KR101551513B1

KR101551513B1 - Silicon-based liquid crystal orientating agent, liquid crystal orientated film and liquid crystal display element

Info

Publication number: KR101551513B1
Application number: KR1020107029687A
Authority: KR
Inventors: 리에 군지; 겐이치 모토야마; 겐지 사카모토
Original assignee: 닛산 가가쿠 고교 가부시키 가이샤
Priority date: 2008-06-04
Filing date: 2009-06-03
Publication date: 2015-09-08
Also published as: CN102084288A; CN102084288B; JPWO2009148099A1; WO2009148099A1; KR20110018927A; TW201012853A; TWI452066B; JP5578074B2

Abstract

A liquid crystal alignment film having good liquid crystal alignability and high film stability, and a silicon-based liquid crystal aligning agent capable of forming a liquid crystal display element having the liquid crystal alignment film and being free from external influences of moisture and having excellent electric characteristics do. A hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may also contain an oxygen atom, a phosphorus atom or a sulfur atom, and a hydrocarbon group having 1 to 12 carbon atoms and having an ureido group Or two or more kinds of polysiloxanes and the former hydrocarbon group and the latter hydrocarbon group having an ureido group may be bonded to the same polysiloxane or may be bonded to different polysiloxanes.

Description

TECHNICAL FIELD [0001] The present invention relates to a silicon-based liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element,

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

It is generally known that a liquid crystal display element has a structure in which two substrates on which a liquid crystal alignment film containing polyamic acid and / or polyimide as a main component are formed on a transparent electrode are opposed to each other and a liquid crystal material is filled in the gap. Twisted Nematic (TN) type liquid crystal display devices are most well known, but are classified into a super twisted nematic (STN) type capable of achieving a higher contrast ratio, an in-plane switching (IPS) type having less viewing angle dependency, VA: Vertical Alignmnt) type are developed.

BACKGROUND ART In the field of business applications and liquid crystal projectors for home theaters, a metal halide lamp having a high irradiation intensity is used as a light source, and a liquid crystal alignment film material having not only high heat resistance but also high light resistance is desired.

Under such circumstances, an inorganic liquid crystal alignment film material has attracted attention as well as an organic liquid crystal alignment film material such as polyimide which has been conventionally used.

For example, an orientation agent composition containing a reaction product of a tetraalkoxysilane, a trialkoxysilane, and an alcohol and oxalic acid has been proposed as an inorganic oriented film material of a coating type, and a liquid crystal display device has been proposed. It has been reported that a liquid crystal alignment film excellent in uniformity is formed. (See Patent Document 1)

In addition, a liquid crystal aligning agent composition containing a reaction product of tetraalkoxysilane, a specific trialkoxysilane and water and a specific glycol ether solvent has been proposed to prevent display defects and to provide a liquid crystal having good afterimage characteristics even after driving for a long time It has been reported that a liquid crystal alignment film with less deterioration in the voltage holding ratio with respect to light and heat is formed without deteriorating the performance. (See Patent Document 2)

In recent years, technological innovation of liquid crystal display devices including liquid crystal TVs has been remarkable. In order to achieve this, in particular, long-term reliability improvement of devices has become a bigger problem than ever. For this reason, it is required to obtain a homogeneous liquid crystal alignment film with good reproducibility and to obtain a stable film in the long term.

Particularly, in the process of manufacturing a liquid crystal display device, manufacturing a homogeneous liquid crystal alignment film having good reproducibility without being influenced by the environment has become very important in securing the reliability of the device.

In addition, resistance to moisture invading from the outside of the liquid crystal display element is also important for ensuring long-term reliability.

Japanese Laid-Open Patent Publication No. 09-281502 Japanese Patent Application Laid-Open No. 2005-250244

When the inorganic liquid crystal alignment layer is formed by using a liquid crystal aligning agent, if an alkoxy group or a silanol group remains, the inorganic liquid crystal alignment layer tends to be affected by moisture present in the air. For this reason, until now, it is difficult to obtain a homogeneous liquid crystal alignment film, which results in a problem in that the reliability of the liquid crystal display element is reduced.

In addition, moisture penetrating from the outside of the liquid crystal display element, for example, moisture penetrating from a seal member or the like also affects the liquid crystal alignment film, and thus the reliability of the liquid crystal display element is likely to decrease.

For this reason, improving the resistance to moisture of the liquid crystal alignment film is an important task in securing the reliability of the liquid crystal display element.

The object of the present invention is to provide a liquid crystal alignment film which is capable of forming a liquid crystal alignment film having a good liquid crystal alignment property and a high film stability and being not easily affected by moisture from the outside and capable of forming a liquid crystal alignment film excellent in electric characteristics Based liquid crystal alignment agent, a liquid crystal alignment film obtained from the silicon-based liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

The present invention can achieve the above-mentioned objects, and it is intended to provide the following.

[1] A compound having a hydrocarbon group of 8 to 30 carbon atoms, which may be substituted with a fluorine atom and may also have an oxygen atom, a phosphorus atom or a sulfur atom, and a hydrocarbon group of 1 to 12 carbon atoms, Wherein the hydrocarbon group having one or two or more kinds of polysiloxane and the hydrocarbon group having the former hydrocarbon group and the hydrocarbon group having the latter ureido group may be bonded to the same polysiloxane or may be bonded to different polysiloxanes.

[2] The liquid crystal aligning agent according to the above [1], which contains a polysiloxane (AB) obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (2).

X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)

(X ¹ is a hydrocarbon group of 8 to 30 carbon atoms which may be substituted with a fluorine atom and may also contain an oxygen atom, a phosphorus atom or a sulfur atom, X ² is an alkyl group of 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p is an integer of 0 to 2)

X ³ {Si (OR ² ) ₃ } _q (2)

(X ³ is a hydrocarbon group having 1 to 12 carbon atoms having an ureido group, R ² is an alkyl group having 1 to 5 carbon atoms, and q is an integer of 1 or 2)

[3] The liquid crystal aligning agent according to the above [1], which contains the following polysiloxane (A) and polysiloxane (B).

Polysiloxane (A): polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (1)

X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)

(X ¹ , X ² , R ¹ and p are the same as defined in formula (1) in [1] 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 the same as defined respectively in formula (2) in the above-mentioned [1])

[4] The liquid crystal aligning agent according to the above [2], wherein the polysiloxane (AB) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane further represented by the following formula (3).

(X ⁴ ) _n Si (OR ³ ) _4-n (3)

(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 may have an unsaturated bond or a hetero atom R ³ is an alkyl group of 1 to 5 carbon atoms, and n is an integer of 0 to 3)

[5] The liquid crystal aligning agent according to the above [3], wherein the polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the formula (3).

(X ⁴ ) _n Si (OR ³ ) _4-n (3)

(X ⁴ , R ³ and n are the same as defined respectively in the formula (2) in [4] above)

[6] The liquid crystal aligning agent according to [3] or [5], wherein the polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by formula (2) and an alkoxysilane represented by formula .

(X ⁴ ) _n Si (OR ³ ) _4-n (3)

The alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3) are hydrolyzed and condensed in the organic solvent, and the alkoxysilane represented by the formula (2) is added to the polysiloxane (AB) The liquid crystal aligning agent according to the above [4], which is produced by a method comprising a condensation step.

[8] The process according to [1], wherein the polysiloxane (A) is hydrolyzed and condensed with an alkoxysilane represented by the formula (3) in an organic solvent and then the alkoxysilane represented by the formula The liquid crystal aligning agent according to the above [5], which is produced by the above method.

[9] The process according to [1], wherein the polysiloxane (B) comprises hydrolysis / condensation of an alkoxysilane represented by the formula (3) in an organic solvent, followed by addition of an alkoxysilane represented by the formula (2) The liquid crystal aligning agent according to the above-mentioned [6], which is produced by the above method.

[10] The liquid crystal aligning agent according to any one of [4] to [9], wherein the alkoxysilane represented by the formula (3) is tetraalkoxysilane wherein n in the formula (3) is 0.

The alkoxysilane represented by the formula (1) is contained in the total alkoxysilane for obtaining the polysiloxane (AB) in an amount of 0.1 to 30 mol%, and the alkoxysilane represented by the formula (2) , And 0.1 to 50 mol%, based on the total weight of the liquid crystal aligning agent.

[12] The liquid crystal aligning agent according to any one of [4] to [11], wherein the alkoxysilane represented by the formula (3) is contained in an amount of 20 to 99.8 mol% in the total alkoxysilane for obtaining the polysiloxane (AB).

[13] The liquid crystal aligning agent according to any one of [1] to [12], wherein the polysiloxane content is 0.5 to 15 mass% in terms of SiO ₂ .

[14] The liquid crystal alignment according to any one of the above [3], [5], [6] and [8] to [13], wherein the organic solvent contains an organic solvent dissolving the polysiloxane (A) My.

[15] of the liquid crystal aligning agent, the polysiloxane (A) and polysiloxane (B) is SiO ₂ the sum of silicon atoms contained in them The liquid crystal aligning agent according to any one of [3], [5], [6] and [8] to [14], wherein the liquid crystal aligning agent is contained in an amount of 0.5 to 15 mass%

(3), (5), (6) and (8) to (8), wherein the proportion of the polysiloxane (A): polysiloxane (B) is 5:95 to 99.5: [15] The liquid crystal aligning agent according to any one of [1] to [15].

The total alkoxysilane used for obtaining the polysiloxane (A) is preferably an alkoxysilane represented by the formula (1) in an amount of 0.2 to 30 mol% and an alkoxysilane represented by the formula (3) in an amount of 70 to 99.8 mol% The liquid crystal aligning agent according to any one of [5], [8], [10] and [12] to [16].

The total alkoxysilane used for obtaining the polysiloxane (B) preferably has an alkoxysilane represented by the formula (2) in an amount of 0.5 to 60 mol% and an alkoxysilane represented by the formula (3) in an amount of 40 to 99.5 mol% The liquid crystal aligning agent according to any one of [6], [9], [10] and [12] to [16]

[19] The positive resist composition as described in any one of [1] to [3], wherein the alkoxysilane represented by the formula (2) is at least one selected from the group consisting of γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (2) to (3), wherein the compound is at least one member selected from the group consisting of [(methoxysilyl) propyl] urea, bis [3- (trimethoxysilyl) propyl] urea, 18]. &Lt; / RTI >

[20] A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of [1] to [19] above to a substrate, followed by drying and firing.

[21] A liquid crystal display element having the liquid crystal alignment film according to the above [20].

