ ) ₂ -may be substituted with -CH = CH-, and arbitrary hydrogen may be substituted with fluorine; In alkyl having 1 to 5 carbons which is a substituent of phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary hydrogen may be substituted with fluorine; And the varnish according to the item [1], wherein Q ² is a group represented by any one of formulas (1-1) to (l-89) shown below:

In the following formulae, Z ⁰ , Z ¹ , Z ² , Z ³ and Z ⁴ have the same meanings as those symbols in the formula (2). And groups representing 1,4-cyclohexylene, 1,4-phenylene and pyridine-2,5-diyl are each used as representative of the groups described in the right column shown below:

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

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

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

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

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

[12] [1], wherein the polymer is at least one selected from the group consisting of polyamic acid, polyimide, polyamidoimide, and polyester, and further contains a polymer obtained without using the compound represented by Formula (1). Nice as described in.

[13] The varnish according to [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, polyamidoimide, and polyester.

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

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

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

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

First, the compound represented by following formula (1) used by this invention is demonstrated. Hereinafter, the compound represented by Formula (1) may be represented by compound (1). About the compound represented by another formula, it may be simplified and described similarly.

The silsesquioxane skeleton contained in Formula (1) is a deformation | transformation of cage type octasyl sesquioxane. If the structure in which three oxygen atoms are bonded to one silicon atom is called T structure, and the structure in which two oxygen atoms are bonded to one silicon atom is called D structure, the silsesquioxane skeleton in formula (1) is a T8D2 structure. It can be said.

In formula (1), R <^1> is hydrogen, C1-C45 alkyl, aryl which may have a substituent, or arylalkyl which consists of aryl and alkylene which may have a substituent. This definition means that eight R ¹ are independently selected from the group consisting of hydrogen, a plurality of alkyls, a plurality of aryls and a plurality of arylalkyls. Examples of the case where eight R ^{1 's} consist of different groups include at least one of two or more alkyls, two or more aryls, two or more arylalkyls, and at least one aryl. Is made of alkyl and at least one aryl, made of at least one alkyl and at least one arylalkyl, and made of at least 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, its carbon number is ¹ to 45. Preferable carbon number is 1-30. More preferable carbon number is 1-8. And any of its hydrogen may be substituted with fluorine, and any -CH ₂ -may be substituted with -O-, cycloalkylene or cycloalkenylene, and any-(CH ₂ ) _2- May be substituted with -CH = CH-. Preferred examples of alkyl include, one -CH ₂ in the alkyl, alkoxy, alkyl having 1 to 8 carbon atoms in the unsubstituted alkyl, 2-29 carbon atoms of 1 to 30 carbon atoms - a group as a substituted cycloalkylene, 2 to 20 carbon atoms alkenyl, C2-C20 alkenyloxy of alkyl, alkenyl alkyloxy Al of 2 to 20 carbon atoms, one of the carbon atoms in the -CH ₂ l~8 alkyl-substituted in the cycloalkyl alkenylene group, and these groups In which any hydrogen is substituted with fluorine. Cycloalkylene and cycloalkenylene are preferably 3 to 8 carbon atoms.

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

Examples of alkyl fluorides having 1 to 30 carbon atoms include 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl and tridecafluoro -1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H, 1H, 2H, 2H-dodecyl and perfluoro-1H , lH, 2H, 2H-tetradecyl.

Examples of the alkoxyalkyl having 2 to 29 carbon atoms are 3-methoxypropyl, methoxyethoxy undecyl and 3-heptafluoroisopropoxypropyl.

Examples of the group in which one -CH ₂ -is substituted with cycloalkylene in alkyl having 1 to 8 carbons include cyclohexylmethyl, adamantaneethyl, cyclopentyl, cyclohexyl, 2-bicycloheptyl, and cyclooctyl to be. Cyclohexyl is an example in which -CH ₂ -of methyl is substituted with cyclohexylene. Cyclohexylmethyl is an example in which -CH ₂ -of ethyl is substituted with cyclohexylene.

Examples of alkenyl having 2 to 20 carbon atoms are vinyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl, 10-undecenyl, and 21-docosenyl.

An example of alkenyloxyalkyl having 2 to 20 carbon atoms is allyloxyundecyl.

Examples of the group in which one -CH ₂ -is substituted with cycloalkenylene in alkyl having 1 to 8 carbon atoms include 2- (3-cyclohexenyl) ethyl, 5- (bicycloheptenyl) ethyl, and 2-cyclo Pentenyl, 3-cyclohexenyl, 5-norbornene-2-yl, and 4-cyclooctenyl.

Preferred examples in the case where R ¹ in Formula (1) is aryl which may have a substituent are phenyl, naphthyl, and phenyl in which at least one hydrogen is substituted with halogen or alkyl having 1 to 10 carbon atoms. Preferred examples of halogen are fluorine, chlorine and bromine. In the alkyl having 1 to 10 carbon atoms, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O- or phenylene, and arbitrary-(CH ₂ ) _2- May be substituted with -CH = CH-. That is, a preferable example in the case where R ¹ is aryl which may have a substituent is phenyl, naphthyl, alkylphenyl, alkyloxyphenyl, alkenylphenyl, and optionally -CH ₂ -is phenyl in alkyl having 1 to 10 carbon atoms. Phenyl having a group substituted with ene as a substituent, and a group in which at least one hydrogen is substituted with halogen in these groups. In the present invention, when simply referred to as phenyl without particular mention, unsubstituted phenyl means. The same applies to naphthyl.

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

Examples of alkylphenyls include 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 the 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 -is substituted with phenylene in alkyl having 1 to 10 carbon atoms include 4- (2-phenylvinyl) phenyl, 4-phenyloxyphenyl, 3-phenylmethylphenyl , Biphenyl, and terphenyl. 4- (2-phenylvinyl) phenyl is an example in which one -CH ₂ -is substituted with phenylene and the remaining-(CH ₂ ) ₂ -is substituted with -CH = CH- in the propyl group of propylphenyl. .

In phenyl, examples of the group in which a part of hydrogen is substituted with halogen and another hydrogen is substituted with alkyl, alkyloxy or alkenyl include 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-di Bromo-4-methylphenyl, 3,5-dibromo-4-methylphenyl, 2,3-difluoro-4-methylphenyl, 3-chloro-4-methoxyphenyl, 3-bromo-4-methoxy Phenyl, 3,5-dibromo-4-methoxyphenyl, 2,3-difluoro-4-methoxyphenyl, 2,3-difluoro-4-ethoxyphenyl, 2,3-difluoro Ro-4-propoxyphenyl, and 4-vinyl-2,3,5,6-tetrafluorophenyl.

Next, the case where R <^1> in Formula (1) is arylalkyl which consists of aryl and alkylene which may have a substituent is given. In alkylene of arylalkyl, any hydrogen may be substituted with fluorine, any -CH ₂ may be substituted with -O- or cycloalkylene, and optional-(CH ₂ ) ₂ -is It may be substituted by -CH = CH-. A preferable example of arylalkyl is phenylalkyl which consists of phenyl and alkylene which may have a substituent. At this time, preferable carbon number of alkylene is 1-12, and more preferable carbon number is 1-8.

Examples of phenylalkyl consisting of unsubstituted phenyl and alkylene include 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.

Preferable examples of the substituent of phenyl are halogen and alkyl having 1 to 10 carbon atoms. In the alkyl having 1 to 10 carbon atoms, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O-, cycloalkylene or phenylene, and arbitrary-( CH ₂ ) ₂ -may be substituted with -CH = CH-. Examples of phenylalkyl in which at least one hydrogen of phenyl is substituted with 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 ) Profile.

Examples of phenylalkyl in which at least one hydrogen of phenyl is substituted with chlorine are 4-chlorophenylmethyl, 2-chlorophenylmethyl, 2,6-dichlorophenylmethyl, 2,4-dichlorophenylmethyl, 2,3,6 -Trichlorophenylmethyl, 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-chloro Phenyl) ethyl, 3- (3-chlorophenyl) propyl, 3- (4-chlorophenyl) propyl, 3- (2,4,5-trichlorophenyl) propyl, 3- (2,3,6-trichloro Phenyl) 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, l- (4-chlorophenyl) ethyl, 2- (4-chlorophenyl) propyl, 2- (2-chloro Phenyl) propyl, and 1- (4-chlorophenyl) butyl.

