WO2011068123A1 - Silicon-containing liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

Disclosed dare: a liquid crystal alignment film having good liquid crystal alignment properties and high film stability; and a silicon-containing liquid crystal aligning agent which enables the formation of a liquid crystal element equipped with the liquid crystal alignment film, insusceptible to external moisture and having excellent electrical properties. Specifically disclosed is a liquid crystal aligning agent which is characterized by comprising at least one polysiloxane compound that has a C_8-30 hydrocarbon group optionally substituted by a fluorine atom and optionally having an oxygen atom, a phosphorus atom or a sulfur atom and a C_2-20 hydrocarbon group having one primary, secondary or tertiary nitrogen atom and optionally having an oxygen atom or a sulfur atom, wherein the former hydrogen group and the latter hydrogen group may be bound to the same polysiloxane compound or may be bound to different polysiloxane compounds from each other.

Description

Silicon-based liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a silicon-based liquid crystal aligning agent containing polysiloxane obtained by polycondensation of alkoxysilane, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal aligning film.

The liquid crystal display element has a structure in which two substrates each having a liquid crystal alignment film mainly composed of polyamic acid and / or polyimide are provided on a transparent electrode, and a liquid crystal substance is filled in the gap. It is generally known. The most well-known method is a TN (Twisted Nematic) type liquid crystal display element, but an STN (Super Twisted Nematic) type that can realize a higher contrast ratio, and IPS (In- Plane switching (VA) type, vertical alignment (VA) type, etc. have been developed.

In business applications and applications of liquid crystal projectors for home theaters, metal halide lamps with high irradiation intensity are used as light sources, and liquid crystal alignment film materials having high light resistance as well as high heat resistance are desired.
Under such circumstances, inorganic liquid crystal alignment film materials have been attracting attention along with conventionally used organic liquid crystal alignment film materials such as polyimide.

For example, as a material for a coating-type inorganic alignment film, an alignment agent composition containing a reaction product of tetraalkoxysilane, trialkoxysilane, alcohol, and oxalic acid has been proposed. It has been reported that a liquid crystal alignment film excellent in vertical alignment, heat resistance and uniformity is formed. (See Patent Document 1.)
In addition, a liquid crystal aligning agent composition containing a reaction product of tetraalkoxysilane, specific trialkoxysilane and water and a specific glycol ether solvent has been proposed to prevent display failure and afterimage characteristics even after long-time driving. It has been reported that a liquid crystal alignment film is formed without lowering the ability to align liquid crystal and having little decrease in voltage holding ratio against light and heat. (See Patent Document 2.)

In recent years, technological innovation of liquid crystal display elements such as liquid crystal TVs has been remarkable, and in order to achieve this, improvement of the long-term reliability of the elements has become a greater challenge than ever. Therefore, it has been required to obtain a uniform liquid crystal alignment film with good reproducibility and to obtain a stable film over a long period of time.
In particular, in the process of manufacturing a liquid crystal display element, obtaining a uniform liquid crystal alignment film with good reproducibility without being affected by the environment has become very important for ensuring the reliability of the element. .
In addition, resistance to moisture entering from the outside of the liquid crystal display element is also important for ensuring long-term reliability.

JP 09-281502 A JP 2005-250244 A

The inorganic liquid crystal alignment film is easily affected by moisture present in the air if an alkoxy group or silanol group remains when the film is formed using a liquid crystal aligning agent. Therefore, conventionally, it has been difficult to obtain a uniform liquid crystal alignment film, and as a result, the reliability of the liquid crystal display element is lowered, which is a big problem.
Furthermore, since moisture entering from the outside of the liquid crystal display element, for example, moisture entering from the sealing material portion or the like, affects the liquid crystal alignment film, there is a concern that the reliability of the liquid crystal display element is lowered.
Therefore, improving the resistance of the liquid crystal alignment film to moisture is an important issue in improving the reliability of the liquid crystal display element.

An object of the present invention is to provide a liquid crystal alignment film that has excellent liquid crystal alignment properties, can form a liquid crystal alignment film with high film stability, is hardly affected by moisture from the outside, and has excellent electrical characteristics of a liquid crystal display element. A silicon-based liquid crystal aligning agent that can be formed, a liquid crystal aligning film obtained from the silicon-based liquid crystal aligning agent, and a liquid crystal display device having the liquid crystal aligning film.

The present invention can achieve the above-mentioned problems, and the gist thereof is as follows.
[1] A hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and which may have an oxygen atom, a phosphorus atom or a sulfur atom, and one nitrogen atom 1 type or 2 types in which the nitrogen atom is a primary, secondary or tertiary nitrogen atom and a hydrocarbon group having 2 to 20 carbon atoms which may have an oxygen atom or a sulfur atom The above-described polysiloxane is contained, and the former hydrocarbon group and the latter hydrocarbon group may be bonded to the same polysiloxane, or may be bonded to different polysiloxanes. A liquid crystal aligning agent characterized by that.
[2] A hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may have an oxygen atom, a phosphorus atom or a sulfur atom, and one nitrogen atom One kind of polyoxysilane having both a nitrogen atom which is a primary, secondary or tertiary nitrogen atom and a hydrocarbon group having 2 to 20 carbon atoms which may have an oxygen atom or a sulfur atom. The liquid crystal aligning agent according to [1], which contains siloxane, or contains two types of polysiloxanes each having the former hydrocarbon group and the latter hydrocarbon group separately.

[3] containing the polysiloxane (AB) obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (2), The liquid crystal aligning agent as described in [2].
X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)
(X ¹ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may contain an oxygen atom, a phosphorus atom or a sulfur atom, and X ² is a carbon atom. An alkyl group having 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p represents an integer of 0 to 2.)
X ³ {Si (OR ² ) ₃ } _q (2)
(X ³ has one nitrogen atom, the nitrogen atom is a primary, secondary or tertiary nitrogen atom, and a carbon atom having 2 to 20 carbon atoms which may have an oxygen atom or a sulfur atom. A hydrogen group, R ² is an alkyl group having 1 to 5 carbon atoms, and q represents an integer of 1 or 2.)
[4] The liquid crystal aligning agent according to [1] or [2], comprising the following polysiloxane (A) and polysiloxane (B).
Polysiloxane (A): polysiloxane obtained by polycondensation of alkoxysilane containing alkoxysilane represented by formula (1).
X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)
(X ¹ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may contain an oxygen atom, a phosphorus atom or a sulfur atom, and X ² is a carbon atom. An alkyl group having 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p represents an integer of 0 to 2.)
Polysiloxane (B): Polysiloxane obtained by polycondensation of alkoxysilane containing alkoxysilane represented by formula (2).
X ³ {Si (OR ² ) ₃ } _q (2)
(X ³ has one nitrogen atom, the nitrogen atom is a primary, secondary or tertiary nitrogen atom, and a carbon atom having 2 to 20 carbon atoms which may have an oxygen atom or a sulfur atom. A hydrogen group, R ² is an alkyl group having 1 to 5 carbon atoms, and q represents an integer of 1 or 2.)

[5] The liquid crystal aligning agent according to [3], wherein the polysiloxane (AB) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (3). .
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ is the number of carbon atoms which may be substituted with a hydrogen atom or a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group, and which may have a hetero atom. 1 to 6 hydrocarbon groups, R ³ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.)
[6] The polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (3). The liquid crystal aligning agent as described in [4].
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ is the number of carbon atoms which may be substituted with a hydrogen atom or a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group, and which may have a hetero atom. 1 to 6 hydrocarbon groups, R ³ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.)
[7] The polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (2) and an alkoxysilane containing the alkoxysilane represented by the formula (3). The liquid crystal aligning agent as described in [4] or [6].
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(A hydrogen atom or a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group, and having 1 to 6 carbon atoms which may have a hetero atom) A hydrocarbon group, R ³ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3)

[8] A hydrocarbon having 2 to 20 carbon atoms, having one nitrogen atom, which is a primary, secondary or tertiary nitrogen atom and may have an oxygen atom or a sulfur atom The group has one nitrogen atom, the nitrogen atom is a primary, secondary, or tertiary nitrogen atom and may have an oxygen atom or a sulfur atom and has 2 to 20 carbon atoms The liquid crystal aligning agent according to any one of [1] to [7], which is a group or an alkylene group.
[9] An alkyl having 2 to 20 carbon atoms which has one nitrogen atom and the nitrogen atom is a primary, secondary or tertiary nitrogen atom and may have an oxygen atom or a sulfur atom The liquid crystal aligning agent according to [8], wherein the group or alkylene group is a group represented by the formula (S1).
-P ¹ -N-P ² P ³ (S1)
(Wherein P ¹ is an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, and P ² is a carbon atom which may have a hydrogen atom, an oxygen atom or a sulfur atom. An alkyl group having 1 to 5 atoms, and P ³ is an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, or a carbon atom which may have an oxygen atom or a sulfur atom (It is an alkyl group of the number 1 to 10.)
[10] The liquid crystal aligning agent according to any one of [1] to [9], wherein the polysiloxane content is 0.5 to 15% by mass in terms of SiO ₂ concentration.
[11] The liquid crystal aligning agent according to any one of [5] to [10], wherein the alkoxysilane represented by the formula (3) is a tetraalkoxysilane in which n in the formula (3) is 0.
[12] A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of [1] to [11].