According to the present invention, a silicon-based liquid crystal alignment agent capable of forming a liquid crystal alignment film exhibiting good liquid crystal alignability and obtaining a liquid crystal display element having excellent electric characteristics is obtained. Further, 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, particularly a liquid crystal display element with high reliability of electric characteristics and stable high quality can be obtained.

The mechanism by which the liquid crystal aligning agent of the present invention is used to obtain a liquid crystal alignment film having a good liquid crystal alignment property, particularly a highly reliable liquid crystal alignment film which is not easily affected by moisture from the outside is not so clear. However, From the comparison between the examples and the comparative examples, it was confirmed that the polysiloxane contained in the liquid crystal aligning agent of the present invention has a specific carbon atom Is believed to be attributable to having a number of hydrocarbon groups together with a hydrocarbon group having a specific carbon number having an ureido group.

The liquid crystal aligning agent of the present invention may be substituted with a fluorine atom and may have a hydrocarbon group of 8 to 30 carbon atoms, preferably 8 to 22 carbon atoms, which may contain an oxygen atom, a phosphorus atom or a sulfur atom, Specific hydrocarbon groups containing one or two or more kinds of polysiloxane having a hydrocarbon group of 1 to 12 carbon atoms, preferably 1 to 7 carbon atoms, and having the former specific hydrocarbon group and the latter ureido group are obtained by the following first and second aspects May be bonded to the same polysiloxane, or they may be bonded to different polysiloxanes as in the second embodiment. Hereinafter, the first and second aspects of the present invention will be described.

[First Aspect of the Present Invention]

(AB) obtained by polycondensing an alkoxysilane represented by the following formula (1) and an alkoxysilane containing an alkoxysilane represented by the following formula (2).

X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)

(X ¹ , X ² , R ¹ , p are each as defined above)

X ³ {Si (OR ² ) ₃ } _q (2)

(X ³ , R ² , and q are the same as defined above)

[Polysiloxane (AB)]

X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)

In the formula (1), X ¹ (hereinafter also referred to as the first specific organic group) is as defined above, but the hydrocarbon group having 8 to 30 carbon atoms, preferably 8 to 22 carbon atoms, Direction. Examples of the first specific organic group include an alkyl group, a fluoroalkyl group, an alkenyl group, a phenethyl group, a vinylphenylalkyl group, a naphthyl group, and a fluorophenylalkyl group. Of the oxygen atom, phosphorus atom or sulfur atom possessed by the first specific organic group, an oxygen atom is preferable, and examples thereof include an allyloxyalkyl group, a benzoyloxyalkyl group, an alkoxyphenoxyalkyl group, and an epoxycycloalkyl group. Especially, the alkoxysilane in which the first specific organic group is an alkyl group or a fluoroalkyl group is preferable because it is relatively inexpensive and commercially available and easy to obtain. The polysiloxane (AB) used in the present invention may have a plurality of first specific organic groups.

In the formula (1), X ² is an alkyl group of 1 to 7 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, X ² is a methyl group or an ethyl group.

R ¹ in the formula (1) is an alkyl group of 1 to 5 carbon atoms, 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 them, 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 is an alkyl group having 1 to 5 carbon atoms)

Specific examples of the alkoxysilane represented by the above formula (1) are mentioned, but the present invention is not limited thereto.

Examples of the silane coupling agent include octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexa Heptadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyltrimethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane, But are not limited to, triethoxysilane, undecyltrimethoxysilane, 21-dococenyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane , Heptadecafluorodecyltriethoxysilane, isooctyltriethoxysilane, phenethyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, m-vinylphenylethyltrimethoxysilane, p-vinylphenylethyltrimethoxysilane, Lt; RTI ID = 0.0 > (1 (Naphthyl) triethoxysilane, (1-naphthyl) trimethoxysilane, allyloxydecyltriethoxysilane, benzoyloxypropyltrimethoxysilane, 3- (4-methoxyphenoxy) (Meth) acrylates such as 1 - [(2-triethoxysilyl) ethyl] cyclohexane-3,4-epoxide, 2- (diphenylphosphino) ethyltriethoxysilane, diethoxymethyloctadecylsilane, dimethoxymethyl Octadecyl silane, octadecyl silane, octadecyl silane, diethoxydodecyl methyl silane, dimethoxydodecyl methyl silane, diethoxydecyl methyl silane, dimethoxydecyl methyl silane, diethoxy octyl methyl silane, dimethoxy octyl methyl silane, Hexyldimethyloctadecylsilane and the like. Among them, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyl Heptadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyltriethoxysilane, heptadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane, Ethoxysilane, or undecyltrimethoxysilane, diethoxymethyloctadecylsilane, and diethoxydodecylmethylsilane are preferable.

The amount of the alkoxysilane represented by the formula (1) having the first specific organic group is preferably less than 0.1 mol% in the total alkoxysilane used for obtaining the polysiloxane (AB) , It is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and still more preferably 1 mol% or more. If it is more than 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 22 mol% or less, still more preferably 15 mol% to be.

X ³ {Si (OR ² ) ₃ } _q (2)

The X ³ in the formula (2) (hereinafter also referred to as the second specific organic group) is as defined above, but the number of carbon atoms of the hydrocarbon group having an ureido group is preferably 1 to 7. R ² in the formula (2) is the same as defined above, but is 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 alkoxysilane represented by the formula (2-1) include, but are not limited to, the following. (R) -N-1-phenylethyl-N ' -triethoxysilane, [gamma] -ureidopropyltrimethoxysilane, [gamma] -ureidopropyltripropoxysilane, (R) -N-1-phenylethyl-N'-trimethoxysilylpropylurea, and the like.

Among them, γ-ureidopropyltriethoxysilane or γ-ureidopropyltrimethoxysilane is particularly preferable because it is readily available as a commercial product.

Specific examples of the alkoxysilane represented by the formula (2-2) include, but are not limited to, the following. For example, there may be mentioned bis [3- (triethoxysilyl) propyl] urea, bis [3- (triethoxysilyl) ethyl] urea, bis [3- (trimethoxysilyl) (Tripropoxysilyl) propyl] urea. Among them, bis [3- (triethoxysilyl) propyl] urea is particularly preferable because it is commercially available and readily available.

The polysiloxane (AB) used in the present invention may have a plurality of alkoxysilanes represented by the formula (2).

The amount of the alkoxysilane represented by the formula (2) having the second specific organic group is preferably less than 0.1 mol% in the total alkoxysilane used for obtaining the polysiloxane (AB) It is preferably 0.1 mol% or more, more preferably 0.2 mol% or more, and still more preferably 0.5 mol% or more. On the other hand, if it exceeds 50 mol%, the liquid crystal alignment film to be formed may not be sufficiently cured, so that it is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% to be.

In the polysiloxane (AB), the alkoxysilane represented by the formula (1) is contained preferably in an amount of 0.1 to 30 mol%, particularly preferably 0.5 to 22 mol%, of the total alkoxysilane to be used, Is preferably contained in an amount of 0.1 to 50 mol%, particularly preferably 0.5 to 30 mol% in the total alkoxysilane in which the alkoxysilane is used.

The polysiloxane (AB) of the present invention is preferably an alkoxysilane represented by the following formula (3) in addition to the alkoxysilanes represented by the formulas (1) and (2). Since the alkoxysilane represented by the formula (3) can impart various properties to the polysiloxane (AB), one or more species can be selected and used depending on the required characteristics.

(X ⁴ ) _n Si (OR ³ ) _4-n (3)

X ⁴ in the formula (3) is the same as defined above, but when X ⁴ is a hydrocarbon group having 1 to 6 carbon atoms (hereinafter also referred to as a third specific organic group), the third specific organic group may be an aliphatic And may have a ring structure or a branched structure such as a hydrocarbon, an aliphatic ring, an aromatic ring and a hetero ring, and may contain an unsaturated bond or a hetero atom such as an oxygen atom, a sulfur atom, and 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 acryloyl group or the like as described above.

R ³ in the formula (3) is as defined above, but is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. In the formula (3), n is the same as defined above, but preferably represents an integer of 0 to 2.

Specific examples of the alkoxysilane represented by the formula (3) include, but are not limited to,

Specific examples of the alkoxysilane in the case where X ⁴ is a hydrogen atom in the alkoxysilane of the formula (3) include trimethoxysilane, triethoxysilane, tripropoxysilane and tributoxysilane .

Specific examples of the alkoxysilane in the case where X ⁴ is the third specific organic group in the alkoxysilane of the formula (3) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Propyltriethoxysilane, methyltripropoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3 -Isocyanate propyltriethoxysilane, trifluoropropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxy Diethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, m-vinylphenyltrimethoxysilane, p-vinylphenyltrimethoxysilane, trimethylethoxysilane, trimethyl Methoxysilane and the like.

The polysiloxane (AB) used in the present invention is intended for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules, and as long as the effect of the present invention is not impaired, the third specific organic group .

In the alkoxysilane represented by the formula (3), the alkoxysilane wherein n is 0 is tetraalkoxysilane. Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention since it easily condenses with the alkoxysilane represented by the formula (1) and the formula (2).

As the alkoxysilane wherein n is 0 in the above formula (3), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable. desirable.

When the alkoxysilane represented by the formula (3) is used in combination, the amount of the alkoxysilane represented by the formula (3) is preferably 20 to 99.8 mol% in the total alkoxysilane used for obtaining the polysiloxane (AB). And more preferably 35 to 99.8 mol%. More preferably, the alkoxysilane represented by the formula (3) is 50 to 99.8 mol%.

[Second aspect of the present invention]

Is a liquid crystal aligning agent containing the following polysiloxane (A) and the following polysiloxane (B).

X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)

(X ¹ , X ² , R ¹ , p are each as defined above)

X ³ {Si (OR ² ) ₃ } _q (2)

(X ³ , R ² , and q are the same 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)

Here, X ¹ , X ² , R ¹ and p in the formula (1) are the same as defined above, and each preferable example is the same as above.

The description of the alkoxysilane represented by the formula (1) is the same as the description of the alkoxysilane represented by the formula (1) in the section of the polysiloxane (AB), and all explanations including the preferred embodiments are applied. The polysiloxane (A) used in the present invention may have a plurality of first 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 for obtaining the polysiloxane (A), good liquid crystal alignability may not be obtained , Preferably 0.2 mol% or more, more preferably 0.5 mol% or more, and still more preferably 1 mol% or more. On the other hand, if it exceeds 30 mol%, the liquid crystal alignment film to be formed may not be sufficiently cured, so that it is preferably 30 mol% or less, more preferably 25 mol% or less, furthermore preferably 20 mol% .