Examples of phenylalkyl in which at least one hydrogen of phenyl is substituted with bromine include 2-bromophenylmethyl, 4-bromophenylmethyl, 2,4-dibromophenylmethyl, 2,4,6-tribromo Phenylmethyl, 2,3,4,5-tetrabromophenylmethyl, 2,3,4,5,6-pentabromophenylmethyl, 2- (4-bromophenyl) ethyl, 3- (4-bro Mophenyl) 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 substituted with alkyl having 1 to 10 carbon atoms include 2-methylphenylmethyl, 3-methylphenylmethyl, 4-methylphenylmethyl, 4-decylphenylmethyl, (3,5-dimethylphenyl Methyl, 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.

Examples of the phenylalkyl in which at least one hydrogen of phenyl is substituted with alkyl having 1 to 10 carbon atoms, in which hydrogen in the alkyl is substituted with fluorine are 3-trifluoromethylphenylmethyl and 2- (4-trifluoro). Methylphenyl) ethyl, 2- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexylphenyl) ethyl, 2- (4-heptadecafluorooctylphenyl) ethyl, 1- (3- Trifluoromethylphenyl) ethyl, 1- (4-trifluoromethylphenyl) ethyl, 1- (4-nonnafluorobutylphenyl) ethyl, 1- (4-tridecafluorohexylphenyl) ethyl, 1- (4 -Heptadecafluorooctylphenyl) ethyl, 2- (4-nonafluorobutylphenyl) propyl, 1-methyl-1- (4-nonafluorobutylphenyl) ethyl, 2- (4-tridecafluorohexyl Phenyl) propyl, 1-methyl-1- (4-tridecafluorohexylphenyl) ethyl, 2- (4-heptadecafluorooctylphenyl) propyl, and 1-methyl-1- (4-heptadecafluoro Octylphenyl) ethyl.

Examples of phenylalkyl in which at least one hydrogen of phenyl is substituted with alkyl having 1 to 10 carbon atoms, in which -CH ₂ -in this alkyl is substituted with -CH = CH-, is 2- (4-vinylphenyl) ethyl , 1- (4-vinylphenyl) ethyl, and 1- (2- (2-propenyl) phenyl) ethyl.

Examples of phenylalkyl in which at least one hydrogen of phenyl is substituted with alkyl having 1 to 10 carbon atoms, in which case -CH ₂ -in this alkyl is substituted with -O-, 4-methoxyphenylmethyl, 3-methoxy Phenylmethyl, 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-nonadecafluorodecenyl Oxyphenyl) propyl.

Phenylalkyl in which at least one hydrogen of phenyl is substituted with alkyl having 1 to 10 carbon atoms, wherein one of -CH ₂ -in this alkyl is substituted with cycloalkylene, another -CH ₂ -is- Illustrative examples of the case of O-substitution include cyclopentylphenylmethyl, cyclopentyloxyphenylmethyl, cyclohexylphenylmethyl, cyclohexylphenylethyl, cyclohexylphenylpropyl, and cyclohexyloxyphenylmethyl.

At least one hydrogen of the phenyl as the phenylalkyl substituted by alkyl having a carbon number of 1~10, -CH ₂ in the alkyl-example in one of the substituted phenylene is, one more -CH ₂ - is -O Examples of the substitution with-include 2- (4-phenoxyphenyl) ethyl, 2- (4-phenoxyphenyl) propyl, 2- (2-phenoxyphenyl) propyl, and 4-biphenylylmethyl. , 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 substituted with different groups include 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-chloro3,5-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-methylphenyl Methyl, 3-bromo-4-methylphenylmethyl, 2,3-dibromo-4-methylphenylmethyl, 2,3,5-tribromo-4-methylphenylmethyl, 2,3,5,6-tetrabro Parent-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 substituted with -O- and / or cycloalkylene are 3-phenoxypropyl, phenylcyclohexyl, and phenoxycyclohexyl. Examples of phenylalkyl in which-(CH ₂ ) ₂ -of alkylene constituting phenylalkyl is substituted with -CH = CH- include 1-phenylvinyl, 2-phenylvinyl, 3-phenyl-2-propenyl, 4 -Phenyl-4-pentenyl.

Examples of phenylalkyl in which hydrogen of phenyl is substituted with fluorine or methyl, and-(CH ₂ ) ₂ -in alkylene is substituted with -CH = CH-, 4-fluorophenylvinyl, 2,3-difluoro Rophenylvinyl, 2,3, 4, 5, 6-pentafluorophenylvinyl, and 4-methylphenylvinyl.

Preferred examples of the above-mentioned examples of R ¹ are alkyl having 1 to 8 carbon atoms, phenyl, naphthyl, phenyl having a substituent, or phenylalkyl comprising phenyl and alkylene which may have a substituent. More preferred examples are phenyl, naphthyl, phenyl having a substituent, or phenylalkyl consisting of phenyl and alkylene which may have a substituent. In the alkyl having 1 to 8 carbon atoms, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O-, cycloalkylene or cycloalkenylene, and arbitrary-( CH ₂ ) ₂ -may be substituted with -CH = CH-.

Examples of phenyl having a substituent are phenyl in which at least one hydrogen is substituted with halogen, methyl or methoxy. In phenylalkyl consisting of phenyl and alkylene which may have a substituent, any hydrogen of phenyl may be substituted with fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy. In the alkylene group of the phenylalkyl, whose carbon number is 1 to 8, and any -CH ₂ - is -O- and may be substituted or a cycloalkylene, any - (CH _{2) 2} - is -CH = CH- may be substituted. In these groups, when phenyl has a plurality of substituents, these substituents may be the same group or may be different groups. And it is preferable that all R <^1> in Formula (1) is the same group chosen from the example of these preferable R <^1> .

Moreover, specific examples of more preferable R ¹ include phenyl, halogenated phenyl, phenyl having at least one methyl, methoxyphenyl, naphthyl, phenylmethyl, phenylethyl, phenylbutyl, 2-phenylpropyl and 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, C1-C10 alkyl, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or at least 1 hydrogen is halogen or C1-C10 Phenyl substituted with 5 alkyl. In each of the alkyl having 1 to 5 carbons which is a substituent of the alkyl having 1 to 10 carbon atoms and phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary-(CH ₂ ) ₂ -is It may be substituted by -CH = CH- or -C≡C-, and arbitrary hydrogen may be substituted by halogen.

Preferred examples of Q ¹ include hydrogen, chlorine, alkyl having 1 to 10 carbon atoms, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl in which at least one hydrogen is substituted with halogen or alkyl having 1 to 5 carbon atoms. to be. In this case, the alkyl group of 1 to 10 carbon atoms, any - (CH _{2) 2} - may be substituted with -CH = CH-, arbitrary hydrogen may be substituted with fluorine. And, in the substituents of the phenyl carbon atoms l~5 alkyl, arbitrary -CH ₂ - may be substituted with -O-, arbitrary hydrogen may be substituted with fluorine.

More preferred examples of Q ¹ include hydrogen, chlorine, -CF ₃ , -OCF ₃ , methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hex Siloxy, heptyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, 2-fluoro Ethyl, 3-fluoropropyl, vinyl, 1-propenyl, 2-propenyl, allyl, 3-butenyl, 3-pentenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and phenyl.

In Formula (1), Q <^2> is group represented by following 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 substituted with -O-, and arbitrary -CH = may be substituted with -N =. In 1, 4- cyclohexylene, two nonadjacent carbons may be bridge | crosslinked. And, there may be any hydrogen in any ring is substituted with alkyl of halogen, -CN, -NO _2, or 1 to 5 carbon atoms. In the alkyl having 1 to 5 carbon atoms of the ring substituents, arbitrary -CH ₂ - may be substituted with -O-, arbitrary - (CH _{2) 2} - is -CH = CH- or -C≡C- May be substituted, and arbitrary hydrogen may be substituted by halogen.

Preferable examples of A ^{1 to} A ⁴ are 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 And 1,4-cyclohexylene substituted with fluorine or alkyl having 1 to 5 carbon atoms, and 1,4-phenylene with at least one hydrogen substituted with fluorine, chlorine or alkyl having 1 to 5 carbon atoms.

More preferable examples of A ^{1 to} A ⁴ include 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, and 1,4- in which at least one hydrogen is substituted with fluorine or methyl. Cyclohexylene, and at least one hydrogen, is 1,4-phenylene substituted with fluorine, chlorine, methyl, ethyl or propyl. In addition to these, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, and pyridazine-3,6-diyl are also preferable. 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-di Fluoro-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 formula (2) are a bonding group. Z ⁰ is alkylene having 1 to 10 carbon atoms. And, any -CH ₂ in the alkylene-is or may be substituted with -O-, -COO- or -OCO-. Preferred examples of Z ⁰ are alkylene having 1 to 8 carbon atoms, in which any -CH ₂ -may be substituted with -O-. In order to bond a large group to Si, the Grignard reaction or the hydrosilylation reaction is usually used. When using the hydrosilylation reaction, large groups are bonded to Si via -C ₂ H _4- . That is, a preferable example of Z ⁰ in formula (2) is (Si) -C ₂ H _4- (CH ₂ ) _f- , (Si) when the bonding point to Si is represented by (Si). -C ₂ H _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- . In these formulas, f is an integer of 0-5, h is an integer of 1-4. And at this time, k in Formula (2) is 1. When using the Grignard reaction, k in equation (2) is zero. The case where k is 1 and Z ⁰ is methylene is also an example of using a Grignard reaction. Moreover, when it is not necessary to consider hydrolysis, you can make Si-C1 group react with the big group which has a hydroxyl group at the terminal. At this time, Z ⁰ is -O-.