[13] A liquid crystal display device comprising the liquid crystal alignment film according to [12].
[14] The polysiloxane (AB) is obtained by hydrolyzing and condensing the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3) in an organic solvent. The liquid crystal aligning agent as described in said [5] manufactured by the method including the process of adding the alkoxysilane represented and hydrolyzing and condensing.
[15] The polysiloxane (A) is hydrolyzed and condensed with an alkoxysilane represented by the formula (3) after hydrolysis and condensation in an organic solvent. The liquid crystal aligning agent as described in said [6] manufactured by the method including the process of condensing.
[16] After the polysiloxane (B) is hydrolyzed and condensed with an alkoxysilane represented by the formula (3) in an organic solvent, the alkoxysilane represented by the formula (2) is added to the hydrolyzed The liquid crystal aligning agent as described in said [7] manufactured by the method including the process to condense.

According to the present invention, it is possible to obtain a silicon-based liquid crystal aligning agent that can form a liquid crystal alignment film that exhibits good liquid crystal alignment properties and has high film stability, and that can provide a liquid crystal display element having excellent electrical characteristics. In addition, since the liquid crystal alignment film of the present invention is not easily affected by moisture from the outside, a highly reliable liquid crystal display element, in particular, a highly reliable liquid crystal display element with high electrical property reliability can be obtained. .

It is not always clear why the liquid crystal aligning agent of the present invention is used to obtain a highly reliable liquid crystal aligning film that is not easily affected by moisture from the outside. However, from the comparison of the examples of the present invention and the comparative examples described later, in the examples of the present invention, even when the water treatment is performed under specific conditions, the electrical characteristics of the water resistance are as large as those without water treatment. Since an excellent liquid crystal cell is obtained, the polysiloxane contained in the liquid crystal aligning agent of the present invention has a hydrocarbon group having a specific number of carbon atoms and one nitrogen atom, and the nitrogen atom is primary, It seems to be caused by having a hydrocarbon group of a specific carbon number which is a secondary or tertiary nitrogen atom and has an oxygen atom or a sulfur atom.

The liquid crystal aligning agent of the present invention may be a hydrocarbon group having 8 to 30 carbon atoms (hereinafter referred to as the first group) which may be substituted with a fluorine atom and may have an oxygen atom, a phosphorus atom, or a sulfur atom. One nitrogen atom), and the nitrogen atom may be a primary, secondary or tertiary nitrogen atom and may have an oxygen atom or a sulfur atom. And a hydrocarbon group having 2 to 20 carbon atoms (hereinafter also referred to as a second specific organic group).
The liquid crystal aligning agent of this invention contains 1 type, or 2 or more types of polysiloxane which has these 1st specific organic groups and 2nd specific organic groups, However, 1st specific organic group and 2nd These specific organic groups may be bonded to the same polysiloxane, or may be bonded to different polysiloxanes. Among them, the liquid crystal aligning agent of the present invention contains one type of polysiloxane having both the first specific organic group and the second specific organic group, or the former hydrocarbon group and the latter hydrocarbon group. It is preferable to contain two types of polysiloxanes each having the above.

Among them, the first specific organic group preferably has 8 to 22 carbon atoms which may be substituted with a fluorine atom and may have an oxygen atom, a phosphorus atom or a sulfur atom. 8-18 hydrocarbon groups are preferred.
The first specific organic group mainly has an effect of aligning the liquid crystal in one direction, and examples thereof include an alkyl group, a fluoroalkyl group, an alkenyl group, a phenethyl group, a vinylphenylalkyl group, a naphthyl group, a fluoro Examples thereof include a phenylalkyl group. Of the oxygen atom, phosphorus atom or sulfur atom possessed by the first specific organic group, an oxygen atom is preferred. Examples thereof include an allyloxyalkyl group, a benzoyloxyalkyl group, an alkoxyphenoxyalkyl group, and an epoxycycloalkyl group. Is mentioned. In particular, an alkoxysilane in which the first specific organic group is an alkyl group or a fluoroalkyl group is preferable because it is relatively inexpensive and easily available as a commercial product.

The second specific organic group has one nitrogen atom, and the nitrogen atom is a primary, secondary, or tertiary nitrogen atom, and preferably has 2 to 12, more preferably carbon atoms. 2 to 10 hydrocarbon groups are preferred.
In the second specific organic group, the nitrogen atom is a primary nitrogen atom when the nitrogen atom is bonded to two hydrogen atoms as in —NH ₂ . The nitrogen atom is a secondary nitrogen atom when the nitrogen atom is bonded to a hydrogen atom and R as in —NHR. The nitrogen atom being a tertiary nitrogen atom means a case where the nitrogen atom is bonded to R and R ′ as in —NRR ′. Here, R and R ′ represent a monovalent hydrocarbon group which may have an oxygen atom or a sulfur atom.
The second specific organic group is preferably a group represented by the following formula (S1).
-P ¹ -N-P ² P ³ (S1)
Here, P ¹ is an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, and P ² is a carbon atom which may have a hydrogen atom, an oxygen atom or a sulfur atom. An alkyl group having 1 to 5 atoms, and P ³ is an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, or a carbon which may have an oxygen atom or a sulfur atom An alkyl group having 1 to 10 atoms.

Specific examples of the group represented by the formula (S1) include the following.
Aminopropyl group, 2-aminoethylthioethyl group, N, N-diethyl-3-aminopropyl group, 3- (N, N-dimethylaminopropyl) group, diethylaminomethyl group, N-methylaminopropyl group, N- Ethylaminoisobutyl group, n-butylaminopropyl group,
t-butylaminopropyl group, bis (2-hydroxyethyl) -3-aminopropyl group, 3- (N-allylamino) propyl group, 3- (t-butoxycarbonylamino) propyl group, 3- (ethoxycarbonylamino) Propyl group, 3- (4-hydroxybutanamido) propyl group, N-phenylaminopropyl group,
3-cyclohexylaminopropyl group, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyl group, N- (3-acryloxy-2-humanoxypropyl) -3-aminopropyl group, 3-(( 2-methacryloyloxy) ethoxy) carbonylamino) propyl group, 3-((vinyloxymethoxy) carbonylamino) propyl group, (E) -3- (3-carboxyacrylamide) propyl group, —CH ₂ —CH ₂ —CH _{2 -NH-CH 2 -CH 2 -CH} 2 -, - CH 2 -CH 2 -CH 2 -N (CH 3) -CH 2 -CH 2 -CH 2 - and the like.

Below, the 1st aspect and 2nd aspect which are the preferable aspects of the liquid crystal aligning agent of this invention are demonstrated.
[First embodiment of the present invention]
It is a liquid crystal aligning agent containing polysiloxane (AB) obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by the following formula (1) and the alkoxysilane represented by the following formula (2). .
X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)
X ¹ in Formula (1) is the first specific organic group, and the definition thereof is as described above including the preferred embodiment.
X ² in the formula (1) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, it is a methyl group or an ethyl group.
R ¹ in the formula (1) is an alkyl group having 1 to 5, preferably 1 to 3, carbon atoms, more preferably a methyl group or an ethyl group. P in the formula (1) is an integer of 0 to 2, preferably 0 to 1.

Among these, the alkoxysilane represented by the formula (1) is preferably an alkoxysilane represented by the following formula (1-1).
R ⁴ Si (OR ⁵ ) ₃ (1-1)
(R ⁴ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom, and R ⁵ represents an alkyl group having 1 to 5 carbon atoms.)

Although the specific example of the alkoxysilane represented by the said Formula (1) is given, it is not limited to this.
For example, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane, Heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyltriethoxysilane, undecyltrimethoxysilane, 21-docosenyltriethoxysilane, trideca Fluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecaful Rhodecyltriethoxysilane, isooctyltriethoxysilane, phenethyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, m-vinylphenylethyltrimethoxysilane, p-vinylphenylethyltrimethoxysilane, (1-naphthyl) triethoxysilane , (1-naphthyl) trimethoxysilane, allyloxyundecyltriethoxysilane, benzoyloxypropyltrimethoxysilane, 3- (4-methoxyphenoxy) propyltrimethoxysilane, 1-[(2-triethoxysilyl) ethyl] Cyclohexane-3,4-epoxide, 2- (diphenylphosphino) ethyltriethoxysilane, diethoxymethyloctadecylsilane, dimethoxymethyloctadecylsilane, diethoxydodecyl Chirushiran, dimethoxy dodecyl methyl silane, diethoxy decyl methyl silane, dimethoxy decyl methyl silane, diethoxy-octyl methyl silane, dimethoxy octyl methyl silane, ethoxy dimethyl octadecyl silane, methoxy dimethyloctadecylsilane like. Among them, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane , Heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyltriethoxysilane, or undecyltrimethoxysilane, diethoxymethyloctadecylsilane, or di Ethoxydodecylmethylsilane is preferred.

When the amount of the alkoxysilane represented by the formula (1) having the first specific organic group is less than 0.1 mol% in the total alkoxysilane used for obtaining the polysiloxane (AB), Since good liquid crystal orientation may not be obtained, it is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and further preferably 1 mol% or more. Moreover, since it may not fully harden | cure the liquid crystal aligning film formed when it exceeds 30 mol%, 30 mol% or less is preferable, More preferably, it is 22 mol% or less, More preferably, it is 15 mol% or less. .

X ³ {Si (OR ² ) ₃ } _q (2)
X ³ in the above formula (2) is the second specific organic group, and the definition thereof is as described above including the preferred embodiment. R ² in the formula (2) is as defined above, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
In the alkoxysilane represented by the formula (2), when q is 1, it is an alkoxysilane represented by the formula (2-1).
X ³ Si (OR ² ) ₃ (2-1)
When q is 2, it is an alkoxysilane represented by the formula (2-2).
(R ² O) ₃ Si—X ³ —Si (OR ² ) ₃ (2-2)
Specific examples of the alkoxysilanes represented by the above formulas (2-1) and (2-2) are shown below, but are not limited thereto.