The polysiloxane (A) used in the present invention is preferably a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing at least one alkoxysilane represented by the following formula (3). The alkoxysilane represented by the formula (3) may impart various properties to the polysiloxane. Therefore, one or more alkoxysilanes represented by the formula (3) may be selected and used according to necessity.

(X ⁴ ) _n Si (OR ³ ) _4-n (3)

Herein, X ⁴ and R ³ in the formula (3) are the same as those in the formula (3) of the polysiloxane (AB) term and the specific examples of the alkoxysilane represented by the formula (3) Are the same as those in the polysiloxane (AB) term.

In the present invention, the polysiloxane (A) may have one or more kinds of third specific organic groups, so long as the effects of the present invention are not impaired for the purpose of improving adhesiveness to a substrate and improving affinity with liquid crystal molecules .

In the case of using the alkoxysilane represented by the formula (3) in obtaining the polysiloxane (A), the alkoxysilane represented by the formula (3) accounts for 70 to 99.8 mol% of the total alkoxysilane used for obtaining the polysiloxane (A) , More preferably 75 to 99.8 mol%, and still more preferably 80 to 99.8 mol%.

In the present invention, the polysiloxane (A) is preferably a polysiloxane obtained by polycondensation of 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).

[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)

Here, X ³ , R ^2, and q in the formula (2) are the same as defined above, and each preferable example is the same as above.

The 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 of the polysiloxane (AB), and all explanations including the preferred embodiments are applied. 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).

The amount of the alkoxysilane represented by the formula (2) having the second specific organic group is preferably less than 0.5 mol% in the total alkoxysilane used for obtaining the polysiloxane (B) The content is preferably 0.5 mol% or more. More preferably, it is 1.0 mol% or more. More preferably, it is 2.0 mol% or more. On the other hand, when it exceeds 60 mol%, the liquid crystal alignment film to be formed may not be sufficiently cured, so that it is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% .

The polysiloxane (B) used in the present invention can be obtained by polycondensation of an alkoxysilane represented by the formula (2) and an alkoxysilane containing at least one alkoxysilane represented by the following formula (3).

(X ⁴ ) _n Si (OR ³ ) _4-n (3)

Here, X ⁴ , R ³ and n in the formula (3) are the same as those described in the polysiloxane (AB) term including the preferred embodiment thereof, and also the specific examples of the alkoxysilane represented by the formula (3) AB). &Lt; / RTI >

The polysiloxane (B) used in the present invention is intended for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules, and as long as the effect of the present invention is not impaired, the polysiloxane (B) do.

When the alkoxysilane represented by the formula (3) is used in combination with the polysiloxane (B), the proportion of the alkoxysilane represented by the formula (3) in the total alkoxysilane used for obtaining the polysiloxane (B) is preferably 40 to 99.5 mol% , More preferably 50 to 99.5 mol%, and still more preferably 60 to 99.5 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 an 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 containing the above-mentioned formulas (1) and (2) as essential components in an organic solvent. The polysiloxane (AB) is usually obtained as a solution obtained by polycondensing the alkoxysilane and uniformly dissolving it in an organic solvent.

The polycondensation method of the alkoxysilane includes, for example, a method of hydrolyzing and condensing an alkoxysilane in a solvent such as an alcohol or a glycol.

At this time, the hydrolysis-condensation reaction may be partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, 0.5-fold molar water of the total alkoxy groups in the alkoxysilane can be theoretically added, but it is usually preferable to add an excess amount of water in excess of 0.5-molar mol.

In the present invention, the amount of water used in the reaction may be appropriately selected according to the desired amount, and is usually 0.5 to 2.5 times the total alkoxy group in the alkoxysilane.

For the purpose of promoting the hydrolysis and condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, and fumaric acid; Alkali such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine and the like; A catalyst such as a metal salt of hydrochloric acid, sulfuric acid, nitric acid or the like is used. Further, it is also common to accelerate hydrolysis / condensation reaction by heating a solution in which alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected according to the desired one. For example, heating and stirring at 50 占 폚 for 24 hours, heating and stirring under reflux for 1 hour, and the like.

As another method, for example, a method of polycondensing a mixture of alkoxysilane, a solvent and oxalic acid by heating may be mentioned. Specifically, oxalic acid is added to the alcohol in advance to prepare an alcohol solution of oxalic acid, and then the alkoxysilane is mixed while heating the solution. At this time, the amount of oxalic acid to be used is preferably 0.2 to 2 mol per 1 mol of the total alkoxy groups of the alkoxysilane. The heating in this method can be carried out at a liquid temperature of 50 to 180 ° C. Preferably, the solution is heated for several tens of minutes to several tens of hours under reflux so as not to evaporate or volatilize the solution.

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

The solvent used for polycondensing the alkoxysilane (hereinafter also referred to as a polymerization solvent) is not particularly limited as long as it dissolves the alkoxysilane. In addition, even when the alkoxysilane is not dissolved, it may be any one that dissolves along with the progress of the polycondensation reaction of the alkoxysilane. Generally, an organic solvent having good compatibility with alcohols, glycols, glycol ethers, or alcohols is used because alcohol is produced by the polycondensation reaction of alkoxysilane.

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, Butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, Glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and ethylene glycol 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 Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, Glycol ethers such as ethylene glycol dimethyl ether, glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether, and N-methyl-2-pyrrolidone, N, Acetamide,? -Butyrolactone, dimethylsulfoxide, tetramethylurea, hexamethylphosphotriamide and m-cresol.

In the present invention, a plurality of the polymerization solvents may be mixed and used.

As another method for obtaining the polysiloxane (AB) of the present invention, an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the formula (3) are hydrolyzed and condensed in an organic solvent, And a step of hydrolysis and condensation by adding an alkoxysilane to the polysiloxane (AB).

X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)

(X ¹ , X ² , R ¹ and p are each as defined above)

X ³ {Si (OR ² ) ₃ } _q (2)

(X ³ , R ^2, and q are each as defined above)

(X ⁴ ) _n Si (OR ³ ) _4-n (3)

(X < ⁴ >, R < ³ > and n are each as defined above)

At this 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, 0.5-fold molar water of the total alkoxy group in the alkoxysilane may be theoretically added. It is usually preferable to add an excess amount of water in excess of 0.5-molar mol.

In the present invention, the amount of water used in the reaction may be appropriately selected according to the desired amount, but is preferably 0.5 to 2.5 times the total alkoxy group in the alkoxysilane.

For the purpose of promoting the hydrolysis and condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, and fumaric acid; Alkali such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine and the like; A catalyst such as a metal salt of hydrochloric acid, sulfuric acid, nitric acid or the like is used. Further, it is also common to accelerate 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 according to the desired one. For example, heating and stirring at 50 占 폚 for 24 hours, heating and stirring under reflux for 1 hour, and the like.

The alkoxysilane represented by the formula (2) is added to a 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 above-mentioned method and the stirring is continued to obtain a polysiloxane AB). &Lt; / RTI > At this time, by heating the solution, the hydrolysis / condensation reaction can be further promoted. At that time, the heating temperature and the heating time can be appropriately selected according to the desired one. For example, heating and stirring at 50 占 폚 for 24 hours, heating and stirring under reflux for 1 hour, and the like.

The solvent used in the polycondensation of the alkoxysilane (hereinafter also referred to as a polymerization solvent) is the same as the polymerization solvent described in the above-mentioned " Polysiloxane (AB) Production Method ", and the same is true for the specific examples. do.

The polymerization solution of the polysiloxane obtained by the above method (hereinafter also referred to as polymerization solution) is preferably a solution in which the silicon atom of the entire alkoxysilane charged as the raw material in terms of SiO ₂ (hereinafter referred to as SiO ₂ concentration) is preferably 20 mass% By mass or less, more preferably 5 to 15% by mass. By selecting an arbitrary concentration in this concentration range, it is possible to obtain a homogeneous solution by suppressing gel formation.

[Production method of polysiloxane (A)] [

The method for obtaining the polysiloxane (A) for use in the present invention is not particularly limited, but the present invention can be obtained by condensing an alkoxysilane containing the alkoxysilane of the above formula (1) as an essential component in an organic solvent. The polysiloxane (A) is usually obtained as a solution in which the alkoxysilane is polycondensed and uniformly dissolved in an organic solvent.

Examples of the polycondensation method in the present invention include a method of hydrolyzing and condensing the above alkoxysilane in a solvent such as an alcohol or a glycol. At this time, the hydrolysis-condensation reaction may be partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, 0.5-fold molar water of the total alkoxide group in the alkoxysilane can be theoretically added, and it is usually preferable to add an excess amount of water in excess of 0.5-molar mol.

When a plurality of alkoxysilanes are used in obtaining the polysiloxane (A), they may be mixed as a mixture of alkoxysilanes in advance, or a plurality of alkoxysilanes may be mixed in sequence.

The method of polycondensation used to obtain the polysiloxane (A), the polymerization solvent and the like are the same as those described in the section of the production method of the polysiloxane (AB), and the preferable range thereof is also the same.

As a separate method for producing the polysiloxane (A), a step of hydrolyzing / condensing the alkoxysilane represented by the formula (3) in an organic solvent and then adding the alkoxysilane represented by the formula (1) (A) having a hydroxyl group in the molecule.

X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)

(X ¹ , X ² , R ¹ and p are each as defined above)

(X ⁴ ) _n Si (OR ³ ) _4-n (3)

(X < ⁴ >, R < ³ > and n are each as defined above)

At this 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, 0.5-fold molar water of the total alkoxy group in the alkoxysilane is theoretically added. Normally, an excess amount of water is preferably added in an amount of 0.5-fold mol, more preferably 0.5 to 2.5-fold mol Do.

The catalyst used for promoting the hydrolysis and condensation reaction, or the heating method and the like are generally the same as the catalyst described in [Method for producing polysiloxane (AB)] or the heating method.

A solution of the polysiloxane (A) can be prepared by adding an alkoxysilane represented by the formula (1) to a solution obtained by the above-mentioned method in which the alkoxysilane represented by the formula (3) is hydrolyzed and condensed and stirring is continued. At this time, by heating the solution, the hydrolysis / condensation reaction can be further promoted. At that time, the heating temperature and the heating time can be appropriately selected according to the desired one. For example, heating and stirring at 50 占 폚 for 24 hours, or heating and stirring for 1 hour under reflux.

