TWI452066B - Silicon liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display components - Google Patents

Description

Lanthanide liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

The present invention relates to a liquid crystal alignment agent comprising a polyoxyalkylene obtained by polycondensing an 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.

In the liquid crystal display device, two substrates having a liquid crystal alignment film mainly composed of polyphosphoric acid and/or polyimide are disposed on the transparent electrode, and a structure in which a liquid crystal material is filled in the gap is generally known. The TN (Twisted Nematic) type liquid crystal display element is known as a TN (Twisted Nematic) type liquid crystal display element, but an INS (In-Plane Switching) type which has a higher contrast STN (Super Twisted Nematic) type and has less viewing angle dependence has been developed. Vertical alignment (VA: Vertical Alignment) type.

In the use of liquid crystal projectors for commercial use and home theaters, a strong metal halide lamp using an irradiation intensity for a light source requires not only high heat resistance but also a liquid crystal alignment film material having high light resistance.

In such a situation, an inorganic liquid crystal alignment film material, which is also an organic liquid crystal alignment film material such as polyimide which has been used in the past, has also been attracting attention.

For example, as a material of a coating-type inorganic alignment film, an alignment agent composition containing a reaction product of a tetraalkoxynonane, a trialkoxysilane, and an alcohol and oxalic acid has been proposed, and a liquid crystal display element has also been proposed. A liquid crystal alignment film having excellent vertical alignment, heat resistance, and uniformity is formed on the electrode substrate. (Refer to Patent Document 1).

Further, a liquid crystal alignment agent composition containing a tetraalkoxynonane, a specific trialkoxysilane, a reaction product with water, and a specific glycol ether solvent has been proposed, and it has been proposed to prevent display defects for a long time. After the driving, the afterimage characteristics are also good, the ability to align the liquid crystal is not lowered, and the liquid crystal alignment film having a small decrease in voltage and heat voltage is obtained. (Refer to Patent Document 2).

In recent years, the liquid crystal TV has been attracting attention from the technical innovation of the liquid crystal display device. In order to achieve this, the long-term reliability of the device has been increasing and has become a major issue. Therefore, in order to obtain a homogeneous liquid crystal alignment film having good reproducibility, it is also required to obtain a film which can be stabilized for a long period of time.

In particular, in the process of manufacturing a liquid crystal display element, it is important to ensure the reliability of the device by producing a liquid crystal alignment film having good reproducibility and homogeneity without being affected by the environment.

Moreover, it is also important to ensure long-term reliability in terms of resistance to moisture intrusion from the outside of the liquid crystal display element.

[Advanced technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 09-281502

[Patent Document 2] JP-A-2005-250244

When the inorganic liquid crystal alignment film is formed by using a liquid crystal alignment agent, when an alkoxy group or a stanol is left, it is likely to be affected by moisture present in the air. Therefore, it has been difficult to obtain a homogeneous liquid crystal alignment film, and as a result, there has been a problem in that the reliability of the liquid crystal display element is lowered.

Further, moisture intruding from the outside of the liquid crystal display element, for example, moisture invading the self-sealing material portion also affects the liquid crystal alignment film, and thus the reliability of the liquid crystal display element is lowered.

Therefore, in order to improve the resistance to moisture of the liquid crystal alignment film, it 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 which is excellent in liquid crystal alignment and has high film stability, and which can form a liquid crystal alignment film which is not easily affected by moisture from the outside and which has excellent electrical characteristics of a liquid crystal display element. A liquid crystal alignment agent, a liquid crystal alignment film obtained from the quinone-based liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

The present invention is intended to achieve the above problems, and the following is the main content.

[1] A liquid crystal alignment agent characterized by containing one or more kinds of polyoxyalkylene oxides having a carbon which may be substituted by a fluorine atom and which may have an oxygen atom, a phosphorus atom or a sulfur atom. a hydrocarbon group having 8 to 30 atoms and a hydrocarbon group having 1 to 12 carbon atoms having a urea group, and the hydrocarbon group of the former and the hydrocarbon group having a urea group of the latter may be bonded to the same polyoxyalkylene or may be combined. In each of the polyoxyalkylenes.

[2] The liquid crystal alignment agent according to the above [1], which comprises a polycondensation polymerization obtained by alkoxysilane having an alkoxydecane represented by the formula (1) and an alkoxydecane represented by the formula (2). Oxane (AB);

X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1)

(X ¹ is a hydrocarbon group which may be substituted by a fluorine atom and may have an oxygen atom, a phosphorus atom or a sulfur atom and has 8 to 30 carbon atoms, X ² is an alkyl group having 1 to 5 carbon atoms, and R ¹ is a carbon atom; 1 to 5 alkyl groups, p represents an integer from 0 to 2)

X ³ {Si(OR ² ) ₃ } _q (2)

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

[3] The liquid crystal alignment agent according to the above [1], which comprises the following polyoxyalkylene oxide (A) and polysiloxane (B); polyoxyalkylene (A): polycondensation contains the formula (1) a polyoxyalkylene obtained from an alkoxy decane of an alkoxy decane;

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 by the formula (1) in the above [1]).

Polyoxane (B): a polyoxyalkylene obtained by polycondensing an alkoxy decane containing an alkoxydecane represented by the formula (2);

X ³ {Si(OR ² ) ₃ } _q (2)

(X ³ , R ² , and q are the same as those defined by the formula (2) in the above [1]).

[4] The liquid crystal alignment agent according to the above [2], wherein the polyoxyalkylene oxide (AB) is a polyfluorene oxide obtained by further polycondensing an alkoxysilane having an alkoxydecane represented by the following formula (3). alkyl;

(X ⁴ ) _n Si(OR ³ ) _4-n (3)

(X ⁴ is a hydrogen atom or may be substituted by a halogen atom, a vinyl group, a glycidoxy group, a thiol group, a methacryloxy group, an isocyanate group or a propyleneoxy group, and may have an unsaturated bond or a hetero atom The hydrocarbon group having 1 to 6 carbon atoms, R ³ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3).

[5] The liquid crystal alignment agent according to the above [3], wherein the polyoxyalkylene (A) is a polycondensation-containing alkoxydecane represented by the formula (1) and an alkoxydecane represented by the formula (3). Polyoxyalkylene obtained from oxoxane.

(X ⁴ ) _n Si(OR ³ ) _4-n (3)

(X ⁴ , R ³ and n are the same as those defined by the formula (2) in each of the above [4]).

[6] The liquid crystal alignment agent according to the above [3], wherein the polyoxyalkylene (B) is polycondensed and contains an alkoxydecane represented by the formula (2) and an alkoxy group represented by the formula (3). A polyoxyalkylene obtained from alkoxy alkane.

(X ⁴ ) _n Si(OR ³ ) _4-n (3)

(X ⁴ , R ³ and n are the same as those defined by the formula (2) in each of the above [4]).

[7] The liquid crystal alignment agent according to the above [4], wherein the polyoxyalkylene (AB) contains an alkoxydecane represented by the formula (1) and an alkoxydecane represented by the formula (3) in an organic form. The mixture is hydrolyzed and condensed in a solvent, and then a method of adding alkoxysilane of the formula (2) to carry out a step of hydrolysis and condensation is carried out.

[8] The liquid crystal alignment agent according to the above [5], wherein the polyoxyalkylene (A) is obtained by hydrolyzing and condensing the alkoxydecane represented by the formula (3) in an organic solvent. (1) The alkoxydecane shown is produced by a method of performing the steps of hydrolysis and condensation.

[9] The liquid crystal alignment agent according to the above [6], wherein the polyoxyalkylene (B) is obtained by hydrolyzing and condensing the alkoxydecane represented by the formula (3) in an organic solvent. (2) The alkoxydecane shown is produced by a method of performing the steps of hydrolysis and condensation.

[10] The liquid crystal alignment agent according to any one of the above [4], wherein the alkoxydecane represented by the formula (3) is a tetraalkoxydecane wherein n in the formula (3) is 0.

[11] The liquid crystal alignment agent according to any one of the above [1], wherein the alkoxydecane represented by the above formula (1) is in a peralkyl alkane having a polyoxane (AB). The content is 0.1 to 30 mol%, and the alkoxydecane represented by the above formula (2) is contained in the total alkoxy decane in an amount of 0.1 to 50 mol%.

[12] The liquid crystal alignment agent according to any one of the above [4], wherein the alkoxydecane represented by the above formula (3) is in a peralkyl alkane having a polyoxane (AB). The content is 20 to 99.8 mol%.

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

[14] The liquid crystal alignment agent according to any one of [8], wherein the polyoxyalkylene (A) and the polyoxyalkylene are further dissolved. (B) an organic solvent.

[15] The liquid crystal alignment agent according to any one of the above [3], wherein the polysiloxane (A) and the polysiloxane are mixed in the liquid crystal alignment agent. When the total amount of germanium atoms contained in each of the deuterium oxides (B) is SiO ₂ , the content thereof is from 0.5 to 15% by mass.

[16] The liquid crystal alignment agent according to any one of [3], [5], [6], or [8] to [15], wherein the polyoxyalkylene (A): polyoxyalkylene (B) The ratio is 5:95 to 99.5:0.5 when calculated by the amount of helium atoms contained in them.

[17] The liquid crystal alignment agent according to any one of [5], [8], [10], wherein the polyalkane used for obtaining the polyoxyalkylene (A) is used. In the oxoxane, the alkoxydecane represented by the formula (1) is 0.2 to 30 mol%, and the alkoxydecane represented by the formula (3) is 70 to 99.8 mol%.

[18] The liquid crystal alignment agent according to any one of the above [6], wherein the polyalkane used for obtaining the polyoxyalkylene (B) is used. In the oxoxane, the alkoxydecane represented by the formula (2) is from 0.5 to 60 mol%, and the alkoxydecane represented by the formula (3) is from 40 to 99.5 mol%.

The liquid crystal alignment agent of any one of the above-mentioned [2], wherein the alkoxy decane represented by the above formula (2) is selected from γ-ureidopropyltriethoxy decane, γ- Ureidopropyltrimethoxydecane, γ-ureidopropyltripropoxydecane, bis[3-(triethoxycarbinyl)propyl]urea, bis[3-(trimethoxycarbendyryl) At least one of a group of propyl]urea and bis[3-(tripropoxycarbenyl)propyl]urea.

