TWI553040B - 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 containing a polyoxyalkylene obtained by polycondensing an alkoxysilane, and 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 recent years, in the display mode of a liquid crystal display element, a vertical (VA) liquid crystal display element is widely used for a large-screen liquid crystal television or a high-definition movable use (a display unit of a digital camera or a mobile phone). In the VA method, a MVA method (Multi Vertical Alignment) in which a protrusion for controlling a liquid crystal tilting direction is formed on a TFT substrate or a filter substrate, or a slit is formed on an ITO electrode of a substrate, and liquid crystal is controlled by an electric field. PVA (Patterned Vertical Alignment) mode. In terms of other alignment methods, there is a PSA (Polymer sustained Alignment) method. Among the VA methods, the PSA method is a technology that has attracted much attention in recent years.

In this method, a photopolymerizable compound is added to the liquid crystal, and after the liquid crystal panel is produced, an electric field is applied to irradiate the liquid crystal panel with ultraviolet rays (UV) in a liquid crystal tilting state. As a result, the polymer compound is photopolymerized to fix the alignment direction of the liquid crystal, pretilt is generated, and the response speed is increased. The method is characterized in that a slit is formed on an electrode constituting a single side of the liquid crystal panel, and even if a projection such as an MVA protrusion or a slit such as a PVA is not provided on the opposite electrode pattern, the operation can be simplified or the manufacturing can be simplified. Get excellent peace Plate transmittance (refer to Patent Document 1).

However, in the liquid crystal display device of this type, the solubility of the polymerizable compound added to the liquid crystal is low, and if the amount of addition is increased, there is a problem that precipitation occurs at a low temperature. On the other hand, when the amount of the polymerizable compound added is reduced, a good alignment state and a response speed cannot be obtained. Moreover, the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity in the liquid crystal, and there is a problem that the reliability of the liquid crystal display element is lowered.

Therefore, it is proposed to provide a liquid crystal alignment film which is formed by applying a liquid crystal alignment agent formed by using a polymer having a photoreactive side chain introduced into a polymer molecule onto a substrate and firing it. In the liquid crystal layer, a liquid crystal display element is produced by applying UV to the liquid crystal layer, and a liquid crystal display element having a fast response speed can be obtained without adding a polymerizable compound to the liquid crystal (refer to Patent Document 2).

Further, an organic liquid crystal alignment film material is also known as an organic liquid crystal alignment film material such as polyimide which has been conventionally used. For example, in the material of the coating type inorganic alignment film, an alignment agent composition containing a reaction product of tetraalkyloxane, trialkoxide, alcohol, and oxalic acid is proposed, and is disclosed in a liquid crystal display. A liquid crystal alignment film having excellent vertical alignment, heat resistance, and uniformity is formed on the electrode substrate of the device (refer to Patent Document 3). Further, a liquid crystal alignment agent composition containing a reaction product of tetraalkyloxane, a specific trialkoxysilane, and water and a specific glycol ether solvent has been proposed, and it has been disclosed that formation defects are prevented from being formed, and After the long-term driving, the afterimage characteristics are still good, the liquid crystal alignment film is reduced, and the liquid crystal alignment film having less reduction in light and heat is maintained. Offer 4).

[Previous Technical Literature] [Japanese Patent Literature]

[Patent Document 1] JP-A-2004-302061

[Patent Document 2] JP-A-2011-95967

[Patent Document 3] Japanese Patent Publication No. 09-281502

[Patent Document 4] JP-A-2005-250244

In the vertical alignment VA mode (mode), it is necessary to use a strong vertical alignment force in the vertical alignment. However, when the polymerizable compound is not used, if the vertical alignment force is increased, the response speed after UV irradiation will change. Slow, and if the response speed after UV irradiation is increased, the vertical alignment force will decrease. The vertical alignment force and the response speed increase after UV irradiation are in a trade-off relationship.

An object of the present invention is to provide a liquid crystal display device in which a liquid crystal without a polymerizable compound is used in the same manner as in the PSA method and the response speed after UV irradiation is increased, without lowering the vertical alignment force. A liquid crystal alignment agent capable of improving a response speed after UV irradiation, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

The features of the present invention are as follows.

[1] A liquid crystal alignment agent comprising a polyoxyalkylene (A) having an alkoxysilane represented by the following formula (1) and an alkoxy group represented by the formula (3) The alkane decane of decane is obtained by polycondensation.

R ¹ Si(OR ² ) ₃ (1) (R ¹ represents a structure of the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms).

(Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Y ² single bond, containing double a linear or branched hydrocarbon group having a carbon number of 3 to 8 or -(CR ¹⁷ R ¹⁸ ) _b - (b is an integer of 1 to 15, and R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a carbon number 1 to 3 alkyl groups.) Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 having an aliphatic alcohol skeleton, and any of these cyclic groups The hydrogen atom may be selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, and a fluorine atom. Substituted by a group: Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a hetero ring, and any hydrogen atom on the ring group may have a carbon number of 1 to 3 The alkyl group, the alkoxy group having 1 to 3 carbon atoms, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom are substituted. n is an integer of 0 to 4. Y ⁶ based hydrogen atom, an alkyl group having 1 to 18 carbon atoms, the carbon atoms of the fluorinated alkyl group having 1 to 18, Or alkoxy having 1 to 18 carbon atoms containing alkoxy group of 1 to 18 of.)

R ³ Si(OR ⁴ ) ₃ (3) (R ³ is an alkyl group having 1 to 30 carbon atoms which is substituted by an acrylic group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group. R ⁴ is an alkyl group having 1 to 5 carbon atoms.)

[2] The liquid crystal alignment agent according to the above [1], wherein, in the above formula (3), R ³ is an acrylic group, an acryloxy group, a methacryl group, a methacryloxy group or a styrene. The alkyl group having a carbon number of 3 to 10 is substituted.

[3] The liquid crystal alignment agent according to the above [1] or [2], which further comprises a polycondensation obtained by polycondensing an alkoxysilane having 50% to 100% of the alkoxydecane represented by the formula (5). Oxane (B).

Si(OR ¹⁵ ) ₄ (5) (R ¹⁵ is an alkyl group having 1 to 5 carbon atoms.)

[4] The liquid crystal alignment agent according to the above [3], wherein the polyoxyalkylene (B) is a polyfluorene obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (3). alkyl.

[5] The liquid crystal alignment agent according to the above [3] or [4] wherein the polyoxyalkylene (B) is further obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (6). Polyoxyalkylene.

R ¹⁶ Si(OR ¹⁷ ) ₃ (6) (R ¹⁶ is an alkyl group having 1 to 5 carbon atoms and R ¹⁷ is an alkyl group having 1 to 5 carbon atoms).

[6] The liquid crystal alignment agent according to any one of the above [1], wherein at least one of polyoxyalkylene (A) and polyoxyalkylene (B) is further A polyoxyalkylene obtained by polycondensing an alkoxysilane containing an alkoxydecane represented by the following formula (4).

(R ¹³ ) _n Si(OR ¹⁴ ) _4-n (4) (in the formula (4), R ¹³ is a hydrogen atom, or may be a hetero atom, a halogen atom, an amine group, a glycidoxy group, a thiol group, Isocyanate group, ureido-substituted hydrocarbon group having 1 to 10 carbon atoms, R ¹⁴ alkyl group having 1 to 5 carbon atoms, and n-type 0 to 3 integer.

The liquid crystal alignment agent of any one of the above-mentioned formula (1), wherein the alkoxy oxane represented by the above formula (1) is a total alkoxy group used in the polyoxane (A). The decane contains 2 to 20 mol%, and the alkoxy decane represented by the above formula (3) contains 5 to 80 mol% of the peralkyl alkane used in the polyoxyalkylene (A).

[8] A liquid crystal alignment film obtained by applying the liquid crystal alignment agent according to any one of the above [1] to [7], and drying and baking the liquid crystal alignment agent.