The polymer solution (hereinafter also referred to as polymer solution) is (hereinafter referred to, SiO ₂ in terms of concentration), the concentration in terms of a silicon atom of the total of alkoxysilane added to the SiO ₂ as a material of the polysiloxane (A) obtained in the method 20 by weight % Or less, more preferably 5 to 15 mass%. By selecting an arbitrary concentration in this concentration range, it is possible to obtain a homogeneous solution by suppressing gel formation.

[Production method of polysiloxane (B)] [

The method for obtaining the polysiloxane (B) of the present invention is not particularly limited, but the present invention is the same as the above-mentioned [production method of polysiloxane (A)].

When a plurality of alkoxysilanes are used to obtain the polysiloxane (B), they may be mixed as a mixture of alkoxysilanes in advance, or a plurality of alkoxysilanes may be sequentially mixed.

As another method, there is a method of hydrolyzing and condensing an alkoxysilane represented by the formula (3) in an organic solvent, followed by hydrolysis and condensation by adding an alkoxysilane represented by the formula (2) And a manufacturing method.

X ³ {Si (OR ² ) ₃ } _q (2)

(X ³ , R ^2, and q are each as defined above)

(X ⁴ ) _n Si (OR ³ ) _4-n (3)

(X < ⁴ >, R < ³ > and n are each as defined above)

At this 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, 0.5-fold molar water of the total alkoxy group in the alkoxysilane may be theoretically added. It is usually preferable to add an excess amount of water in excess of 0.5-molar mol.

A solution of the polysiloxane (B) can be prepared by adding an alkoxysilane represented by the formula (2) to a solution obtained by the above-mentioned method in which the alkoxysilane represented by the formula (3) is hydrolyzed and condensed and continuing the stirring . At this time, by heating the solution, the hydrolysis / condensation reaction can be further promoted. At that time, the heating temperature and the heating time can be appropriately selected according to the desired one. For example, heating and stirring at 50 占 폚 for 24 hours, or heating and stirring for 1 hour under reflux.

The solvent used in the polycondensation of the alkoxysilane (hereinafter also referred to as a polymerization solvent) is the same as the polymerization solvent described in the above-mentioned [Production method of polysiloxane (A)], and the same applies to the specific examples. .

[Solution of polysiloxane (AB), polysiloxane (A) and polysiloxane (B)] [

In the present invention, the polymerization solution obtained by the above method may be directly used as a solution of the polysiloxane (AB), the polysiloxane (A) and the polysiloxane (B), or the solution obtained by the above method may be concentrated, (AB), the polysiloxane (A), and the polysiloxane (B) may be prepared by dissolving the polysiloxane (A) or substituting with another solvent.

At this time, the solvent to be used (hereinafter also referred to as an addition solvent) may be the same as or different from the polymerization solvent. This addition solvent is not particularly limited as long as the polysiloxane (AB), the polysiloxane (A) and the polysiloxane (B) are uniformly dissolved, and one or more kinds of solvents can be arbitrarily selected and used.

Specific examples of the addition solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like; And esters such as methyl acetate, ethyl acetate and ethyl lactate.

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 jet or the like.

[Other components]

In the present invention, other components other than the polysiloxane (AB) polysiloxane (A) and the polysiloxane (B) such as inorganic microfine particles, metaloxyl oligomers, metaloxyl polymers, leveling agents, 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, or magnesium fluoride fine particles are preferable, and in particular, they are preferably in a colloidal solution state. The colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a colloidal solution of a commercial product. In the present invention, by containing the inorganic fine particles, the surface shape and other functions of the formed cured coating can be imparted. The inorganic fine particles preferably have an average particle diameter of 0.001 to 0.2 mu m, more preferably 0.001 to 0.1 mu m. When the average particle diameter of the inorganic fine particles exceeds 0.2 탆, the transparency of the cured coating formed using the coating liquid to be prepared may be lowered.

The dispersion medium of the inorganic fine particles includes water and an organic solvent. The colloidal solution preferably has a pH or pKa adjusted to 1 to 10, more preferably 2 to 7, from the viewpoint of stability of the coating liquid for forming a film.

Examples of the organic solvent for use in the dispersion medium of the colloid solution include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexyleneglycol, 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? -Butyrolactone; And ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols or ketones are preferred. These organic solvents may be used alone or as a dispersion medium by mixing two or more kinds thereof.

As the metal oxal oligomer and the metal oxalic polymer, a single or complex oxide precursor such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium or zinc is used. The metal roxanic oligomer and the metaloxane polymer may be commercially available products or may be obtained from monomers such as metal alkoxides, nitrates, hydrochlorides, and carboxylates by a conventional method such as hydrolysis.

Specific examples of the metalloxane oligomer and the metaloxane polymer include siloxane oligomers such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485 and SS-101 manufactured by Colcoat Co., Polymer, and titanoxane oligomer such as titanium-n-butoxide tetramer manufactured by Kanto Chemical. These may be used alone or in combination of two or more.

As the leveling agent and the surfactant, known ones can be used, and commercially available products are particularly preferable because they are readily available.

The method of mixing the above-mentioned other components with the polysiloxane may be carried out simultaneously with the polysiloxane, and thereafter, it is not particularly limited.

[Liquid crystal aligning agent]

The liquid crystal aligning agent of the present invention is the above-described polysiloxane (AB), or a solution containing the polysiloxane (A) and the polysiloxane (B), as well as other components as required. At this time, as the solvent, at least one solvent selected from the group consisting of the above-mentioned polymerization solvent and an additive solvent is used. The content of the polysiloxane (AB) in the first liquid crystal alignment, or the polysiloxane content of the sum of (A) and polysiloxane (B) is, SiO ₂ in terms of the concentration of each polysiloxane (AB), or the polysiloxane (A) and polysiloxane (B) Is preferably 0.5 to 15% by mass, more preferably 1 to 6% by mass in terms of SiO ₂ . When the SiO ₂ concentration is in the range of the above-mentioned SiO ₂ concentration, a desired film thickness can be easily obtained by one 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 preferably such that the total silicon content of the polysiloxane (A) relative to the total silicon amount of the polysiloxane (A) The atomic weight is preferably 5 mol% or more. When the total amount of silicon atoms contained in the polysiloxane (A) is less than 5 mol%, it becomes difficult to obtain a good vertical alignment property. If the total amount of silicon atoms contained in the polysiloxane (A) exceeds 99.5 mol%, the content of the polysiloxane (B) becomes small and it becomes difficult to obtain good water reliability. Therefore, it is preferably 99.5 mol% or less.

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), as well as other components added as required, may be uniformly mixed. Typically, polysiloxane (AB), polysiloxane (A) and polysiloxane (B) are polycondensed in a solvent, so a solution of polysiloxane (AB), polysiloxane (A) and polysiloxane (B) It is easy to add other components. Furthermore, the method of using the polymerization solution as it is is most convenient.

When adjusting the content of the polysiloxane (AB), the polysiloxane (A) and the polysiloxane (B) in the liquid crystal aligning agent, at least one solvent selected from the group consisting of the polymerization solvent and the additive solvent described above may be used have.

[Liquid Crystal Alignment Layer]

The liquid crystal alignment film of the present invention can be obtained by using the liquid crystal aligning agent of the present invention. For example, the cured film obtained by applying the liquid crystal aligning agent of the present invention to a substrate, followed by drying and firing, may be used as the liquid crystal alignment film as it is. It is also possible to make the liquid crystal alignment film by rubbing the cured film, irradiating with polarized light, light of a specific wavelength or the like, or treating with an ion beam or the like.

The substrate to which the liquid crystal aligning agent is applied is not particularly limited as long as it is a substrate having high transparency, but a substrate on which a transparent electrode for driving the liquid crystal is formed is preferable.

Specific examples include glass plates, polycarbonates, poly (meth) acrylates, polyether sulfone, polyallylates, polyurethanes, polysulfones, polyethers, polyether ketones, trimethylpentenes, polyolefins, polyethylene terephthalates, Ruthenium, rhenitrile, triacetylcellulose, diacetylcellulose, acetate butyrate cellulose, and the like.

Examples of the application method of the liquid crystal aligning agent include a spin coating method, a printing method, an ink jet method, a spraying method and a roll coating method. From the viewpoint of productivity, a transfer printing method is widely used industrially, Lt; / RTI >

The drying step after application of the liquid crystal aligning agent is not necessarily required, but it is preferable to include a drying step when the time from the application to the firing is not constant for each substrate or when the firing is not performed immediately after application. The drying may be carried out as long as the solvent is removed to such an extent that the shape of the coated film is not deformed by transporting the substrate or the like, and the drying means is not particularly limited. 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 for 1 to 5 minutes.

The coating film formed by applying the liquid crystal aligning agent by the above method can be fired to form a cured film. In this case, the firing temperature can be any temperature of 100 to 350 DEG C, but is preferably 140 to 300 DEG C, more preferably 150 to 230 DEG C, and even more preferably 160 to 220 DEG C to be. The firing time can be fired at any time between 5 minutes and 240 minutes. Preferably 10 to 90 minutes, and more preferably 20 to 90 minutes. The heating can be carried out by a commonly known method, for example, a hot plate, a hot air circulating oven, an IR oven, a belt furnace or the like.

Polysiloxane in the liquid crystal alignment film progresses polycondensation in the firing step. However, in the present invention, the polycondensation does not need to be carried out completely unless the effect of the present invention is impaired. However, it is preferable to perform firing at a temperature of 10 ° C or more at a heat treatment temperature such as sealing hardening, which is required in a liquid crystal cell manufacturing process.

The thickness of the cured film can be selected as required, but is preferably 5 nm or more, more preferably 10 nm or more, because the reliability of the liquid crystal display element can be easily obtained. 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 is not extremely increased, which is preferable.

The cured film may be used as a liquid crystal alignment film as it is, but it may be formed as a liquid crystal alignment film by rubbing the cured film, irradiating polarized light, light of a specific wavelength or the like, or treating it with an ion beam or the like.

[Liquid crystal display element]

The liquid crystal display of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above-described method, and then manufacturing a liquid crystal cell by a known method. As an example of manufacturing a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is fixed by a sealant with a spacer interposed therebetween, and liquid crystal is injected and sealed. At this time, the size of the spacer used is 1 to 30 mu m, preferably 2 to 10 mu m.

The method of injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which the liquid crystal cell produced is reduced in pressure, a liquid crystal is injected, and a dropping method in which liquid crystal is dropped and then encapsulated.

The substrate used for the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency, but is usually a substrate on which a transparent electrode for driving the liquid crystal is formed.

A specific example is the same as the substrate described in [liquid crystal alignment film].

In a high-performance device such as a TFT-type device, a device such as a transistor is formed between an electrode for liquid crystal driving and a substrate.

