JP5578074B2 - Silicon-based liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

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

  The liquid crystal display element has a structure in which two substrates, each having a liquid crystal alignment film mainly composed of polyamic acid and / or polyimide on a transparent electrode, are arranged to face each other, and a liquid crystal material is filled in a gap between the substrates. It is generally known. The most well-known method is a TN (Twisted Nematic) type liquid crystal display element, but an STN (Super Twisted Nematic) type that can realize a higher contrast ratio than this, and an IPS (Insert) with less viewing angle dependency. -Plane Switching (VA) type, vertical alignment (VA) type, etc. have been developed.

In business applications and home theater liquid crystal projector applications, a metal halide lamp with 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, inorganic liquid crystal alignment film materials have been attracting attention along with organic liquid crystal alignment film materials such as polyimide that have been used conventionally.

For example, as a material for a coating-type inorganic alignment film, an alignment agent composition containing a reaction product of tetraalkoxysilane, trialkoxysilane, alcohol, and oxalic acid has been proposed. It has been reported that a liquid crystal alignment film excellent in vertical alignment, heat resistance and uniformity is formed. (See Patent Document 1.)
In addition, a liquid crystal aligning agent composition containing a reaction product of tetraalkoxysilane, specific trialkoxysilane and water and a specific glycol ether solvent has been proposed to prevent display failure and afterimage characteristics even after long-time driving. It has been reported that a liquid crystal alignment film is formed without decreasing the ability to align liquid crystal and having little decrease in voltage holding ratio against light and heat. (See Patent Document 2.)
In recent years, technological innovation of liquid crystal display elements such as liquid crystal TVs has been remarkable, and in order to achieve this, improvement of the long-term reliability of the elements has become a greater challenge than ever. Therefore, it has been required to obtain a uniform liquid crystal alignment film with good reproducibility and to obtain a stable film for a long time.
In particular, in the process of manufacturing a liquid crystal display element, it is very important to manufacture a uniform liquid crystal alignment film with good reproducibility without being affected by the environment in order to ensure the reliability of the element. Yes.

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

JP 09-281502 A JP 2005-250244 A

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

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

The present invention can achieve the above-described problems, and the gist thereof is as follows.
[1] The number of carbon atoms having a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and which may have an oxygen atom, a phosphorus atom or a sulfur atom, and a ureido group 1 type or 2 types or more of polysiloxanes having 1 to 12 hydrocarbon groups, the former hydrocarbon groups and the hydrocarbon groups having the latter ureido groups are all bonded to the same polysiloxane. Or a liquid crystal aligning agent that may be bonded to different polysiloxanes.
[2] The polysiloxane (AB) obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (2) Liquid crystal aligning agent.
_{^{X 1 (X 2) p Si}} (OR 1) 3-p (1)
(X ¹ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may contain an oxygen atom, a phosphorus atom or a sulfur atom, and X ² is a carbon atom. An alkyl group having 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p represents an integer of 0 to 2.)
X ³ {Si (OR ² ) ₃ } _q (2)
(X ³ is a hydrocarbon group having 1 to 12 carbon atoms having a ureido group, R ² is an alkyl group having 1 to 5 carbon atoms, and q represents an integer of 1 or 2.)
[3] The liquid crystal aligning agent according to [1], comprising the following polysiloxane (A) and polysiloxane (B).
Polysiloxane (A): polysiloxane obtained by polycondensation of alkoxysilane containing alkoxysilane represented by formula (1),
_{^{X 1 (X 2) p Si}} (OR 1) 3-p (1)
(X ¹ , X ² , R ¹ , and p are the same as those 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 those defined in Formula (2) in [1] above.)

[4] The liquid crystal alignment according to [2], wherein the polysiloxane (AB) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (3): Agent.
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ may be substituted with a hydrogen atom, 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. It is a good hydrocarbon group having 1 to 6 carbon atoms, R ³ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3).
[5] The polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (3). The liquid crystal aligning agent as described in [3].
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ , R ³ and n are the same as those defined in Formula (2) in [4] above).
[6] The polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (2) and an alkoxysilane containing the alkoxysilane represented by the formula (3). The liquid crystal aligning agent as described in [3] or [5].
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ , R ³ and n are the same as those defined in Formula (2) in [4] above).

[7] The polysiloxane (AB) is obtained by hydrolyzing and condensing the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3) in an organic solvent. The liquid crystal aligning agent as described in said [4] manufactured by the method including the process of adding the alkoxysilane represented and hydrolyzing and condensing.
[8] The polysiloxane (A) is hydrolyzed and condensed with an alkoxysilane represented by the formula (1) after hydrolyzing and condensing the alkoxysilane represented by the formula (3) in an organic solvent. The liquid crystal aligning agent as described in said [5] manufactured by the method including the process of condensing.
[9] The polysiloxane (B) is hydrolyzed / condensed with an alkoxysilane represented by the formula (3) in an organic solvent, and then added with an alkoxysilane represented by the formula (2). The liquid crystal aligning agent as described in said [6] manufactured by the method including the process of condensing.
[10] The liquid crystal aligning agent according to any one of [4] to [9], wherein the alkoxysilane represented by the formula (3) is a tetraalkoxysilane in which n in the formula (3) is 0.
[11] The alkoxysilane represented by the formula (1) is contained in an amount of 0.1 to 30 mol% in the total alkoxysilane for obtaining the polysiloxane (AB), and is represented by the formula (2). The liquid crystal aligning agent according to [2] , [4] or [7] , wherein the alkoxysilane is contained in an amount of 0.1 to 50 mol% in all alkoxysilanes.
[12] The alkoxysilane represented by the formula (3) is contained in 20 to 99.8 mol% in the total alkoxysilane for obtaining the polysiloxane (AB), and is described in the above [4] or [7] Liquid crystal aligning agent.
[13] The liquid crystal aligning agent according to any one of [1] to [12], wherein the polysiloxane content is 0.5 to 15% by mass in terms of SiO ₂ concentration.