[9] A liquid crystal display device comprising the liquid crystal alignment film according to [8] above.

[10] A liquid crystal display device, which is characterized in that the liquid crystal alignment agent according to any one of the above [1] to [7] is used, and a liquid crystal cell obtained by holding liquid crystal on two substrates that have been fired is used. The UV is irradiated in a state where a voltage is applied.

[11] A liquid crystal display device according to any one of [1] to [7], wherein the liquid crystal alignment agent is adhered to the two substrates which are fired, and a voltage is applied thereto. The UV is irradiated.

According to the present invention, it is possible to provide a liquid crystal alignment agent which can irradiate UV in the same manner as the PSA method using a liquid crystal which does not contain a polymerizable compound, and enhance the response speed after UV irradiation without lowering the vertical alignment force. And a liquid crystal alignment film obtained from the liquid crystal alignment agent and a liquid crystal display element having the liquid crystal alignment film.

[Formation of the Invention] <polyoxane (A)>

The polyoxyalkylene (A) contained in the liquid crystal alignment agent of the present invention is obtained by polycondensing an alkoxysilane having an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the formula (3). Polyoxane. Further, in the production of a decane which is a decane, in detail, it is represented by hydrolysis ‧ polycondensation, but in the present specification, it is only described as polycondensation.

R ¹ Si(OR ² ) ₃ (1) R ¹ (hereinafter also referred to as a specific organic group) of the alkoxydecane represented by the formula (1) represents a structure of the following formula (2), and R ² represents a carbon number of 1 ~5, preferably 1 to 3 alkyl groups. )

R ³ Si(OR ⁴ ) ₃ (3)

R ³ is an alkyl group having 1 to 30 carbon atoms, preferably 3 to 10 carbon atoms, which is substituted by an acrylic group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group, and R ⁴ represents carbon. A number of 1 to 5 alkyl groups.

In the formula (2), Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- By. Among them, the selection of a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO-, from the easy synthesis of side chain structure The point of view is better. Further, it is more preferable to select a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In the formula (2), a Y ² single bond, a linear or branched hydrocarbon group having a carbon number of 3 to 8 containing a double bond, or -(CR ¹⁷ R ¹⁸ ) _b - (b is an integer of 1 to 15, R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Among them, from the viewpoint of more remarkably improving the response speed of the liquid crystal display element, -(CH ₂ ) _b - (b is an integer of 1 to 10) is more preferable.

In the formula (2), Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- By. Among them, it is easy to select one of the single bonds, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- The viewpoint of synthesizing the side chain structure is preferred. Further, it is more preferable to select a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO- or -OCO-.

In the formula (2), Y ⁴ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, and any hydrogen atom system on the ring group may have a carbon number of 1 to 3 Any of an alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Further, the Y ⁴ system may be a divalent organic group selected from an organic group having a carbon number of 12 to 25 of the aliphatic alcohol skeleton. Among them, an organic group having 12 to 25 carbon atoms which has any one of a benzene ring, a cyclohexane ring or a lipid alcohol skeleton is preferred.

In the formula (2), Y ⁵ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom system on the cyclic group may have a carbon number of 1 to 3 Any of an alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom.

In the formula (2), n is an integer of 0 to 4. Preferably, it is an integer of 0-2.

In the formula (2), a Y ⁶ hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a carbon number of 1 to 18 are contained. Any of fluoroalkoxy groups. Among them, any one of an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms. It is better. More preferably, it is any one of an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably, it is any one of an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

The use of a liquid crystal alignment agent comprising a side chain and a photoreactive group of a polyoxyalkylene is not conclusive as to the combination of the response speed characteristics and the good vertical alignment, but it can be inferred that The liquid crystal skeleton has a similarly constructed side chain, and has both a response speed and a vertical alignment property which are usually related to a trade-off relationship.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula (2) are as shown in the following Tables 1 to 42 (2-1) to (2-629). Shown.

c is an integer of 1 to 10 carbon atoms

c is an integer of 1 to 10 carbon atoms

c is an integer of 1 to 10 carbon atoms

a is an integer of 1 to 10 carbon atoms

a is an integer of 1 to 10 carbon atoms

a is an integer of 1 to 10 carbon atoms

a is an integer of 1 to 10 carbon atoms

a is an integer of 1 to 10 carbon atoms

a and c are each independently an integer of 1 to 10 carbon atoms

c is an integer of 1 to 10 carbon atoms

c is an integer of 1 to 10 carbon atoms

c is an integer of 1 to 10 carbon atoms

c is an integer of 1 to 10 carbon atoms

c is an integer of 1 to 10 carbon atoms

c is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b is an integer of 1 to 10 carbon atoms

b, c are each independently an integer of 1 to 10 carbon atoms

b, c are each independently an integer of 1 to 10 carbon atoms

The alkoxydecane represented by the formula (1) has an R ² -valent alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, it is an R ² methyl group or an ethyl group.

The alkoxy decane represented by the formula (1) can be synthesized by a known synthesis method (for example, JP-A-61-286393). The specific examples are exemplified below, but are not limited thereto.

(In the formula [1-19]~Form [1-21], R ⁵ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, R ⁶ -based carbon number 1 to 22 alkyl, alkoxy, fluoroalkyl or fluoroalkoxy.)

(In the formula [1-22]~Form [1-24], R ⁷ represents a single bond, -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -(CH ₂ ) _n O-( n is an integer of 1 to 5), -OCH ₂ - or CH ₂ -, R ⁸ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

(In the formula [1-25] and the formula [1-26], R ⁹ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, - CH ₂ - or O-, R ¹⁰ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group.

(In the formula [1-27] and the formula [1-28], R ¹¹ is an alkyl group having 3 to 12 carbon atoms, and a cis-trans isomer of 1,4-cyclohexylene is a trans isomer. .)

(In the formula [1-29] and the formula [1-30], R ¹² is an alkyl group having 3 to 12 carbon atoms, and a cis-trans isomer of 1,4-cyclohexylene is a trans isomer. .)

(In the formula [1-31], B ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, B ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group, and B ₂ is an oxygen group. Atom or -COO-* (except that the attached "*" bond is bonded to B ₃ ), B ₁ oxygen atom or -COO-* (only, the attached "*" bond bond and (CH ₂ )a ₂ ) Bonding). Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.

The alkoxysilane represented by the above formula (1) is soluble in a solvent as a siloxane polymer, liquid crystal alignment property as a liquid crystal alignment film, pretilt angle characteristics, voltage holding ratio, and accumulated charge. The characteristics are used in one type or in combination of two or more types. Further, it can be used in combination with an alkoxydecane having a long-chain alkyl group having 10 to 18 carbon atoms.

The alkoxysilane represented by the above formula (1) can be produced by a known method.

The alkoxydecane represented by the above formula (1) is preferably 1 mol% or more in order to obtain a good liquid crystal alignment property in the peralkyl alkane which is used for obtaining a polyoxyalkylene. More preferably, it is 1.5 mol% or more. More preferably, it is 2 mol% or more. Further, in order to obtain sufficient hardening characteristics for the formed liquid crystal alignment film, it is preferably 30 mol% or less. More preferably, it is 25 mol% or less.

R ³ (hereinafter also referred to as a second specific organic group) of the alkoxydecane represented by the formula (3) is an acrylic group, an acryloxy group, a methacryl group or a methacryloxy group or a styryl group. Substituted alkyl. One or more hydrogen atom groups may be substituted, and preferably one. The alkyl group has a carbon number of 1 to 30, more preferably 3 to 10, still more preferably 5 to 10.

The alkoxysilane of the formula (3) has an R ⁴ alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, particularly preferably 1 or 2 carbon atoms.