In the case of a transmissive liquid crystal device, it is common to use a substrate as described above, but in a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as it is only on one substrate. At this time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

In the PSA type display element, a pretilt angle of the liquid crystal can be developed by irradiating energy lines such as ultraviolet rays and deflected ultraviolet rays while applying a voltage to the liquid crystal cell.

Example

Hereinafter, the present invention will be described in detail by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not construed as being limited to the following Examples.

The abbreviations in this embodiment are as follows.

TEOS: tetraethoxysilane

UPS:? - ureidopropyltriethoxysilane

BisUREA: bis [3- (triethoxysilyl) propyl] urea

C12: Dodecyltriethoxysilane

C18: octadecyltriethoxysilane

F13: tridecafluoroctyltrimethoxysilane

MC18: Diethoxymethyloctadecylsilane

Phe: Penetyltrimethoxysilane

Ben: Benzoyloxypropyltrimethoxysilane

ACPS: (3-acryloxypropyl) trimethoxysilane

VTES: triethoxyvinylsilane

MAPS: 3-methacryloxypropyltriethoxysilane

HG: Hexylene glycol (also known as 2-methyl-2,4-pentanediol)

BCS: butyl cellosolve (aka: ethylene glycol monobutyl ether)

MeOH: methanol

EtOH: ethanol

PGME: Propylene glycol monoethyl ether

PB: Propylene glycol monobutyl ether

DEG: diethylene glycol

NMP: N-methylpyrrolidone

&Lt; Synthesis Example 1 &

To a 200 ml (milliliter) four-neck reaction flask equipped with a thermometer and reflux tube, 48.85 g of MeOH, 19.58 g of TEOS, 2.08 g of C18 and 0.28 g of a 92% by mass methanol solution of UPS (0.26 g of UPS) And stirred to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 24.52 g of MeOH, 3.60 g of water and 0.90 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, the resultant was heated under reflux for one hour and then cooled (cooled) to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 6 mass%.

BCS mixing 15.0 g of the obtained 30.0 g of the polysiloxane solution, SiO ₂ in terms of solid content of the obtained liquid crystal aligning agent (K1) of 4% by weight.

&Lt; Synthesis Example 2 &

35.33 g of MeOH, 31.25 g of TEOS, 2.77 g of C12 and 2.39 g of a 92% by mass methanol solution of UPS (2.20 g of UPS) were charged into a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube and stirred , A solution of an alkoxysilane monomer was prepared. To this solution, a solution prepared by previously mixing 17.76 g of MeOH, 9.00 g of water and 1.50 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 1 hour under reflux, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 10 mass%.

BCS mixing 45.0 g of the obtained 30.0 g of the polysiloxane solution, SiO ₂ in terms of solid content of the obtained liquid crystal aligning agent (K2) of 4% by weight.

&Lt; Synthesis Example 3 &

36.36 g of MeOH, 29.51 g of TEOS, 3.47 g of C18 and 4.79 g of a 92 mass% methanol solution of UPS (4.41 g of UPS) were charged into a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube and stirred , A solution of an alkoxysilane monomer was prepared. To this solution, a solution prepared by previously mixing 18.37 g of MeOH, 6.00 g of water and 1.50 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 1 hour under reflux, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 10 mass%.

To 30.0 g of the obtained polysiloxane solution, 45.0 g of BCS was mixed to obtain a liquid crystal aligning agent (K3) having a solid content in terms of SiO ₂ of 4 mass%.

&Lt; Synthesis Example 4 &

46.07 g of MeOH, 13.54 g of TEOS, 2.08 g of C18 and 8.62 g (UPS 7.93 g) of a 92% by mass methanol solution of UPS were charged into a 200 ml four-neck reaction flask equipped with a reflux condenser, , A solution of an alkoxysilane monomer was prepared. To this solution, a solution prepared by previously mixing 23.38 g of MeOH, 5.40 g of water and 0.90 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 1 hour under reflux, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 6 mass%.

To 30.0 g of the obtained polysiloxane solution, 15.0 g of BCS was mixed to obtain a liquid crystal aligning agent (K4) having a solid content in terms of SiO ₂ of 4 mass%.

&Lt; Synthesis Example 5 &

48.88 g of MeOH, 19.37 g of TEOS, 2.08 g of C18 and 0.73 g (BisUREA 0.44 g) of a 60% by mass ethanol solution of BisUREA were added to a 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube and stirred , A solution of an alkoxysilane monomer was prepared. To this solution, a solution obtained by previously mixing 24.44 g of MeOH, 3.60 g of water and 0.90 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 1 hour under reflux, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 6 mass%.

To 30.0 g of the obtained polysiloxane solution, 15.0 g of BCS was mixed to obtain a liquid crystal aligning agent (K5) having a solid content in terms of SiO ₂ of 4 mass%.

&Lt; Synthesis Example 6 &

49.31 g of MeOH, 17.92 g of TEOS, 2.34 g of ACPS, 0.83 g of C18 and 0.57 g (UPS 0.52 g) of a 92% by mass methanol solution of UPS were placed in a 200 ml four-neck reaction flask equipped with a reflux condenser, And the mixture was stirred and stirred to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 24.66 g of MeOH, 3.47 g of water and 0.90 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 1 hour under reflux, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 6 mass%.

To 30.0 g of the obtained polysiloxane solution, 15.0 g of PGME was mixed to obtain a liquid crystal aligning agent (K6) having a solid content concentration of 4 mass% in terms of SiO ₂ .

&Lt; Synthesis Example 7 &

49.44 g of MeOH, 20.00 g of TEOS, 0.77 g of MC18 and 0.57 g of a 92% by mass methanol solution of UPS (0.52 g of UPS) were charged into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube and stirred , A solution of an alkoxysilane monomer was prepared. To this solution was added a solution of 24.72 g of MeOH, 3.60 g of water and 0.90 g of oxalic acid as a catalyst dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 1 hour under reflux, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 6 mass%.

PGME mixing 15.0 g of the obtained 30.0 g of the polysiloxane solution, SiO ₂ in terms of solid content of the obtained liquid crystal aligning agent (K7) of 4% by weight.

&Lt; Synthesis Example 8 &

23.30 g of HG, 7.77 g of BCS, 39.17 g of TEOS and 2.26 g of Phe were added to a 200 ml four-neck reaction flask equipped with a reflux condenser, a thermometer and a reflux condenser, and stirred to prepare a solution of an alkoxysilane monomer. To this solution, a solution prepared by previously mixing 11.65 g of HG, 3.88 g of BCS, 10.8 g of water and 0.18 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 30 minutes under reflux, 0.57 g (UPS: 0.27 g) of a 92% by mass methanol solution of UPS was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 6% by mass.

BSC mixing 15.0 g of the obtained 30.0 g of the polysiloxane solution, SiO ₂ in terms of solid content concentration of 4 mass% to obtain a liquid crystal aligning agent (K8).

&Lt; Synthesis Example 9 &

49.95 g of MeOH, 19.58 g of TEOS, 1.42 g of Ben, and 0.29 g of a 92% by mass methanol solution of UPS (0.27 g of UPS) were added to a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube and stirred , A solution of an alkoxysilane monomer was prepared. To this solution was added a solution of 24.98 g of MeOH, 3.60 g of water and 0.18 g of oxalic acid as a catalyst dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 1 hour under reflux, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 6 mass%.

BSC mixing 15.0 g of the obtained 30.0 g of the polysiloxane solution, SiO ₂ in terms of solid content of the obtained liquid crystal aligning agent (K9) of 4% by weight.

&Lt; Synthesis Example 10 &

23.34 g of HG, 7.78 g of BCS, 40.83 g of TEOS and 0.94 g of F13 were charged into a 200 ml four-neck reaction flask equipped with a reflux condenser, a thermometer and a reflux condenser, and stirred to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 11.67 g of HG, 3.89 g of BCS, 10.80 g of water and 0.18 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Then, after heated for 30 minutes under reflux, a 92 mass% methanol solution of UPS 0.57 g (UPS 0.52 g) the input, and then heated for 30 minutes under the additional return path, bangraeng to SiO ₂ in terms of solid content concentration of 12 mass% To obtain a polysiloxane solution.

To 30.0 g of the obtained polysiloxane solution, 42.0 g of EtOH and 18.0 g of PGME were mixed to obtain a liquid crystal aligning agent (K10) having a solid content concentration of 4 mass% in terms of SiO ₂ .

&Lt; Synthesis Example 11 &

22.48 g of HG, 7.49 g of BCS, 38.75 g of TEOS and 4.17 g of C18 were added to a 200 ml four-neck reaction flask equipped with a reflux condenser, a thermometer and a reflux condenser, and stirred to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 11.24 g of HG, 3.74 g of BCS, 10.80 g of water and 0.18 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Then, after heated for 30 minutes under reflux, a 92 mass% methanol solution of UPS 1.15 g (UPS 1.06 g) the input, and then heated for 30 minutes under the additional return path, bangraeng to SiO ₂ in terms of solid content concentration of 12 mass% To obtain a polysiloxane solution.

Mixing HG 48.7 g, BCS 11.3 g of the obtained 30.0 g of the polysiloxane solution, SiO ₂ in terms of solid content of the obtained liquid crystal aligning agent (K11) of 4% by weight.

&Lt; Synthesis Example 12 &

22.86 g of HG, 7.62 g of BCS, 27.50 g of TEOS, 11.42 g of VTES and 1.67 g of C18 were added to a 200 ml four-neck reaction flask equipped with a reflux condenser, a thermometer and a reflux condenser to prepare a solution of the alkoxysilane monomer . To this solution, a solution prepared by previously mixing 11.43 g of HG, 3.81 g of BCS, 10.80 g of water and 0.9 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 30 minutes under reflux, a mixed solution of 1.15 g (UPS 1.06 g), HG 0.64 and 0.21 g of a 92% by mass methanol solution of UPS was charged, further heated for 30 minutes under reflux, To obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 12 mass%.

To 30.0 g of the obtained polysiloxane solution, 26.57 g of HG, 3.94 g of BCS and 29.49 g of PB were mixed to obtain a liquid crystal aligning agent (K12) having a solid content concentration of 4 mass% in terms of SiO ₂ .

&Lt; Synthesis Example 13 &

20.75 g of HG, 6.92 g of BCS, 32.92 g of TEOS, 8.71 g of MAPS and 4.17 g of C18 were added to a 200 ml four-neck reaction flask equipped with a reflux condenser, a thermometer and a reflux condenser to prepare a solution of alkoxysilane monomer . A solution prepared by previously mixing 10.38 g of HG, 3.46 g of BCS, 10.80 g of water and 0.9 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 30 minutes under reflux, a mixed solution of 0.57 g (UPS 0.52 g), HG 0.32 and 0.11 g of a 92 mass% methanol solution of UPS was charged, further heated for 30 minutes under reflux, To obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 12 mass%.