[14] The liquid crystal aligning agent according to [3], [5], [6], [8] or [9] , further comprising an organic solvent that dissolves polysiloxane (A) and polysiloxane (B) .
[15] In the liquid crystal aligning agent, the polysiloxane (A) and the polysiloxane (B) are contained in an amount of 0.5 to 15% by mass in terms of SiO _{2 in} terms of the total silicon atoms contained therein [3], [ [5] The liquid crystal aligning agent according to [6], [8], [9] or [14] .
[16] The above-mentioned [3], [5], [6] wherein the ratio of polysiloxane (A): polysiloxane (B) is 5:95 to 99.5: 0.5 in terms of the amount of silicon atoms contained in them. ], [8] , [9], [14] or [15].
[17] The alkoxysilane represented by the formula (1) is 0.2 to 30 mol% with respect to the total alkoxysilane used to obtain the polysiloxane (A), and is represented by the formula (3). The liquid crystal aligning agent according to [5] or [8] , wherein the alkoxysilane is 70 to 99.8 mol%.
[18] The alkoxysilane represented by the formula (2) is 0.5 to 60 mol% with respect to the total alkoxysilane used to obtain the polysiloxane (B), and is represented by the formula (3). The liquid crystal aligning agent according to [6] or [9] , wherein the alkoxysilane is 40 to 99.5 mol%.
[19] The alkoxysilane represented by the formula (2) is γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, bis [3- (triethoxysilyl) propyl. ] [2] to [12] , which is at least one selected from the group consisting of urea, bis [3- (trimethoxysilyl) propyl] urea, and bis [3- (tripropoxysilyl) propyl] urea [14] The liquid crystal aligning agent according to any one of [18].
[20] A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of [1] to [19] to a substrate, drying and baking.
[21] A liquid crystal display device having the liquid crystal alignment film according to [20].

  ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal aligning film which shows favorable liquid crystal aligning property can be formed, and the silicon type liquid crystal aligning agent from which the liquid crystal display element excellent in an electrical property is obtained is obtained. In addition, since the liquid crystal alignment film of the present invention is not easily affected by moisture from the outside, a highly reliable liquid crystal display element, in particular, a highly reliable liquid crystal display element with high electrical property reliability can be obtained. .

  Although it is not always clear why the liquid crystal aligning agent of the present invention is used, it is not always clear about the mechanism for obtaining a good liquid crystal aligning property, in particular, a highly reliable liquid crystal aligning film that is hardly affected by external moisture. From the comparison between the embodiment of the present invention and the comparative example, in the embodiment of the present invention, a liquid crystal cell having excellent electrical characteristics equivalent to that in the case where the water treatment is performed or not is obtained. This is probably because the polysiloxane contained in the liquid crystal aligning agent has both a hydrocarbon group having a specific number of carbon atoms and a hydrocarbon group having a specific number of carbon atoms having a ureido group.

  The liquid crystal aligning agent of the present invention is a hydrocarbon having 8 to 30 carbon atoms, preferably 8 to 22 carbon atoms which may be substituted with fluorine atoms and may contain oxygen, phosphorus or sulfur atoms. Containing one or two or more kinds of polysiloxane having 1 to 12 carbon atoms, preferably 1 to 7 carbon atoms having a ureido group, and the former specific hydrocarbon group and the latter The specific hydrocarbon group having a ureido group may be bonded to the same polysiloxane as in the first embodiment described below, and each of the different hydrocarbon groups may be different from each other as in the second embodiment described below. It may be bonded to siloxane. Below, the 1st aspect and 2nd aspect of this invention are demonstrated.

[First embodiment of the present invention]
It is a liquid crystal aligning agent containing polysiloxane (AB) obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by the following formula (1) and the alkoxysilane represented by the following formula (2). .
_{^{X 1 (X 2) p Si}} (OR 1) 3-p (1)
(X ¹ , X ² , R ¹ and p are as defined above.)
X ³ {Si (OR ² ) ₃ } _q (2)
(X ³ , R ² and q are as defined above.)
[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 is a hydrocarbon group having 8 to 30 carbon atoms, preferably 8 to 22 carbon atoms. Thus, the liquid crystal is aligned in one 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 preferred. Examples thereof include an allyloxyalkyl group, a benzoyloxyalkyl group, an alkoxyphenoxyalkyl group, and an epoxycycloalkyl group. Is mentioned. In particular, an alkoxysilane in which the first specific organic group is an alkyl group or a fluoroalkyl group is preferable because it is relatively inexpensive and easily available as a commercial product. The polysiloxane (AB) used in the present invention may have a plurality of first specific organic groups.
X ² in formula (1) is an alkyl group having 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 Formula (1) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. P in Formula (1) is an integer of 0-2, preferably 0-1.

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

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

When the amount of the alkoxysilane represented by the formula (1) having the first specific organic group is less than 0.1 mol% in the total alkoxysilane used for obtaining the polysiloxane (AB), Since good liquid crystal orientation may not be obtained, it is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and further preferably 1 mol% or more. Moreover, since it may not fully harden | cure the liquid crystal aligning film formed when it exceeds 30 mol%, 30 mol% or less is preferable, More preferably, it is 22 mol% or less, More preferably, it is 15 mol% or less. .
X ³ {Si (OR ² ) ₃ } _q (2)
X ³ (hereinafter also referred to as a second specific organic group) in the above formula (2) is as defined above, but the hydrocarbon group having a ureido group preferably has 1 to 7 carbon atoms. . R ² in formula (2) is as defined above, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

In the alkoxysilane represented by the formula (2), when q is 1, it is an alkoxysilane represented by the formula (2-1).
X ³ Si (OR ² ) ₃ (2-1)
Moreover, when q is 2, it is an alkoxysilane represented by Formula (2-2).
_{^{(R 2 O) 3 Si-}} X 3- Si (OR 2) 3 (2-2)
Although the specific example of the alkoxysilane represented by Formula (2-1) is given, it is not limited to these. For example, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R) -N-1-phenylethyl-N′-triethoxysilylpropylurea, (R) — N-1-phenylethyl-N′-trimethoxysilylpropylurea and the like can be mentioned.
Among these, γ-ureidopropyltriethoxysilane or γ-ureidopropyltrimethoxysilane is particularly preferable because it is easily available as a commercial product.

Although the specific example of the alkoxysilane represented by Formula (2-2) is given, it is not limited to these. For example, bis [3- (triethoxysilyl) propyl] urea, bis [3- (triethoxysilyl) ethyl] urea, bis [3- (trimethoxysilyl) propyl] urea, bis [3- (tripropoxysilyl) Propyl] urea and the like. Among these, bis [3- (triethoxysilyl) propyl] urea is particularly preferable because it is easily available as a commercial product.
The polysiloxane (AB) used in the present invention may have a plurality of alkoxysilanes represented by the formula (2).

  When the amount of the alkoxysilane represented by the formula (2) having the second specific organic group is less than 0.1 mol% in the total alkoxysilane used for obtaining the polysiloxane (AB), In some cases, the reliability with respect to good water may not be obtained, so 0.1 mol% or more is preferable, more preferably 0.2 mol% or more, and still more preferably 0.5 mol% or more. Moreover, since it may not fully harden | cure the liquid crystal aligning film formed when it exceeds 50 mol%, 50 mol% or less is preferable, More preferably, it is 40 mol% or less, More preferably, it is 30 mol% or less. It is.