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

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

In the present invention, a liquid crystal alignment film which exhibits good liquid crystal alignment properties can be formed, and an oxime liquid crystal alignment agent which can obtain a liquid crystal display element excellent in electrical characteristics can be obtained. Further, since the liquid crystal alignment film of the present invention is not easily affected by moisture from the outside, a liquid crystal display element having high reliability can be obtained, and in particular, a liquid crystal display element having high reliability of electrical characteristics and stable high image quality can be obtained.

According to the use of the liquid crystal alignment agent of the present invention, it is possible to obtain a good liquid crystal alignment property, and in particular, a mechanism for obtaining a highly reliable liquid crystal alignment film which is not easily affected by external moisture is fully explained, and will be described later. In comparison with the comparative examples, in the examples of the present invention, liquid crystal cells having the same excellent electrical characteristics can be obtained even in the case of water treatment, and the liquid crystal cells having the same excellent electrical characteristics can be obtained. The polyoxyalkylene contained in the alignment agent is a hydrocarbon group having a specific carbon number in combination with a hydrocarbon group having a specific carbon number of the urea group.

To implement the type of invention

The liquid crystal alignment agent of the present invention contains one or more types of polyoxyalkylene oxides, and the polyoxyalkylene has a carbon atom number of 8 to 30 which may be substituted by a fluorine atom and may contain an oxygen atom, a phosphorus atom or a sulfur atom. It is preferably a hydrocarbon group of 8 to 22 and a hydrocarbon group having a ureido group having 1 to 12 carbon atoms, preferably 1 to 7 carbon atoms, and the specific hydrocarbon group of the former and the specific hydrocarbon group having a urea group of the latter are as follows The first form can be combined with the same polyoxane and, as in the second form described below, can be combined with the respective polyoxyalkylene. The first type and the second type of the present invention will be described below.

[First form of the invention]

It is a liquid crystal alignment agent containing a polyoxyalkylene (AB) containing a polycondensation alkoxysilane of the following formula (1) and an alkoxysilane of the alkoxydecane 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).

[polyoxane (AB)]

X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1)

In the formula (1), X ¹ (hereinafter also referred to as a first specific organic group) is a hydrocarbon group having a carbon number of 8 to 30, preferably 8 to 22, as defined above, having a liquid crystal alignment The effect of 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. Among the oxygen atom, phosphorus atom or sulfur atom having the first specific organic group, an oxygen atom is preferred, and as such an example, an allyloxyalkyl group, a benzamidineoxyalkyl group or an alkoxyphenoxy group may be mentioned. Alkyl group, epoxycycloalkyl group, and the like. In particular, when the first specific organic group is an alkyl group or a fluoroalkyl alkoxy decane, it is preferable because it is relatively inexpensive to be commercially available. The polyoxyalkylene (AB) used in the present invention may also have a plurality of first specific organic groups.

X ² in the formula (1) is an alkyl group having 1 to 7 carbon atoms, preferably 1 to 3 carbon atoms. X ² -methyl or ethyl is more preferred.

R ¹ in the formula (1) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. p in the formula (1) is 0 to 2, preferably an integer of 0 to 1.

Among them, the alkoxydecane represented by the formula (1) is preferably an alkoxydecane represented by the following formula (1-1).

R ⁴ Si(OR ⁵ ) ₃ (1-1)

(R ⁴ represents a hydrocarbon group having 8 to 30 carbon atoms which may be substituted by a fluorine atom, and R ⁵ represents an alkyl group having 1 to 5 carbon atoms).

Although a specific example of the alkoxydecane represented by the above formula (1) is given, it is not limited thereto.

For example, octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane, dodecyltrimethoxydecane, dodecyltriethoxy Baseline, cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxydecane, heptadecyltriethoxydecane,octadecyltrimethoxydecane, Octadecyltriethoxydecane, nonadecyltrimethoxydecane, nonadecyltriethoxydecane, undecyltriethoxydecane,undecyltrimethoxydecane,21- Dodecyltriethoxydecane, tridecafluorooctyltrimethoxydecane, tridecafluorooctyltriethoxydecane, heptadecafluorodecyltrimethoxydecane, heptadecafluorodecyltriethoxy Baseline, isooctyltriethoxydecane, phenethyltriethoxydecane, pentafluorophenylpropyltrimethoxydecane, m-vinylphenylethyltrimethoxydecane, p-vinylbenzene Ethyltrimethoxydecane, (1-naphthyl)triethoxydecane, (1-naphthyl)trimethoxynonane, allyloxyundecyltriethoxydecane, benzene醯-methoxypropyltrimethoxydecane, 3-(4-methoxyphenoxy)propyltrimethoxydecane, 1-[(2-triethoxycarbinyl)ethyl]cyclohexane- 3,4-epoxide, 2-(diphenylphosphino)ethyltriethoxydecane, diethoxymethyloctadecyldecane, dimethoxymethyloctadecyldecane, two Ethoxydodecylmethylnonane, dimethoxydodecylmethyldecane, diethoxymethylmethyldecane, dimethoxydecylmethyldecane, diethoxyoctyl Base decane, dimethoxyoctylmethyl decane, ethoxy dimethyl octadecyl decane, methoxy dimethyl octadecyl decane, and the like. Also included are octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane, dodecyltrimethoxydecane, dodecyltriethoxy Decane, cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxydecane, heptadecyltriethoxydecane,octadecyltrimethoxydecane, ten Octaalkyltriethoxydecane, nonadecyltrimethoxynonane, nonadecyltriethoxydecane, undecyltriethoxydecane, or undecyltrimethoxydecane,diethyl Preferably, oxymethyloctadecyldecane or diethoxydodecylmethyldecane is preferred.

The alkoxydecane represented by the formula (1) having the above first specific organic group is used in an amount of less than 0.1 mol% in the peralkoxydecane to be used for obtaining the polyoxyalkylene (AB). The liquid crystal alignment property is not obtained, so it is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and still more preferably 1 mol% or more. Further, when it exceeds 30 mol%, the formed liquid crystal alignment film may be insufficiently cured, and is preferably 30 mol% or less, more preferably 22 mol% or less, still more preferably 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, and the hydrocarbon group having a ureido group preferably has 1 to 7 carbon atoms. R ² in the formula (2) is preferably an alkyl group having 1 to 3 carbon atoms, preferably a methyl group or an ethyl group, as defined above.

In the alkoxydecane represented by the formula (2), when q is 1, it is an alkoxydecane represented by the formula (2-1).

X ³ Si(OR ² ) ₃ (2-1)

Further, when q is 2, it is an alkoxydecane represented by the formula (2-2).

(R ² O) ₃ Si-X ^3- Si(OR ² ) ₃ (2-2)

Although specific examples of the alkoxydecane represented by the formula (2-1) are given, they are not limited thereto. For example, γ-ureidopropyltriethoxydecane, γ-ureidopropyltrimethoxydecane, γ-ureidopropyltripropoxydecane, (R)-N-1-phenyl B can be mentioned. A group of -N'-triethoxycarbamidopropyl urea, (R)-N-1-phenylethyl-N'-trimethoxycarbamidopropyl urea, and the like.

Among them, γ-ureidopropyltriethoxydecane or γ-ureidopropyltrimethoxydecane is also preferably commercially available as a commercial product.

Although specific examples of the alkoxydecane represented by the formula (2-2) are given, they are not limited thereto. For example, bis[3-(triethoxymethanealkyl)propyl]urea, bis[3-(triethoxycarbenyl)ethyl]urea, bis[3-(trimethoxycarbamomethane) may be mentioned. Base) propyl] urea, bis[3-(tripropoxymethyl decyl) propyl] urea, and the like. Among them, bis[3-(triethoxycarbenyl)propyl]urea is also commercially available as a commercial product.

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

The alkoxydecane represented by the formula (2) having the above second specific organic group is used in an amount of less than 0.1 mol% of the peralkoxydecane used to obtain the polyoxyalkylene (AB). In the case where a good water-reliability characteristic is not obtained, it is preferably 0.1 mol% or more, more preferably 0.2 mol% or more, and still more preferably 0.5 mol% or more. On the other hand, when it exceeds 50 mol%, the formed liquid crystal alignment film may not be sufficiently cured. Therefore, it is preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less.

In the polyoxane (AB), the alkoxydecane represented by the formula (1) is preferably from 0.1 to 30 mol%, particularly preferably from 0.5 to 22 mol%, based on the total alkoxydecane used. The content of the total alkoxydecane used in the alkoxydecane represented by the formula (2) is preferably 0.1 to 50 mol%, particularly preferably 0.5 to 30 mol%.

In addition to the alkoxydecane represented by the formula (1) and the formula (2), the polyoxyalkylene (AB) of the present invention is preferably an alkoxydecane represented by the following formula (3). Since the alkoxydecane represented by the formula (3) can impart various properties to the polyoxyalkylene oxide (AB), one or a plurality of kinds can be used depending on the necessary properties.

(X ⁴ ) _n Si(OR ³ ) _4-n (3)

Although X ⁴ in the above formula (3) is as defined above, when X ⁴ is a hydrocarbon group having 1 to 6 carbon atoms (hereinafter also referred to as a third specific organic group), the third specific organic group may have, for example, a fat. The ring structure or branched structure of a hydrocarbon, an aliphatic ring, an aromatic ring or a heterocyclic ring may contain an unsaturated bond or a hetero atom such as an oxygen atom, a sulfur atom or a phosphorus atom. Further, the third specific organic group may be substituted by a halogen atom, a vinyl group, a glycidoxy group, a thiol group, a methacryloxy group, an isocyanate group, a propyleneoxy group or the like as described above.

R ³ in the formula (3) is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, as defined above. The n in the formula (3) is preferably an integer represented by 0 to 2 as defined above.

Although a specific example of the alkoxydecane represented by the above formula (3) is given, it is not limited thereto.

In the alkoxydecane of the formula (3), specific examples of the alkoxydecane in the case where X ⁴ is a hydrogen atom include trimethoxydecane, triethoxydecane, tripropoxydecane, and tributoxy group. Decane and so on.