Specific examples when X ³ is a primary amine: 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethyl Silane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylmethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, 2- (2-aminoethylthioethyl) ) Trimethoxysilane,
2-aminoethylaminomethyltrimethoxysilane, 2-aminoethylaminoethyltriethoxysilane, 2-aminoethylaminoethyltrimethoxysilane, 2-aminoethylaminoethyltriethoxysilane, γ-ureidopropyltriethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, 3- (2-aminoethylaminopropyl) Dimethoxymethylsilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl] triethoxysilane,
Specific examples when X ³ is a secondary or tertiary amine: (N, N-diethyl-3-aminopropyl) triethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, 3- ( N, N-dimethylaminopropyl) triethoxysilane, 3- (N, N-dimethylaminopropyl) trimethoxysilane, diethylaminomethyltriethoxysilane, diethylaminomethyltrimethoxysilane, N-methylaminopropyltriethoxysilane, N- Methylaminopropyltrimethoxysilane, N-ethylaminoisobutyltriethoxysilane, N-ethylaminoisobutyltrimethoxysilane, n-butylaminopropyltriethoxysilane, n-butylaminopropyltrimethoxysilane, t-butylaminopropyltriethoxy Silane , T-butylaminopropyltrimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltrimethoxysilane, 3- (N-allylamino) propyl Triethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, (3-triethoxysilylpropyl) -t-butylcarbamate,
(3-trimethoxysilylpropyl) -t-butylcarbamate, triethoxysilylpropylethylcarbamate, trimethoxysilylpropylethylcarbamate, N- (3-triethoxysilylpropyl) -4-hydroxybutyramide, N- (3- Trimethoxysilylpropyl) -4-hydroxybutyramide, N-phenylaminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, 3-cyclohexylaminopropyltriethoxysilane, 3-cyclohexylaminopropyltrimethoxysilane, bis ( Triethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) amine, bis (triethoxysilylpropyl) -N-methylamine, bis (trimethoxysilylpropyl) -N-methyl Amine, bis (methyldiethoxysilylpropyl) amine, bis (methyldimethoxysilylpropyl) amine, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2 -Hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-humanroxypropyl) -3-aminopropyltriethoxysilane, N- (3-acryloxy-2-humanroxypropyl) -3 -Aminopropyltrimethoxysilane, O- (methacryloxyethyl) -N- (triethoxysilylpropyl) urethane, O- (methacryloxyethyl) -N- (trimethoxysilylpropyl) urethane, O- (vinyloxyethyl) -N- (triethoxysilylpropyl Urethane, O- (vinyloxyethyl) -N- (trimethoxysilylpropyl) urethane, triethoxysilylpropyl Marea Mick acid, trimethoxysilylpropyl Marea Mick acid.

The polysiloxane (AB) used in the present invention can be obtained by using one or more types of alkoxysilanes represented by the formula (1) and (2). be able to.
When the amount of the alkoxysilane represented by the formula (2) having the second specific organic group is less than 0.5 mol% in the total alkoxysilane used for obtaining the polysiloxane (AB), In some cases, the reliability with respect to good water may not be obtained, so 0.5 mol% or more is preferable, and 1 mol% or more is more preferable. When the amount exceeds 50 mol%, the stability of the polysiloxane solution may be poor, so that it is preferably 50 mol% or less, more preferably 40 mol% or less.

In the polysiloxane (AB), the alkoxysilane represented by the formula (1) is preferably contained in an amount of 0.1 to 30 mol%, particularly preferably 0.5 to 22 mol% in the total alkoxysilane used. In addition, it is preferable that 0.5 to 50 mol%, particularly preferably 1.0 to 30 mol% is contained in all alkoxysilanes in which the alkoxysilane represented by the formula (2) is used.

The polysiloxane (AB) of the present invention can be obtained preferably by using an alkoxysilane represented by the following formula (3) in addition to the alkoxysilane represented by the formula (1) and the formula (2). . Since the alkoxysilane represented by the formula (3) can impart various characteristics to the polysiloxane (AB), one or more kinds can be selected and used according to the required characteristics.
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
Here, X ⁴ is a hydrogen atom or a carbon atom which may be substituted with a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group, and which may have a hetero atom. A hydrocarbon group having 1 to 6 atoms (hereinafter also referred to as a third specific organic group), R ³ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.
When X ⁴ is a third specific organic group, the third specific organic group has a ring structure or branched structure such as an aliphatic hydrocarbon, an aliphatic ring, an aromatic ring, or a heterocyclic ring. It may also contain an unsaturated bond or a hetero atom such as an oxygen atom, a sulfur atom or a phosphorus atom. The third specific organic group may be substituted with a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group, an acryloxy group, or the like as described above.
R ³ in the formula (3) is as defined above, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. N in the formula (3) is as defined above, and preferably represents an integer of 0 to 2.

Although the specific example of the alkoxysilane represented by the said Formula (3) is given, it is not limited to this.
In the alkoxysilane of the formula (3), specific examples of the alkoxysilane when X ⁴ is a hydrogen atom include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane and the like.

Further, in the alkoxysilane of the formula (3), specific examples of the alkoxysilane when X ⁴ is the third specific organic group include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxy Silane, propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, allyltriethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-isocyanatopropyltrie Toxisilane, trifluoropropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane , Diphenyldiethoxysilane, m-vinylphenyltrimethoxysilane, p-vinylphenyltrimethoxysilane, trimethylethoxysilane, trimethylmethoxysilane and the like.

As long as the polysiloxane (AB) used in the present invention does not impair the effects of the present invention for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules, You may have multiple types.
In the alkoxysilane represented by the formula (3), the alkoxysilane in which n is 0 is more preferably tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane, and particularly tetramethoxysilane or tetraethoxysilane. Is preferred. Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention because it easily condenses with the alkoxysilane represented by the formulas (1) and (2).
When the alkoxysilane represented by the formula (3) is used in combination, the amount of the alkoxysilane represented by the formula (3) is 20 to 99.% in the total alkoxysilane used to obtain the polysiloxane (AB). It is preferably 4 mol%. More preferably, it is 45 to 99.4 mol%. More preferably, the alkoxysilane represented by the formula (3) is 50 to 99.8 mol%.

[Second embodiment of the present invention]
The second aspect of the present invention is a liquid crystal aligning agent containing the following polysiloxane (A) and the following polysiloxane (B).
Polysiloxane (A): polysiloxane obtained by polycondensation of alkoxysilane containing alkoxysilane represented by formula (1).
X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)
(X ¹ , X ² , R ¹ and p are as defined above.)
Polysiloxane (B): Polysiloxane obtained by polycondensation of alkoxysilane containing alkoxysilane represented by formula (2).
X ³ {Si (OR ² ) ₃ } _q (2)
(X ³ , R ² and q are as defined above.)

[Polysiloxane (A)]
The polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (1).
X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)
In the formula (1), X ¹ (first specific organic group), X ² , R ¹ , and p are as defined above, and each preferable one is the same as above.
The description of the alkoxysilane represented by the above formula (1) is the same as the description of the alkoxysilane represented by the formula (1) in the section of the polysiloxane (AB), including preferred embodiments thereof. Moreover, the polysiloxane (A) used for this invention may have multiple types of 1st specific organic groups.

When the amount of the alkoxysilane represented by the formula (1) having the first specific organic group is less than 0.2 mol% in the total alkoxysilane used to obtain the polysiloxane (A), Since good liquid crystal orientation may not be obtained, it is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, and further preferably 1 mol% or more. Further, when it exceeds 30 mol%, the liquid crystal alignment film to be formed may not be sufficiently cured. Therefore, it is preferably 30 mol% or less, more preferably 25 mol% or less, still more preferably 20 mol% or less. It is.

The polysiloxane (A) used in the present invention is obtained by polycondensation of an alkoxysilane containing at least one alkoxysilane represented by the following formula (3) together with the alkoxysilane represented by the formula (1). Siloxane is preferred. Since the alkoxysilane represented by the formula (3) can impart various properties to the polysiloxane, one or more types are selected from the alkoxysilanes represented by the formula (3) as necessary. Used.
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
X ⁴ and R ³ in the formula (3) are the same as those described in the formula (3) in the section of the polysiloxane (AB), including preferred embodiments thereof, and are represented by the formula (3). Specific examples of the alkoxysilane are the same as described in the section of polysiloxane (AB).

In the present invention, the polysiloxane (A) has one or more kinds of the third specific organic group as long as the effects of the present invention are not impaired for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules. You may do it.
When the alkoxysilane represented by the formula (3) is used in combination when obtaining the polysiloxane (A), the alkoxy represented by the formula (3) in all the alkoxysilanes used to obtain the polysiloxane (A). The silane content is preferably 70 to 99.8 mol%, more preferably 75 to 99.8 mol%, and still more preferably 80 to 99.8 mol%.
In the present invention, the polysiloxane (A) is a polycondensate obtained by polycondensing at least one compound selected from the group consisting of an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the formula (3). Siloxane is preferred.