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

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

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

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

  As long as the polysiloxane (AB) used in the present invention does not impair the effects of the present invention for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules, You may have multiple types.

In the alkoxysilane represented by the formula (3), the alkoxysilane in which n is 0 is tetraalkoxysilane. Tetraalkoxysilane is preferable for obtaining the polysiloxane of the present invention because it easily condenses with the alkoxysilane represented by the formulas (1) and (2).
As the alkoxysilane in which n is 0 in the above formula (3), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.
When using together the alkoxysilane represented by Formula (3), the usage-amount of the alkoxysilane represented by Formula (3) is 20-99. In all the alkoxysilanes used in order to obtain polysiloxane (AB). It is preferably 8 mol%. More preferably, it is 35-99.8 mol%. More preferably, the alkoxysilane represented by Formula (3) is 50-99.8 mol%.

[Second embodiment of the present invention]
It is a liquid crystal aligning agent containing the following polysiloxane (A) and the following polysiloxane (B).
Polysiloxane (A): polysiloxane obtained by polycondensation of alkoxysilane containing alkoxysilane represented by formula (1),
_{^{X 1 (X 2) p Si}} (OR 1) 3-p (1)
(X ¹ , X ² , R ¹ and p are as defined above.)
Polysiloxane (B): Polysiloxane obtained by polycondensation of alkoxysilane containing alkoxysilane represented by formula (2).
X ³ {Si (OR ² ) ₃ } _q (2)
(X ³ , R ² and q are as defined above.)
[Polysiloxane (A)]
The polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (1).
_{^{X 1 (X 2) p Si}} (OR 1) 3-p (1)
In the formula (1), X ¹ , X ² , R ¹ , and p are as defined above, and preferred examples thereof are also the same as described above.

  The explanation of the alkoxysilane represented by the above formula (1) is the same as the explanation of the alkoxysilane represented by the formula (1) performed in the section of the above polysiloxane (AB), and all including preferred embodiments thereof. The explanations apply. Moreover, the polysiloxane (A) used for this invention may have multiple types of 1st specific organic groups.

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

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

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

[Polysiloxane (B)]
The polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (2).
X ³ {Si (OR ² ) ₃ } _q (2)
In the formula (2), X ³ , R ² and q are as defined above, and preferred examples thereof are also the same as described above.
In addition, the explanation of the alkoxysilane represented by the formula (2) is the same as the explanation of the alkoxysilane represented by the formula (2) described in the section of the polysiloxane (AB), including preferred embodiments thereof. All explanations apply. Moreover, the polysiloxane (B) used for this invention may have multiple types of 2nd 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 good when it is less than 0.5 mol% in the total alkoxysilane used to obtain the polysiloxane (B). Therefore, 0.5 mol% or more is preferable because reliable characteristics against water may not be obtained. More preferably, it is 1.0 mol% or more. More preferably, it is 2.0 mol% or more. Moreover, since it may not fully harden | cure the liquid crystal aligning film formed when it exceeds 60 mol%, 60 mol% or less is preferable, More preferably, it is 50 mol% or less, More preferably, it is 40 mol% or less. It is.

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

As long as the polysiloxane (B) used in the present invention does not impair the effects of the present invention for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules, one or more kinds of the third specific organic group are used. You may have.
In the polysiloxane (B), when the alkoxysilane represented by the formula (3) is used in combination, the alkoxysilane represented by the formula (3) is 40 in all the alkoxysilanes used to obtain the polysiloxane (B). It is preferable that it is -99.5 mol%, More preferably, it is 50-99.5 mol%, More preferably, it is 60-99.5 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 the alkoxysilane represented by the formula (3).

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

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

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

  When using multiple types of alkoxysilane when obtaining the polysiloxane (AB) of this invention, you may mix as a mixture which mixed alkoxysilane beforehand, and may mix multiple types of alkoxysilane sequentially.

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

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

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

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

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

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

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

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

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

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

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

[Other ingredients]
In the present invention, as long as the effects of the present invention are not impaired, other components other than polysiloxane (AB) polysiloxane (A) and polysiloxane (B), such as inorganic fine particles, metalloxane oligomers, metalloxane polymers, Components such as a leveling agent and a surfactant may be contained.

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

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

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

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

  In the present invention, the mixing ratio of the polysiloxane (A) and the polysiloxane (B) in the liquid crystal aligning agent is determined based on the total amount of silicon atoms contained in the polysiloxane (A) and the polysiloxane (B). ) 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 good vertical alignment. Moreover, since the content rate of polysiloxane (B) will become small and the reliability with respect to favorable water will become difficult to be obtained when the total amount of silicon atoms contained in polysiloxane (A) exceeds 99.5 mol%. 5 mol% or less is preferable.

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

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

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

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

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

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

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

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

Hereinafter, although a synthesis example and an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is restrict | limited to the following Example and is not interpreted.
The explanation of the abbreviations in this embodiment is as follows.
TEOS: Tetraethoxysilane UPS: γ-Ureidopropyltriethoxysilane BisUREA: Bis [3- (triethoxysilyl) propyl] urea C12: Dodecyltriethoxysilane C18: Octadecyltriethoxysilane F13: Tridecafluorooctyltrimethoxysilane MC18 : Diethoxymethyloctadecylsilane Phe: phenethyltrimethoxysilane Ben: benzoyloxypropyltrimethoxysilane ACPS: (3-acryloxypropyl) trimethoxysilane VTES: triethoxyvinylsilane MAPS: 3-methacryloxypropyltriethoxysilane HG: to Xylene glycol (also known as 2-methyl-2,4-pentanediol)
BCS: Butyl cellosolve (also known as ethylene glycol monobutyl ether)
MeOH: methanol EtOH: ethanol PGME: propylene glycol monoethyl ether PB: propylene glycol monobutyl ether DEG: diethylene glycol NMP: N-methylpyrrolidone

<Synthesis Example 1>
In a 200 mL (milliliter) four-necked reaction flask equipped with a thermometer and a reflux tube, 48.85 g of MeOH, 19.58 g of TEOS, 2.08 g of C18, and 0.28 g of a 92 mass% methanol solution of UPS (UPS 0. 26 g) was charged and stirred to prepare an alkoxysilane monomer 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 to this solution over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes after completion of the addition. Then, after heating for 1 hour under reflux, it was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 6% by mass.
The resulting polysiloxane solution 30.0g respect mixed BCS15.0g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the liquid crystal alignment agent (K1).