Further, in the alkoxydecane of the formula (3), specific examples of the alkoxydecane in the case where X ⁴ is the third specific organic group include methyltrimethoxydecane and methyltriethoxydecane. Ethyltrimethoxydecane, ethyltriethoxydecane, propyltrimethoxydecane, propyltriethoxydecane, methyltripropoxydecane, 3-hydrothiopropyltriethoxydecane , thiomethylmethyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, allyltriethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3 - methacryloxypropyl triethoxy decane, 3-propenyloxypropyl trimethoxy decane, 3-propenyloxypropyl triethoxy decane, 3-isocyanate propyl triethoxy decane, Trifluoropropyltrimethoxydecane, chloropropyltriethoxydecane, bromopropyltriethoxydecane, 3-hydrothiopropyltrimethoxydecane, dimethyldiethoxydecane, dimethyl Dimethoxy decane, diethyl diethoxy decane, diethyl dimethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, m-B Alkenylphenyltrimethoxydecane, p-vinylphenyltrimethoxydecane, trimethylethoxydecane, trimethylmethoxydecane, and the like.

The polysiloxane (AB) used in the present invention has one or more plurals for the purpose of improving adhesion to a substrate, affinity with liquid crystal molecules, and the like without impairing the effects of the present invention. The above third specific organic group.

In the alkoxydecane represented by the formula (3), the alkoxydecane-based tetraalkoxydecane in which n is 0. Since the tetraalkoxy decane is easily condensed with the alkoxy decane represented by the formula (1) and the formula (2), it is preferably used for obtaining the polyoxyalkylene of the present invention.

In the above formula (3), as the alkoxydecane in which n is 0, tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane or tetrabutoxydecane is preferred, and particularly preferred is tetramethyl. Oxydecane or tetraethoxydecane.

When the alkoxydecane represented by the formula (3) is used in combination, the alkoxydecane represented by the formula (3) is used in an amount of from 20 to 99.8 in the peralkyl alkane to be used for obtaining the polyoxyalkylene (AB). Moher% is better. It is preferably 35 to 99.8 mol%. More preferably, the alkoxydecane represented by the formula (3) is 50 to 99.8 mol%.

[Second type of the invention]

It is a liquid crystal alignment agent containing the following polyoxyalkylene (A) and the following polyoxyalkylene (B).

Polyoxane (A): a polyoxyalkylene obtained by polycondensing an alkoxydecane containing an alkoxydecane represented by the formula (1),

X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1)

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

Polyoxane (B): a polyoxyalkylene obtained by polycondensing an alkoxydecane containing an alkoxydecane represented by the formula (2).

X ³ {Si(OR ² ) ₃ } _q (2)

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

[polyoxane (A)]

The polyoxyalkylene (A) is a polyoxyalkylene obtained by polycondensation of an alkoxydecane containing an alkoxydecane represented by the following formula (1).

X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1)

X ¹ , X ² , R ¹ , and p of the formula (1) are as defined above, and each is preferably the same as described above.

The description of the alkoxydecane represented by the above formula (1) is the same as the description of the alkoxydecane represented by the formula (1) carried out in the above polyoxyalkylene (AB), and is also applicable to the preferred form. Description. Further, the polyoxyalkylene (A) used in the present invention may have a plurality of first specific organic groups.

The amount of the alkoxydecane represented by the formula (1) having the first specific organic group is sometimes less than 0.2 mol% of the peralkoxydecane used to obtain the polyoxyalkylene (A). The liquid crystal alignment property is not obtained, so it is preferably 0.2 mol% or more, more preferably 0.5 mol% or more, and still more preferably 1 mol% or more. On the other hand, when the amount is more than 30% by mole, the formed liquid crystal alignment film 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.

The polyoxyalkylene (A) used in the present invention, together with the alkoxydecane represented by the formula (1), is obtained by polycondensation containing at least one alkoxydecane of the alkoxydecane represented by the following formula (3). Polyoxyalkylene is preferred. The alkoxydecane represented by the formula (3) imparts various properties to the polyoxyalkylene. Therefore, it is necessary to use one or a plurality of alkoxysilanes selected from the formula (3) as necessary.

(X ⁴ ) _n Si(OR ³ ) _4-n (3)

Wherein X ⁴ and R ³ of the formula (3) are the same as those described in the formula (3) containing the preferred polyoxyxane (AB), and further, the alkane represented by the formula (3) Specific examples of the oxoxane are also the same as those described in the polyoxyalkylene (AB) term.

In the present invention, the polyoxyalkylene (A) may have one or more kinds of substances for the purpose of improving the adhesion to the substrate and improving the affinity with the liquid crystal molecules without impairing the effects of the present invention. Three specific organic groups.

In the case where the polyoxyalkylene (A) is used in combination with the alkoxydecane represented by the formula (3), the alkoxy group represented by the formula (3) is to be obtained from the peralkoxydecane used in the polyoxyalkylene (A). The decane is preferably from 70 to 99.8 mol%, more preferably from 75 to 99.8 mol%, still more preferably from 80 to 99.8 mol%.

In the present invention, the polyoxyalkylene (A) is a polycondensation obtained by polycondensing at least one compound selected from the group consisting of an alkoxydecane represented by the formula (1) and an alkoxydecane represented by the formula (3). The decane is preferred.

[polyoxane (B)]

The polyoxyalkylene (B) is a polyoxyalkylene obtained by polycondensing an alkoxydecane containing an alkoxydecane represented by the formula (2).

X ³ {Si(OR ² ) ₃ } _q (2)

Wherein X ³ , R ² and q of the formula (2) are as defined above, and each of them is preferably the same as described above.

Further, the description of the alkoxydecane represented by the formula (2) is the same as the description of the alkoxydecane represented by the formula (2) described in the above polyoxyalkylene (AB), and is also preferably contained. A full description of the type. Further, the polyoxyalkylene (B) used in the present invention may have a plurality of second specific organic groups.

The polyoxyalkylene (B) used in the present invention may have a plurality of alkoxydecanes represented by the formula (2).

The alkoxydecane represented by the formula (2) having the second specific organic group is used in a total amount of 0.5% by mole of the total alkoxy decane used in the case of obtaining the polyoxyalkylene (B). It is not possible to obtain a good water-reliability characteristic, and it is preferably 0.5 mol% or more. Preferably, it is 1.0 mol% or more. More preferably, it is 2.0% or more. On the other hand, when it exceeds 60 mol%, the formed liquid crystal alignment film may not be sufficiently cured, and therefore it is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less.

In addition, the polyoxyalkylene (B) used in the present invention is at least one of the alkoxydecanes represented by the following formula (3), and can be polycondensed at the same time as the alkoxydecane represented by the formula (2). Obtained from alkoxy decane.

(X ⁴ ) _n Si(OR ³ ) _4-n (3)

Wherein X ⁴ , R ³ and n of the formula (3) are as described in the item of the polyoxyalkylene (AB) having a preferred form, and the specific examples of the alkoxydecane represented by the formula (3) are also The same is true for the oxime (AB) term.

The polysiloxane (B) used in the present invention may have one or more kinds of substances for the purpose of improving adhesion to a substrate, affinity with liquid crystal molecules, and the like without impairing the effects of the present invention. Three specific organic groups.

In the polyoxane (B), when the alkoxydecane represented by the formula (3) is used in combination, the alkoxy group represented by the formula (3) is to be obtained from the peralkoxydecane used in the polyoxyalkylene (B). The decane is preferably from 40 to 99.5 mol%, more preferably from 50 to 99.5 mol%, still more preferably from 60 to 99.5 mol%.

In the present invention, the polyoxyalkylene (B) is preferably a polyoxyalkylene obtained by polycondensing an alkoxysilane having an alkoxydecane represented by the formula (2) and an alkoxydecane represented by the formula (3).

[Manufacturing method of polyoxyalkylene (AB)]

The method for obtaining the polyoxyalkylene (AB) used in the present invention is not particularly limited. In the present invention, the alkoxydecane of the above formula (1) and formula (2), which are essential components, is obtained by condensation in an organic solvent. In general, polyoxyalkylene (AB) is obtained by polycondensing the above alkoxysilane as a solution which is uniformly dissolved in an organic solvent.

Examples of the method of polycondensing the alkoxysilane include a method of hydrolyzing and condensing an alkoxysilane in a solvent such as an alcohol or a glycol.

At this time, the hydrolysis ‧ condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add only 0.5 times the mole of water of the alkoxy group to the alkoxy decane, and it is generally preferred to add an excess amount of water to 0.5 times the mole.

In the present invention, the amount of water used in the above reaction may be appropriately selected depending on the necessity, and is usually 0.5 to 2.5 times moles of the total alkoxy group in the alkoxydecane.

Further, generally, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid is used for the purpose of promoting hydrolysis and condensation reaction; and ammonia, methylamine, ethylamine, ethanolamine, triethylamine is used. Etc.; use metal salts such as hydrochloric acid, sulfuric acid, nitric acid; etc.; In addition, by heating the solution in which the alkoxydecane is dissolved, it is possible to further promote the hydrolysis and condensation reaction as a general practice. At this time, the heating temperature and the heating time can be appropriately selected as needed. For example, a method of heating and stirring at 50 ° C for 24 hours, a method of heating and reflux for 1 hour under reflux, and the like can be mentioned.

Further, as another method, for example, a method in which a mixture of alkoxysilane, a solvent, and oxalic acid is heated and then subjected to polycondensation is mentioned. Specifically, a method in which oxalic acid is added as an alcohol solution of oxalic acid to an alcohol and then the alkoxysilane is mixed while heating the solution is used. At this time, the amount of oxalic acid to be used is preferably 0.2 to 2 moles for the total alkoxy group 1 mole having an alkoxydecane. The heating in this method can be carried out at a liquid temperature of 50 to 180 °C. It is preferably a method of heating under reflux for several tens of minutes to several ten hours without causing evaporation or volatilization of the liquid.

When the polyoxyalkylene oxide (AB) of the present invention is used, when a plurality of alkoxysilanes are used, the alkoxysilane may be previously mixed to form a mixture, or a plurality of alkoxysilanes may be sequentially mixed.

The solvent (hereinafter also referred to as a polymerization solvent) used in the polycondensation of the alkoxysilane is not particularly limited as long as it can dissolve the alkoxysilane. Further, in the case where the alkoxydecane is not dissolved, the dissolution may be carried out only while the polycondensation reaction with the alkoxysilane is carried out. In general, since an alcohol is produced by a polycondensation reaction of an alkoxysilane, an organic solvent having good compatibility with an alcohol, a glycol, a glycol ether, or an 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, hexanediol, and 1,3- Propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, Glycols such as 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol: ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, Ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol diethylene glycol 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 single Glycol ethers such as butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, N- Base-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethyl hydrazine, tetramethyl urea, hexamethyl phosphate Guanamine, m-cresol and the like.