[Polysiloxane (B)]
The polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (2).
X ³ {Si (OR ² ) ₃ } _q (2)
X ³ of the formula (2) in this case ^(the second specific organic group), R ² and q are as defined above, is the same as the respective preferred.
Further, description of the alkoxysilane represented by the formula (2) is the same as the description of the alkoxysilane represented by the formula (2) described in the section above polysiloxane (AB), it will include the preferred embodiments All explanations apply. Moreover, the polysiloxane (B) used in the present invention may have a plurality of second specific organic groups.
The polysiloxane (B) used in the present invention may have a plurality of alkoxysilanes represented by the formula (2).

When the amount of the alkoxysilane represented by the formula (2) having the second specific organic group is less than 1 mol% in the total alkoxysilane used for obtaining the polysiloxane (B), good water is used. Since the reliability characteristic with respect to may not be obtained, 1 mol% or more is preferable. More preferably, it is 2 mol% or more. In the case of 60 mol% or more, since the stability of the polysiloxane solution may be poor, it is preferably 60 mol% or less, and more preferably 50 mol% or less.

The polysiloxane (B) used in the present invention is obtained by polycondensing an alkoxysilane containing at least one of the alkoxysilanes represented by the following formula (3) together with the alkoxysilane represented by the formula (2). be able to.
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
In the formula (3), X ⁴ , R ³ and n are as described in the section of the polysiloxane (AB) including preferred embodiments thereof, and specific examples of the alkoxysilane represented by the formula (3) The examples are the same as those described in the section on polysiloxane (AB).

As long as the polysiloxane (B) used in the present invention does not impair the effects of the present invention for the purpose of improving the adhesion to the substrate and the affinity with the liquid crystal molecules, one or more kinds of the third specific organic group are used. You may have.
In the polysiloxane (B), when the alkoxysilane represented by the formula (3) is used in combination, the alkoxysilane represented by the formula (3) is 40 in all the alkoxysilanes used to obtain the polysiloxane (B). It is preferably ˜99 mol%, more preferably 50 to 99 mol%.
In the present invention, the polysiloxane (B) is preferably a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (2) and an alkoxysilane containing the alkoxysilane represented by the formula (3).

[Production Method of Polysiloxane (AB)]
The method for obtaining the polysiloxane (AB) used in the present invention is not particularly limited. In the present invention, it is obtained by condensing an alkoxysilane having the above-mentioned formulas (1) and (2) as essential components in an organic solvent. Usually, polysiloxane (AB) is obtained as a solution obtained by polycondensation of the above alkoxysilane and uniformly dissolved in an organic solvent.
Examples of the method for polycondensing alkoxysilane include a method of hydrolyzing and condensing alkoxysilane in a solvent such as alcohol or glycol.
At that time, the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 moles of water of all alkoxy groups in the alkoxysilane, but it is usually preferable to add an excess amount of water over 0.5 moles.
In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 times mol of all alkoxy groups in alkoxysilane.

Usually, for the purpose of promoting hydrolysis / condensation reaction, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid and fumaric acid; alkalis such as ammonia, methylamine, ethylamine, ethanolamine and triethylamine A metal salt such as hydrochloric acid, sulfuric acid or nitric acid; In addition, it is also common to further promote the hydrolysis / condensation reaction by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired. For example, a method of heating / stirring at 50 ° C. for 24 hours, a method of heating / stirring under reflux for 1 hour and the like can be mentioned.

As another method, for example, a method of heating and polycondensing a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to alcohol in advance to obtain an alcohol solution of oxalic acid, the alkoxysilane is mixed while the solution is heated. In that case, the amount of succinic acid used is preferably 0.2 to 2 mol with respect to 1 mol of all alkoxy groups of the alkoxysilane. Heating in this method can be performed at a liquid temperature of 50 to 180 ° C. A method of heating for several tens of minutes to several tens of hours under reflux is preferred so that the liquid does not evaporate or volatilize.

In obtaining the polysiloxane (AB) of the present invention, when a plurality of types of alkoxysilanes are used, the alkoxysilanes may be mixed in advance as a mixture, or a plurality of types of alkoxysilanes may be mixed sequentially.

The solvent used for polycondensation of alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it can dissolve alkoxysilane. Moreover, even when alkoxysilane does not melt | dissolve, what melt | dissolves as the polycondensation reaction of alkoxysilane progresses is sufficient. In general, since an alcohol is generated by a polycondensation reaction of alkoxysilane, an alcohol, a glycol, a glycol ether, or an organic solvent having good compatibility with the alcohol is used.

Specific examples of the polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5 -Glycols such as pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, Lenglycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene Glycol ethers such as N-glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone Dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide, m-cresol and the like.
In the present invention, a plurality of the above polymerization solvents may be mixed and used.

Furthermore, as another method for obtaining the polysiloxane (AB) of the present invention, the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3) are hydrolyzed and condensed in an organic solvent. Then, the manufacturing method of polysiloxane (AB) including the process of adding the alkoxysilane represented by Formula (2), and hydrolyzing and condensing is mentioned.
X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)
(X ¹ , X ² , R ¹ , and p are as defined above.)
X ³ {Si (OR ² ) ₃ } _q (2)
(X ³ , R ² , and q are as defined above.)
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ , R ³ , and n are as defined above.)
At that time, the hydrolysis / condensation reaction of the alkoxysilane represented by the formulas (1) and (3) may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 moles of water of all alkoxy groups in the alkoxysilane, but it is usually preferable to add an excess amount of water over 0.5 moles.

In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 times mol of all alkoxy groups in alkoxysilane.
Usually, for the purpose of promoting hydrolysis / condensation reaction, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid and fumaric acid; alkalis such as ammonia, methylamine, ethylamine, ethanolamine and triethylamine A metal salt such as hydrochloric acid, sulfuric acid or nitric acid; In addition, it is also common to further promote the hydrolysis / condensation reaction by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired. For example, a method of heating and stirring at 50 ° C. for 24 hours, a method of heating and stirring for 1 hour under reflux, and the like can be mentioned.

The alkoxysilane represented by the formula (2) is added to the solution obtained by hydrolysis and condensation of the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3) obtained by the method described above. By continuing stirring, a solution of polysiloxane (AB) can be produced. At this time, the hydrolysis / condensation reaction can be further promoted by heating the solution. At that time, the heating temperature and the heating time can be appropriately selected as desired. For example, a method of heating and stirring at 50 ° C. for 24 hours, a method of heating and stirring for 1 hour under reflux, and the like can be mentioned.
The solvent used for polycondensation of alkoxysilane (hereinafter, also referred to as polymerization solvent) is the same as the polymerization solvent described in the above [Production method of polysiloxane (AB)], and specific examples thereof are also the same. A plurality of these solvents may be used.
The polysiloxane polymerization solution (hereinafter also referred to as polymerization solution) obtained by the above method is a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO ₂ (hereinafter referred to as SiO ₂ conversion concentration). ) Is preferably 20% by mass or less, more preferably 5 to 15% by mass. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.

[Production Method of Polysiloxane (A)]
The method for obtaining the polysiloxane (A) used in the present invention is not particularly limited. In the present invention, the polysiloxane (A) is obtained by condensing an alkoxysilane having the above-described alkoxysilane of the formula (1) as an essential component in an organic solvent. Usually, the polysiloxane (A) is obtained as a solution obtained by polycondensation of the alkoxysilane and uniformly dissolved in an organic solvent.
Examples of the polycondensation method in the present invention include a method of hydrolyzing and condensing the alkoxysilane in a solvent such as alcohol or glycol. At that time, the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 moles of water of all alkoxide groups in the alkoxysilane, but it is usually preferable to add an excess amount of water over 0.5 moles.
In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 times mol of all alkoxy groups in alkoxysilane.
Moreover, when using multiple types of alkoxysilane when obtaining polysiloxane (A), you may mix as a mixture which mixed alkoxysilane beforehand, and may mix multiple types of alkoxysilane sequentially.

The polycondensation method and the polymerization solvent used for obtaining the polysiloxane (A) are the same as those described in the section of the production method of the polysiloxane (AB), and the preferred ranges thereof are also the same.
As another method for producing the polysiloxane (A), the alkoxysilane represented by the formula (3) is hydrolyzed and condensed in an organic solvent, and then the alkoxysilane represented by the formula (1) is added to the water. A method for producing polysiloxane (A) including a step of decomposing and condensing may be mentioned.
X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)
(X ¹ , X ² , R ¹ and p are as defined above.)
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ , R ³ , and n are as defined above.)
At that time, the hydrolysis / condensation reaction of the alkoxysilane represented by the formula (3) may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically 0.5 times mole of water of all alkoxy groups in the alkoxysilane may be added, but it is usually preferable to add an excess amount of water more than 0.5 times mole, The molar ratio is preferably 2 to 2.5 times.
Further, the catalyst used for the purpose of promoting the hydrolysis / condensation reaction, or the heating method is usually the same as the catalyst described in [Production method of polysiloxane (AB)] or the heating method.

By adding the alkoxysilane represented by the formula (1) to the solution obtained by hydrolyzing and condensing the alkoxysilane represented by the formula (3) obtained by the method described above, the stirring of the polysiloxane (A) is continued. A solution can be produced. At this time, the hydrolysis / condensation reaction can be further promoted by heating the solution. At that time, the heating temperature and the heating time can be appropriately selected as desired. For example, heating and stirring at 50 ° C. for 24 hours, heating and stirring for 1 hour under reflux, and the like can be mentioned.
The polysiloxane (A) polymerization solution obtained by the above method (hereinafter also referred to as polymerization solution) has a concentration obtained by converting silicon atoms of all alkoxysilanes charged as raw materials into SiO ₂ (hereinafter referred to as SiO ₂ concentration). Is generally 20% by mass or less, and more preferably 5 to 15% by mass. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.