<Synthesis Example 2>
A 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 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 (UPS 2.20 g). And stirring to prepare an alkoxysilane monomer 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 to this solution over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after the completion of the addition. Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 10% by mass.
The resulting polysiloxane solution 30.0g respect mixed BCS45.0G, give in terms of SiO ₂ solid content concentration of 4 mass% of the liquid crystal alignment agent (K2)

<Synthesis Example 3>
A 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 36.36 g of MeOH, 29.51 g of TEOS, 3.47 g of C18, and 4.79 g (UPS 4.41 g) of a 92 mass% methanol solution of UPS. And stirring to prepare an alkoxysilane monomer solution. A solution prepared by mixing 18.37 g of MeOH, 6.00 g of water and 1.50 g of oxalic acid as a catalyst in advance was added dropwise to this solution over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after the completion of the addition. Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 10% by mass.
The resulting polysiloxane solution 30.0g respect mixed BCS45.0g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the liquid crystal alignment agent (K3).

<Synthesis Example 4>
A 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 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 mass% methanol solution of UPS. And stirring to prepare an alkoxysilane monomer solution. To this solution, a solution in which 23.38 g of MeOH, 5.40 g of water and 0.90 g of oxalic acid as a catalyst were mixed dropwise over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the dropwise addition. Then, after heating for 1 hour under reflux, it was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 6% by mass.
The resulting polysiloxane solution 30.0g respect mixed BCS15.0g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the liquid crystal alignment agent (K4).

<Synthesis Example 5>
A 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 48.88 g of MeOH, 19.37 g of TEOS, 2.08 g of C18, and 0.73 g of BisUREA in 60 mass% ethanol (BisUREA 0.44 g). And stirring to prepare an alkoxysilane monomer solution. To this solution, a solution in which 24.44 g of MeOH, 3.60 g of water and 0.90 g of oxalic acid as a catalyst were added dropwise over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the addition. Then, after heating for 1 hour under reflux, it was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 6% by mass.
The resulting polysiloxane solution 30.0g respect mixed BCS15.0g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the liquid crystal alignment agent (K5).

<Synthesis Example 6>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 49.31 g of MeOH, 17.92 g of TEOS, 2.34 g of ACPS, 0.83 g of C18, and 0.57 g of UPS in a 92 wt% methanol solution (UPS 0 .52 g) was added and stirred to prepare an alkoxysilane monomer solution. To this solution, a solution in which 24.66 g of MeOH, 3.47 g of water and 0.90 g of oxalic acid as a catalyst were previously added dropwise over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the addition. Then, after heating for 1 hour under reflux, it was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 6% by mass.
The resulting polysiloxane solution 30.0g respect mixed PGME15.0g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the liquid crystal alignment agent (K6).

<Synthesis Example 7>
A 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 49.44 g of MeOH, 20.00 g of TEOS, 0.77 g of MC18, and 0.57 g of UPS 92 mass% methanol solution (UPS 0.52 g). And stirring to prepare an alkoxysilane monomer solution. To this solution, a solution in which 24.72 g of MeOH, 3.60 g of water and 0.90 g of oxalic acid as a catalyst were previously added dropwise over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes after completion of the addition. Then, after heating for 1 hour under reflux, it was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 6% by mass.
The resulting polysiloxane solution 30.0g respect mixed PGME15.0g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the liquid crystal alignment agent (K7).

<Synthesis Example 8>
A 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 23.30 g of HG, 7.77 g of BCS, 39.17 g of TEOS, and 2.26 g of Phe, and stirred to prepare an alkoxysilane monomer solution. 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 over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the addition. . Thereafter, after heating for 30 minutes under reflux, 0.57 g (UPS 0.27 g) of a 92 mass% UPS solution in methanol was allowed to cool to obtain a polysiloxane solution having a solid content concentration of 6 mass% in terms of SiO ₂ .
The resulting polysiloxane solution 30.0g respect mixed BSC15.0g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the liquid crystal alignment agent (K8).

<Synthesis Example 9>
A 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 49.95 g of MeOH, 19.58 g of TEOS, 1.42 g of Ben, and 0.29 g of UPS 92 mass% methanol solution (UPS 0.27 g). And stirring to prepare an alkoxysilane monomer solution. To this solution, a solution in which 24.98 g of MeOH, 3.60 g of water and 0.18 g of oxalic acid as a catalyst were mixed dropwise over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes after completion of the dropwise addition. Then, after heating for 1 hour under reflux, it was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 6% by mass.
The resulting polysiloxane solution 30.0g respect mixed BSC15.0g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the liquid crystal alignment agent (K9).

<Synthesis Example 10>
A 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube was charged with 23.34 g of HG, 7.78 g of BCS, 40.83 g of TEOS, and 0.94 g of F13, and stirred to prepare an alkoxysilane monomer solution. . 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 stirred at room temperature for 30 minutes after completion of the addition. . Thereafter, after heating for 30 minutes under reflux, 0.57 g (UPS 0.52 g) of 92 mass% UPS solution was added, and after heating for 30 minutes under reflux, the mixture was allowed to cool and then solidified in terms of SiO ₂ A polysiloxane solution having a concentration of 12% by mass was obtained.
43.0 g of EtOH and 18.0 g of PGME were mixed with 30.0 g of the obtained polysiloxane solution to obtain a liquid crystal aligning agent (K10) having a solid content concentration in terms of SiO ₂ of 4% by mass.

<Synthesis Example 11>
A 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 22.48 g of HG, 7.49 g of BCS, 38.75 g of TEOS, and 4.17 g of C18, and stirred to prepare an alkoxysilane monomer solution. . To this solution, HG 11.24 g, BCS 3.74 g, water 10.80 g and 0.18 g of oxalic acid as a catalyst were added dropwise over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes after completion of the addition. . Thereafter, after heating for 30 minutes under reflux, 1.15 g (UPS 1.06 g) of a 92 mass% UPS solution in methanol was added, and after heating for 30 minutes under reflux, the mixture was allowed to cool and then solidified in terms of SiO ₂ A polysiloxane solution having a concentration of 12% by mass was obtained.
HG48.7g The obtained polysiloxane solution 30.0 g, were mixed BCS11.3G, give in terms of SiO ₂ solid content concentration of 4 mass% of the liquid crystal alignment agent (K11).