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

Further, as another method for obtaining the polyoxyalkylene oxide (AB) of the present invention, the alkoxydecane represented by the formula (1) and the alkoxydecane represented by the formula (3) are contained in an organic solvent. After the hydrolysis and condensation, a method for producing a polyoxyalkylene (AB) in which the alkoxydecane represented by the formula (2) is subjected to hydrolysis and condensation is added.

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).

In this case, the hydrolysis/condensation reaction of the alkoxydecane represented by the formula (1) and the formula (3) may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add 0.5 times mole of water of the alkoxy group in the alkoxysilane, and it is generally preferred to add water in excess of 0.5 times mole.

In the present invention, the amount of water used in the above reaction can be appropriately selected as required, and it is usually 0.5 to 2.5 times moles of the total alkoxy group in the alkoxydecane.

Further, in general, for the purpose of promoting hydrolysis and condensation, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid can be used; ammonia, methylamine, ethylamine, ethanolamine, triethylamine Such as alkali; metal salts such as hydrochloric acid, sulfuric acid, nitric acid; etc.; Further, by heating and dissolving the solution of the alkoxysilane, the hydrolysis and the condensation reaction can be further promoted as a general method. At this time, the heating temperature and the heating time can be appropriately selected as needed. For example, a method of heating at 50 ° C for 24 hours, stirring, a method of heating under reflux for 1 hour, stirring, and the like can be given.

In the solution obtained by the above method, the alkoxydecane represented by the formula (1) and the alkoxydecane represented by the formula (3) are subjected to hydrolysis and condensation, and the alkoxydecane represented by the formula (2) is added, and stirring is continued. A solution of polyoxyalkylene (AB) can be produced. At this time, the hydrolysis and the condensation reaction can be further promoted by heating the solution. At this time, the heating temperature and the heating time can be appropriately selected as needed. For example, a method of heating at 50 ° C for 24 hours, stirring, a method of heating under reflux for 1 hour, stirring, and the like can be given.

The solvent used in the polycondensation of the alkoxysilane (hereinafter also referred to as a polymerization solvent) is the same as the polymerization solvent described in the above [Production Method of Polyoxane (AB)], and the specific examples are the same. Use multiple species.

The poly-silicon obtained in the above method of polymerization of alumoxane solution (hereinafter also referred to as polymerization solution), as a raw material of silicon was charged atoms of full Silane alkoxy of SiO ₂ in terms of a concentration (hereinafter, referred to as concentration in terms of SiO ₂₎ It is preferably 20% by mass or less, preferably 5 to 15% by mass. By selecting any concentration in the concentration range, gel formation can be suppressed, and a homogeneous solution can be obtained.

[Manufacturing method of polyoxyalkylene (A)]

The method for obtaining the polyoxyalkylene oxide (A) used in the present invention is not particularly limited, but in the present invention, the alkoxydecane having the alkoxydecane of the above formula (1) as an essential component may be used in an organic solvent. It is obtained by condensation. Generally, the polyoxyalkylene (A) is obtained by polycondensing the above alkoxysilane to obtain a solution uniformly dissolved in an organic solvent.

The polycondensation method in the present invention may, for example, be a method in which the alkoxydecane is hydrolyzed and condensed in a solvent such as an alcohol or a glycol. At this time, the hydrolysis ‧ condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add only 0.5 times mole of water of the all alkoxide group in the alkoxysilane, but it is generally preferred to add water in an amount of 0.5 times mole.

In the present invention, the amount of water used in the above reaction can be appropriately selected as required, but it is usually 0.5 to 2.5 times moles of the total alkoxy group in the alkoxydecane.

Further, when a polyoxyalkylene oxide (A) is obtained, a plurality of alkoxysilanes may be used, and a mixture of alkoxysilanes may be mixed in advance, or a plurality of alkoxysilanes may be sequentially mixed.

The polycondensation method to be used for obtaining the polyoxyalkylene (A), the polymerization solvent and the like are the same as those described in the production method of the polyoxyalkylene (AB), and the preferred range thereof is also the same.

As another method for producing the polyoxyalkylene oxide (A), the alkoxydecane represented by the formula (3) is subjected to hydrolysis and condensation in an organic solvent, and then the alkoxydecane represented by the formula (1) is added. A method for producing a polyoxyalkylene (A) which is a step of hydrolysis and condensation.

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).

In this case, the hydrolysis/condensation reaction of the alkoxydecane represented by the formula (3) may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically only 0.5 times mole of water of the alkoxy group in the alkoxy decane is added, and it is generally preferred to add 0.5 times mole of water to the excess amount, 0.5 times to 2.5 times the mole. It is better.

Further, the catalyst or the heating method used for the purpose of promoting the hydrolysis/condensation reaction is generally the same as the catalyst described in [Production Method of Polyoxane (AB)] or heating.

The solution obtained by the above method is obtained by adding alkoxydecane represented by the formula (1) to a solution obtained by hydrolysis and condensation of the alkoxydecane represented by the formula (3) and stirring, to prepare a solution of the polyoxane (A). At this time, by adding the solution, the hydrolysis and condensation reaction can be further promoted. At this time, the heating temperature and the heating time can be appropriately selected as needed. For example, a method of heating at 50 ° C for 24 hours, stirring, or refluxing for 1 hour, heating, stirring, and the like can be mentioned.

A polymerization solution (hereinafter also referred to as a polymerization solution) of the polyoxyalkylene (A) obtained by the above method. The concentration of the ruthenium atom of the peralkoxy decane charged as a raw material in terms of SiO ₂ (hereinafter referred to as SiO ₂ equivalent concentration). It is usually 20% by mass or less, preferably 5 to 15% by mass. In this concentration range, gel formation is suppressed by selecting an arbitrary concentration to obtain a homogeneous solution.

[Manufacturing method of polyoxyalkylene (B)]

The method for obtaining the polyoxyalkylene (B) of the present invention is not particularly limited, and the present invention is the same as the above [method of producing polyoxane (A)].

When a plurality of alkoxydecanes are used in the case of obtaining a polyoxyalkylene (B), a mixture of alkoxysilanes may be mixed in advance, or a plurality of alkoxydecane may be sequentially mixed.

In another method, a polyfluorene containing a step of hydrolyzing and condensing the alkoxydecane represented by the formula (3) in an organic solvent and then adding the alkoxydecane represented by the formula (2) A method for producing oxyalkylene (B).

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).

In this case, the hydrolysis/condensation reaction of the alkoxydecane represented by the formula (3) may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add only 0.5 times the mole of water of the alkoxy group in the alkoxysilane, and it is generally preferred to add water in an amount of 0.5 times the molar amount.

In the present invention, the amount of water used in the above reaction can be appropriately selected depending on the necessity, and it is usually 0.5 to 2.5 times moles of the total alkoxy group in the alkoxydecane.

Further, the catalyst or the heating method used for the purpose of promoting the hydrolysis/condensation reaction is generally the same as the catalyst described in [Production Method of Polyoxane (AB)] or heating.

The alkoxydecane represented by the formula (3) obtained by the above method is subjected to hydrolysis and condensation, and the alkoxydecane represented by the formula (2) is added, and stirring is continued to produce a polyoxyalkylene (B). Solution. At this time, by adding the solution, the hydrolysis and condensation reaction can be further promoted. At this time, the heating temperature and the heating time can be appropriately selected as needed. For example, a method of heating at 50 ° C for 24 hours, stirring, or heating under reflux for 1 hour or the like may be mentioned.

The solvent used in the polyalkylene oxide (hereinafter also referred to as a polymerization solvent) is the same as the polymerization solvent described in the above [Production Method of Polyoxane (A)], and the specific examples are the same, and a plurality of kinds may be used. These solvents.

[Polyoxane (AB), polyoxane (A) and polyoxane (B) solutions]

In the present invention, the polymerization solution obtained by the above method can be directly used as a solution of polyoxyalkylene (AB), polyoxyalkylene (A) and polyoxyalkylene (B), and the solution obtained by the above method may also be used as necessary. Concentration or addition of a solvent to dilute or replace it with other solvents, as a solution of polyoxyalkylene (AB), polyoxyalkylene (A) and polyoxyalkylene (B).

In this 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 it can uniformly dissolve the polyoxane (AB), the polyoxyalkylene (A), and the polyoxyalkylene (B), and may be used arbitrarily or in combination.

Specific examples of the solvent to be added include a solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; and methyl acetate and ethyl acetate; An ester such as ethyl lactate.

These solvents can improve the viscosity of the liquid crystal alignment agent or the coating property when the liquid crystal alignment agent is applied onto the substrate by spin coating, fast drying printing, ink jetting or the like.

[Other ingredients]

In the present invention, other components other than the polyoxyalkylene (AB) polyoxane (A) and the polyoxyalkylene (B) may be contained without impairing the effects of the present invention, and for example, inorganic fine particles or metal evil may be contained. A component such as a metalloxane oligomer, a metal oxane polymer, a leveling agent, or a surfactant.

As the inorganic fine particles, fine particles such as cerium oxide fine particles, alumina fine particles, titania fine particles, or magnesium fluoride fine particles are preferred, and in particular, a colloidal solution state is preferred. The colloidal solution is a colloidal solution in which inorganic fine particles are dispersed in a dispersion medium or also as a vending product. In the present invention, by containing inorganic fine particles, the surface shape and other functions of the formed cured film can be imparted. The inorganic fine particles are preferably 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 of the inorganic fine particles include water and an organic solvent. The colloidal solution is preferably adjusted to have a pH or pKa of from 1 to 10, preferably from 2 to 7, from the viewpoint of the stability of the coating liquid for forming a film.

Examples of the organic solvent used as the dispersion medium of the colloidal solution include methanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, and B. Alcohols such as diol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylyl; dimethylformamide and dimethylacetamide And guanamines such as N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; and ethers such as tetrahydrofuran and 1,4-dioxane. Among these, alcohols or ketones are preferred. These organic solvents can be used singly or in combination of two or more kinds of dispersion media.

As the metal oxane oligomer or the metal olefin polymer, a single or composite oxide precursor such as ruthenium, titanium, aluminum, ruthenium, osmium, iridium, tin, indium or zinc can be used. The metal oxane oligomer and the metal oxane polymer may be commercially available or obtained by a usual method such as hydrolysis of a monomer such as a metal alkoxide, a nitrate, a hydrochloride or a carboxylate.