[Production Method of Polysiloxane (B)]
The method for obtaining the polysiloxane (B) of the present invention is not particularly limited, but in the present invention, it is the same as the above-mentioned [Production method of polysiloxane (A)].
When using multiple types of alkoxysilane when obtaining polysiloxane (B), you may mix as a mixture which mixed alkoxysilane beforehand, and may mix multiple types of alkoxysilane sequentially.
As an alternative method, a process comprising hydrolyzing and condensing an alkoxysilane represented by the formula (3) in an organic solvent, followed by adding an alkoxysilane represented by the formula (2) and hydrolyzing and condensing the polysilane. A method for producing siloxane (B) is exemplified.
X ³ {Si (OR ² ) ₃ } _q (2)
(X ³ , R ² , and q are as defined above.)
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ , R ³ , and n are as defined above.)
At that time, the hydrolysis / condensation reaction of the alkoxysilane represented by the formula (3) may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 moles of water of all alkoxy groups in the alkoxysilane, but it is usually preferable to add an excess amount of water over 0.5 moles.

In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 times mol of all alkoxy groups in alkoxysilane.
Further, the catalyst used for the purpose of promoting the hydrolysis / condensation reaction, or the heating method is usually the same as the catalyst described in [Production method of polysiloxane (AB)] or the heating method.
By adding the alkoxysilane represented by the formula (2) to the solution obtained by hydrolysis and condensation of the alkoxysilane represented by the formula (3) obtained by the above-described method and continuing stirring, the polysiloxane (B ) Solution. At this time, the hydrolysis / condensation reaction can be further promoted by heating the solution. At that time, the heating temperature and the heating time can be appropriately selected as desired. For example, heating and stirring at 50 ° C. for 24 hours, heating and stirring for 1 hour under reflux, and the like can be mentioned.
The solvent used for polycondensation of alkoxysilane (hereinafter, also referred to as polymerization solvent) is the same as the polymerization solvent described in the above-mentioned [Production method of polysiloxane (A)], and specific examples are also the same. A plurality of these solvents may be used.

[Solution of polysiloxane (AB), polysiloxane (A) and polysiloxane (B)]
In the present invention, the polymerization solution obtained by the above method may be used as it is as a solution of polysiloxane (AB), polysiloxane (A) and polysiloxane (B), and if necessary, obtained by the above method. The obtained solution may be concentrated, diluted by adding a solvent, or substituted with another solvent to obtain a solution of polysiloxane (AB), polysiloxane (A), and polysiloxane (B).
In that case, the solvent to be used (hereinafter also referred to as additive solvent) may be the same as the polymerization solvent, or may be another solvent. The additive solvent is not particularly limited as long as polysiloxane (AB), polysiloxane (A), and polysiloxane (B) are uniformly dissolved, and one or a plurality of types can be arbitrarily selected and used. .
Specific examples of the additive solvent include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and ethyl lactate in addition to the solvents mentioned as examples of the polymerization solvent. .
These solvents can improve the applicability when the liquid crystal aligning agent is applied onto the substrate by adjusting the viscosity of the liquid crystal aligning agent, or by spin coating, flexographic printing, ink jetting or the like.

[Other ingredients]
In the liquid crystal aligning agent of this invention, unless the effect of this invention is impaired, other components other than polysiloxane (AB), polysiloxane (A), and polysiloxane (B), for example, inorganic fine particles, metalloxane oligomers , A metalloxane polymer, a leveling agent, a surfactant and the like may be contained.

As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and those in the state of a colloidal solution are particularly preferable. This colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a commercially available colloidal solution. In the present invention, the inclusion of inorganic fine particles makes it possible to impart the surface shape of the formed cured film and other functions. The inorganic fine particles preferably have an average particle size of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed using the prepared coating liquid may be lowered.
Examples of the dispersion medium for the inorganic fine particles include water and organic solvents. As the colloidal solution, the pH or pKa is preferably adjusted to 1 to 10, more preferably 2 to 7, from the viewpoint of the stability of the coating solution for film formation.

Examples of the organic solvent used for the dispersion medium of the colloidal solution include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether. Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone And ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols or ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.

As the metalloxane oligomer and metalloxane polymer, single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used. The metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from a monomer such as a metal alkoxide, nitrate, hydrochloride, or carboxylate by a conventional method such as hydrolysis.
Specific examples of the metalloxane oligomer and the metalloxane polymer include commercially available siloxane oligomers such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat. Alternatively, siloxane polymers and titanoxane oligomers such as titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Inc. may be mentioned. You may use these individually or in mixture of 2 or more types.
The leveling agent, surfactant and the like may be known ones, and commercially available products are particularly preferred because they are easily available.
Moreover, the method of mixing the above-mentioned other components with polysiloxane may be simultaneous with or after polysiloxane, and is not particularly limited.

[Liquid crystal aligning agent]
The liquid crystal aligning agent of the present invention is a solution containing the above-described polysiloxane (AB), or polysiloxane (A) and polysiloxane (B), and other components as necessary. At that time, as the solvent, at least one solvent selected from the group consisting of the polymerization solvent and the additive solvent described above is used. The content of polysiloxane (AB) in the liquid crystal aligning agent, or the total content of polysiloxane (A) and polysiloxane (B) is the SiO ₂ equivalent concentration of polysiloxane (AB) or polysiloxane (A ) And polysiloxane (B) in terms of the total silicon atoms, the SiO ₂ equivalent concentration is preferably 0.5 to 15% by mass, more preferably 1 to 6% by mass. When the concentration is within the above SiO ₂ equivalent concentration range, it is easy to obtain a desired film thickness by a single application, and a sufficient pot life of the solution can be easily obtained.

In the present invention, the mixing ratio of the polysiloxane (A) and the polysiloxane (B) in the liquid crystal aligning agent is determined based on the total amount of silicon atoms contained in the polysiloxane (A) and the polysiloxane (B). The total amount of silicon atoms contained in (A) is preferably 5 mol% or more. When the amount of the total silicon atoms contained in the polysiloxane (A) is less than 5 mol%, it is difficult to obtain good vertical alignment. Moreover, when the amount of the total silicon atoms contained in the polysiloxane (A) exceeds 99.5 mol%, the content ratio of the polysiloxane (B) becomes small, and it becomes difficult to obtain good water reliability. 99.5 mol% or less is preferable.

The method for preparing the liquid crystal aligning agent of the present invention is not particularly limited. The polysiloxane (AB) used in the present invention, or the polysiloxane (A) and the polysiloxane (B), and other components added as necessary may be in a uniformly mixed state. Usually, polysiloxane (AB), polysiloxane (A) and polysiloxane (B) are polycondensed in a solvent, so a solution of polysiloxane (AB), polysiloxane (A) and polysiloxane (B) is prepared It is convenient to use it as it is or to add other components to the solution as required. Furthermore, the method using the polymerization solution as it is is the simplest.
Moreover, when adjusting content of polysiloxane (AB), polysiloxane (A), and polysiloxane (B) in a liquid crystal aligning agent, at least 1 sort (s) chosen from the group which consists of the polymerization solvent mentioned above and an addition solvent. These solvents can be used.

[Liquid crystal alignment film]
The liquid crystal aligning film of this invention is obtained using the liquid crystal aligning agent of this invention. For example, after applying the liquid crystal aligning agent of this invention to a board | substrate, the cured film obtained by drying and baking can also be used as a liquid crystal aligning film as it is. The cured film may be rubbed, irradiated with polarized light or light having a specific wavelength, or treated with an ion beam or the like to form a liquid crystal alignment film.
The substrate on which the liquid crystal aligning agent is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate on which a transparent electrode for driving liquid crystal is formed on the substrate is preferable.

Specific examples include glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, tri Examples thereof include a substrate in which a transparent electrode is formed on a plastic plate such as acetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose.

Examples of the method for applying the liquid crystal aligning agent include spin coating, printing, ink jet, spraying, roll coating, and the like.In terms of productivity, the transfer printing method is widely used industrially. The present invention is also preferably used.
The drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, a drying process is included. Is preferred. The drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C. for 0.5 to 30 minutes, preferably 1 to 5 minutes can be mentioned.

The coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film. In this case, the firing temperature can be any temperature of 100 ° C. to 350 ° C., preferably 140 ° C. to 300 ° C., more preferably 150 ° C. to 230 ° C., and still more preferably 160 ° C. to 220 ° C. It is. Firing can be performed at an arbitrary time of 5 minutes to 240 minutes. The time is preferably 10 to 90 minutes, more preferably 20 to 90 minutes. For the heating, a generally known method such as a hot plate, a hot air circulation oven, an IR oven, a belt furnace or the like can be used.
The polysiloxane in the liquid crystal alignment film undergoes polycondensation in the firing step. However, in the present invention, it is not necessary to completely polycondense unless the effects of the present invention are impaired. However, it is preferable to perform firing at a temperature that is 10 ° C. or more higher than the heat treatment temperature required for the liquid crystal cell manufacturing process, such as sealing agent curing.

The thickness of the cured film can be selected as necessary, but is preferably 5 nm or more, more preferably 10 nm or more, since the reliability of the liquid crystal display element can be easily obtained. Moreover, when the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large.
The cured film can be used as a liquid crystal alignment film as it is. It is also possible.