<Synthesis Example 12>
A 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube was charged with 1.67 g of HG 22.86 g, BCS 7.62 g, TEOS 27.50 g, VTES 11.42 g, and C18, and stirred to obtain a solution of an alkoxysilane monomer. Was prepared. 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 stirred at room temperature for 30 minutes after completion of the addition. . Then, after heating for 30 minutes under reflux, a mixed solution of 1.15 g (UPS 1.06 g) of 92% by mass methanol of UPS, HG0.64 and 0.21 g of BS was added, and further heated under reflux for 30 minutes. Thereafter, it was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 12% by mass.
HG26.57g The obtained polysiloxane solution 30.0 g, were mixed BCS3.94g and PB29.49G, obtain in terms of SiO ₂ solid content concentration of 4 mass% of the liquid crystal alignment agent (K12).

<Synthesis Example 13>
A 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 20.75 g of HG, 6.92 g of BCS, 32.92 g of TEOS, 8.17 g of MAPS and 4.17 g of C18, and stirred to obtain a solution of an alkoxysilane monomer. Was prepared. To this solution, 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 over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the addition. . Then, after heating for 30 minutes under reflux, a mixed solution of 0.57 g of UPS 92 mass% methanol (UPS 0.52 g), HG 0.32 and BS 0.11 g was added and further heated under reflux for 30 minutes. after, SiO ₂ in terms of solid concentration was obtained 12 wt% of the polysiloxane solution was allowed to cool.
HG26.89g The obtained polysiloxane solution 30.0 g, were mixed BCS4.13g and PB28.98G, obtain in terms of SiO ₂ solid content concentration of 4 mass% of the liquid crystal alignment agent (K13).

<Comparative Synthesis Example 1>
A 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 22.63 g of HG, 7.54 g of BCS, 39.58 g of TEOS, and 4.17 g of C18, and stirred to prepare a solution of an 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 over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after the completion of the addition. . Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent solid content concentration of 12% by mass.
The resulting polysiloxane solution 30.0g and HG56.0G, mixed BCS4.0G, give in terms of SiO ₂ solid content concentration of 4 mass% of the liquid crystal alignment agent (L1).
Table 1 shows the mixing ratio of alkoxysilanes in Synthesis Examples 1 to 11 and Comparative Synthesis Example 1.

作製した液晶セルの液晶配向性及び電気特性は以下の方法により評価、測定した。

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

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

<Example 1>
The liquid crystal aligning agent (K1) obtained in Synthesis Example 1 was subjected to pressure filtration with a membrane filter having a pore diameter of 0.45 μm, and then formed into a film on a glass substrate with an ITO transparent electrode by a spin coating method. The substrate was dried on a hot plate at 80 ° C. for 5 minutes and then baked in a hot air circulation clean oven at 210 ° C. for 60 minutes to form a liquid crystal alignment film having a thickness of about 80 nm.
Two substrates were prepared, and a spacer having a particle diameter of 6 μm was sprayed on the surface of the liquid crystal alignment film of one substrate, and then an epoxy adhesive was applied to the outer edge of the substrate by screen printing. Thereafter, the substrates were laminated so that the liquid crystal alignment films faced each other, and were cured after pressure bonding to produce empty cells.
This empty cell was allowed to stand in an environment of room temperature 23 ° C. and humidity 98% for 20 hours to adsorb moisture (water treatment), and then a liquid crystal (MLC-6608 (trade name) manufactured by Merck) was vacuum-injected. Injected. At this time, degassing of the empty cell before liquid crystal injection was performed in 5 minutes. Thereafter, the injection hole was sealed with a UV curable resin to prepare a liquid crystal cell (with water treatment).
On the other hand, an empty cell produced by the same method as described above is left in an environment of room temperature 23 ° C. and humidity 43% for 20 hours, and liquid crystal (MLC-6608 (trade name) manufactured by Merck) is injected by vacuum injection. Thereafter, the injection hole was sealed with a UV curable resin to prepare a liquid crystal cell (without water treatment).
The electrical characteristics of the liquid crystal cell were measured by the method described above. The results are shown in Table 2.

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

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

表２から明らかなように、実施例１〜１３の液晶セルでは、水処理有りの場合も、水処理無しの場合と比較して、イオン密度が上昇しないことが判った。一方、比較例１の液晶セルでは、水処理有りの場合は、水処理無しの場合と比較して、イオン密度が大きく上昇した。

As is clear from Table 2, in the liquid crystal cells of Examples 1 to 13, it was found that the ion density did not increase when water treatment was performed, compared to the case without water treatment. On the other hand, in the liquid crystal cell of Comparative Example 1, when the water treatment was performed, the ion density was significantly increased as compared with the case without the water treatment.

<Synthesis Example 21>
A 1 L (liter) four-necked reaction flask equipped with a thermometer and a reflux tube 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 an alkoxysilane monomer. did. To this solution, a solution in which 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 were added dropwise over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the addition. . Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent solid content concentration of 12% by mass.
To polysiloxane solution 30.0g obtained by mixing HG56.04g and BCS3.96g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (K21).

<Synthesis Example 22>
A 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube was charged with 22.99 g of HG, 7.66 g of BCS, 27.78 g of TEOS and 11.09 g of C12, and stirred to prepare a solution of an alkoxysilane monomer. A solution prepared by 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 to the solution over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes after completion of the addition. . Then, after heating at 67 ° C. for 1 hour, the mixture was allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent solid content concentration of 10% by mass.
To polysiloxane solution 30.0g obtained by mixing HG36.69g and BCS8.31g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (K22).

<Synthesis Example 23>
A 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 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, and stirred to obtain an alkoxysilane monomer. A solution of was prepared. A solution in which 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 were added dropwise to this solution over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes after completion of the addition. . Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent solid content concentration of 12% by mass.
To polysiloxane solution 30.0g obtained by mixing HG48.67g and BCS11.33g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (K23).

<Synthesis Example 24>
A 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 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, and stirred to obtain an alkoxysilane monomer. A solution of was prepared. A solution prepared by mixing HG 11.77 g, BS 3.92 g, water 10.8 g and oxalic acid 0.18 g as a catalyst was added dropwise to the solution over 30 minutes at room temperature. . Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent solid content concentration of 12% by mass.
To polysiloxane solution 30.0g obtained by mixing HG48.71g and BCS11.29g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (K24).

<Synthesis Example 25>
A 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 22.79 g of HG, 7.60 g of BCS, 39.58 g of TEOS, and 3.87 g of MC18, and stirred to prepare a solution of the alkoxysilane monomer. To this solution, HG 11.39 g, BS 3.80 g, water 10.8 g and 0.18 g of oxalic acid as a catalyst were added dropwise over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the addition. . Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent solid content concentration of 12% by mass.
The obtained polysiloxane solution 60.0 g, mixed HG97.37g and BCS22.63g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (K25).