Specific examples of the metal oxane oligomer and the metal oxane polymer include methyl phthalate 51, methyl citrate 53A, ethyl decanoate 40, and ethyl ester manufactured by Colcoat Co., Ltd. A taucan oligomer such as a decanoate 48, an EMS-485 or an SS-101, or a siloxane oxide or a titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Ltd. These can be used individually or in mixture of 2 or more types.

Further, a leveling agent, a surfactant, and the like can be used, and it is preferable to use a commercially available product in particular.

Further, the method of mixing the above other components with polyoxyalkylene may be carried out simultaneously with or after the polyoxyalkylene.

[Liquid alignment agent]

The liquid crystal alignment agent of the present invention is the above polyoxyalkylene oxide (AB), or polyoxyalkylene oxide (A) and polyoxyalkylene oxide (B), and other components are contained as necessary. In this case, as the solvent, at least one solvent selected from the group consisting of the above-mentioned polymerization solvent and an additive solvent can be used. The content of the polyoxane (AB) in the liquid crystal alignment agent, or the total content of the polyoxyalkylene (A) and the polyoxyalkylene (B), the concentration of the polysiloxane (AB) in terms of SiO ₂ , The concentration of SiO _{2 in the} total amount of ruthenium atoms of the polyoxyalkylene (A) and the polyoxyalkylene (B) is preferably from 0.5 to 15% by mass, preferably from 1 to 6% by mass. It is only in the range of the above-mentioned SiO ₂ conversion concentration, and it is possible to perform coating once, and it is easy to obtain a desired film thickness, and it is easy to obtain a sufficient solution operation time.

In the present invention, the mixing ratio of the polyoxyalkylene (A) to the polyoxyalkylene (B) in the liquid crystal alignment agent is the total amount of germanium atoms contained in the polyoxyalkylene (A) and the polyoxyalkylene (B). In general, the total amount of ruthenium atoms contained in the polyoxyalkylene (A) is preferably 5 mol% or more. When the total amount of ruthenium atoms contained in the polyoxyalkylene (A) is less than 5 mol%, it is difficult to obtain good vertical alignment. Further, when the total amount of ruthenium atoms contained in the polyoxyalkylene (A) exceeds 99.5 mol%, the content ratio of the polyoxane (B) becomes small, and good water reliability cannot be obtained, so that 99.5 is obtained. Moore% is better than below.

The method of preparing the liquid crystal alignment agent of the present invention is not particularly limited. In the polyoxyalkylene (AB), polyoxane (A), and polyoxyalkylene (B) used in the present invention, other components added as necessary may be uniformly mixed. Generally, polyoxane (AB), polyoxyalkylene (AB), polyoxyalkylene (A) and polyoxyalkylene (B) are polycondensed in a solvent, so polyoxyalkylene (AB) or polyoxyalkylene (A) can be used as it is. And a solution of polyoxyalkylene (B), or it is convenient to add other components to the solution as necessary. Further, the method of directly using the above polymerization solution is the easiest.

Further, when the content of the polyoxyalkylene (AB), the polyoxyalkylene (A), and the polyoxyalkylene (B) in the liquid crystal alignment agent is adjusted, it may be a group selected from the above-mentioned polymerization solvent and added solvent. At least one solvent.

[Liquid alignment film]

The liquid crystal alignment film of the present invention can be obtained by using the liquid crystal alignment agent of the present invention. For example, the liquid crystal alignment agent of the present invention is applied to a substrate and then dried. The cured film obtained by firing can be directly used as a liquid crystal alignment film. Further, the cured film can be made into a liquid crystal alignment film by rubbing, irradiation with polarized light or light of a specific wavelength, or treatment with an ion beam or the like.

The substrate to which the liquid crystal alignment agent is applied is not particularly limited as long as it has high transparency. However, it is preferable to form a substrate for using a transparent electrode for driving liquid crystal on the substrate.

Specific examples thereof include glass plate, polycarbonate, poly(meth)acrylate, polyether oxime, polyacrylate, polyurethane, polyfluorene, polyether, polyether ketone, trimethylpentene, and polyolefin. A substrate on which a transparent electrode is formed, such as a polyethylene terephthalate, a (meth)acrylonitrile, a triacetin cellulose, a diacetyl cellulose, an acetate butyrate cellulose or the like.

Examples of the coating method of the liquid crystal alignment agent include a spin coating method, a printing method, an ink jet method, a spray method, and a roll coating method, and the transfer printing method is widely used industrially from the viewpoint of productivity. Suitable for use in the present invention.

The drying step after the application of the liquid crystal alignment agent is preferably carried out, although it is not necessary, but the time from the application to the baking is different depending on the substrate, or when it is not directly fired after coating. This drying is not particularly limited as long as the solvent is removed by the substrate transfer or the like without deforming the shape of the coating film. For example, a method of drying for 0.5 to 30 minutes, preferably 1 to 5 minutes, may be carried out on a hot plate having a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C.

The coating film formed by coating the liquid crystal alignment agent by the above method can be cured to form a cured film. In this case, the firing temperature may be carried out at any temperature of from 100 ° C to 350 ° C, preferably from 140 ° C to 300 ° C, more preferably from 150 ° C to 230 ° C, and particularly preferably from 160 ° C to 220 ° C. The firing is carried out at any time from 5 minutes to 240 minutes. It is preferably from 10 to 90 minutes, preferably from 20 to 90 minutes. As the heating, a generally known method can be used, and for example, a hot plate, a hot air circulating oven, an IR oven, a conveyor belt furnace, or the like can be used.

The polyoxyalkylene in the liquid crystal alignment film is subjected to polycondensation in the firing step. However, in the present invention, it is not necessary to completely carry out polycondensation without limiting the effects of the present invention. However, in the liquid crystal cell manufacturing process, it is necessary to carry out the firing at a high temperature of 10 ° C or higher by sealing the heat treatment temperature such as curing.

The thickness of the cured film may be selected as necessary, and is preferably 5 nm or more, and more preferably 10 nm or more, and the reliability of the liquid crystal display element can be easily obtained. Further, when the thickness of the cured film is preferably 300 nm or less, and preferably 150 nm or less, the power consumption of the liquid crystal display element is not extremely large, which is preferable.

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

[Liquid Crystal Display Element]

The liquid crystal display device of the present invention is obtained by forming a liquid crystal alignment film on a substrate by the above method, and then producing a liquid crystal cell by a known method. An example of the production of the liquid crystal cell is a method in which a pair of substrates on which a liquid crystal alignment film is formed is sandwiched with a spacer, fixed by a sealing agent, and liquid crystal is injected and sealed. At this time, the spacer used has a size of 1 to 30 μm, preferably 2 to 10 μm.

The method of injecting the liquid crystal is not particularly limited, and a vacuum method in which a liquid crystal is produced by decompression, a vacuum method in which a liquid crystal is injected, a dropping method in which a liquid crystal is dropped, and the like is sealed.

The substrate used for the liquid crystal display element is not particularly limited as long as it has high transparency. Generally, a substrate for using a transparent electrode for driving liquid crystal is formed on the substrate.

The specific example is the same as the substrate described in [Liquid Crystal Alignment Film].

Further, for a high-function element such as a TFT type element, an element such as a transistor formed between an electrode to be driven by a liquid crystal and a substrate can be used.

In the case of a transmissive liquid crystal element, the substrate is generally used. However, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used only on the substrate on the chip side. At this time, a material such as aluminum which reflects light can be used in the electrode of the substrate.

Further, in the PSA type display device, the pretilt angle of the liquid crystal can be expressed by applying ultraviolet rays or biasing to an energy ray such as ultraviolet rays while applying a voltage to the liquid crystal cell.

[Examples]

The present invention will be specifically described below by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples.

The abbreviations in this embodiment are as follows.

TEOS: tetraethoxy decane

UPS: γ-ureidopropyl triethoxy decane

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

C12: dodecyltriethoxydecane

C18: octadecyltriethoxydecane

F13: tridecafluorooctyltrimethoxydecane

MC18: diethoxymethyloctadecyldecane

Phe: phenethyltrimethoxydecane

Ben: benzyl methoxypropyl trimethoxy decane

ACPS: (3-propenyloxypropyl)trimethoxydecane

VTES: triethoxyvinyl decane

MAPS: 3-methacryloxypropyltriethoxydecane

HG: hexanediol (alias: 2-methyl-2,4-pentanediol)

BCS: butyl cellosolve (alias: 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>

To a 200 mL four-neck 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 a 92% by mass methanol solution of 0.28 g (UPS 0.26 g) of UPS were charged and stirred. A solution of alkoxydecane monomer. To the solution, a solution of 24.52 g of MeOH, 3.60 g of water and 0.90 g of oxalic acid as a catalyst was mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 6 mass% in terms of SiO ₂ .

10.0 g of BCS was mixed with 30.0 g of the obtained polyoxane solution to obtain a liquid crystal alignment agent (K1) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 2>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, MeOH 35.33 g, 31.25 g of TEOS, 2.77 g of C12, and UPS 92% by mass methanol solution 2.39 g (UPS 2.20 g) were stirred to prepare an alkane. A solution of a oxoxane monomer. To the solution, a mixture of 17.76 g of MeOH, 9.00 g of water and 1.50 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 10% by mass in terms of SiO ₂ .

40.0 g of BCS of the obtained polyoxane solution was mixed to obtain a liquid crystal alignment agent (K2) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 3>

MeOH, 36.36 g of TEOS 29.51 g, 3.47 g of C18, and UPS 92% by mass methanol solution 4.79 g (UPS 4.41 g) were placed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, and stirred to prepare A solution of alkoxydecane monomer. To the solution, a solution of 18.37 g of MeOH, 6.00 g of water, and 1.50 g of oxalic acid as a catalyst was added thereto, and the mixture was dropped at room temperature for 30 minutes. After the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 10% by mass in terms of SiO ₂ .

40.0 g of BCS of the obtained polyoxane solution was mixed to obtain a liquid crystal alignment agent (K3) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 4>

46.07 g of MeOH, 13.54 g of TEOS, 2.08 g of C18, and UPS 92% by mass methanol solution 8.62 g (UPS 7.93 g) were placed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, and stirred to prepare A solution of alkoxy oxane monomer. To the solution, a solution of 23.38 g of MeOH, 5.40 g of water and 0.90 g of oxalic acid as a catalyst was added dropwise thereto at room temperature for 30 minutes, and after the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 6 mass% in terms of SiO ₂ .