Although a specific example of the alkoxysilane represented by the formula (3) is mentioned, it is not limited to this. For example, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, methacryloxymethyltrimethoxydecane, methacryl Oxymethyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, propyleneoxyethyltrimethoxydecane, propylene oxime Oxyethyl triethoxy decane, styrylethyl trimethoxy decane, styrylethyl triethoxy decane, 3-(N-styrylmethyl-2-aminoethylamino group ) propyl trimethoxy decane, 3-methyl propylene methoxy hexyl trimethoxy decane, 3-methyl propylene methoxy hexyl triethoxy decane, 3- propylene decyl hexyl methoxy decane, 3 - propylene methoxy hexyl triethoxy decane, 3-methyl propylene methoxy octyl trimethoxy decane, 3-methyl propylene oxy octyl triethoxy decane, 3- propylene oxiran octane Tris-methoxydecane, 3-propenyloxyoctyltriethoxydecane.

The alkoxydecane represented by the formula (3) is preferably 5 mol% or more in order to obtain a good liquid crystal response speed in the peralkyl alkane to obtain a polyoxyalkylene. More preferably, it is 10 mol% or more. More preferably, it is 20 mol% or more. Further, in order to improve the vertical alignment, it is preferably 70 mol% or less, more preferably 60 mol% or less.

In the production of the polyoxane (A), in addition to the alkoxydecane represented by the formulas (1) and (3), the purpose of improving the adhesion to the substrate and the affinity with the liquid crystal molecules is Without damaging the effects of the present invention, One or a plurality of alkoxysilanes represented by the following formula (4) are used. Since the alkoxysilane represented by the formula (4) can impart various properties to the polyoxyalkylene, one or a plurality of kinds can be selected depending on the desired properties.

(R ¹³ ) _n Si(OR ¹⁴ ) _4-n (4) (in the formula (4), R ¹³ is a hydrogen atom, or may be a hetero atom, a halogen atom, an amine group, a glycidoxy group, a thiol group, a hydrocarbon group having 1 to 10 carbon atoms which is substituted with an isocyanate group or a urea group. R ¹⁴ is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and n is 0 to 3, preferably 0 to 2 carbon atoms. Integer)

The R ¹³ hydrogen atom or the organic group having 1 to 10 carbon atoms (hereinafter also referred to as a third organic group) of the alkoxydecane represented by the formula (4). Examples of the third organic group may include an aliphatic hydrocarbon such as an aliphatic ring, an aromatic ring, and a heterocyclic ring structure; an unsaturated bond; and a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, etc. It may be an organic group having a branched structure and having 1 to 6 carbon atoms. Further, the organic group may be substituted with a halogen atom, an amine group, a glycidoxy group, a thiol group, an isocyanate group, a urea group or the like.

Although a specific example of the alkoxysilane represented by the formula (4) is mentioned, it is not limited to this. For example, 3-(2-aminoethylaminopropyl)trimethoxydecane, 3-(2-aminoethylaminopropyl)triethoxydecane, 2-aminoethylamino group Methyltrimethoxydecane, 2-(2-aminoethylthioethyl)triethoxydecane, 3-hydrothiopropyltriethoxydecane, thiomethyltrimethoxydecane, Vinyl triethoxy decane, 3-isocyanate propyl triethoxy decane, trifluoropropyl trimethoxy decane, chloropropyl triethoxy decane, bromopropyl triethoxy decane, 3-hydrogen Thiopropyltrimethoxydecane, dimethyldiethoxydecane, dimethyldimethoxydecane, two Ethyldiethoxydecane, diethyldimethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, 3-aminopropylmethyldiethoxydecane, 3 - aminopropyl dimethyl ethoxy decane, trimethyl ethoxy decane, trimethyl methoxy decane, γ-ureidopropyl triethoxy decane, γ-ureidopropyl trimethoxy Decane and γ-ureidopropyltripropoxydecane.

In the alkoxydecane represented by the formula (4), the alkoxy oxane wherein n is 0 is a tetraalkane. The tetraalkyloxane is more suitable for obtaining the polyoxyalkylene of the present invention because it is easily condensed with the alkoxydecane represented by the formulae (1) and (3).

In the formula (4), the alkoxy oxane wherein n is 0 is preferably tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane or tetrabutoxy decane, especially in the fourth group. Oxydecane or tetraethoxydecane is preferred.

In the present invention, the alkoxydecane represented by the formula (1) preferably contains 2 to 20 mol%, particularly preferably 3, of the peralkyl alkane used in the production of the polyoxyalkylene (A). ～15 mol%, and the alkoxy decane represented by the formula (3), in the peralkoxy decane used in the production of the polyoxyalkylene (A), preferably contains 5 to 80 mol%, particularly It is preferably contained in an amount of 10 to 70 mol%.

<polyoxane (B)>

The polyoxyalkylene (B) is a polyoxyalkylene obtained by polycondensing an alkoxysilane having an alkoxydecane represented by the formula (5) in an amount of from 50 mol% to 100 mol%.

Si(OR ¹⁵ ) ₄ (5)

R ^{15 of the} alkoxydecane represented by the formula (5) represents an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms.

Specific examples of the alkoxydecane represented by the formula (5) are preferably tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane or tetrabutoxydecane, particularly tetramethoxy. Preferably, decane or tetraethoxy decane is preferred.

The polyoxyalkylene (B) may be an alkoxydecane represented by the formula (3) described in the production of the polyfluorene oxide (A), in addition to the alkoxysilane represented by the formula (5). And a polyoxane obtained by polycondensation of an alkoxysilane of R ³ Si(OR ⁴ ) ₃ . The description of the alkoxysilane represented by the formula (3) can be applied to the above description of the polyoxyalkylene (A).

The polyoxyalkylene (B) may be a polyoxoxane obtained by further polycondensing an alkoxysilane containing an alkoxydecane represented by the formula (6) in addition to the alkoxydecane represented by the formula (5). .

R ¹⁶ Si(OR ¹⁷ ) ₃ (6)

The R ¹⁶ of the alkoxydecane represented by the formula (6) is an alkyl group having 1 to 5 carbon atoms. The number of carbon atoms of the alkyl group is preferably from 1 to 4, more preferably from 1 to 3.

The alkoxy decane represented by the formula (6) has an R ¹⁷ alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, particularly preferably 1 or 2 carbon atoms.

Although a specific example of the alkoxysilane represented by the formula (6) is given, it is not limited thereto. For example, methyl triethoxy decane, methyl trimethoxy decane, dimethyl trimethoxy decane, dimethyl triethoxy decane, n-propyl trimethoxy decane, n-propyl three Ethoxy decane.

In addition to the alkoxydecane represented by the formula (5), in particular, a liquid crystal alignment agent containing a polyoxyalkylene (B) obtained by further polycondensing an alkoxysilane having an alkoxydecane represented by the formula (6). It has a high vertical alignment force and is preferred.

In order to increase the response speed of the liquid crystal display element by applying a voltage while using a liquid crystal to which no polymerizable compound is added, a second alkoxysilane represented by the formula (3) having a specific organic group is used. The peroxane in the polyoxyalkylene is preferably 10 mol% or more. More preferably 20 mol% or more. More preferably, it is 30% or more. Further, in order to sufficiently cure the formed liquid crystal alignment film, it is preferably 75 mol% or less.

In the production of the polyoxyalkylene (B), in addition to the alkoxydecane represented by the formula (3), the formula (5), and the formula (6), the adhesion to the substrate, the affinity with the liquid crystal molecules, and the like are improved. For the purpose of preventing the effects of the present invention, one or a plurality of alkoxysilanes of the formula (4) described above may be used in the production of the above polyoxane (A), (R ¹³ ) _n Si(OR ¹⁴ ) _4-n . The description of the alkoxydecane represented by the formula (4) applies to the above description of the polyoxyalkylene (A).

The alkoxydecane represented by the formula (4) imparts various properties to the polyoxane, and therefore, one or a plurality of kinds can be selected depending on the desired properties.