The resulting polysiloxane solution, 30.0 g HG 26.89 g, a mixture of 4.13 g BCS and PB 28.98 g, SiO ₂ in terms of solid content concentration of 4 mass% to obtain a liquid crystal aligning agent (K13).

22.63 g of HG, 7.54 g of BCS, 39.58 g of TEOS and 4.17 g of C18 were added to a 200 ml four-neck reaction flask equipped with a reflux condenser, a thermometer and a reflux condenser, and stirred to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 11.32 g of HG, 3.77 g of BS, 10.8 g of water and 0.18 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for one hour and then cooled to obtain a polysiloxane solution having a solid content concentration of 12 mass% in terms of SiO ₂ .

30.0 g of the obtained polysiloxane solution, 56.0 g of HG and 4.0 g of BCS were mixed to obtain a liquid crystal aligning agent (L1) having a solid content concentration of 4 mass% in terms of SiO ₂ .

The mixing ratios of alkoxysilanes in Synthesis Examples 1 to 11 and Comparative Synthesis Example 1 are shown in Table 1.

The liquid crystal alignability and electric characteristics of the produced liquid crystal cell were evaluated and measured by the following methods.

[Liquid crystal alignment property]

The liquid crystal cell produced by the above-described method was observed with a polarizing microscope to confirm the alignment state of the liquid crystal. The case where the liquid crystal cell was entirely free of defects, the case where the liquid crystal cell had a uniform alignment state, the case where alignment defects were observed in a part of the liquid crystal cell, and the case where the liquid crystal cell was not vertically aligned.

[Electrical characteristics]

The ion density when a triangular wave of voltage ± 10 V and frequency of 0.01 Hz was applied to the liquid crystal cell was measured. The measurement temperature was 80 占 폚. The measurement apparatus was a 6245-type liquid crystal physical property evaluation apparatus manufactured by Toyo Technica Co., Ltd.

&Lt; Example 1 >

The liquid crystal aligning agent (K1) obtained in Synthesis Example 1 was pressure-filtered through a membrane filter having a pore size of 0.45 mu m, and then a film was formed on a glass substrate with an ITO transparent electrode by spin coating. The substrate was dried on a hot plate at 80 DEG C for 5 minutes and then fired in a hot air circulating type clean oven at 210 DEG C for 60 minutes to form a liquid crystal alignment film having a film thickness of about 80 nm.

Two of these substrates were prepared, spacers having a particle diameter of 6 mu m were dispersed on the liquid crystal alignment film surface of the substrate of the single-wafer substrate, and an epoxy adhesive was applied to the outer edge of the substrate by screen printing. Thereafter, the substrate was bonded so as to face the liquid crystal alignment film, and after the press bonding, the substrate was cured to prepare an empty cell.

This blank cell was allowed to stand for 20 hours under an environment of a room temperature of 23 占 폚 and a humidity of 98%, and water was adsorbed (water treatment), and then a liquid crystal (MLC-6608 (trade name) manufactured by Merck) was injected by a vacuum injection method. At this time, degassing of the blank cell before injecting the liquid crystal was performed for 5 minutes. Thereafter, the injection holes were sealed with a UV curable resin to prepare a liquid crystal cell (with water treatment).

Meanwhile, the blank cells prepared by the same method as described above were left for 20 hours under an environment of a room temperature of 23 DEG C and a humidity of 43%, and liquid crystals (MLC-6608 (trade name) manufactured by Merck & , And the injection hole was sealed with a UV curable resin to prepare a liquid crystal cell (without water treatment).

The electrical characteristics of the liquid crystal cell were measured by the above method. The results are shown in Table 2.

&Lt; Examples 2 to 13 >

Using the liquid crystal aligning agents K2 to K13 obtained in Synthesis Examples 2 to 13, liquid crystal cells were prepared in the same manner as in Example 1, and electrical characteristics were measured. The results are shown in Table 2.

&Lt; 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-mentioned method, and the electric characteristics of the liquid crystal cell were measured by the above-mentioned method. The results are shown in Table 2.

Example
Comparative Example Liquid crystal aligning agent Liquid crystal orientation Electrical Characteristics (pC / ㎠) No water treatment With water treatment

Example One K1 ○ <10 <10 2 K2 ○ <10 <10 3 K3 ○ <10 <10 4 K4 ○ <10 <10 5 K5 ○ <10 <10 6 K6 ○ <10 <10 7 K7 ○ <10 <10 8 K8 ○ <10 <10 9 K9 ○ <10 <10 10
11
12 K10
K11
K12 ○ <10 <10 ○ <10 <10 ○ <10 <10 13 K13 ○ <10 10 Comparative Example One L1 ○ <10 40

As is evident from Table 2, in the liquid crystal cells of Examples 1 to 13, it was found that the ion density did not increase even in the case of water treatment, as compared with the case of no water treatment. On the other hand, in the case of the liquid crystal cell of Comparative Example 1, in the case of water treatment, the ion density significantly increased as compared with the case of no water treatment.

&Lt; Synthesis Example 21 &

(Liter) four-neck reaction flask equipped with a reflux condenser, thermometer and reflux condenser was charged with 113.17 g of HG, 37.72 g of BCS, 197.91 g of TEOS and 20.84 g of C18 and stirred to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 56.59 g of HG, 18.86 g of BS, 54.0 g of water and 0.90 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for one hour and then cooled to obtain a polysiloxane solution having a solid content concentration of 12 mass% in terms of SiO ₂ .

The resulting polysiloxane solution, 30.0 g, 56.04 g and HG by mixing BCS 3.96 g, SiO ₂ in terms of solid content concentration of 4 mass% of the diluted solution to obtain the polysiloxane (K21).

&Lt; Synthesis Example 22 >

A thermometer and a reflux condenser, 11.09 g of HG 22.99 g, BCS 7.66 g, TEOS 27.78 g and C12 were added and stirred to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 11.50 g of HG, 3.83 g of BS, 15.0 g of water and 0.15 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, the resultant was heated at 67 캜 for 1 hour and then cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 10% by mass.

To 30.0 g of the obtained polysiloxane solution, 36.69 g of HG and 8.31 g of BCS were mixed to obtain a polysiloxane diluted solution (K22) having a solid content concentration of 4 mass% in terms of SiO ₂ .

&Lt; Synthesis Example 23 >

22.26 g of HG, 7.42 g of BCS, 38.33 g of TEOS, 4.17 g of C18 and 2.00 g of C12 were added to a 200 ml four-neck reaction flask equipped with a reflux condenser, a thermometer and a reflux condenser to prepare a solution of the alkoxysilane monomer Respectively. To this solution, a solution prepared by previously mixing 11.13 g of HG, 3.71 g of BS, 10.8 g of water and 0.18 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for one hour and then cooled to obtain a polysiloxane solution having a solid content concentration of 12 mass% in terms of SiO ₂ .

The resulting polysiloxane solution, 30.0 g, 48.67 g and HG by mixing BCS 11.33 g, SiO ₂ in terms of solid content concentration of 4 mass% of the diluted solution to obtain the polysiloxane (K23).

&Lt; Synthesis Example 24 &

23.54 g of HG, 7.85 g of BCS, 27.08 g of TEOS, 4.17 g of C18 and 10.7 g of MTES were charged and stirred into a 200 ml four-neck reaction flask equipped with a reflux condenser, a thermometer and a reflux tube to prepare a solution of the alkoxysilane monomer Respectively. To this solution, a solution prepared by previously mixing 11.77 g of HG, 3.92 g of BS, 10.8 g of water and 0.18 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for one hour and then cooled to obtain a polysiloxane solution having a solid content concentration of 12 mass% in terms of SiO ₂ .

The resulting polysiloxane solution, 30.0 g, 48.71 g and HG by mixing BCS 11.29 g, SiO ₂ in terms of solid content concentration of 4 mass% of the diluted solution to obtain the polysiloxane (K24).

&Lt; Synthesis Example 25 >

A thermometer, and a reflux condenser, 3.87 g of HG, 7.60 g of BCS, 39.58 g of TEOS, and 3.87 g of MC18 were added and stirred to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 11.39 g of HG, 3.80 g of BS, 10.8 g of water and 0.18 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for one hour and then cooled to obtain a polysiloxane solution having a solid content concentration of 12 mass% in terms of SiO ₂ .

To 60.0 g of the obtained polysiloxane solution, 97.37 g of HG and 22.63 g of BCS were mixed to obtain a polysiloxane diluted solution (K25) having a solid content concentration of 4 mass% in terms of SiO ₂ .

&Lt; Synthesis Example 26 &

A reflux condenser, and a reflux condenser were charged 23.42 g of HG, 7.81 g of BCS, 41.25 g of TEOS and 0.94 g of F13 and stirred to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 11.71 g of HG, 3.90 g of BS, 10.8 g of water and 0.18 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for one hour and then cooled to obtain a polysiloxane solution having a solid content concentration of 12 mass% in terms of SiO ₂ .

To 60.0 g of the obtained polysiloxane solution, 84.00 g of EtOH and 36.00 g of PGME were mixed to obtain a polysiloxane diluted solution (K26) having a solid content concentration of 4 mass% in terms of SiO ₂ .

&Lt; Synthesis Example 27 >

23.59 g of HG, 7.86 g of BCS, 39.58 g of TEOS and 2.26 g of Phe were added to a 200 ml four-neck reaction flask equipped with a reflux condenser, a thermometer and a reflux condenser, and stirred to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 11.79 g of HG, 3.93 g of BS, 10.8 g of water and 0.18 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for one hour and then cooled to obtain a polysiloxane solution having a solid content concentration of 12 mass% in terms of SiO ₂ .

The resulting polysiloxane solution, 60.0 g, HG 97.42 g, BCS, and a mixture of 22.58 g, SiO ₂ in terms of solid content concentration of 4 mass% of the diluted solution to obtain the polysiloxane (K27).

&Lt; Synthesis Example 28 >

23.30 g of HG, 7.77 g of BCS, 39.58 g of TEOS and 2.84 g of Ben were added to a 200 ml four-neck reaction flask equipped with a reflux condenser, a thermometer and a reflux condenser to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 11.65 g of HG, 3.88 g of BS, 10.8 g of water and 0.18 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for one hour and then cooled to obtain a polysiloxane solution having a solid content concentration of 12 mass% in terms of SiO ₂ .