10.0 g of BCS was mixed with 30.0 g of the obtained polyoxane solution to obtain a liquid crystal alignment agent (K4) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 5>

48.88 g of MeOH, 19.37 g of TEOS, 2.08 g of C18, and BisUREA's 60% by mass ethanol solution 0.73 g (BisUREA 0.44 g) were placed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, and stirred to prepare A solution of alkoxy oxane monomer. To the solution, a solution of 24.44 g of MeOH, 3.60 g of water and 0.90 g of oxalic acid as a catalyst was added dropwise thereto at room temperature for 30 minutes, and after the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 6 mass% in terms of SiO ₂ .

10.0 g of BCS was mixed with 30.0 g of the obtained polyoxane solution to obtain a liquid crystal alignment agent (K5) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 6>

49.31 g of MeOH, 17.92 g of TEOS, 2.34 g of ACPS, 0.83 g of C18, and UPS 92% by mass methanol solution 0.57 g (UPS 0.52 g) were placed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. After stirring, a solution of the alkoxydecane monomer is prepared. To the solution, a solution of 24.66 g of MeOH, 3.47 g of water, and 0.90 g of oxalic acid as a catalyst was added dropwise thereto at room temperature for 30 minutes, and after the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 6 mass% in terms of SiO ₂ .

10.0 g of PGME was mixed with 30.0 g of the obtained polyoxane solution to obtain a liquid crystal alignment agent (K6) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 7>

49.44 g of MeOH, 20.00 g of TEOS, 0.77 g of MC18, and UPS 92% by mass methanol solution 0.57 g (UPS 0.52 g) were placed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, and stirred to prepare A solution of alkoxy oxane monomer. To the solution, a solution of 24.72 g of MeOH, 3.60 g of water and 0.90 g of oxalic acid as a catalyst was added dropwise thereto at room temperature for 30 minutes, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 6 mass% in terms of SiO ₂ .

10.0 g of PGME was mixed with 30.0 g of the obtained polyoxane solution to obtain a liquid crystal alignment agent (K7) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 8>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 23.30 g of HG, 7.77 g of BCS, 39.17 g of TEOS, and 2.26 g of Phe were charged, and the mixture was stirred to prepare a solution of the alkoxydecane monomer. Into this solution, a solution of 11.65 g of HG, 3.88 g of BCS, 10.8 g of water, and 0.18 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes, and the mixture was allowed to stand at room temperature for 30 minutes. Stir. Thereafter, the mixture was heated under reflux for 30 minutes, and then 0.57 g (UPS: 0.27 g) of a 92 mass% methanol solution of the UPS was cooled to obtain a polyoxyalkylene solution having a solid content concentration of 6 mass% in terms of SiO ₂ .

10.0 g of BSC was mixed with 30.0 g of the obtained polyoxane solution to obtain a liquid crystal alignment agent (K8) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 9>

Into a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 49.95 g of MeOH, 19.58 g of TEOS, 1.42 g of Ben, and 0.29 g of a 98 mass% methanol solution of UPS (UPS 0.27 g) were placed, and stirred to prepare an alkoxylate. A solution of a decylene monomer. To the solution, a solution of 24.98 g of MeOH, 3.60 g of water, and 0.18 g of oxalic acid as a catalyst was added thereto, and the mixture was dropped at room temperature for 30 minutes, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 6 mass% in terms of SiO ₂ .

10.0 g of BSC was mixed with 30.0 g of the obtained polyoxane solution to obtain a liquid crystal alignment agent (K9) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 10>

Into a four-neck reaction flask equipped with a thermometer and a reflux tube, 23.34 g of HG, 7.78 g of BCS, 40.83 g of TEOS, and 0.94 g of F13 were charged, and the mixture was stirred to prepare a solution of an alkoxydecane monomer. Into this solution, a solution of 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 mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, after heating for 30 minutes under reflux, 0.57 g (UPS 0.52 g) of a 92 mass% methanol solution of the UPS was charged, and after heating for 30 minutes under reflux, the solid content was adjusted to 12 mass in terms of SiO _{2 .} % polyoxane solution.

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

<Synthesis Example 11>

To a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 22.48 g of HG, 7.49 g of BCS, 38.75 g of TEOS, and 4.18 g of C18 were placed, and the mixture was stirred to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 11.24 g of HG, 3.74 g of BCS, 10.80 g of water, and 0.18 g of oxalic acid as a catalyst was added in advance for 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 30 minutes, and then charged into a UPS 92% by mass methanol solution (1.15 g (UPS 1.06 g), and further heated under reflux for 30 minutes, and then cooled to obtain a solid content concentration of 12 by mass in terms of SiO _{2 .} % polyoxane solution.

To 30.0 g of the obtained polyoxane solution, 48.7 g of HG and 11.3 g of BCS were mixed to obtain a liquid crystal alignment agent (K11) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 12>

Into a four-neck reaction flask equipped with a thermometer and a reflux tube, 22.86 g of HG, 7.62 g of BCS, 27.50 g of TEOS, 11.42 g of VTES, and 1.67 g of C18 were placed, and the mixture was stirred to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 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 mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 30 minutes, and then a mixed solution of 1.15 g (UPS 1.06 g) of 92 mass% methanol solution of UPS, HG 0.64, and 0.21 g of BS was charged, followed by heating under reflux for 30 minutes, and then cooled. A polyoxyalkylene solution having a solid content concentration of 12% by mass in terms of SiO ₂ .

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

<Synthesis Example 13>

Into a four-neck reaction flask equipped with a thermometer and a reflux tube, 20.75 g of HG, 6.92 g of BCS, 32.92 g of TEOS, 8.71 g of MAPS, and 4.17 g of C18 were placed, and the mixture was stirred to prepare a solution of an alkoxydecane monomer. Into this solution, a solution of 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 mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 30 minutes, and then a mixed solution of 0.57 g (UPS 0.52 g) of 92 mass% methanol solution of UPS, HG 0.32 and 0.11 g of BS was charged, and the mixture was heated under reflux for 30 minutes, and then cooled. A polyoxyalkylene solution having a solid content concentration of 12% by mass in terms of SiO ₂ .

To 30.0 g of the obtained polyoxane solution, 26.89 g of HG, 4.14 g of BCS, and 28.98 g of PB were mixed, and a liquid crystal alignment agent (K13) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

<Comparative Synthesis Example 1>

To a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 22.63 g of HG, 7.54 g of BCS, 39.58 g of TEOS, and 4.17 g of C18 were placed, and the mixture was stirred to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 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 mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 12% by mass in terms of SiO ₂ .

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

The blending of alkoxydecane in Synthesis Examples 1 to 11 and Comparative Synthesis Example 1 is shown in Table 1.

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

[Liquid alignment]

The liquid crystal cell produced by the above method was observed with a polarizing microscope, and the alignment state of the liquid crystal was confirmed. When the liquid crystal cell shows a uniform alignment state without defects, it is ○, and when one of the liquid crystal cells sees an alignment defect and when there is no vertical alignment, it is ×.

[Electrical Characteristics]

The ion density at the time of applying a triangular wave of a voltage of ±10 V and a number of cycles of 0.01 Hz on the liquid crystal cell was measured. The measurement temperature was carried out at 80 °C. The measuring device used was a 6245 liquid crystal physical property evaluation device manufactured by Dongyang Technica Co., Ltd.

<Example 1>

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

Two sheets of the substrate were prepared, and a spacer having a particle diameter of 6 μm was spread on the liquid crystal alignment film surface of the single substrate, and then an epoxy-based adhesive was applied to the outer edge portion of the substrate by a curtain printing method. Thereafter, the substrate is attached to face the liquid crystal alignment film, and after pressing, it is hardened to produce a cell.

The cell was allowed to stand in an environment of room temperature 23 ° C and a humidity of 98% for 20 hours, and after adsorbing water (water treatment), liquid crystal (MLC-6608 (trade name) manufactured by Merck Co., Ltd.) was subjected to vacuum injection. Inject. At this time, degassing of the cells before the liquid crystal injection was performed for 5 minutes. Thereafter, the injection hole was sealed with a UV-curable resin to produce a liquid crystal cell (with water treatment).

In addition, the cells prepared in the same manner as described above were allowed to stand in an environment of room temperature 23 ° C and a humidity of 43% for 20 hours, and liquid crystal (MLC-6608 (trade name) manufactured by Merck Co., Ltd.) was injected by a vacuum injection method. Thereafter, the injection holes were sealed with a UV curable resin to produce liquid crystal cells (anhydrous treatment).

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

<Examples 2 to 13>

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

<Comparative Example 1>

The liquid crystal cell was produced by the above method using the liquid crystal alignment agent L1 obtained in Comparative Synthesis Example 1, and the electrical characteristics of the liquid crystal cell were measured by the above method. The results are shown in Table 2.

As shown in Table 2, in the liquid crystal cells of Examples 1 to 13, even if water treatment was carried out, the ion density did not rise as compared with the case of the anhydrous treatment. On the other hand, in the liquid crystal cell of Comparative Example 1, when water treatment was performed, the ion density was much higher than that in the case of no water treatment.

<Synthesis Example 21>

Into a 1 L (liter) four-neck reaction flask equipped with a thermometer and a reflux tube, 113.17 g of HG, 37.72 g of BCS, 197.91 g of TEOS, and 20.84 g of C18 were placed, and the mixture was stirred to prepare a solution of an alkoxydecane monomer. Into this solution, a solution of 56.59 g of HG, 18.86 g of BS, 54.0 g of water, and 0.90 g of oxalic acid as a catalyst was mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 12% by mass in terms of SiO ₂ .

With respect to 30.0 g of the obtained polyoxane solution, 56.04 g of HG and 3.96 g of BCS were mixed to obtain a polyoxynitane diluted solution (K21) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 22>

Into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 22.99 g of HG, 7.66 g of BCS, 27.78 g of TEOS, and 11.09 g of C12 were placed, and the mixture was stirred to prepare a solution of an alkoxydecane monomer. Into this solution, a solution of 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 mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated at 67 ° C for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 10% by mass in terms of SiO ₂ .