When producing a liquid crystal alignment agent in which polysiloxane (A) and polyoxyalkylene (B) are mixed, (A) and (B) in terms of a mixing ratio of polyoxyalkylene (A) to polyoxyalkylene (B) The weight is preferably 10:90~50:50, especially 20:80~40:60.

<Method for producing polyoxyalkylene>

The method for obtaining the polyoxyalkylene used in the present invention is not particularly limited. In the polyoxyalkylene (A), an alkoxysilane having the above formula (1) and formula (3) as an essential component, or a polyoxyalkylene (B), The above formula (5) is an essential component, and is preferably obtained by condensing an alkoxydecane having an arbitrary component of the formula (3) and the formula (6) in an organic solvent. Usually, polyoxyalkylene is obtained by polycondensing such an alkoxysilane to obtain a solution uniformly dissolved in an organic solvent.

In the method of polycondensing polyoxymethane, for example, a method of hydrolyzing and condensing an alkoxysilane in a solvent such as an alcohol or a glycol may be mentioned. 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 0.5 times mole of water to the total alkoxy group in the alkoxysilane, but it is usually preferred to add more than 0.5 times mole of water.

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

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; ammonia or methyl group; a base such as an amine, ethylamine, ethanolamine or triethylamine; a metal salt such as hydrochloric acid, sulfuric acid or nitric acid. Further, in general, the solution in which the alkoxysilane is dissolved by heating can further promote the hydrolysis and condensation reaction. At this time, the heating temperature and the heating time can be appropriately selected as desired. For example, heating at 50 ° C, stirring for 24 hours, heating under reflux, stirring for 1 hour, or the like may be mentioned.

Further, as another method, for example, a method in which a mixture of alkoxysilane, a solvent, and oxalic acid is heated to be polycondensed. Specifically, a method in which oxalic acid is added to an alcohol to form an oxalic acid alcohol solution in advance, and the alkoxysilane is mixed in a state in which the solution is heated. At this time, the amount of oxalic acid used has an alkane The total alkoxy group of oxoxane is preferably 0.2 to 2 moles. 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 a plurality of alkoxysilanes are used in the case of obtaining a polyoxyalkylene oxide, the alkoxysilane may be previously mixed into a mixture, and a plurality of alkoxysilanes may be sequentially mixed.

The solvent (hereinafter referred to as a polymerization solvent) used in the polycondensation of the alkoxysilane is not particularly limited as long as it is a soluble alkoxysilane. Further, even when the alkoxysilane is not dissolved, it can be dissolved at the same time when the polycondensation reaction of the alkoxysilane is carried out. In general, since an alcohol is formed by a polycondensation reaction of an alkoxysilane, an alcohol, a glycol, a glycol ether, or an organic solvent having good compatibility with an alcohol can be used.

Specific examples of such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and hexanediol; 3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol , 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6- Glycols such as 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 dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether , glycol ethers such as propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, N-methyl-2- Pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethyl hydrazine, tetramethyl urea, hexamethylphosphonium, M-cresol and the like.

In the present invention, the above-mentioned polymerization solvent may be used in combination of plural kinds.

The polymerization solution of the polyoxyalkylene obtained by the above method (hereinafter referred to as a polymerization solution) is converted into a concentration of SiO ₂ in terms of a raw material in terms of a ruthenium atom of the all-alkoxysilane (hereinafter referred to as SiO _{2 ).} The converted concentration is preferably 20% by mass or less, and more preferably 5 to 15% by mass. In this concentration range, colloid formation can be suppressed by selecting an arbitrary concentration to obtain a homogeneous solution.

<Polyoxirane solution>

In the present invention, the polymerization solution obtained by the above method can be directly used as a solution of polysiloxane, or the solution obtained by the above method can be concentrated, or diluted with a solvent, or substituted with other solvent as a polymerization. A solution of oxoxane.

In this case, the solvent to be used (hereinafter referred to as an additive solvent) may be the same as the polymerization solvent, or may be another solvent. The solvent to be added is not particularly limited as long as the polyoxyalkylene can be uniformly dissolved, and one type or plural types can be arbitrarily selected and used.

Specific examples of the solvent to be added include acetone, methyl ethyl ketone, and methyl isobutyl, in addition to the solvent of the above-mentioned polymerization solvent. Ketones such as ketones; esters of methyl acetate, ethyl acetate, ethyl lactate, and the like.

These solvents can improve the viscosity adjustment of the liquid crystal alignment agent, or can improve the coating property when the liquid crystal alignment agent is coated on the substrate by spin coating, flexographic printing, and ink jetting.

<Other ingredients>

In the present invention, other components other than polyoxymethane may contain, for example, inorganic fine particles, metalloxane oligomers, metalloxane polymers, and the like without impairing the effects of the present invention. A leveling agent, or even a component such as a surfactant.

The inorganic fine particles are preferably fine particles such as cerium oxide fine particles, alumina fine particles, titanium oxide fine particles, or magnesium fluoride fine particles, and particularly preferably in a state of a colloidal solution. The colloidal solution may be a dispersion of inorganic fine particles to a dispersion medium, or may be a colloidal solution of a commercial product. In the present invention, by containing inorganic fine particles, the surface shape and other functions of the formed cured film can be imparted. In terms of inorganic fine particles, the average particle diameter is 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 cured film formed using the prepared coating liquid may have low transparency.

Examples of the dispersion medium of the inorganic fine particles include water or an organic solvent. In terms of the stability of the coating liquid for coating film formation, it is preferable to adjust the pH to a pH or a pKa of 1 to 10 from the viewpoint of the stability of the coating liquid. More preferably 2~7.

Examples of the organic solvent used in the dispersion medium of the colloidal solution include methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, and pentanediol. Alcohols such as hexanediol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatics such as toluene and xylene a hydrocarbon; an amide such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone; an ester of ethyl acetate, butyl acetate or γ-butyrolactone; An ether such as tetrahydrofuran or 1,4-dioxane. Among these, alcohols or ketones are preferred. These organic solvents may be used singly or in combination of two or more kinds as a dispersion medium.

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

A specific example of a commercially available metalloxane oligomer or a metalloxane polymer, methyl decanoate 51, methyl decanoate 53A, ethyl citrate 40, manufactured by COLCOAT Co., Ltd. A titanyl oxide oligomer such as a decane oxime oligomer such as Ethyl citrate 48, EMS-485 or SS-101, or a siloxane polymer or a n-butadiene titanate tetrapolymer manufactured by Kanto Chemical Co., Ltd. These may be used alone or in combination of two or more.

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

Further, the method of mixing the above other components in the polyoxyalkylene may be carried out simultaneously with the polyoxyalkylene or may not be particularly limited.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention contains a solution of the above polyoxyalkylene oxide and, if necessary, other components. In this case, as the solvent, a solvent selected from the group consisting of a polymerization solvent of the above polyoxyalkylene and an added solvent can be used. The content of the polyoxyalkylene in the liquid crystal alignment agent is preferably from 0.5 to 15% by mass, and more preferably from 1 to 6% by mass, in terms of SiO ₂ . In the range of such SiO ₂ conversion concentration, it is easy to obtain a desired film thickness by one application, and it is easy to obtain a sufficient solution life.

The method of preparing the liquid crystal alignment agent of the present invention is not particularly limited. The polyoxyalkylene used in the present invention may be in a state of being uniformly mixed as needed. Usually, the polyoxyalkylene can be polycondensed in a solvent, and thus the solution of the polyoxyalkylene can be used as it is, or it is convenient to add other components to the solution of the polyoxyalkylene as needed. The method of directly using a polymerization solution of polyoxyalkylene is most convenient.

Further, when the content of the polyoxyalkylene in the liquid crystal alignment agent is adjusted, a solvent selected from the group consisting of the polymerization solvent of the polyoxane and the added solvent can be used.