[Liquid crystal display element]
The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then preparing a liquid crystal cell by a known method. As an example of manufacturing a liquid crystal cell, a method is generally employed in which a pair of substrates on which a liquid crystal alignment film is formed are fixed with a sealant with a spacer interposed therebetween, and liquid crystal is injected and sealed. In this case, the size of the spacer used is 1 to 30 μm, preferably 2 to 10 μm.
The method for injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method for injecting liquid crystal after the inside of the manufactured liquid crystal cell is decompressed, and a dropping method for sealing after dropping the liquid crystal.
The substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate.
Specific examples are the same as those of the substrate described in the above section [Liquid crystal alignment film].
As a high-performance element such as a TFT type element, an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.

In the case of a transmissive liquid crystal element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used if only one substrate is used. It is. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.
In addition, in a PSA type display element using a liquid crystal containing a polymerizable compound, the pretilt angle of the liquid crystal can be expressed by irradiating energy rays such as ultraviolet rays and polarized ultraviolet rays while applying a voltage to the liquid crystal cell.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is restrict | limited to the following Example and is not interpreted.
The explanation of the abbreviations in this example is as follows.
TEOS: Tetraethoxysilane TBC: (3-Triethoxysilylpropyl) -t-butylcarbamate BISA: Bis (trimethoxysilylpropylamine)
DMAPS: 3- (N, N-dimethylaminopropyl) trimethoxysilane C12: dodecyltriethoxysilane C18: octadecyltriethoxysilane F13: tridecafluorooctyltrimethoxysilane MC18: diethoxymethyloctadecylsilane MTES: methyltriethoxysilane Phe: phenethyltrimethoxysilane Ben: benzoyloxypropyltrimethoxysilane ACPS: (3-acryloxypropyl) trimethoxysilane MAPS: 3-methacryloxypropyltriethoxysilane HG: hexylene glycol (also known as 2-methyl-2, 4-pentanediol)
BCS: Butyl cellosolve (also known as ethylene glycol monobutyl ether)
PGME: propylene glycol monoethyl ether PB: propylene glycol monobutyl ether EtOH: ethanol APS: γ-aminopropyltriethoxysilane

<Synthesis Example 1>
In a 200 mL (milliliter) four-necked reaction flask equipped with a thermometer and reflux tube, HG: 22.52 g, BCS: 7.51 g, TEOS: 39.17 g, C18: 4.17 g, and TBC:. A solution of alkoxysilane monomer was prepared by mixing 64 g. A solution prepared by mixing HG: 11.26 g, BCS: 3.75 g, water: 10.80 g and oxalic acid: 0.18 g as a catalyst was added dropwise to the solution over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.68 g, and BCS: 11.32 g were mixed to obtain a liquid crystal aligning agent (K1) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 2>
HG: 21.5 g, BCS: 7.17 g, TEOS: 35.42 g, C18: 4.17 g, and TBC: 6.43 g were mixed in a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube. Thus, a solution of the alkoxysilane monomer was prepared. To this solution, a solution in which HG: 10.75 g, BCS: 3.58 g, water: 10.80 g and oxalic acid: 0.18 g as a catalyst were previously added dropwise over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.65 g, and BCS: 11.35 g were mixed to obtain a liquid crystal aligning agent (K2) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 3>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 21.11 g, BCS: 7.04 g, TEOS: 38.75 g, and C18: 4.17 g were mixed to obtain an alkoxysilane monomer. A solution of was prepared. To this solution, a solution in which HG: 10.55 g, BCS: 3.52 g, water: 10.80 g and oxalic acid: 0.90 g as a catalyst were previously added dropwise over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 30 minutes, and then a mixed solution of BISA: 1.37 g, 1.97HG: 01.97 g, BCS: 0.66 g was added. Furthermore, the mixture was heated under reflux for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.65 g, and BCS: 11.35 g were mixed to obtain a liquid crystal aligning agent (K3) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 4>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 21.69 g, BCS: 7.23 g, TEOS: 38.75 g, and C18: 4.17 g were mixed to obtain an alkoxysilane monomer. A solution of was prepared. To this solution, a solution prepared by mixing HG: 10.85 g, BCS: 3.62 g, water: 10.80 g and 0.9 g of oxalic acid as a catalyst in advance over 30 minutes was added dropwise at room temperature. The solution was stirred for 30 minutes and then refluxed for 30 minutes, and then a mixed solution of DMAPS: 0.83 g, HG: 0.88 g, BCS: 0.29 g was added. The mixture was further heated under reflux for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.65 g, and BCS: 11.35 g were mixed to obtain a liquid crystal aligning agent (K4) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 5>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 18.88 g, BCS: 6.29 g, TEOS: 27.08 g, C18: 4.17 g, and TBC: 19.29 g Mixing to prepare a solution of alkoxysilane monomer. A solution prepared by mixing HG: 9.44 g, BCS: 3.15 g, water: 10.8 g and oxalic acid: 0.90 g as a catalyst was added dropwise to this solution over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.57 g, and BCS: 11.43 g were mixed to obtain a liquid crystal aligning agent (K5) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 6>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 22.10 g, BCS: 7.37 g, TEOS: 36.67 g, MC18: 1.55 g, and TBC: 6.43 g Mixing to prepare a solution of alkoxysilane monomer. To this solution, a solution in which HG: 11.05 g, BCS: 3.68 g, water: 10.80 g and oxalic acid: 0.36 g as a catalyst were previously added dropwise over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.66 g, and BCS: 11.34 g were mixed to obtain a liquid crystal aligning agent (K6) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 7>
Mix HG: 22.10 g, BCS: 7.37 g, TEOS: 35.42 g, Phe: 2.26 g, and TBC: 6.43 g in a 200 mL four-necked reaction flask equipped with a thermometer and reflux tube. Thus, a solution of the alkoxysilane monomer was prepared. To this solution, a solution prepared by mixing HG: 11.05 g, BCS: 3.68 g, water: 11.8 g and oxalic acid: 0.90 g as a catalyst was added dropwise over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.66 g, and BCS: 11.34 g were mixed to obtain a liquid crystal aligning agent (K7) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 8>
HG: 21.81 g, BCS: 7.27 g, TEOS: 35.42 g, Ben: 2.84 g, and TBC: 6.43 g were mixed in a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube. Thus, a solution of the alkoxysilane monomer was prepared. A solution prepared by mixing HG: 10.90 g, BCS: 3.63 g, water: 10.80 g and oxalic acid: 0.9 g as a catalyst was added dropwise to the solution over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.65 g, and BSC: 11.35 g were mixed to obtain a liquid crystal aligning agent (K8) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 9>
In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, HG: 22.29 g, BCS: 7.43 g, TEOS: 37.08 g, F13: 0.94 g, TBC: 6.43 g were mixed. Then, a solution of the alkoxysilane monomer was prepared. A solution prepared by mixing HG: 11.14 g, BCS: 3.71 g, water: 10.80 g and oxalic acid: 0.18 g as a catalyst was added dropwise to the solution over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.67 g, and BCS: 11.33 g were mixed to obtain a liquid crystal aligning agent (K9) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 10>
In a 200 mL four-necked reaction flask equipped with a thermometer and reflux tube, HG: 22.16 g, BCS: 7.39 g, TEOS: 32.50 g, ACPS: 4.69 g, C18: 1.67 g, and TBC : 6.43 g was mixed to prepare an alkoxysilane monomer solution. A solution prepared by mixing HG: 11.08 g, BCS: 3.69 g, water: 10.21 g and oxalic acid: 0.18 g as a catalyst was added dropwise to this solution over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 26.68, BCS: 4.01 g, PB: 29.32 g were mixed to obtain a liquid crystal aligning agent (K10) having a SiO ₂ equivalent concentration of 4 mass%. .

<Synthesis Example 11>
In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, HG: 22.02 g, BCS: 7.34 g, TEOS: 32.50 g, MAPS: 4.97 g and C18: 1.67 g, TBC : 6.43 g was mixed to prepare an alkoxysilane monomer solution. To this solution, a solution in which HG: 11.01 g, BCS: 3.67 g, water: 10.21 g and oxalic acid: 0.18 g as a catalyst were mixed dropwise at room temperature over 30 minutes. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.66 g, and BCS: 11.34 g were mixed to obtain a liquid crystal aligning agent (K11) having a SiO ₂ equivalent concentration of 4 mass%.
<Synthesis Example 12>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 21.69 g, BCS: 7.23 g, TEOS: 38.75 g, and C18: 4.17 g were mixed to obtain an alkoxysilane monomer. A solution of was prepared. A solution prepared by mixing HG: 10.85 g, BCS: 3.62 g, water: 10.80 g and oxalic acid: 0.90 g as a catalyst was added dropwise to the solution over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 30 minutes, and then a mixed solution of APS: 0.89 g, HG: 0.83 g, and BCS: 0.28 g was added. Furthermore, the mixture was heated under reflux for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.66 g, and BCS: 11.34 g were mixed to obtain a liquid crystal aligning agent (K12) having a SiO ₂ equivalent concentration of 4 mass%.

<Comparative Synthesis Example 1>
In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, HG: 22.63 g, BCS: 7.54 g, TEOS: 39.58 g and C18: 4.17 g were mixed to obtain an alkoxysilane monomer. A solution of was prepared. To this solution, a solution in which HG: 11.32 g, BS: 3.77 g, water: 10.8 g, and oxalic acid: 0.18 g as a catalyst were added dropwise over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 56.04 g, and BCS: 3.96 g were mixed to obtain a liquid crystal aligning agent (L1) having a SiO ₂ equivalent concentration of 4 mass%.
Table 1 shows the mixing ratio of alkoxysilanes in Synthesis Examples 1 to 12 and Comparative Synthesis Example 1.