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

Preferred examples of Z ^{1 to} Z ³ are a single bond, -O-, -CH = CH-, -C≡C-, -CO0-, -OCO- and alkylene having 1 to 10 carbon atoms. In this alkylene, arbitrary -CH ₂ -may be substituted with -O-, -NH-, -COO-, or -OCO-, and arbitrary-(CH ₂ ) ₂ -is -CH = CH- or -C≡C- may be substituted, and arbitrary hydrogen may be substituted with fluorine.

More preferred examples of Z ^{1 to} Z ³ are 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 - a.

Z <^4> in Formula (2) is a single bond or C1-C10 alkylene. In the alkylene having 1 to 10 carbon atoms, any -CH ₂ -may be substituted with -O-, -NH-, -SiR ² _2- , -COO-, or -OCO-, and optionally -(CH ₂ ) ₂ -may be substituted with -CH = CH- or C≡C-, and arbitrary hydrogen may be substituted with fluorine. R ² is alkyl having 1 to 10 carbon atoms, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which at least one hydrogen is substituted with halogen or alkyl having 1 to 5 carbon atoms. In each of the alkyl having 1 to 5 carbons which is a substituent of the alkyl having 1 to 10 carbon atoms and phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary-(CH ₂ ) ₂ -is It may be substituted by -CH = CH- or -C≡C-, and arbitrary hydrogen may be substituted by halogen.

Preferred examples of Z ⁴ are a single bond and an alkylene having 1 to 10 carbon atoms which may be substituted with any -CH ₂ -with -O-, -COO-, -OCO-, or -SiR ² _2- . At this time, a preferable example of R <^2> is C1-C4 alkyl, cyclopentyl, cyclohexyl, or phenyl.

More preferred 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- , and -Si (Ph) ₂ (CH ₂ ) ₃ -and -Si (Me) ₂ -O-Si (Me) _2- (CH ₂ ) _3- . Wherein Me is methyl and Ph is phenyl.

Y in Formula (2) is group which has 2-oxa propane- 1, 3- di oil. 2-oxapropane-1,3-diyl is the following divalent group. This group is an acid anhydride group. That is, compound (1) is tetracarboxylic dianhydride.

The group shown below is an example of group which has 2-oxapropane- 1, 3- dioil.

The example which further refined Formula (2) is shown next. In the following equation, Z ^0, Z ^1, Z ^2, Z ³ and Z ⁴ represent a sign thereof and as defined in equation (2). And the group which represents 1, 4- cyclohexylene, 1, 4- phenylene, and pyridine-2, 5- diyl is used as a representative of the group of the right column shown next, respectively.

In said formula, Formula (1-1)-Formula (1-42) and Formula (1-46)-Formula (1-86) are more preferable, Formula (1-1)-Formula (1-31), 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 prepared as in Scheme 1, using the compound represented by the formula (lm) as a starting material.

Scheme 1

That is, in the presence of a basic compound such as triethylamine, the compound represented by formula (1a) is reacted with the compound represented by formula (1m) and the dichlorosilane derivative represented by formula (3) in an organic solvent. You can get it. In said scheme, R <^1> , Q <^1> and Q <^2> have the same meaning as these symbols in Formula (1), respectively, and M is monovalent alkali metal ion. Compound (Lm) can be produced by hydrolyzing and condensation polymerization of the silane compound R ¹ SiA ₃ in the presence or absence of a monovalent alkali metal hydroxide and water. A is a hydrolyzable group, and chlorine and alkoxy having 1 to 4 carbon atoms are preferable. Examples of monovalent alkali metal hydroxides are lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide. Among these, sodium hydroxide and potassium hydroxide are preferred. The usage-amount of monovalent alkali metal hydroxide is 0.3-1.5 in molar ratio with respect to said silane compound. More preferable molar ratio is 0.4-0.8. And the quantity of water to add is 1.0-1.5 in molar ratio with respect to a silane compound. More preferable molar ratio is 1.1-1.3. Preferred examples of the organic solvent are linear, branched or cyclic monovalent alcohols. Alcohol is believed to contribute to controlling the structure in the condensation process.

Compound (1) can also be obtained using a hydrosilylation reaction, as shown in Scheme 2.

Scheme 2

That is, compound (1m) is first reacted with dichlorosilane derivative represented by formula (3a) to form compound (1-H). Subsequently, in the presence of a platinum catalyst, the terminal alkenyl compound represented by Formula (3b) can be reacted with this, and compound (1-b) can be obtained. In this scheme, the meanings of R ¹ , Q ¹ , M and Y are the same as described above, and Q ³ is a residue from which Z ⁰ and Y are removed from formula (2). The above scheme is an example of the case where Z ⁰ in Formula (2) is -CH ₂ CH _2- .

The following example shows how to use the Grignard reaction.

Scheme 3

In Scheme 3, X is halogen and the meaning of the other symbols is as previously described. First, trichlorosilane derivative represented by formula (3c) is reacted with compound (lm) to make compound (1-C1). And compound (1-c) can be obtained by Grignard reaction of this compound (1-Cl) and compound (3d). Compound (1) can also be manufactured by Scheme 4.

Scheme 4

The meaning of the symbols in scheme 4 are as described previously. Compound (1-d) can be obtained by de-HC1 reaction of said compound (1-C1) and compound (3e) which has a hydroxyl group at the terminal.

The bonding group in formula (2) can be produced by conventional chemical methods. For example, the method described in Unexamined-Japanese-Patent No. 2002-371026, pages 11-14 (pages 14-17 of EP 1245660 A2 publication) can be referred. Even if a suitable method is not described in this publication, a method suitable for the purpose can be found from a reference book generally sold. Examples of such references are Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Synthesos, John WiIey & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press), and New Experimental Chemistry (Maruzen).

A large number of compounds (1) can be produced by applying the above scheme and the method of producing the bonding group. Specific examples of the compound (1) are shown in Tables 1 to 11. These are examples regarding Z ⁰ , Q ³ and Y in the formula (1-e). That is, in Formula (1), R <^1> is phenyl (Ph), Q <^1> is an example in case of methyl (Me), and the compound (l) used by this invention is not limited to these examples.

Next, the varnish for liquid crystal aligning film formation of this invention is demonstrated.

In the following description, the varnish for liquid crystal aligning film formation of this invention may be described as the varnish of this invention. The varnish of this invention contains the polymer obtained by making compound (1) which has two acid anhydride groups, and the compound which has at least two functional groups reacting with an acid anhydride group react. The functional group which reacts with an acid anhydride is group which has active hydrogen. For example, an amino group, a carboxy group, a sulfonic acid group, a hydroxyl group, a hydroxyphenyl group, an amide group, a hydrazino group, a hydrazinocarbonyl group, a mercapto group, etc. are mentioned. Preferred examples of the polymer included in the varnish of the present invention include a mixture of a polyamine acid obtained by reacting a compound (1) with a diamine, a soluble polyimide obtained by a dehydration reaction of the polyamine acid, a compound (1) and dicarboxylic acids; It is polyamidoimide obtained by making diamine react, and polyester obtained by making compound (1) and diol react. Dicarboxylic acid means dicarboxylic acid or its derivative (s). Examples of dicarboxylic acid derivatives are dicarboxylic acid anhydrides, dicarboxylic acid dihalides and dicarboxylic acid diesters.

When manufacturing the said polyamine acid, soluble polyimide, polyamidoimide, or polyester, you may use together tetracarboxylic dianhydride (henceforth another TCDA) other than compound (1). In that case, the preferable usage-amount of compound (1) is 0.001 mol% or more by the ratio based on the total amount of tetracarboxylic dianhydride. Although it is not added to the Example of this specification, it is confirmed by experiment that the effect of compound (1) is recognized even at such a very small ratio. The preferable ranges of this ratio are 0.01-75 mol%, and a more preferable range is 0.01-50 mol%. The range is more preferably 0.1 to 50 mol%, and particularly preferably 0.1 to 20 mol%. By using compound (1) in this ratio, the liquid crystal aligning film in which the balance was maintained in rubbing tolerance, liquid crystal alignability, and display quality can be formed.