<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, after the liquid crystal alignment agent of the present invention is applied onto a substrate, it is dried and fired to obtain a cured film which can be directly used as a liquid crystal alignment film. Further, the cured film may be rubbed, irradiated with polarized light or light of a specific wavelength, or the like, or subjected to treatment with an ion beam or the like, or liquid crystal display after filling the liquid crystal. The element illuminates UV in a state where a voltage is applied.

In the case of coating a substrate of a liquid crystal alignment agent, the substrate having high transparency is not particularly limited, but a substrate for driving a transparent electrode for liquid crystal is preferably formed on the substrate.

Specific examples include glass plates, polycarbonates, poly(meth)acrylates, polyether oximes, polyaromatic esters, polyurethanes, polyfluorenes, polyethers, polyether ketones, and top three A substrate on which a transparent electrode is formed on a plastic plate such as pentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, cellulose triacetate, cellulose diacetate or cellulose acetate butyrate .

In the coating method of the liquid crystal alignment agent, a spin coating method, a printing method, an ink jet method, a spray method, a roll coating method, and the like are mentioned, but from the viewpoint of productivity, the transfer printing method is widely used in the industry. It is also suitable for use in the present invention.

Although the drying step after the application of the liquid crystal alignment agent is not necessary, the time from the application to the completion of the firing is not necessary for each substrate, or when the coating is not immediately applied, the drying step is included. good. In the drying, the solvent is removed to such an extent that the shape of the coating film is not deformed by the conveyance of the substrate, and the drying means is not particularly limited. For example, it can be dried at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C on a hot plate for 0.5 to 30 minutes, preferably 1 to 5 minutes.

The coating film formed by coating the liquid crystal alignment agent by the above method can be fired 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, but is preferably from 140 ° C to 300 ° C, more preferably from 150 ° C to 230 ° C, still more preferably from 160 ° C to 220 ° C. The firing time can be performed at any time from 5 minutes to 240 minutes. Preferably 10 to 90 minutes, more preferably 20~80 points. As the heating system, a generally known method such as a hot plate, a hot air circulating oven, an IR oven, a belt heating furnace or the like can be used.

The polydecane in the liquid crystal alignment film is subjected to a polycondensation step in the firing step. However, the present invention does not need to be completely condensed by condensation without damaging the effects of the present invention. However, it is preferred that the heat treatment is performed at a temperature higher than 10 ° C or higher than the heat treatment temperature of the sealant hardening required in the production process of the liquid crystal cell.

Although the thickness of the cured film can be selected as needed, it is preferably 5 nm or more, more preferably 10 nm or more, because it is easy to obtain the reliability of the liquid crystal display element. Moreover, when the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, it is preferable that the power consumption of the liquid crystal display element does not become extremely large.

<Liquid crystal display element>

The liquid crystal display device of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above-described method, and then forming a liquid crystal cell by a known method. As an example of the production of a liquid crystal cell, generally, a method in which a pair of substrates on which a liquid crystal alignment film is formed is sandwiched by a spacer, fixed with a sealant, and filled with a liquid crystal is used. At this time, the size of the spacer used is 1 to 30 μm, preferably 2 to 10 μm.

The method of injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which a liquid crystal cell to be produced is decompressed and then injected into a liquid crystal, a dropping method in which liquid crystal is dropped, and sealing is performed.

By using a liquid crystal cell into which a liquid crystal is introduced, between the electrodes of the substrate on both sides thereof When UV is applied while a voltage is applied, a crosslinkable group such as an acrylic group or a methacrylic group in the liquid crystal alignment film is polymerized and crosslinked at the present time, and the response speed of the liquid crystal display is made faster. Here, the applied voltage is 5 to 50 Vp-p, preferably 5 to 30 Vp-p. The amount of UV irradiation to be irradiated is 1 to 60 J, preferably 40 J or less, and when the amount of UV irradiation is small, it is possible to suppress a decrease in reliability due to breakage of a member constituting the liquid crystal display, and to reduce the UV irradiation time to manufacture The upper rhythm is better and better.

The substrate to be used for the liquid crystal display device is not particularly limited as long as it has high transparency. Usually, a substrate on which a transparent electrode for driving a liquid crystal is formed is formed on the substrate. It is the same as the substrate described in the specific example [liquid crystal alignment film]. Electrode patterns or protrusion patterns such as standard PVA or MVA can also be used. Similarly to the liquid crystal display of the PSA type, a line/slit electrode pattern of 1 to 10 μm is formed on a single side substrate, and even in a structure in which a slit pattern or a protrusion pattern is not formed on the opposite substrate, It is also possible to operate, and with the liquid crystal display thus constructed, the manufacturing process can be simplified, and high transmittance can be obtained.

Further, in a TFT-type element-like high functional element, a transistor in which a liquid crystal element is formed between an electrode for driving a liquid crystal and a substrate can be used.

As the transmissive liquid crystal element, a substrate as described above is generally used. However, in the case of a reflective liquid crystal display element, a material such as aluminum which reflects light can be used only on a single side substrate, and a germanium wafer can also be used. Etc. opaque substrate.

[Examples]

The invention is further specifically described below by way of examples of the invention, but the invention is not limited thereto.

<Synthesis Example 1 of Compound 8>

In a 500 ml four-necked flask equipped with a magnetic stirrer, 1.71 g of metallic magnesium was placed, and the inside of the vessel was replaced with nitrogen and sealed. After adding 2 ml of THF (dehydrated), a solution of 20.68 g of compound 7 was dissolved in 155 ml of THF (dehydrated) in a state of vigorous stirring, and it was dripped for 1 hour. Thereafter, the temperature was raised to 55 ° C, and the mixture was stirred for 2 hours to confirm the disappearance of metallic magnesium. Subsequently, under ice cooling (internal temperature 4 ° C), 30.53 g of tetramethoxy decane was added all at once, and the mixture was heated under reflux and stirred for 3 hours. After cooling the reaction liquid to room temperature, 210 ml of a saturated aqueous ammonium chloride solution was added, and the resulting insoluble matter was filtered off under reduced pressure. Further, the filtrate was washed with 260 ml of n-hexane. The aqueous phase portion of the filtrate was removed, and the organic phase was washed with 200 ml of pure water. The organic phase was concentrated to dryness to give a crude compound 21.65 g. This was distilled under reduced pressure, and the mixture was distilled off under the conditions of an external temperature of 220 to 230 ° C and a pressure of 0.8 torr to obtain 5.74 g of Compound 8 (yield 25%).

¹ H-NMR (400 MHz) in CDCl ₃ : 0.90 ppm (t, J = 7.2 Hz, 3H), 1.00-1.09 ppm (m, 2H), 1.20-1.34 ppm (m, 9H), 1.40-1.52 ppm (m) , 2H), 1.83-1.91ppm (m, 4H), 2.41-2.51ppm (m, 1H), 3.62ppm (s, 9H), 7.23ppm (d, J = 8.2 Hz, 2H), 7.56ppm (d, J=8.2 Hz, 2H)

<Synthesis Example 2 of Compound 10>

Into a 500 ml four-necked flask equipped with a magnetic stirrer, 30.00 g of Compound 9, potassium carbonate 25.24 g, and DMF 120 g were placed, and 22.10 g of bromoallyl was dropped at room temperature. Thereafter, the mixture was stirred at 50 ° C for 11 hours. The reaction solution was diluted with 500 g of ethyl acetate, and the organic phase was washed three times with 200 g of pure water. The organic phase was dried over sodium sulfate. After filtered, the filtrate was concentrated and dried to yield 34.80 g of Compound 10 (yield 100%).