<Synthesis Example 26>
A 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube was charged with 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 an alkoxysilane monomer solution. 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 over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after the completion of the addition. . Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent solid content concentration of 12% by mass.
The obtained polysiloxane solution 60.0 g, mixed EtOH84.00g and PGME36.00g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (K26).

<Synthesis Example 27>
A 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 23.59 g of HG, 7.86 g of BCS, 39.58 g of TEOS, and 2.26 g of Phe, 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 stirred at room temperature for 30 minutes after the completion of the addition. . Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent solid content concentration of 12% by mass.
The obtained polysiloxane solution 60.0g, HG97.42g, and mixed BCS22.58g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (K27).

<Synthesis Example 28>
A 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube was charged with 23.30 g of HG, 7.77 g of BCS, 39.58 g of TEOS, and 2.84 g of Ben, and stirred to prepare a solution of the alkoxysilane monomer. 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 to this solution over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the addition. . Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent solid content concentration of 12% by mass.
The obtained polysiloxane solution 60.0g, HG97.40g, and mixed BCS22.60g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (K28).

<Synthesis Example 29>
A 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 34.50 g of MeOH, 27.78 g of TEOS, and 9.58 g of a 92% by weight methanol solution of UPS (UPS 8.81 g), stirred, and alkoxylated. A solution of silane monomer was prepared. 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 to this solution over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes after the completion of the addition. Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 10% by mass.
30.71 g of HG, 8.21 g of BCS, and 6.09 g of DEG were mixed with 30.0 g of the obtained polysiloxane solution to obtain a polysiloxane diluted solution (L21) having a solid content concentration of 4 mass% in terms of SiO ₂ .

<Synthesis Example 30>
A 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 46.76 g of MeOH, 10.42 g of TEOS, and 14.37 g of a 92% by mass methanol solution of UPS (UPS 13.22 g), stirred, and alkoxylated. A solution of silane monomer was prepared. To this solution, a solution in which 23.95 g of MeOH, 3.60 g of water and 0.9 g of oxalic acid as a catalyst were previously added dropwise over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the addition. Then, after heating for 1 hour under reflux, it was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 6% by mass.
The obtained polysiloxane solution 60.0 g, were mixed NMP30.0g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (L22).

<Synthesis Example 31>
A 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 34.47 g of MeOH, 24.31 g of TEOS, 3.91 g of ACPS, and 9.58 g of a 92% by weight methanol solution of UPS (8.88 g of UPS) and stirred. Thus, a solution of the alkoxysilane monomer was prepared. A solution prepared by previously mixing 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 at room temperature for 30 minutes after the completion of the addition. Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 10% by mass.
The obtained polysiloxane solution 40.0g, HG48.0g, and mixed BCS12.0g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (L23).

<Synthesis Example 32>
A 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 37.14 g of MeOH, 34.03 g of TEOS, and 0.96 g of a 92% by mass methanol solution of UPS (UPS 0.88 g), stirred, and alkoxylated. A solution of silane monomer was prepared. A solution prepared by mixing HG 13.93 g, BCS 4.64 g, water 9.00 g and oxalic acid 0.3 g as a catalyst was added dropwise to the solution over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the addition. . Then, after heating for 1 hour under reflux, the mixture was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 10% by mass.
The obtained polysiloxane solution 90.0g, HG108.0g, and mixed BCS27.0g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (L24).

<Synthesis Example 33>
A 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 32.70 g of HG, 10.90 g of BCS, and 18.75 g of TEOS, and stirred to prepare a solution of an alkoxysilane monomer. To this solution, HG 16.35 g, BCS 5.45 g, water 5.40 g, and 0.45 g of oxalic acid as a catalyst were added dropwise over 30 minutes at room temperature, and stirred at room temperature for 30 minutes after completion of the addition. . Then, after heating at 85 ° C. for 30 minutes, a mixed solution of 3.67 g of BisUREA methanol solution (2.67 g of BisUREA 2.20 g), 4.75 g of HG, and 1.58 g of BCS was added, and further heated at 85 ° C. for 30 minutes. Thereafter, it was allowed to cool to obtain a polysiloxane solution having a solid content concentration in terms of SiO ₂ of 6% by mass.
The obtained polysiloxane solution 40.0g, HG17.31g, and mixed BCS2.69g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (L25).

<Synthesis Example 34>
A 200 ml four-necked reaction flask equipped with a thermometer and a reflux tube was charged with 22.53 g of HG, 7.51 g of BCS, and 27.78 g of TEOS, and stirred to prepare an alkoxysilane monomer solution. To this solution, a solution in which 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 were added dropwise over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes after completion of the addition. . Thereafter, after heating for 30 minutes under reflux, a solution prepared by mixing 9.58 g of a 92 mass% UPS solution in methanol (UPS 8.81 g), 5.32 g of HG, and 1.77 g of BCS was added, and further heated for 30 minutes under reflux. after, SiO ₂ in terms of solid concentration was obtained 10 wt% of the polysiloxane solution was allowed to cool.
The obtained polysiloxane solution 60.0g, HG73.35g, and mixed BCS16.65g, SiO ₂ in terms of solid concentration was obtained 4% by weight of the polysiloxane dilute solution (L26).
The compounding ratio of alkoxysilane in the synthesis examples 21 to 34 is shown in Table 21 and Table 22 below.

<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, and the solid content concentration in terms of SiO ₂ was mixed. Obtained a liquid crystal aligning agent (KL1) which is a 4% by mass polysiloxane diluted solution.

<Example 22>
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 (L21) obtained in the same manner as in Synthesis Example 29 were mixed, and the solid content concentration in terms of SiO ₂ was mixed. Obtained the liquid crystal aligning agent (KL2) which is a 4 mass% polysiloxane dilution solution.

<Example 23>
80.0 g of the polysiloxane diluted solution (K21) obtained in the same manner as in Synthesis Example 21 and 20.0 g of the polysiloxane solution (L22) obtained in the same manner as in Synthesis Example 30 were mixed, and the solid content concentration in terms of SiO ₂ was mixed. Liquid crystal aligning agent (KL3) which is a 4 mass% polysiloxane dilution solution was obtained.

<Example 24>
50.0 g of the polysiloxane diluted solution (K22) obtained in the same manner as in Synthesis Example 22 and 50.0 g of the polysiloxane solution (L22) obtained in the same manner as in Synthesis Example 30 were mixed to obtain a solid content concentration in terms of SiO ₂ Obtained a liquid crystal aligning agent (KL4) which is a 4% by mass polysiloxane diluted solution.