The said diamine or diol is selected as a minimum condition to react with compound (1). The selection conditions of other TCDA or dicarboxylic acids used in combination with compound (1) are merely reacting with such diamine or diol, and there are no other limitations. Two or more compounds (1), other TCDA, dicarboxylic acids, diamines and diols may be used, respectively.

Specific examples of other TCDAs and diamines are described in pages 5-9 of the WO 98/31725 A1 brochure, pages 15-31 of the WO 99/33902 A1 brochure, pages 16-35 of the WO 99/33923 A1 brochure, WO 99/34252 A1 Pages 17 to 36 of the pamphlet, pages 15 to 39 of the WO 01/00732 A1 pamphlet and the like. Specific examples of dicarboxylic acids are described in part on pages 9 to 27 of the WO 01/14457 A1 brochure. And it can select arbitrarily from these compounds and derivatives of dicarboxylic acid, and can use.

Preferred examples of other TCDAs are as follows.

Among the other TCDA, structural isomers exist. 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 carbon atoms. In this alkyl, arbitrary -CH ₂ -may be substituted with -O-, arbitrary-(CH ₂ ) ₂ -may be substituted with -CH = CH- or -C≡C-, Any hydrogen may be substituted with fluorine.

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

Diamine which has a silsesquioxane skeleton is also mentioned as an example of diamine. The preferable example of the diamine which has a silsesquioxane skeleton is a compound represented by following formula (4).

In Formula (4), R <^1> and Q <^1> are group defined similarly to these symbols in Formula (1), respectively, and Q <^4> is group represented by following 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 the same groups as those defined in the formula (2), respectively. to be.

The siloxane diamine which has a siloxane bond is also mentioned as an example of a diamine. Preferable examples of this siloxane diamine are compounds represented by the following formula (6).

In said Formula (6), R <^3> and R <^4> is independently C1-C4 alkyl or phenyl. R ⁵ is an alkylene of 1 to 10 carbon atoms, and any -CH ₂ in the alkylene group - may be substituted with -O- or phenylene. Arbitrary hydrogen of this phenylene may be substituted by C1-C4 alkyl. And q is an integer of 1-10.

Preferred examples of NH ₂ -R ⁵ -in the 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 0 (CH ₂ ) _2- , NH _2- (CH ₂ ) ₄ 0 (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 phenylene having methyl as a substituent.

As an example of a diamine, the diamine which has a side chain of a steroid skeleton is mentioned further. Examples of the steroid skeleton are cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, erygosteryl, estoryl, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl , Melatranyl, methyltestosteryl, norresterosteryl, pregnnonyl, β-sitosteryl, stigmasteryl, testosteryl, and cholesterol acetate.

Examples of diols are aliphatic diols, alicyclic diols and aromatic diols, with aliphatic diols being most preferred. And next preferable is an alicyclic diol. Examples of aliphatic diols include 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 the alicyclic diols include 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) -decahydronaphthalene, 2,7-bis (hydroxymethyl) -decahydronaphthalene, bis (hydroxymethyl) tetraline, bis (hydroxymethyl) norbornane, bis (hydroxymethyl ) Tricyclodecane, and bis (hydroxymethyl) pentacyclododecane. Alkylene oxide adducts of these diols can also be used.

And examples of the aromatic diol include hydroquinone, resorcin, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'dihydroxydiphenylbenzophenone, 4 , 4 '-(1-methylethylidene) bisphenol, methylenebisphenol (bisphenol F), 4,4'-cyclohexylidenebisphenol (bisphenol Z), 4,4'-sulfonylbisphenol (bisphenol S), and Alkylene oxide adducts of these diols.

The varnish of this invention can contain another polymer within the range in which the effect of this invention is not impaired. Other polymers are polymers obtained without using compound (l), and examples thereof are polyamic acid, polyimide, polyamide, polyamidoimide, and polyester. The preferable ratio of the other polymer is 0.01 to 99.9 weight% based on the total amount of the polymer component contained in a varnish. The more preferable ranges of this ratio are 30 to 98 weight%, and a more preferable range is 50 to 96 weight%.

In the following description, the polymer obtained using the compound (1) as polyamic acid, soluble polyimide, polyamidoimide, or polyester, or a mixture of two or more thereof is referred to as a polymer having a silsesquioxane skeleton. May be written as "." The varnish of this invention is a composition of the state which melt | dissolved the SQ polymer and the other component added as needed in a solvent. Other components are components other than an SQ polymer, and mean other polymer obtained without using compound (1), and / or additives other than a polymer.

When the organic acid component containing compound (1) or compound (1) and diamine or diol are reacted in a solvent, a solution of SQ polymer is obtained. Depending on the type of raw material selected, the SQ polymer becomes any of polyamine acids, soluble polyimides, polyamidoimides, polyesters, and mixtures of two or more thereof. This solution itself can also be used as the varnish of the present invention. The varnish of this invention is obtained even if it mixes the reaction liquid containing another kind of SQ polymer. 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 of separating the reaction product is a method of distilling off the solvent under reduced pressure. When using a solvent with high boiling point, it is also possible to use the method of adding a poor solvent and precipitating a polymer component.

When manufacturing an SQ polymer, in order to form the reaction terminal of a polymer, you may use together a monoamino compound and dicarboxylic acid anhydride. Examples of monoamino compounds are alkylamines, anilines, and cyclohexylamines, and examples of dicarboxylic anhydrides are maleic anhydride, phthalic anhydride, and nazi anhydride. In order to further improve the adhesiveness to the glass substrate of an oriented film, you may add a silane system or a titanium coupling agent to the varnish of this invention. Examples of the silane coupling agent include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, vinyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Silicone oils such as polydimethylsiloxane and polydiphenylsiloxane can also be used.

The usage-amount of a coupling agent and silicone oil is 0.01 to 5 weight% by the ratio based on the total polymer amount in a varnish. The preferable range of this ratio is 0.1 to 3 weight%. However, this range is a general reference | standard when a silane coupling agent is used and is not characteristic of this invention.

The varnish of this invention can mix | blend another additive as needed other than said coupling agent. For example, when it is desired to improve the coating property, the antistatic property, or the like, a surfactant corresponding to each purpose may be blended. Examples of surfactants are anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, and these can be used within a range that does not impair the properties of the alignment film.

The preferable concentration of the polymer component in the varnish of the present invention is 0.1 to 40% by weight in proportion based on the whole varnish. If the density | concentration of a polymer component exists in this range, the varnish for liquid crystal aligning film formation which has a suitable viscosity is obtained. And since it is also easy to dilute this, it can adjust to the optimum film thickness. In the case of the spinner method and the printing method, in order to maintain film thickness favorably, the density | concentration of a polymer component is usually made into 10 weight% or less in many cases. In other coating methods, for example, the dipping method, the concentration may be lower. In a normal spinner method, a printing method, or the like, the concentration of the polymer component is 0.1% by weight or more, preferably 0.5 to 10% by weight. However, depending on the coating method of the varnish for liquid crystal aligning film formation, it can also be used by thinner density | concentration.

The selection conditions of the solvent used for the varnish of this invention only have the ability to melt the raw material used for manufacture of a polymer, or the obtained polymer, and there are no special restrictions in addition. Therefore, what is necessary is just to select suitably from the solvent normally used at the time of manufacturing polyamine acid, soluble polyimide, polyamidoimide, polyester, etc., and the solvent normally used when using these polymers. Examples of these solvents are aprotic polar organic solvents which are aprotic solvents for polyamic acid, soluble polyimide, polyamidoimide and polyester, and for example, N-methyl-2-pyrrolidone (NMP), dimethyl Midazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N-dimethylacetamide (DMAc), dimethylsulfooxide (DMSO), N, N-dimethylformamide (DMF), N, N- Diethylformamide, diethylacetamide, and γ-butyllactone (GBL). These solvents can also be mixed and used. When manufacturing polyester, general solvents, such as ethers and ketones, can be used.

Another solvent can also be used together for the purpose of improving applicability. Examples of such a solvent include alkyl lactate, 3-methyl-3-methoxybutanol, tetralin isoborone, ethylene glycol monoalkyl ether (e.g., ethylene glycol monobutyl ether (BC)), diethylene glycol monoalkyl ether ( Examples: diethylene glycol monoethyl ether), ethylene glycol monoacetate, ethylene glycol monophenyl acetate, triethylene glycol monoalkyl ether, triethylene glycol monoacetate, propylene glycol monoalkyl ether (e.g. propylene glycol monobutyl ether), malon Acid dialkyl (eg diethyl malonate), propylene glycol monoacetate, dipropylene glycol monoalkyl ether (eg dipropylene glycol monomethyl ether), and dipropylene glycol monoacetate. These solvents can also be mixed and used.