¹ H-NMR (400 MHz) in CDCl ₃ : 0.90 ppm (t, J = 7.2 Hz, 3H), 0.991.09 ppm (m, 2H), 1.18-1.46 ppm (m, 11H), 1.84-1.89 ppm (m) , 4H), 2.37-2.44ppm (m, 1H), 4.51ppm (dt, J = 5.4 Hz, 1.6 Hz, 2H), 5.26ppm (dq, J = 10.6 Hz, 1.6 Hz, 1H), 5.40ppm (dq , J = 17.2 Hz, 1.6 Hz, 1H), 6.07 ppm (ddd, J = 17.2 Hz, 10.6 Hz, 5.4 Hz, 1H), 6.83 ppm (dd, J = 8.8 Hz, 2.9 Hz, 2H), 7.10 ppm ( Dd, J=8.8 Hz, 2.9 Hz, 2H)

<Synthesis Example 3 of Compound 11>

Into a 300 ml four-necked flask equipped with a magnetic stirrer, 20.00 g of Compound 10 and 120 g of toluene were placed, and the mixture was stirred at room temperature. Next, 700 μl of a karstedt catalyst (platinum (0)-1,1,3,3-tetramethyldioxane complex 0.1 mol/L xylene solution) was added, and then 12.4 ml of trimethoxydecane was added dropwise. After stirring at room temperature for 29 hours, the reaction solution was concentrated to dryness to give a crude compound. This was distilled under reduced pressure, and the mixture was distilled under an external temperature of 245 ° C / pressure of 0.8 torr to afford 12.15 g of Compound 11 (yield 43%).

¹ H-NMR (400 MHz) in CDCl ₃ : 0.76-0.82 ppm (m, 2H), 0.89 ppm (t, J = 7.2 Hz, 3H), 0.98-1.08 ppm (m, 2H), 1.18-1.45 ppm (m) , 11H), 1.84-1.93ppm (m, 6H), 2.36-2.43ppm (m, 1H), 3.58ppm (s, 9H), 3.91ppm (t, J = 6.8 Hz, 2H), 6.81ppm (d, J=8.8 Hz, 2H), 7.08ppm (d, J=8.8 Hz, 2H)

The compounds used in this example are abbreviated as follows.

TEOS: tetraethoxy decane

C18: octadecyltriethoxydecane

ACPS: 3-propenyloxypropyltrimethoxydecane

MPMS: 3-methacryloxypropyltrimethoxydecane

M8MS: 3-methylpropenyloxyoctyltrimethoxydecane

MTES: methyl triethoxy decane

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

BCS: 2-butoxyethanol

UPS: 3-ureidopropyltriethoxydecane

<Example 1>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 21.5 g of HG, 7.2 g of BCS, 32.9 g of TEOS, 4.1 g of the compound 8 obtained in Synthesis Example 1, and 5.0 g of MPMS were mixed to prepare an alkoxysilane monomer. Solution. In this solution, a solution prepared by preliminarily mixing 10.7 g of HG, 3.6 g of BCS, 10.8 g of water, and 0.4 g of oxalic acid as a catalyst was dropped at room temperature for 30 minutes, and then at room temperature. Stir for 30 minutes. Thereafter, the mixture was refluxed in an oil bath for 30 minutes, and then a mixed liquid of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added. After refluxing for further 30 minutes, it was left to cool to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

10.0 g of the obtained polyoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent [K1] having a concentration of SiO ₂ of 4% by weight.

<Example 2>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 20.8 g of HG, 6.9 g of BCS, 22.5 g of TEOS, 3.5 g of the compound 11 obtained in Synthesis Example 3, and 19.99 g of MPMS were mixed to prepare an alkoxydecane. A solution of the monomer. In this solution, a solution prepared by preliminarily mixing 10.4 g of HG, 3.5 g of BCS, 10.8 g of water, and 1.1 g of oxalic acid as a catalyst was dropped at room temperature for 30 minutes, and then at room temperature. Stir for 30 minutes. Thereafter, the mixture was refluxed for 30 minutes in an oil bath, and then a mixed liquid of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added in advance. After refluxing for further 30 minutes, it was left to cool to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

10.0 g of the obtained polyoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (S2) having a SiO ₂ conversion concentration of 4% by weight.

A solution of alkoxysilane monomer was prepared by mixing HG 23.8 g, BCS 7.9 g, TEOS 37.1 g, and MTES 3.6 g in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. Into this solution, a solution of 11.9 g of HG, 4.0 g of BCS, 10.8 g of water, and 0.4 g of oxalic acid as a catalyst was mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was refluxed for 30 minutes in an oil bath, and then a mixed liquid of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added in advance. After refluxing for further 30 minutes, it was left to cool to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

10.0 g of the obtained polyoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (U1) having a SiO ₂ conversion concentration of 4% by weight.

The obtained liquid crystal alignment agent intermediate (S2) and the liquid crystal alignment agent intermediate (U1) were mixed at a ratio of 2:8 to obtain a liquid crystal alignment agent [K2] having a SiO ₂ conversion concentration of 4% by weight.

<Example 3>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 20.5 g of HG, 6.9 g of BCS, 22.5 g of TEOS, 4.1 g of the compound 11 obtained in Synthesis Example 3, and 19.9 g of MPMS were mixed to prepare an alkoxysilane monomer. Solution. Into this solution, a solution of 10.3 g of HG, 3.4 g of BCS, 10.8 g of water, and 1.1 g of oxalic acid as a catalyst was mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was refluxed for 30 minutes in an oil bath, and then a mixed liquid of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added in advance. After refluxing for further 30 minutes, it was left to cool to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

10.0 g of the obtained polyoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (S3) having a SiO ₂ conversion concentration of 4% by weight.

The obtained liquid crystal alignment agent intermediate (S3) and the liquid crystal alignment agent intermediate (U1) obtained in Example 2 were mixed at a ratio of 2:8 to obtain a liquid crystal alignment agent [K3] having a SiO ₂ conversion concentration of 4% by weight. .

<Example 4>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 19.1 g of HG, 6.3 g of BCS, 16.3 g of TEOS, 8.2 g of the compound 11 obtained in Synthesis Example 3, and 24.8 g of MPMS were mixed to prepare an alkoxysilane monomer. Solution. Into this solution, a solution of 9.5 g of HG, 3.2 g of BCS, 10.8 g of water, and 1.3 g of oxalic acid as a catalyst was mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was refluxed in an oil bath for 30 minutes, and then a mixed liquid of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added in advance. After refluxing for further 30 minutes, it was left to cool to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

10.0 g of the obtained polyoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (S4) having a SiO ₂ conversion concentration of 4% by weight.

The obtained liquid crystal alignment agent intermediate (S4) and the liquid crystal alignment agent intermediate (U1) obtained in Example 2 were mixed at a ratio of 2:8 to obtain a liquid crystal alignment agent having a SiO ₂ conversion concentration of 4% by weight [K4]. .

<Example 5>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 17.9 g of HG, 6.0 g of BCS, 25.0 g of TEOS, 8.2 g of the compound 11 obtained in Synthesis Example 3, and 19.1 g of M8MS were mixed to prepare an alkoxysilane monomer. Solution. Into this solution, a solution of 9.0 g of HG, 3.0 g of BCS, 10.8 g of water, and 1.1 g of oxalic acid as a catalyst was mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated under an oil bath for 60 minutes, and then left to stand to obtain a polyoxysilane solution having a SiO ₂ conversion concentration of 12% by weight.

10.0 g of the obtained polyoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent [S5] having a concentration of SiO ₂ of 4% by weight.

A solution of alkoxysilane monomer was prepared by mixing HG 23.8 g, BCS 7.9 g, TEOS 37.1 g, and MTES 3.6 g in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. Into this solution, a solution of 11.9 g of HG, 4.0 g of BCS, 10.8 g of water, and 0.4 g of oxalic acid as a catalyst was mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was refluxed for 30 minutes in an oil bath, and then a mixed liquid of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added in advance. After refluxing for further 30 minutes, it was left to cool to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

10.0 g of the obtained polyoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (U2) having a SiO ₂ conversion concentration of 4% by weight.