<Example 25>
90.0 g of the polysiloxane diluted solution (K23) obtained in the same manner as in Synthesis Example 23 and 10.0 g of the polysiloxane solution (L21) obtained in the same manner as in Synthesis Example 29 were mixed, and the solid content concentration in terms of SiO ₂ was mixed. Obtained a liquid crystal aligning agent (KL5) which is a 4% by mass polysiloxane diluted solution.

<Example 26>
90.0 g of the polysiloxane diluted solution (K24) obtained in the same manner as in Synthesis Example 24 and 10.0 g of the polysiloxane solution (L21) obtained in the same manner as in Synthesis Example 29 were mixed to obtain a solid content concentration in terms of SiO ₂ Liquid crystal aligning agent (KL6) which is a 4 mass% polysiloxane dilution solution was obtained.

<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 SiO ₂ equivalent solid content Obtained the liquid crystal aligning agent (KL7) which is a 4 mass% polysiloxane dilution solution.

<Example 28>
60.0 g of the polysiloxane diluted solution (K21) obtained in the same manner as in Synthesis Example 21 and 40.0 g of the polysiloxane solution (L24) obtained in the same manner as in Synthesis Example 32 were mixed, and the solid content concentration in terms of SiO ₂ was mixed. Obtained a liquid crystal aligning agent (KL8) which was a 4% by mass polysiloxane diluted solution.

<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 solid content concentration in terms of SiO ₂ Obtained a liquid crystal aligning agent (KL9) which is a 4% by mass polysiloxane diluted solution.

<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, and the solid content concentration in terms of SiO ₂ was mixed. Obtained a liquid crystal aligning agent (KL10) which was a 4% by mass polysiloxane diluted solution.

<Example 31>
90.0 g of the polysiloxane diluted solution (K27) obtained in the same manner as in Synthesis Example 27 and 10.0 g of the polysiloxane solution (L21) obtained in the same manner as in Synthesis Example 29 were mixed, and the solid content concentration in terms of SiO ₂ was mixed. Obtained a liquid crystal aligning agent (KL11) which was a 4% by mass polysiloxane diluted solution.

<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, and the solid content concentration in terms of SiO ₂ was mixed. Obtained the liquid crystal aligning agent (KL12) which is a 4 mass% polysiloxane dilution solution.

<Example 33>
The polysiloxane diluted solution (K22) 5.0 g obtained in the same manner as in Synthesis Example 22 and 95.0 g of the polysiloxane solution (L24) obtained in the same manner as in Synthesis Example 32 were mixed, and the solid content concentration in terms of SiO ₂ was mixed. Obtained a liquid crystal aligning agent (KL13) which was a 4% by mass polysiloxane diluted solution.

<Example 34>
20.0 g of the polysiloxane diluted solution (K22) obtained in the same manner as in Synthesis Example 22 and 80.0 g of the polysiloxane solution (L24) obtained in the same manner as in Synthesis Example 32 were mixed, and the solid content concentration in terms of SiO ₂ was mixed. Liquid crystal aligning agent (KL14) which is a 4 mass% polysiloxane dilution solution was obtained.

<Example 35>
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 (L26) obtained in the same manner as in Synthesis Example 34 were mixed, and the solid content concentration in terms of SiO ₂ was mixed. Liquid crystal aligning agent (KL15) which is a 4 mass% polysiloxane dilution solution was obtained.
Table 23 shows the compounding ratio of the polysiloxane in Examples 21 to 35.

<Example 36>
The liquid crystal aligning agent (KL1) obtained in Example 21 was subjected to pressure filtration with a membrane filter having a pore diameter of 0.45 μm, and then formed into a film on a glass substrate with an ITO transparent electrode by a spin coating method. The substrate was dried on a hot plate at 80 ° C. for 5 minutes and then baked in a hot air circulation clean oven at 210 ° C. for 60 minutes to form a liquid crystal alignment film having a thickness of about 80 nm.
Two substrates were prepared, and spacers with an average particle diameter of 6 μm were sprayed on the liquid crystal alignment film surface of one substrate, and then an epoxy adhesive was applied to the outer edge of the substrate by screen printing. Next, the substrates were bonded so that the liquid crystal alignment films faced each other, and were cured after pressure bonding to produce empty cells.
The empty cell obtained above was allowed to stand in an environment of room temperature 23 ° C. and humidity 98% for 20 hours to adsorb moisture, and then liquid crystal (MLC-6608, trade name manufactured by Merck & Co., Inc.) was vacuum-injected. Injected. At this time, degassing of the empty cell before liquid crystal injection was performed in 5 minutes. Thereafter, the injection hole was sealed with a UV curable resin to prepare a liquid crystal cell (with water treatment).
On the other hand, another empty cell obtained above was allowed to stand for 20 hours in an environment at room temperature of 23 ° C. and humidity of 43%, and liquid crystal (MLC-6608, a product name manufactured by Merck) was injected by a vacuum injection method. 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 method described above. The results are shown in Table 24.

<Examples 37 to 50>
Using the liquid crystal aligning agents KL2 to KL15 obtained in Examples 22 to 35, liquid crystal cells were produced in the same manner as in Example 36, and the electrical characteristics were evaluated. The results are shown in Table 24.

<Comparative Example 21>
Using the polysiloxane diluted solution (K21) obtained in Synthesis Example 21, a liquid crystal cell was produced in the same manner as in Example 36, and the electrical characteristics of the liquid crystal cell were evaluated. The results are shown in Table 24.

  As is apparent from Table 24, it was found that in the liquid crystal cells of Examples 36 to 50, the ion density did not increase even when water treatment was performed, compared to the case where water treatment was not performed. On the other hand, in the liquid crystal alignment cell of Comparative Example 21, it was found that the ion density greatly increased when water treatment was performed compared to the case where water treatment was not performed.

The liquid crystal display element manufactured using the liquid crystal aligning agent of the present invention can be a highly reliable liquid crystal display device with high reliability, in particular, high electrical property reliability, TN type, STN type, It is suitably used for display elements of various types such as liquid crystal display elements of IPS type, VA type, OCB type, PSA type and the like.

The specification, claims, and abstract of Japanese Patent Application No. 2008-147475 filed on June 4, 2008 and Japanese Patent Application No. 2008-147483 filed on June 4, 2008. Is hereby incorporated by reference as a disclosure of the specification of the present invention.