The alignment film of this invention can be used effectively in all the liquid crystal display elements. In the mode in which a strong rubbing operation is performed in order to obtain a strong orientation control force, the effect of the present invention, in which rubbing damage does not occur or there is no orientation defect, is remarkably recognized. Examples of such modes are IPS mode, STN mode, TN mode, OCB mode, ferroelectric molding, and antiferroelectric molding. In the VA mode, rubbing may be performed for the purpose of controlling the inclined side of the liquid crystal molecules at the time of voltage application, but the same remarkable effect is confirmed in this mode as well.

Although the manufacturing method of the orientation 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. Subsequently, the solvent is evaporated by setting the temperature of the substrate with this electrode to 50 to 150 ° C, preferably 80 to 120 ° C. Then, in the glass substrate with a transparent electrode, a film is formed in this glass substrate surface by baking by making this temperature into 150-400 degreeC, Preferably it is 180-280 degreeC. In particular, when using a plastic substrate, in consideration of the heat resistance temperature of the substrate, baking is preferably performed at a low temperature of about 120 to 160 ° C. And the orientation film of this invention is obtained by rubbing this film surface in one direction using cloth, for example.

Moreover, when apply | coating the surface of this board | substrate with a silane coupling agent, before apply | coating the varnish of this invention to the glass substrate or plastic board | substrate with a transparent electrode, adhesiveness of the orientation film formed in this board | substrate surface and a board | substrate will further improve.

The liquid crystal composition used in the liquid crystal display element of this invention is not specifically limited. In the case of liquid crystal display elements, such as a TN type, STN type, an IPS type, and an OCB type, the liquid crystal composition with positive dielectric anisotropy is used. Preferable 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 Application Laid-Open No. 8-157828, Japanese Patent Application Laid-Open No. 8-231960, and Japanese Patent Laid-Open No. 9-241644 (EP 885272 Al), Japanese Patent Application Laid-Open No. 9-302346 (EP 806466 Al), Japanese Patent Application Laid-Open No. 8-199168 (EP 722998 Al), Japanese Patent Application Laid-Open No. 9-235552, Japanese Patent Application Laid-Open No. 9-255956, Japanese Patent Application Laid-Open No. 9-241643 (EP 885271 Al), Japanese Patent Application Laid-Open No. 10-204016 (EP 844229 A1), Japanese Patent Application Laid-Open No. 10-204436, and Japanese Patent Publication No. 10-231482 Japanese Unexamined Patent Publication No. 2000-087040 and Japanese Unexamined Patent Application Publication No. 2001-48822.

When the liquid crystal aligning film of this invention is used for preparation of a VA type liquid crystal display element, the liquid crystal composition with negative dielectric anisotropy is used. Preferable examples of this liquid crystal composition are JP-A-57-114532, JP-A-2-4725, JP-A-4-224885, JP-A-8-40953 and JP-A-8-104869. Japanese Patent Application Laid-Open No. 10-10168076, Japanese Patent Application Laid-Open No. 10-168453, Japanese Patent Application Laid-Open No. 10-236989, Japanese Patent Application Laid-Open No. 10-236990, Japanese Patent Application Laid-Open No. 10-236992 Japanese Patent Laid-Open No. 10-236993, Japanese Patent Laid-Open No. 10-236994, Japanese Patent Laid-Open No. 10-237000, Japanese Patent Laid-Open No. 10-237004, Japanese Patent Laid-Open No. 10-237024, Japanese Patent Laid-Open No. 10-237035 JP-A-10-237075, JP-A-10-237076, JP-A-10-237448, EP 967261, JP-A-10-287874, JP-A-10-287875 JP-A-10-291945, JP-A-11-029581, JP-A-11-080049, JP-A-2000-256307, JP-A2001-019965 Publication, there is disclosed in Japanese Patent Application Laid-Open 2001-072626 discloses, and Japanese Patent Laid-Open Publication No. 2001-192657.

The rubbing resistance of the alignment film can be evaluated by observing or measuring the mechanical properties until scratch damage (scratches) due to rubbing is likely to occur and scratch damage is formed and the alignment film is destroyed. That is, according to the experiments of the present inventors, the rubbing while applying the load, the load when the scratch damage occurs in the alignment film, or after the scratch damage is formed, the load when reaching the time when the alignment film is broken is related to the rubbing resistance of the alignment film There is this. Therefore, rubbing tolerance can be evaluated by comparing these values. At this time, for example, the load when scratch damage occurs in the alignment film P1 formed of the polymer having a silsesquioxane skeleton is referred to as W1, and the scratch is formed on the alignment film P2 formed of the polymer not containing the silsesquioxane skeleton. When the load at the time of damage occurs as W2, if these ratios (W1 / W2) are 1.05 or more, it can be considered that the rubbing resistance of P1 is higher than that of P2.

EXAMPLE

Although an Example is given to the following and it is demonstrated in detail, this invention is not limited to these Examples. All NMR data in an Example are the values measured in heavy chloroform. GPC was used for the measurement of molecular weight, polystyrene was used as a standard solution, and DMF was used as the eluent. The meaning of the symbol used in an Example is as follows.

Ph: Phenyl

Me: methyl

DDM: 4,4'-diaminodiphenylmethane

DDEt: 4,4'-diaminodiphenylethane

DDS: 4,4'-diaminodiphenylsulfide

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>

The evaluation method of the liquid crystal display element used by the Example below is described. In addition, the various physical properties described in this Example are measured values in 25 degreeC.

(1) cutting by rubbing

When the display was performed by applying a voltage to the liquid crystal display element, the part which was inferior in display was visually observed.

(2) Adhesion of Liquid Crystal Alignment Film to Substrate

For the measurement of the alignment film on the substrate, the peeling load (peel start load) of the alignment film was measured using Shimadzu Corporation, scanning type scratch tester SST101, and the value was used for evaluation. The measurement conditions of peeling load are probe curvature 10 micrometers, scratch speed 20 micrometers / s, amplitude 100 micrometers, and probe pressurization speed 5 micrometers / s.

(3) pretilt angle

Implemented by the crystal rotation method. In addition, the measurement wavelength is 589 nm.

(4) voltage retention

It measured based on the method of "the 14th liquid crystal discussion meeting notice, p 78 other than 水 嶋." The voltage applied to the cell at the time of the measurement is 69 μs of gate width, ± 4.5 V in height, frequency 30 Hz or 0.3 Hz.

Example 1

<Synthesis of acid 2 anhydride with silsesquioxane skeleton>

Compound (b) was synthesized according to the following scheme.

Compound (a) is prepared from compound (a-0) and methyldichlorosilane according to the scheme 2 described above.

Under nitrogen atmosphere, compound (a) (50.0 g; 43.3 mmol) was added to THF (150 ml) and suspended, and platinum-divinylsiloxane complex compound (3.0 wt% toluene solution, 320 µl) was added thereto and heated to 90 ° C. . Allyl succinic anhydride (14.5 g; 103.5 mmol) was dripped at this mixture over 5 minutes, and it refluxed after that for 7 hours. After standing to cool, the solvent was distilled off under reduced pressure, methanol (150 ml) was added, and the mixture was stirred at room temperature for 2 hours. The precipitated solid was collected by filtration with methanol, and this was further dissolved in THF (150 ml), activated carbon (6 g) was added, and the mixture was stirred at room temperature for 2 hours. After filtration separation of the activated carbon, 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), 0.70-0.79 (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 to 2.60 (m, 2H), 7.15 to 7.56 (m, 40H).

²⁹ Si-NMR (solvent: CDCl ₃ ): δ (ppm); -18.1 (d, 2Si), -78.5 (s, 4Si), -79.4 --79.8 (t, 4Si).

Example 2

<Production of Polyamic Acid Varnish (1)>

DDM (2.99 g; 1.51 x 10 ^-2 mo1) and dehydrated NMP (54.0 g) were added to a 200 ml four-necked flask, stirred and dissolved under a dry nitrogen stream, and the solution temperature was lowered to 5 deg. Compound (b) (0.060 g; 4.18 × 10 ⁻⁵ mo1) and CBDA (2.95 g; 1.50 × 10 ⁻² mo1) obtained in Example 1 were added thereto and reacted for 30 hours. 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 Nice A1. Moreover, in the Example of this invention, thickening reaction was advanced, checking the viscosity. And BC was added at the time of the increase in viscosity becoming small, and the progress of a thickening reaction was stopped. After adding BC, the viscosity of the varnish was adjusted by heating, and the heating operation was stopped when it became 55-65 mPa * s. It measured at 25 degreeC using the E-type viscosity meter for the measurement of a viscosity. And the varnish obtained was preserve | saved at low temperature.