A method for producing a liquid crystal cell, a method for evaluating liquid crystal orientation, and a method for measuring electrical characteristics are as follows.

[Method of manufacturing liquid crystal cell]
The liquid crystal aligning agent was filtered under pressure through a membrane filter having a pore diameter of 0.45 μm, and then formed into a film on a glass substrate with an ITO transparent electrode by a spin coating method. The substrate was dried on a hot plate at 80 ° C. for 5 minutes and then baked in a hot air circulation clean oven at 210 ° C. for 60 minutes to form a liquid crystal alignment film having a thickness of about 80 nm. Two substrates were prepared, and a spacer having a particle diameter of 6 μm was sprayed on the surface of the liquid crystal alignment film of one substrate, and then an epoxy adhesive was applied to the outer edge of the substrate by screen printing. Thereafter, the substrates were laminated so that the liquid crystal alignment films faced each other, and were cured after pressure bonding to produce empty cells. This empty cell was allowed to stand in an environment of room temperature 23 ° C. and humidity 98% for 20 hours to adsorb moisture (water treatment), and then liquid crystal (MLC-6608 (trade name) manufactured by Merck) was vacuum-injected. Injected. At this time, degassing of the empty cell before liquid crystal injection was performed in 5 minutes. Thereafter, the injection hole was sealed with a UV curable resin to prepare a liquid crystal cell (with water treatment).
On the other hand, an empty cell produced by the same method as described above is left in an environment of room temperature 23 ° C. and humidity 43% for 20 hours, and liquid crystal (MLC-6608 (trade name) manufactured by Merck) is injected by vacuum injection. Thereafter, the injection hole was sealed with a UV curable resin to prepare a liquid crystal cell (without water treatment).

[Liquid crystal orientation]
The liquid crystal cell (with water treatment) prepared by the method described in [Preparation of liquid crystal cell] was observed with a polarizing microscope, and the alignment state of the liquid crystal was confirmed. In the case where the entire liquid crystal cell shows a uniform alignment state with no defects, it is marked with ◯.
[Electrical characteristics]
The ion density was measured when a triangular wave having a voltage of ± 10 V and a frequency of 0.01 Hz was applied to the liquid crystal cell prepared by the method described in [Preparation of Liquid Crystal Cell]. The measurement temperature was 80 ° C. As a measuring device, a 6245 type liquid crystal property evaluation device manufactured by Toyo Technica Co., Ltd. was used.

<Examples 1 to 12>
Using the liquid crystal aligning agents K1 to K12 obtained in Synthesis Examples 1 to 12, a liquid crystal cell was prepared by the method described above, the liquid crystal alignment was observed, and the electrical characteristics were measured. The results are shown in Table 2.

<Comparative Example 1>
Using the liquid crystal aligning agent L1 obtained in Comparative Synthesis Example 1, a liquid crystal cell was prepared by the above-described method, the liquid crystal alignment was observed, and the electrical characteristics were measured. The results are shown in Table 2.

As is apparent from Table 2, in the liquid crystal cells of Examples 1 to 12, it was found that the ion density did not increase even when water treatment was performed, compared with the case where water treatment was not performed. On the other hand, in the liquid crystal cell of Comparative Example 1, when the water treatment was performed, the ion density was significantly increased as compared with the case without the water treatment.

<Synthesis Example 21>
In a 1 L (liter) four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 113.17 g, BCS: 37.72 g, TEOS: 197.91 g and C18: 20.84 g were mixed to obtain an alkoxysilane. A solution of the monomer was prepared. To this solution, a solution in which HG: 56.59 g, BS: 18.86 g, water: 54.0 g and oxalic acid: 0.90 g as a catalyst were previously added dropwise at room temperature over 30 minutes. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 56.04 g, and BCS: 3.96 g were mixed to obtain a polysiloxane solution (K21) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 22>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 22.99 g, BCS: 7.66 g, TEOS: 27.78 g and C12: 11.09 g were mixed to obtain a solution of alkoxysilane monomer. Was prepared. To this solution, a solution prepared by mixing HG: 11.50 g, BS: 3.83 g, water: 15.0 g and oxalic acid: 0.15 g as a catalyst was added dropwise at room temperature over 30 minutes. This solution was stirred for 30 minutes, heated at 67 ° C. for 30 minutes, and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 10 mass%.
The obtained polysiloxane solution: 30.0 g, HG: 36.69 g and BCS: 8.31 g were mixed to obtain a polysiloxane solution (K22) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 23>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 22.26 g, BCS: 7.42 g, TEOS: 38.33 g, C18: 4.17 g, and C12: 2.00 g were mixed. Then, a solution of the alkoxysilane monomer was prepared. To this solution, a solution in which HG: 11.13 g, BS: 3.71 g, water: 10.8 g, and oxalic acid: 0.18 g as a catalyst were added dropwise over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.67 g and BCS: 11.33 g were mixed to obtain a polysiloxane solution (K23) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 24>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 23.54 g, BCS: 7.85 g, TEOS: 27.08 g, C18: 4.17 g and MTES: 10.7 g were mixed. A solution of the alkoxysilane monomer was prepared. A solution prepared by mixing HG: 11.77 g, BS: 3.92 g, water: 10.8 g and oxalic acid: 0.18 g as a catalyst was added dropwise to the solution over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.71 g and BCS: 11.29 g were mixed to obtain a polysiloxane solution (K24) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 25>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 22.79 g, BCS: 7.60 g, TEOS: 39.58 g, and MC18: 3.87 g were mixed to obtain the alkoxysilane monomer. A solution was prepared. To this solution, a solution in which HG: 11.39 g, BS: 3.80 g, water: 10.8 g, and oxalic acid: 0.18 g as a catalyst were added dropwise at room temperature over 30 minutes in advance. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 60.0 g, HG: 97.37 g, and BCS: 22.63 g were mixed to obtain a polysiloxane solution (K25) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 26>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 23.42 g, BCS: 7.81 g, TEOS: 41.25 g, and F13: 0.94 g were charged, stirred, and alkoxylated. A solution of silane monomer was prepared. A solution prepared by mixing HG: 11.71 g, BS: 3.90 g, water: 10.8 g and oxalic acid: 0.18 g as a catalyst was added dropwise to the solution over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 60.0 g, EtOH: 84.00 g, and PGME: 36.00 g were mixed to obtain a polysiloxane solution (K26) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 27>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 23.59 g, BCS: 7.86 g, TEOS: 39.58 g, and Phe: 2.26 g were charged, stirred, and alkoxylated. A solution of silane monomer was prepared. A solution prepared by mixing HG: 11.79 g, BS: 3.93 g, water: 10.8 g and oxalic acid: 0.18 g as a catalyst was added dropwise to the solution over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 60.0 g, HG: 97.42 g, and BCS: 22.58 g were mixed to obtain a polysiloxane solution (K27) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 28>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 23.30 g, BCS: 7.77 g, TEOS: 39.58 g, and Ben: 2.84 g were charged, stirred, and alkoxylated. A solution of silane monomer was prepared. To this solution, a solution prepared by mixing HG: 11.65 g, BS: 3.88 g, water: 10.8 g and oxalic acid: 0.18 g as a catalyst was added dropwise over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 60.0 g, HG: 97.40 g, and BCS: 22.60 g were mixed to obtain a polysiloxane solution (K28) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 29>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 21.41 g, BCS: 7.14 g, TEOS: 33.33 g, and TBC: 12.86 g were charged, stirred, and alkoxy A solution of silane monomer was prepared. To this solution, HG: 10.71 g, BCS: 3.57 g, water: 10.8 g and oxalic acid 0:. The solution mixed with 18 g was added dropwise at room temperature over 30 minutes. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.64 g and BCS: 11.36 g were mixed to obtain a polysiloxane solution (L21) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 30>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, a solution of alkoxysilane monomer was prepared by mixing HG: 32.70 g, BCS: 10.90 g, and TEOS: 18.75 g. A solution prepared by mixing HG: 16.35 g, BCS: 5.45 g, water: 5.40 g and oxalic acid: 0.45 g as a catalyst was added dropwise to this solution over 30 minutes at room temperature. The solution was stirred for 30 minutes and heated at 85 ° C. for 30 minutes, and a solution in which BISA: 1.71 g, HG: 6.22 g, and BCS: 2.07 g were mixed in advance was added. Further, the mixture was heated at 85 ° C. for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 6% by mass.
The obtained polysiloxane solution: 60.0 g, HG: 25.96 g and BCS: 4.04 g were mixed to obtain a polysiloxane solution (L22) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 31>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 22.88 g, BCS: 7.63 g, TEOS: 38.75 g, and MTES: 1.78 g were mixed to obtain the alkoxysilane monomer. A solution was prepared. To this solution, a solution in which HG: 11.44 g, BCS: 3.81 g, water: 10.80 g and oxalic acid: 0.90 g as a catalyst were previously added dropwise over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 30 minutes, and then a solution in which DMAPS: 0.83 g, HG: 0.88 g, and BCS: 0.29 g were mixed in advance was added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.69 g and BCS: 11.31 g were mixed to obtain a polysiloxane solution (L23) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 32>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 17.65 g, BCS: 5.89 g, TEOS: 20.83 g, and TBC: 32.15 g were mixed to obtain an alkoxysilane monomer. A solution was prepared. To this solution, a solution prepared by mixing HG: 8.83 g, BCS: 2.94 g, 10.80 g and oxalic acid: 0.90 g as a catalyst in advance was added dropwise over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.53 g and BCS: 27.1.47 g were mixed to obtain a polysiloxane solution (L24) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 33>
Mix HG: 21.15 g, BCS: 7.05 g, and TEOS: 29.17 g, ACPS: 4.69 g, and TBC: 12.86 g in a 200 ml four-necked reaction flask equipped with a thermometer and reflux tube. Thus, a solution of the alkoxysilane monomer was prepared. A solution prepared by mixing HG: 10.58 g, BCS: 3.53 g, water: 10.80 g and oxalic acid: 0.18 g as a catalyst was added dropwise to the solution over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 1 hour and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.63 g and BCS: 11.37 g were mixed to obtain a polysiloxane solution (L25) having a SiO ₂ equivalent concentration of 4 mass%.