The obtained liquid crystal alignment agent intermediate (S5) and the liquid crystal alignment agent intermediate (U2) were mixed at a ratio of 2:8 to obtain a liquid crystal alignment agent [K5] having a SiO ₂ conversion concentration of 4% by weight.

<Example 6>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 19.4 g of HG, 6.5 g of BCS, 22.5 g of TEOS, 8.2 g of the compound 11 obtained in Synthesis Example 3, 14.9 g of MPMS, and 3.2 g of M8MS were mixed to prepare an alkoxylate. A solution of a decane monomer. Into this solution, a solution of 9.7 g of HG, 3.2 g of BCS, 10.8 g of water, and 1.1 g of oxalic acid as a catalyst was mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was refluxed for 30 minutes in an oil bath, and then a mixed liquid of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added in advance. After refluxing for further 30 minutes, it was left to cool to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

10.0 g of the obtained polyoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (S6) having a concentration of SiO ₂ of 4% by weight.

The obtained liquid crystal alignment agent intermediate (S6) and the liquid crystal alignment agent intermediate (U2) obtained in Example 5 were mixed at a ratio of 2:8 to obtain a liquid crystal alignment agent having a SiO ₂ conversion concentration of 4% by weight [K6]. .

<Comparative Example 1>

A solution of alkoxysilane monomer was prepared by mixing HG 22.1 g, BCS 7.3 g, TEOS 35.0 g, 4.2 g of C18, and MPMS 5.0 g in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. Into this solution, a solution of 11.0 g of HG, 3.7 g of BCS, 10.8 g of water, and 0.4 g of oxalic acid as a catalyst was mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was refluxed for 30 minutes in an oil bath, and then a mixed liquid of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added in advance. After refluxing for further 30 minutes, it was left to cool to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

10.0 g of the obtained polyoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent [L1] having a SiO ₂ conversion concentration of 4% by weight.

<Comparative Example 2>

A solution of alkoxysilane monomer was prepared by mixing HG 22.6 g, BCS 7.5 g, TEOS 39.2 g, and 4.2 g of C18 in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. Into this solution, a solution of 11.3 g of HG, 3.7 g of BCS, 10.8 g of water, and 0.2 g of oxalic acid as a catalyst was mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was refluxed for 30 minutes in an oil bath, and then a mixed liquid of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added in advance. After refluxing for further 30 minutes, it was left to cool to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

10.0 g of the obtained polyoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (S5) having a concentration of SiO ₂ of 4% by weight.

The obtained liquid crystal alignment agent intermediate (S5) and the liquid crystal alignment agent intermediate (U1) obtained in Synthesis Example 2 were mixed at a ratio of 2:8 to obtain a liquid crystal alignment agent [L2] having a SiO ₂ conversion concentration of 4% by weight. .

<Comparative Example 3>

A solution of alkoxysilane monomer was prepared by mixing HG 20.5 g, BCS 6.8 g, TEOS 22.5 g, 4.2 g of C18, and MPMS 19.9 g in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube. Into this solution, a solution of 10.3 g of HG, 3.4 g of BCS, 10.8 g of water, and 1.1 g of oxalic acid as a catalyst was mixed in advance, and the mixture was dropped at room temperature for 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was refluxed for 30 minutes in an oil bath, and then a mixed liquid of 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added in advance. After refluxing for further 30 minutes, it was left to cool to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight.

10.0 g of the obtained polyoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (L3) having a SiO ₂ conversion concentration of 4% by weight.

<Cell Cell Example 1>

The liquid crystal alignment agent [K1] obtained in Example 1 was spin-coated on the formed The ITO surface of the ITO electrode substrate having a flat ITO electrode. After drying on a hot plate at 80 ° C for 2 minutes, the film was fired in a hot air circulating oven at 200 ° C or 220 ° C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. Two sheets of this substrate were prepared, and a bead spacer of 4 μm or 6 μm was spread on the liquid crystal alignment film surface of one of the substrates, and then a sealant was printed thereon. The other substrate is placed on the inner side of the liquid crystal alignment film surface, and after bonding, the sealing agent is cured to form an empty cell. Liquid crystal MLC-6608 (trade name, manufactured by Merck Co., Ltd.) was injected into an empty cell by a vacuum injection method to prepare a liquid crystal cell into which the liquid crystal was injected.

Thereafter, the obtained liquid crystal cell was placed in a circulating oven at 100 ° C for annealing for 30 minutes. The taken-out unit cell was subjected to microscopic observation in a state where the polarizing plate was in a crossed Nicols, and the state of the liquid crystal alignment disorder domain was observed. The results are shown in Table 43.

<Cell Cell Example 2>

The liquid crystal alignment agent [K2] obtained in Example 2 was spin-coated on an ITO surface of an ITO electrode substrate having an ITO electrode pattern of 5 μm in wire/pitch at a pixel size of 100 × 300 μm. After drying on a hot plate at 80 ° C for 2 minutes, the film was fired in a hot air circulating oven at 200 ° C or 220 ° C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. The liquid crystal alignment agent [K2] obtained in Synthesis Example 2 was spin-coated on the ITO surface on which the electrode pattern was not formed, and dried on a hot plate at 80 ° C for 2 minutes, and then at 200 ° C or 220 ° C in the same manner as the above substrate. The hot air circulating oven was fired for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. Prepare these two substrates, After a 4 μm bead spacer was spread on the liquid crystal alignment film surface of one of the substrates, the sealant was printed thereon. The other substrate is placed on the inner side of the liquid crystal alignment film surface, and after bonding, the sealing agent is cured to form an empty cell. Liquid crystal MLC-6608 (trade name, manufactured by Merck Co., Ltd.) was injected into an empty cell by a vacuum injection method to prepare a liquid crystal cell into which the liquid crystal was injected.

The response speed characteristics of these liquid crystal cells are represented by an oscilloscope reading a time change of the brightness of the liquid crystal panel when an AC voltage of ±5 V and a rectangular wave of a frequency of 1 kHz are applied to the liquid crystal cell. The time when the luminance is not applied is 0%, the voltage of ±5 V is applied, the value of the saturation luminance is 100%, and the time when the luminance changes by 10% to 90% is the initial response speed.

It is measured by the method described later.

Thereafter, UV20J was irradiated from the outside of the liquid crystal cell in a state where a DC voltage of 20 V was applied to the liquid crystal cell. Thereafter, the response speed characteristics were measured again, and the response speed before and after the UV irradiation was compared. The results are shown in Table 44.

Thereafter, the obtained liquid crystal cell was placed in a circulating oven at 100 ° C for annealing for 30 minutes. The taken-out unit cell was placed in a state of crossed Nicols, and the state of the liquid crystal alignment disorder region was observed by microscopic observation. The results are also shown together in Table 44.

<Cell Cell Example 3>

The liquid crystal alignment agent [K2] was changed to the liquid crystal alignment agent [K3] obtained in Example 3, and the others were carried out in the same manner as in the unit cell example 2. A liquid crystal cell was produced, the response speed was measured, and the alignment disorder region after the annealing treatment was observed. The results are shown in Table 44.

<Cell Cell Example 4>

The liquid crystal alignment agent [K2] was changed to the liquid crystal alignment agent [K4] obtained in Example 4, and the other methods were carried out in the same manner as in the cell example 2 to prepare a liquid crystal cell, the measurement response speed, and the observation annealing treatment. The alignment disorder area. The results are shown in Table 44.

<Cell Cell Example 5>

The liquid crystal alignment agent [K2] was changed to the liquid crystal alignment agent [K5] obtained in Example 5, and the other methods were carried out in the same manner as in the unit cell example 2 to prepare a liquid crystal cell, the measurement response speed, and the observation annealing treatment. The alignment disorder area. The results are shown in Table 44.

<Cell Cell Example 6>

The liquid crystal alignment agent [K2] was changed to the liquid crystal alignment agent [K6] obtained in Example 6, and the other methods were carried out in the same manner as in the unit cell example 2 to prepare a liquid crystal cell, the measurement response speed, and the observation annealing treatment. The alignment disorder area. The results are shown in Table 44.