Example 3

<Production of polyamic acid varnish (2)>

Except that the amount of DDM, Compound (b) and CBDA was 2.76 g (1.39 × 10 ^-2 mo1), 0.600 g (4.18 × 10 ^-4 mo1) and 2.65 g (1.35 × 10 ^-2 mo1), respectively. Polyamic acid varnish with a polymer component concentration of 6.0% by weight was obtained in exactly the same manner as in 2. This is called Nice A2.

Example 4

<Production of Polyamic Acid Varnish (3)>

As raw materials, DDEt (1.07 g; 5.04 x 10 ^-3 mo1), APM-CH (2.75 g; 5.04 x 10 ^-3 mo1), Compound (b) (0.06 g; 4.18 x 10 ^-5 mo1) and PMDA (2.19 g; 1.00 × 10 ⁻² mo1), to obtain a polyamic acid varnish in the same manner as in Example 2. This is called Nice B1.

Example 5

<Production of Polyamic Acid Varnish (4)>

For the the ^{DDEt 1.08g (5.09 × 10 -3 mo1} ), APM-CH 2.77g (5.09 × 10 -3 mo1), 0.600g of the compound ^{(b) (4.18 × 10 -4} mo1), PMDA, and 2.13g ( Polyamic acid varnish was obtained by the same method as Example 4 except having used 9.77x10 <^-3> mo1). This is called Nice B2.

Example 6

<Production of Polyamic Acid Varnish (5)>

As a raw material, except that DABD (3.96 g; 9.14 x 10 ^-3 mo1), Compound (b) (0.060 g; 4.18 x 10 ^-5 mo1), and PMDA (1.99 g; 9.10 x 10 ^-3 mo1) were used. Polyamic acid varnish was obtained in the same manner as in Example 2. This is called Nice C1.

Example 7

<Production of Polyamic Acid Varnish (6)>

Example 6 except that 3.65 g (8.44 x 10 ^-3 mo1) of DABD, 0.600 g (4.18 x 10 ^-4 mo1) of Compound (b), and 1.75 g (8.02 x 10 ^-3 mo1) of PMDA were used. In the same manner, a polyamic acid varnish was obtained. This is called Nice C2.

Example 8

<Production (1) of methylated polyamidoimide varnish>

DDEt (1.08g; 5.09 × 10 ^-3 mo1), APM-CH (2.78g; 5.09 × 10 ^-3 mo1) and NMP (20g) were charged to a 50 ml three-necked flask, and stirred under a dry nitrogen stream to dissolve. I was. Compound (b) (0.060 g; 4.18 x 10 ^-5 mo1) and PMDA (1.11 g; 5.O7 x 10 ^-3 mol) were added to this solution, and the mixture was stirred for 1 hour in a nitrogen stream. Next, TPA-C1 (1.03 g; 5.07 × 10 ⁻³ mo1) was added, and pyridine (lml) was further added, followed by stirring for 2 hours. Thereafter, acetic anhydride (20 ml) was added and the mixture was 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 washed twice with pure water (150 ml) and once with methanol (150 ml) for about 30 minutes each. The solid separated by filtration was vacuum dried at 120 ° C. for 7 hours to obtain polyamidoimide (4.8 g). The weight average molecular weight of this polymer was 10,000.

The polyamidoimide (1.0 g) was placed in a three neck flask and dissolved in NMP (20 ml). Sodium hydride (94 mg; 2.3 mmol) at a concentration of 60% by weight was added to the solution, and the mixture was stirred at room temperature for 3 hours. Methyl iodide (430 g; 3.0 mmol) was added to this, and it was made to react at room temperature again for 2 hours. Subsequently, the reactant was poured into pure water (300 ml) to precipitate a polymer and filtrate. This was boiled and washed twice with pure water (150 ml) for 30 minutes, and then washed once with 50 ml of pure-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 polyamidoimide (960 mg). This polymer is called PAI-1. The weight average molecular weight of PAI-1 was 43,000. It was 97% when the substitution rate from the amide hydrogen in PAI-1 to the methyl group was calculated | required from the measured value of NMR. Using NMP and BC as in Example 2, the solution in which PAI-1 was dissolved is called varnish D1.

Example 9

<Production (2) of methylated polyamidoimide varnish>

1.10 g (5.16 × 10 ^-3 mo1) of DDEt, 2.81 g (5.16 × 10 ^-3 mo1) of APM-CH, 0.600 g (4.18 × 10 ^-4 mo1) of Compound (b), 1.08 g (4.95) of PMDA Polyamidoimide (4.8 g) was obtained in the same manner as in Example 8 except that 1.005 g (4.95 x 10 ^-3 mo1) of × ^10-3 mo1) and TPA-C1 were used. The weight average molecular weight of this polymer was 110,000. Subsequently, the methylation reaction of amide hydrogen was performed by the method similar to Example 8, and methylated polyamidoimide (940 mg) was obtained. This polymer is referred to 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%. Using NMP and BC as in Example 2, the solution in which PAI-2 was dissolved is called varnish D2.

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

<Table 12>

[Comparative Examples 1 to 4]

Each varnish was obtained based on Example 2, 4, 6, and 8 except not using a compound (b) and using the raw material diamine as much as a compound (b) quantity. This is referred to as Nice A0, Nice B0, Nice C0 and Nice D0. Varnishes A0, B0 and C0 are polyamic acid varnishes and varnish D0 is a varnish of methylated polyamidoimide.

Examples 10 to 17

<Preparation of the mixed varnish containing the varnish obtained using the compound (b)>

Varnish A1 and varnish A0 were mixed so that the weight ratio of the polymer component contained may be 1: 9, and mixed varnish A1 * A0 was obtained. From varnish A0 and varnish A0, respectively, of varnish A2, B1, B2, C1, C2, D1 and D2 in exactly the same way, mixed varieties A2, A0, Bl, A0, B2, A0, C1, A0, C2, A0, D1, A0 And D2 · A0.

[Comparative Examples 5-7]

<Preparation of a mixed varnish containing no varnish obtained using compound (1)>

Varnish B0 and varnish A0 were mixed so that the weight ratio of the polymer component contained may be 1: 9, respectively, and mixed varnish B0 * A0 was obtained. From varnish A0 and varnish A0 of each of varnishes C0 and D0 in exactly the same manner, mixed varnishes C0, A0 and D0, A0 were obtained.

Example 18

The varnish A1 obtained in Example 2 was diluted with NMP-BC mixed solvent (weight ratio 1/1), and it adjusted so that the density | concentration of a polymer component might be 3 weight%. This diluted varnish was applied onto the substrate with a transparent electrode with a spinner and prebaked at 80 ° C. for about 5 minutes. Subsequently, it baked for 30 minutes at 210 degreeC, the alignment film with a film thickness of 60 nm was formed, and the surface was orientated by rubbing. The same substrate as this is added one more time, 20 micrometers of gap materials are spread | distributed on the alignment film surface of one board | substrate, and the other board | substrate is overlaid so that an alignment film surface may face, and it seals with an epoxy hardening | curing agent, and gap 20 A μm antiparallel cell was made.

The following liquid crystal composition A was injected into this cell, and the injection hole was sealed with the photocuring agent. Subsequently, heat processing was performed for 30 minutes at 110 degreeC, the homogenized orientation cell was produced, and it was set as the liquid crystal display element for observing an orientation state. When this liquid crystal display element was narrowed by two polarizing plates arrange | positioned in the cross nicol state, and it rotated in it, the uniform and clear contrast without an orientation defect was confirmed, and it is a good thing that liquid crystal molecules are oriented favorably by rubbing. Confirmed. That is, it was determined that damage due to rubbing did not occur in the alignment film in this cell. The pretilt angle of this liquid crystal display element was 1.2 degrees.

<Liquid crystal composition A>

Next, except having made the gap into 6.8 micrometers, the liquid crystal display element for voltage retention measurements was manufactured in the same process, and the voltage retention was measured. As a result, the voltage retentions at 30 Hz and 0.3 Hz were 98.2% and 93.0%, respectively. Vth staining was not observed at all.

Next, baking was performed on the board | substrate with a transparent electrode on the conditions similar to the above except having apply | coated with the spinner so that it might become 1 micrometer in film thickness, and the board | substrate for a scratch test was produced. About this board | substrate, the board | substrate of the liquid crystal aligning film was measured using the scanning scratch tester SST10. As a result, the peeling load was 0.113 N.