<Synthesis Example 34>
In a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube, HG: 22.88 g, BCS: 7.63 g, TEOS: 38.75 g, and MTES: 1.78 g were mixed to obtain the alkoxysilane monomer. A solution was prepared. To this solution, a solution in which HG: 11.44 g, BCS: 3.81 g, water: 10.80 g and oxalic acid: 0.90 g as a catalyst were previously added dropwise over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 30 minutes, and then a solution in which APS: 0.89 g, HG: 0.83 g, and BCS: 0.28 g were mixed in advance was added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.
The obtained polysiloxane solution: 30.0 g, HG: 48.69 g and BCS: 11.31 g were mixed to obtain a polysiloxane solution (L26) having a SiO ₂ equivalent concentration of 4 mass%.
The blending ratios of alkoxysilanes in Synthesis Examples 21 to 34 are shown in Tables 3 and 4 below.

<Example 21 to Example 35>
A polysiloxane solution (K21 to K28) having a SiO ₂ equivalent concentration of 4% by mass and a polysiloxane solution (L21 to L26) having a SiO ₂ equivalent concentration of 4% by mass obtained in the same manner as in Synthesis Examples 21 to 34 were obtained. By mixing at the ratios shown in Table 5, liquid crystal aligning agents (KL1 to KL15), which are polysiloxane solutions having a SiO ₂ equivalent concentration of 4% by mass, were obtained.
Using the obtained liquid crystal aligning agent, the liquid crystal cell was produced by the above-mentioned method, the liquid crystal aligning property was observed, and the electrical property was measured. The results are shown in Table 5.

<Comparative Example 21>
Using the polysiloxane solution (K21) obtained in Synthesis Example 21, a liquid crystal cell was prepared by the method described above, the liquid crystal alignment was observed, and the electrical characteristics were measured. The results are shown in Table 6.

As is clear from Table 6, in the liquid crystal cells of Examples 21 to 35, it was found that the ion density did not increase even when water treatment was performed, compared to the case where water treatment was not performed. On the other hand, in the liquid crystal alignment cell of Comparative Example 21, it was found that the ion density greatly increased when water treatment was performed compared to the case where water treatment was not performed.

A liquid crystal display element manufactured using the liquid crystal alignment treatment agent of the present invention can be a highly reliable liquid crystal display device with high reliability, in particular, high electrical property reliability, TN type, STN type, It is suitably used for display elements of various systems such as liquid crystal display elements of IPS type, VA type, OCB type, PSA type and the like.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2009-273775 filed on Dec. 1, 2009 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (16)

1. A hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may have an oxygen atom, a phosphorus atom or a sulfur atom, and one nitrogen atom, and the nitrogen 1 type or 2 types or more of polyoxygen atoms having a primary, secondary or tertiary nitrogen atom and a hydrocarbon group having 2 to 20 carbon atoms which may have an oxygen atom or a sulfur atom It contains siloxane, and the former hydrocarbon group and the latter hydrocarbon group may be bonded to the same polysiloxane, or may be bonded to different polysiloxanes, respectively. A liquid crystal aligning agent.
2. A hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may have an oxygen atom, a phosphorus atom or a sulfur atom, and one nitrogen atom, and the nitrogen Contains one type of polysiloxane having atoms that are both primary, secondary, or tertiary nitrogen atoms and optionally having 2 to 20 carbon atoms that may have oxygen or sulfur atoms 2. The liquid crystal aligning agent according to claim 1, wherein the liquid crystal aligning agent comprises two types of polysiloxanes each having a former hydrocarbon group and a latter hydrocarbon group.
3. The polysiloxane (AB) obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by Formula (2) is contained in Claim 1 or 2. Liquid crystal aligning agent.
   X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)
   (X ¹ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may contain an oxygen atom, a phosphorus atom or a sulfur atom, and X ² is a carbon atom. An alkyl group having 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p represents an integer of 0 to 2.)
   X ³ {Si (OR ² ) ₃ } _q (2)
   (X ³ has one nitrogen atom, the nitrogen atom is a primary, secondary or tertiary nitrogen atom, and a carbon atom having 2 to 20 carbon atoms which may have an oxygen atom or a sulfur atom. A hydrogen group, R ² is an alkyl group having 1 to 5 carbon atoms, and q represents an integer of 1 or 2.)
4. The liquid crystal aligning agent of Claim 1 or 2 containing the following polysiloxane (A) and polysiloxane (B).
   Polysiloxane (A): polysiloxane obtained by polycondensation of alkoxysilane containing alkoxysilane represented by formula (1).
   X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)
   (X ¹ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may contain an oxygen atom, a phosphorus atom or a sulfur atom, and X ² is a carbon atom. An alkyl group having 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p represents an integer of 0 to 2.)
   Polysiloxane (B): Polysiloxane obtained by polycondensation of alkoxysilane containing alkoxysilane represented by formula (2).
   X ³ {Si (OR ² ) ₃ } _q (2)
   (X ³ has one nitrogen atom, the nitrogen atom is a primary, secondary or tertiary nitrogen atom, and a carbon atom having 2 to 20 carbon atoms which may have an oxygen atom or a sulfur atom. A hydrogen group, R ² is an alkyl group having 1 to 5 carbon atoms, and q represents an integer of 1 or 2.)
5. The liquid crystal aligning agent of Claim 3 whose said polysiloxane (AB) is polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane further represented by Formula (3).
   (X ⁴ ) _n Si (OR ³ ) _4-n (3)
   (X ⁴ is the number of carbon atoms which may be substituted with a hydrogen atom or a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group, and which may have a hetero atom. 1 to 6 hydrocarbon groups, R ³ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.)
6. The polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (3). The liquid crystal aligning agent of description.
   (X ⁴ ) _n Si (OR ³ ) _4-n (3)
   (X ⁴ is the number of carbon atoms which may be substituted with a hydrogen atom or a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group, and which may have a hetero atom. 1 to 6 hydrocarbon groups, R ³ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.)
7. The polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (2) and an alkoxysilane containing the alkoxysilane represented by the formula (3). 6. A liquid crystal aligning agent according to 6.
   (X ⁴ ) _n Si (OR ³ ) _4-n (3)
   (A hydrogen atom or a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group, and having 1 to 6 carbon atoms which may have a hetero atom) A hydrocarbon group, R ³ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3)
8. A hydrocarbon group having 2 to 20 carbon atoms which has one nitrogen atom and the nitrogen atom is a primary, secondary or tertiary nitrogen atom and may have an oxygen atom or a sulfur atom, An alkyl group or alkylene group having 2 to 20 carbon atoms, which has one nitrogen atom and the nitrogen atom is a secondary or tertiary nitrogen atom and may have an oxygen atom. The liquid crystal aligning agent in any one of Claims 7.
9. An alkyl group or alkylene group having 2 to 20 carbon atoms which has one nitrogen atom and the nitrogen atom is a primary, secondary or tertiary nitrogen atom and may have an oxygen atom or a sulfur atom The liquid crystal aligning agent according to claim 8, wherein is a group represented by the formula (S1).
   -P ¹ -N-P ² P ³ (S1)
   (Wherein P ¹ is an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, and P ² is a carbon atom which may have a hydrogen atom, an oxygen atom or a sulfur atom. An alkyl group having 1 to 5 atoms, and P ³ is an alkylene group having 1 to 5 carbon atoms which may have an oxygen atom or a sulfur atom, or a carbon atom which may have an oxygen atom or a sulfur atom (It is an alkyl group of the number 1 to 10.)
10. 10. The liquid crystal aligning agent according to claim 1, wherein the polysiloxane content is 0.5 to 15% by mass in terms of SiO ₂ .
11. The liquid crystal aligning agent according to any one of claims 5 to 10, wherein the alkoxysilane represented by the formula (3) is a tetraalkoxysilane in which n in the formula (3) is 0.
12. A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of claims 1 to 11.
13. A liquid crystal display element comprising the liquid crystal alignment film according to claim 12.
14. The polysiloxane (AB) is represented by the formula (2) after hydrolyzing and condensing the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3) in an organic solvent. The liquid crystal aligning agent of Claim 5 manufactured by the method including the process of adding and hydrolyzing and condensing alkoxysilane.
15. The polysiloxane (A) is a step of hydrolyzing and condensing an alkoxysilane represented by the formula (3) in an organic solvent, and then adding and hydrolyzing and condensing the alkoxysilane represented by the formula (1). The liquid crystal aligning agent of Claim 6 manufactured by the method containing this.
16. Step of hydrolyzing and condensing the alkoxysilane represented by the formula (2) after the polysiloxane (B) is hydrolyzed and condensed with the alkoxysilane represented by the formula (3) in an organic solvent. The liquid crystal aligning agent of Claim 7 manufactured by the method containing this.