To 60.0 g of the obtained polysiloxane solution, 97.40 g of HG and 22.60 g of BCS were mixed to obtain a polysiloxane diluted solution (K28) having a solid content concentration of 4 mass% in terms of SiO ₂ .

&Lt; Synthesis Example 29 &

34.50 g of MeOH, 27.78 g of TEOS and 9.58 g of a 92% by mass methanol solution of UPS (8.81 g) (UPS) were charged into a 200 ml four-neck reaction flask equipped with a reflux condenser, a thermometer and a reflux tube and stirred to obtain a solution of the alkoxysilane monomer Was prepared. To this solution, a solution prepared by previously mixing 17.64 g of MeOH, 9.00 g of water and 1.50 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 1 hour under reflux, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 10 mass%.

The resulting polysiloxane solution, 30.0 g, 30.71 g and HG BCS 8.21 g, 6.09 g of DEG were mixed, SiO ₂ in terms of solid content concentration of 4 mass% of the diluted solution to obtain the polysiloxane (L21).

&Lt; Synthesis Example 30 &

46.76 g of MeOH, 10.42 g of TEOS and 14.37 g of a 92% by mass methanol solution of UPS (13.22 g of UPS) were charged into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, Was prepared. To this solution, a solution prepared by previously mixing 23.95 g of MeOH, 3.60 g of water and 0.9 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 1 hour under reflux, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 6 mass%.

60.0 g of the obtained polysiloxane solution was mixed with 30.0 g of NMP to obtain a polysiloxane diluted solution (L22) having a solid content concentration of 4 mass% in terms of SiO ₂ .

&Lt; Synthesis Example 31 &

34.97 g of MeOH, 24.31 g of TEOS, 3.91 g of ACPS and 9.58 g of a 92% by mass methanol solution of UPS (UPS 8.81 g) were charged into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, A solution of silane monomer was prepared. A solution of 17.24 g of MeOH, 9.00 g of water and 1.50 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 1 hour under reflux, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 10 mass%.

Obtained for the polysiloxane solution, 40.0 g, HG 48.0 g, and a mixture of 12.0 g BCS, SiO ₂ in terms of solid content concentration of 4 mass% of the diluted solution to obtain the polysiloxane (L23).

&Lt; Synthesis Example 32 >

37.14 g of MeOH, 34.03 g of TEOS and 0.96 g of a 92% by mass methanol solution of UPS (0.88 g of UPS) were charged into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, Was prepared. To this solution, a solution prepared by previously mixing 13.93 g of HG, 4.64 g of BCS, 9.00 g of water and 0.3 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating for 1 hour under reflux, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 10 mass%.

The resulting polysiloxane solution, 90.0 g, HG 108.0 g, and a mixture of 27.0 g BCS, SiO ₂ in terms of solid content concentration of 4 mass% of the diluted solution to obtain the polysiloxane (L24).

&Lt; Synthesis Example 33 >

32.70 g of HG, 10.90 g of BCS and 18.75 g of TEOS were added to a 200 ml four-necked reaction flask equipped with a reflux condenser, a thermometer and a reflux condenser, and stirred to prepare a solution of the alkoxysilane monomer. A solution prepared by previously mixing 16.35 g of HG, 5.45 g of BCS, 5.40 g of water and 0.45 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Thereafter, after heating at 85 占 폚 for 30 minutes, a solution prepared by mixing 3.67 g (BisUREA 2.20 g) of a 60% by mass methanol solution of BisUREA, 4.75 g of HG and 1.58 g of BCS was added and further heated at 85 占 폚 for 30 minutes Thereafter, the solution was cooled to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 6 mass%.

The resulting polysiloxane solution, 40.0 g, HG 17.31 g, BCS, and a mixture of 2.69 g, SiO ₂ in terms of solid content concentration of 4 mass% of the diluted solution to obtain the polysiloxane (L25).

&Lt; Synthesis Example 34 &

22.53 g of HG, 7.51 g of BCS and 27.78 g of TEOS were added to a 200 ml four-necked reaction flask equipped with a reflux condenser, a thermometer and a reflux condenser, and stirred to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 11.26 g of HG, 3.75 g of BCS, 9.00 g of water and 1.50 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and the mixture was stirred for 30 minutes at room temperature for 30 minutes. Then, after heating for 30 minutes under reflux, 9.58 g (UPS 8.81 g) of 92% by mass methanol solution of UPS, 5.32 g of HG and 1.77 g of BCS were mixed and further heated for 30 minutes under reflux, Followed by cooling down to obtain a polysiloxane solution having a solid content in terms of SiO ₂ of 10 mass%.

The resulting polysiloxane solution, 60.0 g, HG 73.35 g, BCS, and a mixture of 16.65 g, SiO ₂ in terms of solid content concentration of 4 mass% of the diluted solution to obtain the polysiloxane (L26).

The mixing ratios of the alkoxysilanes in Synthesis Examples 21 to 34 are shown in Tables 21 and 22 below.

&Lt; Example 21 >

97.5 g of the polysiloxane diluted solution (K21) obtained in the same manner as in Synthesis Example 21 and 2.5 g of the polysiloxane solution (L21) obtained in the same manner as in Synthesis Example 29 were mixed to obtain a polysiloxane diluted solution having a solid content in terms of SiO ₂ of 4% To obtain a liquid crystal aligning agent (KL1).

&Lt; Example 22 >

Polysiloxane diluted solution obtained by the same manner as in Preparation Example 21 (K21) 90.0 g and the polysiloxane obtained in the same manner as in Synthesis Example 29 solution (L21) 10.0 g of a mixture, SiO ₂ in terms of solid content of the polysiloxane dilute solution of 4% by weight To obtain a liquid crystal aligning agent (KL2).

&Lt; Example 23 >

Polysiloxane diluted solution obtained by the same manner as in Preparation Example 21 (K21) 80.0 g and the polysiloxane obtained in the same manner as in Synthesis Example 30 solution (L22) 20.0 g of a mixture, SiO ₂ in terms of solid content of the polysiloxane dilute solution of 4% by weight (KL3) was obtained.

&Lt; Example 24 >

Polysiloxane diluted solution obtained in the same manner as in Synthesis Example 22 (K22) 50.0 g and the polysiloxane obtained in the same manner as in Synthesis Example 30 solution (L22) 50.0 g of a mixture, SiO ₂ in terms of solid content of the polysiloxane dilute solution of 4% by weight (KL4) was obtained.

&Lt; Example 25 >

Polysiloxane diluted solution obtained by the same manner as in Preparation Example 23 (K23) 90.0 g and the polysiloxane obtained in the same manner as in Synthesis Example 29 solution (L21) 10.0 g of a mixture, SiO ₂ in terms of solid content of the polysiloxane dilute solution of 4% by weight (KL5) as a liquid crystal aligning agent.

&Lt; Example 26 >

Polysiloxane diluted solution obtained in the same manner as in Synthesis Example 24 (K24) 90.0 g and the polysiloxane obtained in the same manner as in Synthesis Example 29 solution (L21) 10.0 g of a mixture, SiO ₂ in terms of solid content of the polysiloxane dilute solution of 4% by weight (KL6) was obtained.

&Lt; Example 27 >

90.0 g of the polysiloxane diluted solution (K21) obtained in the same manner as in Synthesis Example 21 and 10.0 g of the polysiloxane solution (L23) obtained in the same manner as in Synthesis Example 31 were mixed to obtain a polysiloxane diluted solution having a solid content in terms of SiO ₂ of 4% (KL7) was obtained.

&Lt; Example 28 >

Polysiloxane diluted solution obtained by the same manner as in Preparation Example 21 (K21) 60.0 g and the polysiloxane obtained in the same manner as in Synthesis Example 32 solution (L24) 40.0 g of a mixture, SiO ₂ in terms of solid content of the polysiloxane dilute solution of 4% by weight (KL8) was obtained.

&Lt; Example 29 >

90.0 g of the polysiloxane diluted solution (K25) obtained in the same manner as in Synthesis Example 25 and 10.0 g of the polysiloxane solution (L21) obtained in the same manner as in Synthesis Example 29 were mixed to obtain a polysiloxane diluted solution having a solid content in terms of SiO ₂ of 4% To obtain a liquid crystal aligning agent (KL9).

&Lt; Example 30 >

90.0 g of the polysiloxane diluted solution (K26) obtained in the same manner as in Synthesis Example 26 and 10.0 g of the polysiloxane solution (L21) obtained in the same manner as in Synthesis Example 29 were mixed to obtain a polysiloxane diluted solution having a solid content in terms of SiO ₂ of 4% To obtain a liquid crystal aligning agent (KL10).

&Lt; Example 31 >

Polysiloxane diluted solution obtained by the same manner as in Preparation Example 27 (K27) 90.0 g and the polysiloxane obtained in the same manner as in Synthesis Example 29 solution (L21) 10.0 g of a mixture, SiO ₂ in terms of solid content of the polysiloxane dilute solution of 4% by weight (KL11) as a liquid crystal aligning agent.

&Lt; Example 32 >

90.0 g of the polysiloxane diluted solution (K28) obtained in the same manner as in Synthesis Example 28 and 10.0 g of the polysiloxane solution (L21) obtained in the same manner as in Synthesis Example 29 were mixed to obtain a polysiloxane diluted solution having a solid content in terms of SiO ₂ of 4% (KL12) as a liquid crystal aligning agent.

&Lt; Example 33 >

Polysiloxane diluted solution obtained in the same manner as in Synthesis Example 22 (K22) 5.0 g, and the polysiloxane obtained in the same manner as in Synthesis Example 32 solution (L24) by mixing 95.0 g, SiO ₂ in terms of the polysiloxane dilute solution of a 4% by mass of solid content of (KL13). &Lt; tb >< TABLE >

&Lt; Example 34 >

Polysiloxane diluted solution obtained in the same manner as in Synthesis Example 22 (K22) 20.0 g and the polysiloxane obtained in the same manner as in Synthesis Example 32 solution (L24) 80.0 g of a mixture, SiO ₂ in terms of solid content of the polysiloxane dilute solution of 4% by weight (KL14) was obtained.

&Lt; Example 35 >

Polysiloxane diluted solution obtained by the same manner as in Preparation Example 21 (K21) 90.0 g and the polysiloxane obtained in the same manner as in Synthesis Example 34 solution (L26) 10.0 g of a mixture, SiO ₂ in terms of solid content of the polysiloxane dilute solution of 4% by weight (KL15) was obtained.

The compounding ratios of the polysiloxanes in Examples 21 to 35 are shown in Table 23.