[Examples 19-33]

Except having used the varnish shown in Table 13 instead of the varnish A1, the liquid crystal display element for observing an orientation state, the liquid crystal display element for voltage retention measurement, and the scratch test board | substrate were made for each varnish according to the method of Example 18. The result of having evaluated these similarly to Example 18 is shown in Table 13 with the data of Example 18. In Examples 22, 23, 30, and 31, Liquid Crystal Composition B was used instead of Liquid Crystal Composition A.

<Liquid crystal composition A>

Comparative Example 8-14

A liquid crystal display device for observing the alignment state, a liquid crystal display device for voltage retention measurement, according to the method of Example 18, except that a varnish containing no polymer, which is obtained by using compound (1) instead of the varnish A1, was used. Scratch test substrates were made for each varnish. The results of these evaluations in the same manner as in Example 18 are shown in Table 13. In Comparative Examples 10 and 13, Liquid Crystal Composition B was used instead of Liquid Crystal Composition A.

<Table 13>

(Note 1) In the presence or absence of cutting damage,? Indicates that there is no cutting damage due to rubbing on the surface of the alignment film, and the alignment of the liquid crystal is satisfactory, and x indicates gold and damage in the rubbing direction, and is disturbed in the alignment of the liquid crystal. This shows what was observed.

(Remark 2) In the column of marking stains,? Indicates that no Vth stain was recognized, and x indicates that Vth staining was observed.

Example 34

<Production of Polyamic Acid Varnish (7)>

Polyamic acid varnish was obtained by the same method as Example 2 except having used DDS (2.82g), CBDA (1.20g), and PMDA (1.42g) as a raw material. This is called Nice E1.

Example 35

<Production of Polyamic Acid Varnish (8)>

Polyamic acid varnish was obtained by the same method as Example 2 except using DDS4 (3.32g), the compound (b) (0.47g), CBDA (1.0lg), and PMDA (1.19g) as a raw material. This is called Nice F1.

Example 36

<Production of Polyamic Acid Varnish (9)>

Polyamic acid varnish was obtained by the same method as Example 2 except having used DDS5 (3.40g), the compound (b) (0.46g), CBDA (0.98g), and PMDA (1.16g) as a raw material. This is called Nice G1.

Example 37

<Production of Polyamic Acid Varnish (10)>

Polyamic acid varnish was obtained by the same method as Example 2 except using DDEt (2.80g), the compound (b) (0.56g), CBDA (1.2lg), and PMDA (1.43g) as a raw material. This is called varnish H1.

Table 14 shows the molar ratio of the compound (b) with respect to the whole quantity of tetracarboxylic dianhydride in a raw material with respect to the polymer in the varnish of Examples 34-37.

<Table 14>

Comparative Example 15-18

Each varnish was obtained in accordance with Examples 34, 35, 36 and 37, except that compound (b) was not used and the amount of the raw material diamine was reduced as much as compound (b). This is referred to as Nice E0, Nice F0, Nice G0 and Nice H0. Varnishes E0 to H0 are polyamic acid varnishes.

[Examples 38 to 45]

<Preparation of the mixed varnish containing the varnish obtained using the compound (b)>

Varnish E1 and varnish A0 were mixed so that the weight ratio of the polymer component contained might be 1: 9, and the mixed varnish El * A0 was obtained. From the varnishes F1, G1 and H1 and varnish A0 in exactly the same way, the mixed varnishes Fl · A0, Gl · A0 and H1 · A0 were obtained. From each of E0, F0, G0, and H0 in exactly the same manner, mixed varnishes H1, E0, H1, F0, H1, G0, and H1, H0 were obtained.

[Examples 46-57]

Except having used the varnish shown in Table 15 instead of varnish A1, the liquid crystal display element for observing an orientation state, the liquid crystal display element for voltage retention measurement, and the scratch test board | substrate were made for each varnish according to the method of Example 18. The results of these evaluations in the same manner as in Example 18 are shown in Table 15.

<Table 15>

(Remark 1) In the presence or absence of cutting damage, (double-circle) shows that there is no cutting damage by rubbing on the orientation film surface, and orientation of a liquid crystal is favorable.

(Remark 2) In the column of marking stains,? Indicates that Vth staining was not recognized.

As is clear from Table 13 and Table 15, in the liquid crystal display element which shows the pretilt angle 1.0 degree-89.3 degree, the effect on the rubbing damage and cutting of the oriented film obtained using the varnish of this invention was confirmed. This includes TN type liquid crystal display elements, STN type liquid crystal display elements, TFT type liquid crystal display elements, IPS type liquid crystal display elements, VA type liquid crystal display elements, OCB type liquid crystal display elements, ferroelectric liquid crystal display elements, antiferroelectric liquid crystal display elements, and the like. It means that the effects of the present invention can be expected in various types of liquid crystal display elements. And the liquid crystal aligning film of this invention was able to improve the adhesive force to a board | substrate without rubbing damage and a cutting | disconnection. As a result, the voltage retention which is one of the characteristics of a liquid crystal display element was also able to be improved.

The liquid crystal aligning film manufactured using the varnish of this invention has the mechanical strength which can respond to the friction by rubbing, and is especially excellent in adhesiveness with respect to the board | substrate with a transparent electrode, and also excellent in storage stability. Moreover, since such a liquid crystal aligning film can prevent the crack and damage of the surface of an aligning film by a rubbing operation, it can also improve the voltage retention which is one of liquid crystal cell characteristics. That is, a TN type liquid crystal display element, STN type liquid crystal display element, TFT type liquid crystal display element, IPS type liquid crystal display element by making the polymer obtained using the acid dianhydride which has a silsesquioxane skeleton as a component of the varnish for liquid crystal aligning film formation And VA type liquid crystal display element, OCB type liquid crystal display element, ferroelectric liquid crystal display element, antiferroelectric liquid crystal display element, etc. can be improved with a higher performance display element.

Claims (16)