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

<Synthesis Example 23>

Into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 22.26 g of HG, 7.42 g of BCS, 38.33 g of TEOS, C18 of 4.17 g, and C12 of 2.00 g were placed, and the solution of the alkoxydecane monomer was prepared by stirring. . Into this solution, a solution of 11.13 g of HG, 3.71 g of BS, 10.8 g of water, and 0.18 g of oxalic acid as a catalyst was mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 12% by mass in terms of SiO ₂ .

To 30.0 g of the obtained polyoxane solution, 48.67 g of HG and 11.33 g of BCS were mixed to obtain a polysiloxane mixture diluted solution (K23) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 24>

Into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 23.54 g of HG, 7.85 g of BCS, 27.08 g of TEOS, C18 of 4.17 g, and 10.7 g of MTES were placed, and the solution of the alkoxydecane monomer was prepared by stirring. Into this solution, a solution of 11.77 g of HG, 3.92 g of BS, 10.8 g of water, and 0.18 g of oxalic acid as a catalyst was mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 12% by mass in terms of SiO ₂ .

To 30.0 g of the obtained polyoxynitane solution, 48.71 g of HG and 11.29 g of BCS were mixed to obtain a polyoxyalkylene diluted solution (K24) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 25>

Into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 22.79 g of HG, 7.60 g of BCS, 39.58 g of TEOS, and 3.87 g of MC18 were placed, and the mixture was stirred to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 11.39 g of HG, 3.80 g of BS, 10.8 g of water, and 0.18 g of oxalic acid as a catalyst was mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 12% by mass in terms of SiO ₂ .

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

<Synthesis Example 26>

Into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 23.42 g of HG, 7.81 g of BCS, 41.25 g of TEOS, and 0.94 g of F13 were placed, and the mixture was stirred to prepare a solution of an alkoxydecane monomer. Into this solution, a solution of 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 mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 12% by mass in terms of SiO ₂ .

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

<Synthesis Example 27>

Into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 23.59 g of HG, 7.86 g of BCS, 39.58 g of TEOS, and 2.26 g of Phe were placed, and the mixture was stirred to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 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 mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 12% by mass in terms of SiO ₂ .

With respect to 60.0 g of the obtained polyoxane solution, 97.42 g of HG and 22.58 g of BCS were mixed to obtain a polyoxynitane diluted solution (K27) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 28>

Into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 23.30 g of HG, 7.77 g of BCS, 39.58 g of TEOS, and 2.84 g of Ben were placed, and the mixture was stirred to prepare a solution of an alkoxydecane monomer. To the solution, a solution of 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 mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 12% by mass in terms of SiO ₂ .

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

<Synthesis Example 29>

Into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 34.50 g of MeOH, 27.78 g of TEOS, and 9.58 g of a 92 mass% methanol solution of UPS (UPS 8.81 g) were charged, and stirred to prepare an alkoxydecane monomer. Solution. To the solution, a solution of 17.64 g of MeOH, 9.00 g of water, and 1.50 g of oxalic acid as a catalyst was added thereto, and the mixture was dropped at room temperature for 30 minutes, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 10% by mass in terms of SiO ₂ .

30.0 g of the obtained polyoxane solution was mixed with HG 30.71 g, BCS 8.21 g, and DEG 6.09 g to obtain a polyoxysiloxane diluted solution (L21) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 30>

Into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 46.76 g of MeOH, 10.42 g of TEOS, and 14.37 g (UPS 13.22 g) of a 92 mass% methanol solution of UPS were charged, and stirred to prepare an alkoxydecane monomer. Solution. To the solution, a solution of 23.95 g of MeOH, 3.60 g of water, and 0.9 g of oxalic acid as a catalyst was added dropwise thereto at room temperature for 30 minutes, and after the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 6 mass% in terms of SiO ₂ .

60.0 g of the obtained polyoxane solution was mixed with N0.0 (30.0 g) to obtain a polyoxysiloxane diluted solution (L22) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 31>

Into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 34.47 g of MeOH, 24.31 g of TEOS, 3.91 g of ACPS, and 9.58 g of a 98 mass% methanol solution of UPS (UPS 8.81 g) were placed, and stirred to prepare an alkoxy group. A solution of a decane monomer. To the solution, a solution of 17.24 g of MeOH, 9.00 g of water, and 1.50 g of oxalic acid as a catalyst was added dropwise thereto at room temperature for 30 minutes, and after the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 10% by mass in terms of SiO ₂ .

To 40.0 g of the obtained polyoxane solution, 48.0 g of HG and 12.0 g of BCS were mixed to obtain a polyoxysiloxane diluted solution (L23) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 32>

Into a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, 37.14 g of MeOH, 34.03 g of TEOS, and 0.96 g of a 98 mass% methanol solution of UPS (UPS 0.88 g) were charged, and stirred to prepare an alkoxydecane monomer. Solution. To the solution, a solution of 13.93 g of HG, 4.64 g of BCS, 9.00 g of water, and 0.3 g of oxalic acid as a catalyst was mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under reflux for 1 hour, and then cooled to obtain a polyoxyalkylene solution having a solid content concentration of 10% by mass in terms of SiO ₂ .

90.0 g of the obtained polyoxane solution was mixed with HG 108.0 g and BCS 27.0 g to obtain a polyoxysiloxane diluted solution (L24) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 33>

A 200 ml four-neck 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 the alkoxydecane monomer. In the solution, a solution of pre-mixed HG 16.35 g, BCS 5.45 g, 5.40 g of water and 0.45 g of oxalic acid as a catalyst was dropped at room temperature for 30 minutes, and after the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. . Thereafter, the mixture was heated at 85 ° C for 30 minutes, and then a solution of 3.67 g (BisUREA 2.20 g) of a 60 mass% methanol solution of BisUREA, 4.75 g of HG, and 1.58 g of BCS was added, followed by heating at 85 ° C for 30 minutes, followed by cooling. A polyoxyalkylene solution having a solid content concentration of 6 mass% in terms of SiO ₂ .

To 40.0 g of the obtained polyaluminoxane solution, 17.31 g of HG and 2.69 g of BCS were mixed to obtain a polyoxyalkylene diluted solution (L25) having a solid content concentration of 4% by mass in terms of SiO ₂ .

<Synthesis Example 34>

A solution of 22.53 g of HG, 7.51 g of BCS, and 27.78 g of TEOS was placed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, and stirred to prepare a solution of the alkoxydecane monomer. To the solution, a solution of 11.26 g of HG, 3.75 g of BCS, 9.00 g of water, and 1.50 g of oxalic acid as a catalyst was mixed in advance for 30 minutes at room temperature, and after completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Thereafter, after heating for 30 minutes under reflux, a solution of 9.58 g (UPS 8.81 g) of a 92 mass% methanol solution of a UPS, a solution of HG 5.32 g, and 1.77 g of BCS was charged, and then heated under reflux for 30 minutes. The polysiloxane solution having a solid content concentration of 10% by mass in terms of SiO ₂ was obtained by cooling.

With respect to 60.0 g of the obtained polyoxane solution, 73.35 g of HG and 16.65 g of BCS were mixed, and a polysiloxane mixture diluted solution (L26) having a solid content concentration of 4% by mass in terms of SiO ₂ was obtained.

The blending ratio of the alkoxydecane in the above Synthesis Examples 21 to 34 is shown in Table 21 and Table 22 below.

<Example 21>

97.5 g of the polyoxymethane diluted solution (K21) obtained in the same manner as in Synthesis Example 21 and 2.5 g of the polyaluminoxane 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 .} 4% by mass of a liquid crystal alignment agent (KL1) of a polyoxane diluted solution.

<Example 22>

90.0 g of a polyoxymethane diluted solution (K21) obtained in the same manner as in Synthesis Example 21 and 10.0 g of a polyaluminoxane 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 .} 4% by mass of a liquid crystal alignment agent (KL2) of a polyoxane diluted solution.

<Example 23>

80.0 g of the polyoxoxane diluted solution (K21) obtained in the same manner as in Synthesis Example 21 and 20.0 g of the polyadenine 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 .} 4% by mass of a liquid crystal alignment agent (KL3) of a polyoxane diluted solution.

<Example 24>

50.0 g of the polyoxymethane diluted solution (K22) obtained in the same manner as in Synthesis Example 22, and 50.0 g of the polyaluminoxane solution (L22) obtained in the same manner as in Synthesis Example 30, to obtain a solid concentration of 4 in terms of SiO _{2 .} A liquid crystal alignment agent (KL4) of a mass % of a polyoxyalkylene diluted solution.

<Example 25>

Synthesis Example 23 was mixed with the same poly-silicon obtained from a diluted solution alumoxane under (K23) 90.0g, obtained from the same poly-silicon alumoxane solution (L21) 10.0g and Synthesis Example 29, to give a solid content in terms of SiO ₂ concentration 4% by mass of a liquid crystal alignment agent (KL5) of a polyoxane diluted solution.

<Example 26>

90.0 g of the polyoxymethane diluted solution (K24) obtained in the same manner as in Synthesis Example 24, and 10.0 g of the polyaluminoxane 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 .} 4% by mass of a liquid crystal alignment agent (KL6) of a polyoxane diluted solution.

<Example 27>

90.0 g of the polyoxymethane diluted solution (K21) obtained in the same manner as in Synthesis Example 21 and 10.0 g of the polyadenine solution (L23) obtained in the same manner as in Synthesis Example 31 were mixed to obtain a solid content concentration in terms of SiO _{2 .} 4% by mass of a liquid crystal alignment agent (KL7) of a polyoxane diluted solution.

<Example 28>

60.0 g of a polyoxymethane diluted solution (K21) obtained in the same manner as in Synthesis Example 21 and 40.0 g of a polyadenine solution (L24) obtained in the same manner as in Synthesis Example 32 were mixed to obtain a solid content concentration in terms of SiO _{2 .} 4% by mass of a liquid crystal alignment agent (KL8) of a dioxane diluted solution.

<Example 29>

90.0 g of the polyoxymethane diluted solution (K25) obtained in the same manner as in Synthesis Example 25, and 10.0 g of the polyaluminoxane 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 .} 4% by mass of a liquid crystal alignment agent (KL9) of a polyoxane diluted solution.

<Example 30>

90.0 g of the polyoxymethane diluted solution (K26) obtained in the same manner as in Synthesis Example 26, and 10.0 g of the polyaluminoxane 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 .} 4% by mass of a liquid crystal alignment agent (KL10) of a polyoxane diluted solution.