<Unit cell comparison example 1>

The liquid crystal alignment agent [K1] was changed to the liquid crystal alignment agent [L1] obtained in Comparative Example 1, and the others were carried out in the same manner as in the cell embodiment 1. Make a liquid crystal cell. Thereafter, the obtained liquid crystal cell was placed in a circulating oven at 100 ° C for annealing for 30 minutes. The taken-out unit cell was placed in a state of crossed Nicols, and the state of the liquid crystal alignment disorder region was observed by microscopic observation. The results are shown in Table 43.

<Unit cell comparison example 2>

The liquid crystal alignment agent [K2] was changed to the liquid crystal alignment agent [L2] obtained in Comparative Example 2, and the other methods were carried out in the same manner as in Cellular Example 2 to prepare a liquid crystal cell, the measurement response rate, and the observation annealing treatment. The alignment disorder area. The results are shown in Table 44.

<Unit cell comparison example 3>

The liquid crystal alignment agent [K1] was changed to the liquid crystal alignment agent [L3] obtained in Comparative Example 3, and the other methods were carried out in the same manner as in the cell example 1, to prepare a liquid crystal cell, the measurement response speed, and the observation annealing treatment. The alignment disorder area. The results are shown in Table 44.

[response speed characteristics]

The time variation of the brightness of the liquid crystal panel when an AC voltage of ±5 V and a rectangular wave of a frequency of 1 kHz were applied to the liquid crystal cell was read by an oscilloscope. The time when the luminance is 0% when no voltage is applied, the voltage of ±5 V is applied, the saturation luminance value is 100%, and the luminance change is 10% to 90% is the initial response speed.

As is clear from Table 43, in the liquid crystal cell of the unit cell of Example 1, no annealing disorder region was observed after the annealing treatment. Further, in the liquid crystal cell of the cell comparison example 1, after the annealing treatment, a region in which most of the alignment disorder was observed was observed.

Determination of response speed ○: fast (good) ×: slow (poor)

Area observation after annealing

×: The majority (alignment disorder) area can be observed

○: Good

◎: Very good

As is clear from Table 44, in the cell example 2, the response speed after UV irradiation was fast, and the observation result of the region after the annealing treatment also showed good results. On the other hand, in the cell comparison example 2, although the area observation result after the annealing treatment was very good, the response speed was slow. In the cell comparison example 3, although the response speed was fast, most of the regions were observed after the annealing treatment. Further, in the unit cells 3 and 4 using the compound 11, the response speed after the UV irradiation was fast, and the observation result after the annealing treatment was very good.

Even in the cell examples 5 and 6, the response speed after the UV irradiation was fast, and the observation result after the annealing treatment was also very good.

[Industrial availability]

A liquid crystal display element produced by the liquid crystal alignment agent of the present invention can provide a liquid crystal display element in which the response speed after UV irradiation is improved even in the same manner as the PSA method using a liquid crystal which does not contain a polymerizable compound. Further, a liquid crystal alignment agent for a liquid crystal alignment film which can improve a response speed after UV irradiation without lowering the vertical alignment force, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal alignment film can be formed. Liquid crystal display element. Therefore, it can be used for a TFT liquid crystal display element, a TN liquid crystal display element, a VA liquid crystal display element, or the like manufactured by the above method.

In addition, the disclosure of the present specification is hereby incorporated by reference to Japanese Patent Application No. 2011-118824, filed on May 27, 2011, and Japanese Patent Application No. 2011-251377, filed on Nov. 17, 2011. The contents of the manual, the scope of application, the schema and the abstract are all made.

Claims (11)

A liquid crystal alignment agent comprising a polyoxyalkylene obtained by polycondensing an alkoxysilane represented by the following formula (1) and an alkoxysilane having an alkoxydecane represented by the following formula (3). A), R ¹ Si(OR ² ) ₃ (1) (R ¹ represents a structure of the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms) (Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ² single bond, containing double a linear or branched hydrocarbon group having a carbon number of 3 to 8 or -(CR ¹⁷ R ¹⁸ ) _b - (b is an integer of 1 to 15, and R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a carbon number 1 to 3 alkyl groups; Y ³ single bonds, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 having a lipid alcohol skeleton, and any hydrogen on the cyclic group The atomic system may be selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, and a fluorine atom. Substituted by a group; Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring, and a heterocyclic ring, and any hydrogen atom system on the cyclic group may have a carbon number of 1 to 3 An alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom; n is an integer of 0 to 4; Y ⁶ series of alkyl groups having 1 to 18 carbon atoms, fluorine-containing alkyl groups having 1 to 18 carbon atoms, and alkyl groups having 1 to 18 carbon atoms An oxy group or a fluorine-containing alkoxy group having 1 to 18 carbon atoms) R ³ Si(OR ⁴ ) ₃ (3) (R ³ is an acryl group, an acryloxy group, a methacryl group, a methacryloxy group Or a styrene group substituted with an alkyl group having 1 to 30 carbon atoms; and R ⁴ is an alkyl group having 1 to 5 carbon atoms. The liquid crystal alignment agent according to claim 1, wherein, in the above formula (3), R ³ is substituted by an acrylic group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group. An alkyl group having 3 to 10 carbon atoms. The liquid crystal alignment agent according to claim 1, which further comprises a polyoxyalkylene (B) obtained by polycondensing an alkoxysilane having 50% to 100% of an alkoxysilane represented by the following formula (5). , Si(OR ¹⁵ ) ₄ (5) (R ¹⁵ is an alkyl group having 1 to 5 carbon atoms). The liquid crystal alignment agent according to claim 3, wherein the polyoxyalkylene (B) is a polyoxyalkylene obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (3). The liquid crystal alignment agent according to claim 3 or 4, wherein the polyoxyalkylene (B) is a polyfluorene obtained by polycondensing an alkoxysilane having an alkoxysilane represented by the following formula (6). Alkane, R ¹⁶ Si(OR ¹⁷ ) ₃ (6) (R ¹⁶ is an alkyl group having 1 to 5 carbon atoms; and R ¹⁷ is an alkyl group having 1 to 5 carbon atoms). The liquid crystal alignment agent according to claim 1 or 3, wherein at least one of polyoxyalkylene (A) and polyoxyalkylene (B) further contains an alkoxydecane represented by the following formula (4) a polyoxane obtained by polycondensation of alkoxy oxane, (R ¹³ ) _n Si(OR ¹⁴ ) _4-n (4) (in the formula (4), R ¹³ is a hydrogen atom, or may be a hetero atom or a halogen atom , an amine group, a glycidoxy group, a thiol group, an isocyanate group, a sulfonyl group substituted with a hydrocarbon group having 1 to 10 carbon atoms; an R ¹⁴ alkyl group having 1 to 5 carbon atoms; and an integer of 0 to 3; ). The liquid crystal alignment agent according to claim 1, wherein the alkoxysilane represented by the above formula (1) contains 2 to 20 mol% of the peralkyl alkane used in the polyoxyalkylene (A), and The alkoxynonane represented by the above formula (3) contains 5 to 80 mol% of the peralkyl alkane used in the polyoxyalkylene (A). A liquid crystal alignment film obtained by applying the liquid crystal alignment agent according to any one of claims 1 to 7 to a substrate, and drying and baking the liquid crystal alignment agent. A liquid crystal display element comprising the liquid crystal alignment film described in claim 8. A liquid crystal display device which is coated with a liquid crystal alignment agent according to any one of claims 1 to 7 and which is obtained by applying a voltage to a liquid crystal cell in which liquid crystal is adhered to two substrates which are fired. UV is the one. A liquid crystal display device according to any one of claims 1 to 7, wherein the liquid crystal alignment agent is applied to the two substrates that have been fired, and UV is applied while a voltage is applied.