Claims (21)

  A hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may have an oxygen atom, a phosphorus atom or a sulfur atom, and 1 to 12 carbon atoms having a ureido group One or two or more types of polysiloxanes having the following hydrocarbon groups, the former hydrocarbon group and the latter hydrocarbon group having a ureido group may be bonded to the same polysiloxane. Or a liquid crystal aligning agent that may be bonded to different polysiloxanes. The liquid crystal aligning agent of Claim 1 containing the polysiloxane (AB) obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1), and the alkoxysilane represented by Formula (2). .
_{^{X 1 (X 2) p Si}} (OR 1) 3-p (1)
(X ¹ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may contain an oxygen atom, a phosphorus atom or a sulfur atom, and X ² is a carbon atom. An alkyl group having 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p represents an integer of 0 to 2.)
X ³ {Si (OR ² ) ₃ } _q (2)
(X ³ is a hydrocarbon group having 1 to 12 carbon atoms having a ureido group, R ² is an alkyl group having 1 to 5 carbon atoms, and q represents an integer of 1 or 2.) The liquid crystal aligning agent of Claim 1 containing the following polysiloxane (A) and polysiloxane (B).
Polysiloxane (A): polysiloxane obtained by polycondensation of alkoxysilane containing alkoxysilane represented by formula (1),
_{^{X 1 (X 2) p Si}} (OR 1) 3-p (1)
(X ¹ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom and may contain an oxygen atom, a phosphorus atom or a sulfur atom, and X ² is a carbon atom. An alkyl group having 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p represents an integer of 0 to 2.)
Polysiloxane (B): Polysiloxane obtained by polycondensation of alkoxysilane containing alkoxysilane represented by formula (2).
X ³ {Si (OR ² ) ₃ } _q (2)
(X ³ is a hydrocarbon group having 1 to 12 carbon atoms having a ureido group, R ² is an alkyl group having 1 to 5 carbon atoms, and q represents an integer of 1 or 2.) The liquid crystal aligning agent according to claim 2, wherein the polysiloxane (AB) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (3).
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ is the number of carbon atoms which may be substituted with a hydrogen atom or a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group, and which may have a hetero atom. 1 to 6 hydrocarbon groups, R ³ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to ^3. ) The polysiloxane (A) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (1) and an alkoxysilane containing the alkoxysilane represented by the formula (3). The liquid crystal aligning agent of description.
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(X ⁴ is the number of carbon atoms which may be substituted with a hydrogen atom or a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group, and which may have a hetero atom. 1 to 6 hydrocarbon groups, R ³ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to ^3. ) The polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula (2) and an alkoxysilane containing the alkoxysilane represented by the formula (3). 5. A liquid crystal aligning agent according to 5.
(X ⁴ ) _n Si (OR ³ ) _4-n (3)
(A hydrogen atom or a halogen atom, a vinyl group, a glycidoxy group, a mercapto group, a methacryloxy group, an isocyanate group or an acryloxy group, and may have a hetero atom and have 1 to 6 carbon atoms. A hydrocarbon group, R ³ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to ^3. )   The polysiloxane (AB) is represented by the formula (2) after hydrolyzing and condensing the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3) in an organic solvent. The liquid crystal aligning agent of Claim 4 manufactured by the method including the process of adding and hydrolyzing and condensing alkoxysilane.   The polysiloxane (A) is a step of hydrolyzing and condensing an alkoxysilane represented by the formula (3) in an organic solvent, and then adding and hydrolyzing and condensing the alkoxysilane represented by the formula (1). The liquid crystal aligning agent of Claim 5 manufactured by the method containing this.   Step of hydrolyzing and condensing the alkoxysilane represented by the formula (2) after the polysiloxane (B) is hydrolyzed and condensed with the alkoxysilane represented by the formula (3) in an organic solvent. The liquid crystal aligning agent of Claim 6 manufactured by the method containing this.   The liquid crystal aligning agent in any one of Claims 4-9 whose alkoxysilane represented by said Formula (3) is tetraalkoxysilane whose n in Formula (3) is 0. The alkoxysilane represented by the formula (1) is contained in an amount of 0.1 to 30 mol% in the total alkoxysilane for obtaining the polysiloxane (AB), and the alkoxysilane represented by the formula (2) The liquid crystal aligning agent of Claim 2, 4 or 7 contained in 0.1-50 mol% in all the alkoxysilanes. The liquid crystal aligning agent according to claim 4 or 7 , wherein the alkoxysilane represented by the formula (3) is contained in an amount of 20 to 99.8 mol% in all alkoxysilanes for obtaining the polysiloxane (AB). The content of polysiloxane, in terms of SiO ₂ concentration, the liquid crystal alignment agent according to any one of claims 1 to 12 contained 0.5 to 15 mass%. Furthermore, the liquid crystal aligning agent of Claim 3 , 5 , 6 , 8, or 9 containing the organic solvent which melt | dissolves polysiloxane (A) and polysiloxane (B). Liquid crystal in the alignment agent, the polysiloxane (A) and polysiloxane (B) is, according to claim 3, 5, 6 to the total silicon atoms contained therein are contained 0.5 to 15% by weight SiO ₂ in terms, 8 , 9 or 14 liquid crystal aligning agent. The ratio of polysiloxane (A): polysiloxane (B) is from 5:95 to 99.5: 0.5 in terms of the amount of silicon atoms contained in them, 5, 5, 6, 8 , 9 , 14, or
The liquid crystal aligning agent in any one of 15 . The alkoxysilane represented by Formula (1) is 0.2-30 mol% with respect to all the alkoxysilanes used in order to obtain polysiloxane (A), and the alkoxysilane represented by Formula (3) The liquid crystal aligning agent of Claim 5 or 8 which is 70-99.8 mol%. The alkoxysilane represented by Formula (2) is 0.5-60 mol% with respect to all the alkoxysilanes used in order to obtain polysiloxane (B), and is represented by Formula (3) The liquid crystal aligning agent of Claim 6 or 9 which is 40-99.5 mol%. The alkoxysilane represented by the formula (2) is γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, bis [3- (triethoxysilyl) propyl] urea, 19. Any one of claims 2 to 12 and 14 to 18, which is at least one selected from the group consisting of bis [3- (trimethoxysilyl) propyl] urea and bis [3- (tripropoxysilyl) propyl] urea. Liquid crystal aligning agent as described in.   The liquid crystal aligning film obtained by apply | coating the liquid crystal aligning agent in any one of Claims 1-19 to a board | substrate, drying and baking.   The liquid crystal display element which has a liquid crystal aligning film of Claim 20.