Varnish for liquid crystal aligning film formation containing the polymer obtained using the compound represented by following formula (1): Wherein R ¹ is independently hydrogen, alkyl having 1 to 45 carbon atoms, aryl which may have a substituent, or arylalkyl consisting of aryl and alkylene which may have a substituent; In the alkyl having 1 to 45 carbon atoms, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O-, cycloalkylene or cycloalkenylene, and arbitrary- (CH ₂ ) ₂ -may be substituted with -CH = CH-; In alkylene of arylalkyl, arbitrary hydrogen may be substituted with fluorine, any -CH ₂ -may be substituted with -O- or cycloalkylene, and optional-(CH ₂ ) _2- May be substituted with -CH = CH-; Q ¹ is hydrogen, halogen, alkyl of 1 to 10 carbon atoms, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or phenyl in which at least one hydrogen is substituted by halogen or alkyl of 1 to 5 carbon atoms Is; In each of alkyl having 1 to 5 carbon atoms which is a substituent of alkyl having 1 to 10 carbon atoms and phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary-(CH ₂ ) ₂ -is -CH May be substituted with = CH- or -C≡C-, and any hydrogen may be substituted with halogen; And Q ² is a group represented by the following formula (2): Wherein A ¹ , A ² , A ³ and A ⁴ are independently 1,4-cyclohexylene or 1,4-phenylene; Arbitrary -CH ₂ -in these rings may be substituted with -O-, and arbitrary -CH = may be substituted with -N =; In 1,4-cyclohexylene two non-adjacent carbons may be crosslinked; Any hydrogen in all rings may be substituted with halogen, —CN, —NO ₂ or alkyl of 1 to 5 carbon atoms; In the alkyl having 1 to 5 carbon atoms of the ring substituents, arbitrary -CH ₂ - may be substituted with -O-, arbitrary - (CH _{2) 2} - is -CH = CH- or -C≡C- May be substituted, and arbitrary hydrogen may be substituted with halogen; Z ⁰ is alkylene having 1 to 10 carbon atoms, and any of -CH ₂ -in the alkylene may be substituted with -O-, -CO0-, or -OCO-; Z ¹ , Z ² and Z ³ are independently a single bond, -O-, -CH = CH-, -C≡C, -CO0-, -0CO- or alkylene having 1 to 10 carbon atoms; In the alkylene having 1 to 10 carbon atoms, any -CH ₂ -may be substituted with -O-, -S-, -NH-, -SiR ² _2- , -COO-, or -OCO-, Any — (CH ₂ ) ₂ — may be substituted with —CH═CH— or —C≡C—, and any hydrogen may be substituted with fluorine; Z ⁴ 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 substituted with -O-, -NH-, -SiR ² ₂ -COO- or -OCO-, and optionally-(CH ₂ ) ₂ may be substituted with —CH═CH— or —C≡C—, and any hydrogen may be substituted with fluorine; R ² bonded to Si is alkyl having 1 to 10 carbon atoms, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, or at least one hydrogen substituted with halogen or alkyl having 1 to 5 carbon atoms. Phenyl; In each of the alkyl having 1 to 5 carbons which is a substituent of the alkyl having 1 to 10 carbon atoms and phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary-(CH ₂ ) ₂ -is May be substituted with —CH═CH— or —C≡C—, and any hydrogen may be substituted with halogen; k is 0 or 1 and 1, m, n and p are independently 0, 1, 2 or 3; Y is a group having 2-oxapropane-1,3-dioyl. The method of claim 1, R ¹ is independently hydrogen, alkyl having 1 to 30 carbon atoms, phenyl which may have a substituent, phenylalkyl comprising phenyl and alkylene which may have a substituent, or naphthyl; In the alkyl having 1 to 30 carbon atoms, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O-, cycloalkylene or cycloalkenylene, and arbitrary- (CH ₂ ) ₂ -may be substituted with -CH = CH-; In phenyl which may have a substituent, arbitrary hydrogen may be substituted by halogen or alkyl of 1 to 10 carbon atoms; In alkyl having 1 to 10 carbon atoms as a substituent of this phenyl, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O- or phenylene, and arbitrary-( CH ₂ ) ₂ may be substituted with —CH═CH—; Then, in the alkylene group of the phenylalkyl, and whose carbon number is 1 to 12, and any hydrogen may be replaced by fluorine, arbitrary -CH ₂ - may be substituted with -O- or cycloalkylene , Optional-(CH ₂ ) ₂ -may be substituted with -CH = CH-. The method of claim 1, R ¹ is, independently, alkyl having 1 to 8 carbons, phenyl which may have a substituent, phenyl and alkylene which may optionally be substituted with fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy. Phenylalkyl, or naphthyl; In the alkyl having 1 to 8 carbon atoms, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O-, cycloalkylene or cycloalkenylene, and arbitrary- (CH ₂ ) ₂ -may be substituted with -CH = CH-; In phenyl which may have a substituent, arbitrary hydrogen may be substituted by halogen or alkyl of 1 to 10 carbon atoms; In alkyl having 1 to 10 carbon atoms which is a substituent of this phenyl, arbitrary hydrogen may be substituted with fluorine, and arbitrary -CH ₂ -may be substituted with -O-; In alkylene of phenylalkyl, the carbon number is 1 to 8, and optionally -CH ₂ -may be substituted with -O- or cycloalkylene, and optional-(CH ₂ ) ₂ -is -CH = May be substituted with CH-; Q ¹ is hydrogen, halogen, phenyl, alkyl of 1 to 10 carbon atoms, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is substituted with halogen or alkyl of 1 to 5 carbon atoms; In the alkyl having 1 to 10 carbon atoms, any-(CH ₂ ) ₂ -may be substituted with -CH = CH-, and arbitrary hydrogen may be substituted with halogen; The alkyl having 1 to 5 carbon atoms which is a substituent of phenyl, optionally -CH ₂ -may be substituted with -O-, and optional hydrogen may be substituted with halogen. The method of claim 1, R ¹ is, independently, alkyl having 1 to 8 carbons, phenyl which may have a substituent, phenyl and alkylene which may optionally be substituted with fluorine, alkyl having 1 to 4 carbon atoms, vinyl or methoxy. Phenylalkyl, or naphthyl; In the alkyl having 1 to 8 carbon atoms, arbitrary hydrogen may be substituted with fluorine, arbitrary -CH ₂ -may be substituted with -O-, cycloalkylene or cycloalkenylene, and arbitrary- (CH ₂ ) ₂ -may be substituted with -CH = CH-; In phenyl which may have a substituent, arbitrary hydrogen may be substituted by halogen or alkyl of 1 to 10 carbon atoms; In the alkyl having 1 to 10 carbon atoms, arbitrary hydrogen may be substituted with fluorine, and optional -CH ₂ -may be substituted with -O-; In the alkylene group of phenylalkyl, the carbon number is 1 to 8, any -CH- may be substituted with -O- or cycloalkylene, any - (CH _{2) 2} - is -CH = CH May be substituted with-; Q ¹ is hydrogen, halogen, alkyl of 1 to 10 carbon atoms, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl of 1 to 5 carbon atoms; In the alkyl having 1 to 10 carbon atoms, any-(CH ₂ ) ₂ -may be substituted with -CH = CH-, and arbitrary hydrogen may be substituted with halogen; In alkyl having 1 to 5 carbons which is a substituent of phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary hydrogen may be substituted with 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, non Cyclo [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 with at least one hydrogen substituted with halogen or alkyl having 1 to 5 carbon atoms, or 1,4-phenyl with at least one hydrogen substituted with halogen or alkyl having 1 to 5 carbon atoms Nice that is Ren. The method of claim 1, R ¹ is phenyl in which any hydrogen may be substituted with halogen or alkyl having 1 to 10 carbon atoms; In the alkyl having 1 to 10 carbon atoms, arbitrary hydrogen may be substituted with fluorine, and optional -CH ₂ -may be substituted with -O-; Q ¹ is hydrogen, halogen, alkyl of 1 to 10 carbon atoms, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl of 1 to 5 carbon atoms; In the alkyl having 1 to 10 carbon atoms, any-(CH ₂ ) ₂ -may be substituted with -CH = CH-, and arbitrary hydrogen may be substituted with fluorine; In alkyl having 1 to 5 carbons which is a substituent of phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary hydrogen may be substituted with 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, non Cyclo [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 with at least one hydrogen substituted with halogen or alkyl having 1 to 5 carbon atoms, or 1,4-phenyl with at least one hydrogen substituted with halogen or alkyl having 1 to 5 carbon atoms Ren; Z ⁰ is alkylene having 1 to 8 carbon atoms in which any -CH ₂ -may be substituted with -O-; Z ¹ , Z ² and Z ³ are independently a single bond, -O-, -CH = CH-, -C≡C--CO0-, -OCO- or alkylene having 1 to 10 carbon atoms; In the alkylene having 1 to 10 carbon atoms, arbitrary -CH ₂ -may be substituted with -O-, -NH-, -COO-, or -OCO-, and arbitrary-(CH ₂ ) ₂ -is May be substituted with —CH═CH— or —C≡C— and any hydrogen may be substituted with fluorine; Z ⁴ is a single bond or alkylene having 1 to 10 carbon atoms; And -CH ₂ -in the alkylene having 1 to 10 carbon atoms may be substituted with -O-, -COO-, -OCO-, or -SiR ² _2- . The method of claim 1, R ¹ is phenyl or phenyl in which at least one hydrogen is substituted with halogen or alkyl of 1 to 5 carbon atoms; In alkyl having 1 to 5 carbons which is a substituent of phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary hydrogen may be substituted with halogen; Q ¹ is hydrogen, halogen, alkyl of 1 to 10 carbon atoms, phenyl, cyclopropylcyclobutyl, cyclopentyl, cyclohexyl, or phenyl in which at least one hydrogen is replaced by halogen or alkyl of 1 to 5 carbon atoms; In the alkyl having 1 to 10 carbon atoms, any-(CH ₂ ) ₂ -may be substituted with -CH = CH-, and arbitrary hydrogen may be substituted with fluorine; In alkyl having 1 to 5 carbons which is a substituent of phenyl, arbitrary -CH ₂ -may be substituted with -O-, and arbitrary hydrogen may be substituted with fluorine; Q ² is a group represented by any one of formulas (1-1) to (1-89) shown below: (In the following formula, Z <^0> , Z <^1> , Z <^2> , Z <^3> and Z <^4> have the same meaning as these symbols in said Formula (2), and are 1, 4- cyclohexylene, 1, 4- Groups representing phenylene and pyridine-2,5-diyl are each used as representative of the groups described in the right column shown below): The method of claim 1, Varnish characterized in that the polymer is a polyamine acid. The method of claim 1, Varnish characterized in that the polymer is a polyimide. The method of claim 1, Varnish characterized in that the polymer is polyamidoimide. The method of claim 1, Varnish characterized in that said polymer is polyester. The method of claim 1, The polymer is at least one selected from the group consisting of polyamine acid, polyimide, polyamidoimide and polyester. The method of claim 1, The polymer is at least one selected from the group consisting of polyamine acid, polyimide, polyamidoimide and polyester, and further comprising a polymer obtained without using the compound represented by the formula (1). The method of claim 12, The varnish characterized by the polymer obtained without using the compound represented by said Formula (1) being at least 1 chosen from the group which consists of a polyamic acid, a polyimide, a polyamidoimide, and polyester. The alignment film formed using the varnish as described in any one of Claims 1-13. The method of using the varnish of any one of Claims 1-13 in a liquid crystal display element. The liquid crystal display element containing the orientation film of Claim 14.