Liquid crystal aligning agent The polysiloxane (A) The polysiloxane (B) Molar ratio (A) :( B) Example 21 KL1 K21 L21 97.5: 2.5 Example 22 KL2 K21 L21 90: 10 Example 23 KL3 K21 L22 80: 20 Example 24 KL4 K22 L22 50: 50 Example 25 KL5 K23 L21 90: 10 Example 26 KL6 K24 L21 90: 10 Example 27 KL7 K21 L23 90: 10 Example 28 KL8 K21 L24 60: 40 Example 29 KL9 K25 L21 90: 10 Example 30 KL10 K26 L21 90: 10 Example 31 KL11 K27 L21 90: 10 Example 32 KL12 K28 L21 90: 10 Example 33 KL13 K22 L24 5: 95 Example 34 KL14 K22 L24 20: 80 Example 35 KL15 K21 L26 90: 10

&Lt; Example 36 >

The liquid crystal aligning agent (KL1) obtained in Example 21 was pressure-filtered by a membrane filter having a pore size of 0.45 mu m, and then a film was formed on a glass substrate with an ITO transparent electrode by a spin coating method. The substrate was dried on a hot plate at 80 DEG C for 5 minutes and then fired in a hot air circulating type clean oven at 210 DEG C for 60 minutes to form a liquid crystal alignment film having a film thickness of about 80 nm.

Two of these substrates were prepared, spacers having an average particle diameter of 6 mu m were dispersed on the surface of the liquid crystal alignment film of the substrate of the unilamellar base, and an epoxy adhesive was applied to the outer edge of the substrate by screen printing. Subsequently, the substrate was bonded so as to face the liquid crystal alignment film, and after the bonding, the substrate was cured to prepare a blank cell.

The blank obtained above was allowed to stand for 20 hours under an environment of a room temperature of 23 캜 and a humidity of 98% to adsorb moisture, and then a liquid crystal (MLC-6608, trade name, manufactured by Merck) was injected by a vacuum injection method. At this time, degassing of the blank cell before injecting the liquid crystal was performed for 5 minutes. Thereafter, the injection holes were sealed with a UV curable resin to prepare a liquid crystal cell (with water treatment).

On the other hand, the other blank cells obtained above were left for 20 hours under an environment of a room temperature of 23 DEG C and a humidity of 43%, and a liquid crystal (MLC-6608, trade name, manufactured by Merck & Co., Inc.) was injected by vacuum injection method. And sealed with a resin to prepare a liquid crystal cell (without water treatment).

The electrical characteristics of the liquid crystal cell were measured by the above-described method. The results are shown in Table 24.

&Lt; Examples 37 to 50 &

Using the liquid crystal aligning agents KL2 to KL15 obtained in Examples 22 to 35, a liquid crystal cell was prepared in the same manner as in Example 36, and electrical characteristics were evaluated. The results are shown in Table 24.

&Lt; Comparative Example 21 &

A liquid crystal cell was prepared in the same manner as in Example 36 using the polysiloxane diluted solution (K21) obtained in Synthesis Example 21, and the electric characteristics of the liquid crystal cell were also evaluated. The results are shown in Table 24.

Example
Comparative Example Liquid crystal aligning agent Liquid crystal orientation Electrical Characteristics (pC / ㎠) No water treatment With water treatment

Example 36 KL1 ○ <10 <10 37 KL2 ○ <10 <10 38 KL3 ○ <10 <10 39 KL4 ○ <10 <10 40 KL5 ○ <10 <10 41 KL6 ○ <10 <10 42 KL7 ○ <10 <10 43 KL8 ○ <10 <10 44 KL9 ○ <10 <10 45 KL10 ○ <10 <10 46 KL11 ○ <10 <10 47 KL12 ○ <10 <10 48 KL13 ○ <10 <10 49 KL14 ○ <10 <10 50 KL15 ○ <10 <10 Comparative Example 21 K21 ○ <10 40

As is evident from Table 24, in the liquid crystal cells of Examples 36 to 50, ion density was not increased even in the presence of water treatment, as compared with the case of no water treatment. On the other hand, in the case of the liquid crystal alignment cell of Comparative Example 21, in the case of water treatment, it was found that the ion density greatly increased as compared with the case without water treatment.

Industrial availability

The liquid crystal display device manufactured by using the liquid crystal alignment treatment agent of the present invention can provide a liquid crystal display device of high reliability, particularly high reliability of electric characteristics, of high picture quality, and can be used as a liquid crystal display device of TN type, STN type, IPS type, VA type, OCB type, PSA type, and other liquid crystal display devices.

In addition, Japanese Patent Application No. 2008-147475 filed on June 4, 2008 and Japanese Patent Application No. 2008-147483 filed on June 4, 2008, all of which are incorporated herein by reference in their entirety, And has been accepted as the disclosure of the specification of the present invention.

Claims

A hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may also have an oxygen atom, a phosphorus atom or a sulfur atom, and a hydrocarbon group having 1 to 12 carbon atoms and having an ureido group, or The liquid crystal aligning agent containing two or more kinds of polysiloxanes and the former hydrocarbon group and the latter hydrocarbon group having an ureido group may be bonded to the same polysiloxane or may be bonded to different polysiloxanes.

The method according to claim 1,
A liquid crystal aligning agent comprising a polysiloxane (AB) obtained by polycondensing an alkoxysilane represented by the formula (1) and an alkoxysilane containing an alkoxysilane represented by the formula (2).
X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)
(X ¹ is a hydrocarbon group of 8 to 30 carbon atoms which may be substituted with a fluorine atom and may also contain an oxygen atom, a phosphorus atom or a sulfur atom, X ² is an alkyl group of 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p is an integer of 0 to 2)
X ³ {Si (OR ² ) ₃ } _q (2)
(X ³ is a hydrocarbon group having 1 to 12 carbon atoms having an ureido group, R ² is an alkyl group having 1 to 5 carbon atoms, and q is an integer of 1 or 2)

The method according to claim 1,
A liquid crystal aligning agent containing the following polysiloxane (A) and polysiloxane (B).
Polysiloxane (A): polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (1)
X ¹ (X ² ) _p Si (OR ¹ ) _3-p (1)
(X ¹ is a hydrocarbon group of 8 to 30 carbon atoms which may be substituted with a fluorine atom and may also contain an oxygen atom, a phosphorus atom or a sulfur atom, X ² is an alkyl group of 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p is 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 is a hydrocarbon group having 1 to 12 carbon atoms having an ureido group, R ² is an alkyl group having 1 to 5 carbon atoms, and q is an integer of 1 or 2)

3. The method of claim 2,
Wherein the polysiloxane (AB) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane further represented by the following formula (3).
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ is a hydrogen atom or a group having 1 to 30 carbon atoms 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, R ³ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3)

The method of claim 3,
Wherein the polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing an alkoxysilane represented by the formula (3).
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ is a hydrogen atom or a group having 1 to 30 carbon atoms 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, R ³ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3)

The method of claim 3,
Wherein the polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (2) and an alkoxysilane containing an alkoxysilane represented by the formula (3).
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ is a hydrogen atom or a group having 1 to 30 carbon atoms 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, R ³ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3)

5. The method of claim 4,
The polysiloxane (AB) is hydrolyzed and condensed with an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the formula (3) in an organic solvent, and then the alkoxysilane represented by the formula (2) Wherein the liquid crystal aligning agent is a liquid crystal aligning agent.

6. The method of claim 5,
Wherein the polysiloxane (A) is produced by a method comprising hydrolysis / condensation of an alkoxysilane represented by the formula (3) in an organic solvent, followed by addition of an alkoxysilane represented by the formula (1) Liquid crystal aligning agent.

The method according to claim 6,
The polysiloxane (B) is produced by a method comprising hydrolysis / condensation of an alkoxysilane represented by the formula (3) in an organic solvent, followed by addition of an alkoxysilane represented by the formula (2) Liquid crystal aligning agent.

10. The method according to any one of claims 4 to 9,
Wherein the alkoxysilane represented by the formula (3) is tetraalkoxysilane in which n in the formula (3) is 0.

8. The method according to claim 2, 4 or 7,
Wherein the alkoxysilane represented by the formula (1) is contained in the total alkoxysilane for obtaining the polysiloxane (AB) in an amount of 0.1 to 30 mol%, and the alkoxysilane represented by the formula (2) Mol% of the liquid crystal aligning agent.

8. The method according to claim 4 or 7,
Wherein the alkoxysilane represented by the formula (3) contains 20 to 99.8 mol% of the total alkoxysilane for obtaining the polysiloxane (AB).

10. The method according to any one of claims 1 to 9,
Wherein the content of the polysiloxane is 0.5 to 15 mass% in terms of SiO ₂ .

The method according to claim 3, 5, 6, 8, or 9,
Further, a liquid crystal aligning agent containing an organic solvent which dissolves the polysiloxane (A) and the polysiloxane (B).

The method according to claim 3, 5, 6, 8, or 9,
Of the liquid crystal aligning agent, the polysiloxane (A) and polysiloxane (B) is, in terms of the total of silicon atom contained in their SiO ₂ 0.5 to 15% by mass of the liquid crystal aligning agent.

The method according to claim 3, 5, 6, 8, or 9,
Wherein the proportion of the polysiloxane (A): polysiloxane (B) is 5: 95 to 99.5: 0.5 in terms of the silicon atomic amount contained therein.

9. The method according to claim 5 or 8,
A liquid crystal aligning agent having an alkoxysilane represented by the formula (1) in an amount of 0.2 to 30 mol% and an alkoxysilane represented by the formula (3) in an amount of 70 to 99.8 mol% based on the total alkoxysilane used for obtaining the polysiloxane (A) .

10. The method according to claim 6 or 9,
A liquid crystal aligning agent having an alkoxysilane represented by the formula (2) in an amount of 0.5 to 60 mol% and an alkoxysilane represented by the formula (3) in an amount of 40 to 99.5 mol% based on the total alkoxysilane used for obtaining the polysiloxane (B) .

10. The method according to any one of claims 2 to 9,
The alkoxysilane represented by the above formula (2) is preferably selected from the group consisting of? -Ureidopropyltriethoxysilane,? -Ureidopropyltrimethoxysilane,? -Ureidopropyltripropoxysilane, bis [3- (triethoxysilyl) Propyl] urea, bis [3- (trimethoxysilyl) propyl] urea and bis [3- (tripropoxysilyl) propyl] urea.

A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of claims 1 to 9 to a substrate, followed by drying and firing.

A liquid crystal display element having the liquid crystal alignment film according to claim 20.