<Example 31>

90.0 g of a polyoxymethane diluted solution (K27) obtained in the same manner as in Synthesis Example 27, and 10.0 g of a polyaluminoxane 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 .} 4% by mass of a liquid crystal alignment agent (KL11) of a polyoxane diluted solution.

<Example 32>

90.0 g of a polyoxymethane diluted solution (K28) obtained in the same manner as in Synthesis Example 28, and 10.0 g of a polyaluminoxane 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 .} 4% by mass of a liquid crystal alignment agent (KL12) of a polyoxane diluted solution.

<Example 33>

5.0 g of the polyoxymethane diluted solution (K22) obtained in the same manner as in Synthesis Example 22 and 95.0 g of the polyadenine solution (L24) obtained in the same manner as in Synthesis Example 32 were mixed to obtain a solid content concentration in terms of SiO _{2 .} 4% by mass of a liquid crystal alignment agent (KL13) of a polyoxane diluted solution.

<Example 34>

20.0 g of the polyoxymethane diluted solution (K22) obtained in the same manner as in Synthesis Example 22 and 80.0 g of the polyadenine solution (L24) obtained in the same manner as in Synthesis Example 32 were mixed to obtain a solid content concentration in terms of SiO _{2 .} 4% by mass of a liquid crystal alignment agent (KL14) of a polyoxane diluted solution.

<Example 35>

90.0 g of a polyoxymethane diluted solution (K21) obtained in the same manner as in Synthesis Example 21, and 10.0 g of a polyaluminoxane solution (L26) obtained in the same manner as in Synthesis Example 34 were mixed to obtain a solid content concentration in terms of SiO _{2 .} The liquid crystal alignment agent (KL15) of the solution was diluted with 4% by mass of polyoxyalkylene.

The blending of the polyoxyalkylenes in Examples 21 to 35 is shown in Table 23.

<Example 36>

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

Two sheets of the substrate were prepared, and a spacer having an average particle diameter of 6 μm was spread on the liquid crystal alignment film surface of the single substrate, and then an epoxy-based adhesive was applied to the outer edge portion of the substrate by a curtain printing method. Next, the substrate is attached to face the liquid crystal alignment film, and after pressing, it is hardened to produce a cell.

The cells obtained above were allowed to stand in an environment of room temperature 23 ° C and a humidity of 98% for 20 hours, and after adsorbing water, liquid crystal (MLC-6608, trade name of Merck) was injected by a vacuum injection method. At this time, degassing of the cells before the liquid crystal injection was performed for 5 minutes. Thereafter, the injection hole was sealed with a UV-curable resin to produce a liquid crystal cell (with water treatment).

On the other hand, the other cells obtained above were allowed to stand in an environment of a room temperature of 23 ° C and a humidity of 43% for 20 hours, and liquid crystal (MLC-6608, trade name of Merck) was injected by a vacuum injection method. The injection hole was sealed with a UV curable resin to prepare a liquid crystal cell (anhydrous treatment).

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

<Examples 37 to 50>

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

<Comparative Example 21>

Using the polyoxane 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 clear from Table 24, in the liquid crystal cells of Examples 36 to 50, it was judged that the ion density did not rise as compared with the case of the waterless treatment by the water treatment. On the other hand, in the liquid crystal alignment cells of Comparative Example 21, it was judged that the ion density was greatly increased as compared with the case of the waterless treatment by the water treatment.

Industrial availability

The liquid crystal display device produced by using the liquid crystal alignment treatment agent of the present invention has high reliability, particularly high reliability of electrical characteristics, and can be used as a high-quality liquid crystal display device, and is suitable for TN type, STN type, and IPS type. Display elements of various types such as liquid crystal display elements such as VA type, OCB type, and PSA type.

The entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2008-147475, filed on Jun. 4, 2008, and the Japanese Patent Application No. 2008-147483, filed on June 4, 2008, are hereby incorporated by reference. The disclosure of the present invention is disclosed.

Claims (17)

A liquid crystal alignment agent characterized by containing a polycondensation alkoxydecane containing an alkoxydecane represented by the formula (1), an alkoxydecane represented by the formula (2), and an alkoxydecane represented by the formula (3). The obtained polyoxyalkylene (AB); X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1) (X ¹ may be substituted by a fluorine atom, and may contain an oxygen atom, a phosphorus atom, or a sulfur atom a hydrocarbon group having 8 to 30 carbon atoms, X ² is an alkyl group having 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p is an integer of 0 to 2) X ³ {Si(OR ² ₃ } _q (2) (X ³ is a hydrocarbon group having a ureido group having 1 to 12 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms, and q is an integer of 1 or 2) (X ⁴ ) _n substituted with _{^{si (oR 3) 4-n}} (3) (X 4 is a hydrogen atom, a halogen atom or may, vinyl group, glycidoxy, mercapto, methacryloxy group, an isocyanate group or a propylene group Further, it may have a hydrocarbon group having 1 to 6 carbon atoms of an unsaturated bond or a hetero atom, R ³ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3). A liquid crystal alignment agent comprising the following polyoxyalkylene (A) and polyoxyalkylene (B); polyoxyalkylene (A): polycondensation containing the alkoxydecane represented by formula (1) and formula ( 3) a polyoxyalkylene obtained by alkoxydecane of the alkoxydecane shown; X ¹ (X ² ) _p Si(OR ¹ ) _3-p (1) (X ¹ may be substituted by a fluorine atom and may contain a hydrocarbon group having 8 to 30 carbon atoms of an oxygen atom, a phosphorus atom or a sulfur atom, X ² is an alkyl group having 1 to 5 carbon atoms, R ¹ is an alkyl group having 1 to 5 carbon atoms, and p is 0 to 2 (X ⁴ ) _n Si(OR ³ ) _4-n (3) (X ⁴ is a hydrogen atom or may be a halogen atom, a vinyl group, a glycidoxy group, a thiol group, a methacryloxy group, An isocyanate group or a propyleneoxy group substituted, and may have an unsaturated bond or a hydrocarbon atom having 1 to 6 carbon atoms in the hetero atom, R ³ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3) silicon siloxane (B): containing polycondensation of formula (2) Silane alkoxy and the formula (3) obtained from the alkoxy silane-alkoxy silane-siloxane poly silicon shown; X ³ {Si (OR ² ₃ } _q (2) (X ³ is a hydrocarbon group having a ureido group having 1 to 12 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms, and q is an integer of 1 or 2) (X ⁴ ) _n Si(OR ³ ) _4-n (3) (X ⁴ is a hydrogen atom or may be a halogen atom, a vinyl group, a glycidoxy group, a thiol group, a methacryloxy group, an isocyanate group or a propyleneoxy group. Further, it may have a hydrocarbon group having 1 to 6 carbon atoms which is an unsaturated bond or a hetero atom, R ³ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3). The liquid crystal alignment agent of claim 1, wherein the polyoxyalkylene (AB) is obtained by containing an alkoxydecane represented by the formula (1) and an alkoxydecane represented by the formula (3) in an organic solvent. Hydrolyze it. After condensation, the alkoxydecane represented by the formula (2) is added for hydrolysis. Manufactured by the method of the condensation step. The liquid crystal alignment agent of claim 2, wherein the polyoxyalkylene (A) is obtained by hydrolyzing an alkoxydecane represented by the formula (3) in an organic solvent. After condensation, the alkoxydecane represented by the formula (1) is added for hydrolysis. Manufactured by the method of the condensation step. The liquid crystal alignment agent of claim 2, wherein the polyoxyalkylene (B) is obtained by hydrolyzing an alkoxydecane represented by the formula (3) in an organic solvent. After condensation, the alkoxydecane represented by the formula (2) is added for hydrolysis. Manufactured by the method of the condensation step. The liquid crystal alignment agent according to any one of the preceding claims, wherein the alkoxydecane represented by the above formula (3) is a tetraalkoxydecane wherein n in the formula (3) is 0. The liquid crystal alignment agent of claim 1, wherein the alkoxydecane represented by the above formula (1) is contained in the total alkoxy decane of the polyoxane (AB) in an amount of 0.1 to 30 m. %, and the above formula (2) is shown The alkoxydecane is contained in the total alkoxy decane in an amount of from 0.1 to 50 mol%. The liquid crystal alignment agent of claim 1, wherein the alkoxydecane represented by the above formula (3) is contained in the peroxy alkane of the polyoxane (AB) in an amount of 20 to 99.8 mol. %. The liquid crystal alignment agent of the first aspect of the invention, wherein the content of the polyoxymethane is 0.5 to 15% by mass in terms of SiO ₂ conversion concentration. The liquid crystal alignment agent of claim 2, further comprising an organic solvent which dissolves the polyoxyalkylene oxide (A) and the polyoxyalkylene oxide (B). The liquid crystal alignment agent of the second aspect of the invention, wherein the liquid crystal alignment agent contains a total amount of germanium atoms contained in each of the polyoxyalkylene (A) and the polyoxyalkylene (B) in terms of SiO ₂ It is 0.5 to 15% by mass. The liquid crystal alignment agent of claim 2, wherein the ratio of polyoxyalkylene (A): polyoxyalkylene (B) is 5:95 to 99.5:0.5 in terms of the amount of germanium atoms contained in them. The liquid crystal alignment agent of claim 2, wherein the alkoxy decane represented by the formula (1) is 0.2 to 30 moles for the peralkoxy decane to be used for obtaining the polyoxyalkylene (A). %, and the alkoxydecane represented by the formula (3) is 70 to 99.8 mol%. The liquid crystal alignment agent of claim 2, wherein the alkoxy decane represented by the formula (2) is 0.5 to 60 m for the peralkoxy decane to be used for obtaining the polyoxyalkylene (B). %, and the alkoxydecane represented by the formula (3) is 40 to 99.5 mol%. Such as the liquid crystal of any of the first and second items of the patent application scope An alignment agent, wherein the alkoxydecane represented by the above formula (2) is selected from the group consisting of γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxynonane, γ-ureidopropyltripropoxide Base decane, bis[3-(triethoxymethanealkyl)propyl]urea, bis[3-(trimethoxymethylalkyl)propyl]urea, and bis[3-(tripropoxymethane) At least one of the group of propyl]urea. A liquid crystal alignment film obtained by applying a liquid crystal alignment agent according to any one of claims 1 to 15 to a substrate, drying and firing. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 16 of the patent application.