KR20150038300A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element and method for manufacturing liquid crystal display element - Google Patents

Abstract

(R¹ 은 하기 식 (2) 의 구조를 나타내고, R² 는 탄소수 1 ∼ 5 의 알킬기를 나타낸다.)

A liquid crystal aligning agent containing a polysiloxane (A) obtained by reacting an alkoxysilane represented by the formula (1) and an alkoxysilane containing an alkoxysilane represented by the formula (3).

(R ¹ represents a structure represented by the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal display device, and a manufacturing method of a liquid crystal display device. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment film,

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

Among the display methods of liquid crystal display elements, the vertical (VA) type liquid crystal display elements have been widely used in large-sized liquid crystal televisions and high-precision mobile applications (display portions of digital cameras and cellular phones). The VA system includes a MVA system (Multi Vertical Alignment) in which a projection for controlling the direction in which the liquid crystal falls is formed on a TFT substrate or a color filter substrate, a slit is formed in the ITO electrode of the substrate, A PVA (Patterned Vertical Alignment) method is known. As another alignment method, there is a PSA (Polymer Sustained Alignment) method. Among the VA methods, the PSA method is a technology that has recently attracted attention. In this method, a photopolymerizable compound is added to a liquid crystal, and after the liquid crystal panel is manufactured, an electric field is applied to irradiate the liquid crystal panel with UV (ultraviolet rays) in a state in which the liquid crystal falls. As a result, the alignment direction of the liquid crystal is fixed by photopolymerization of the polymerizable compound, and the response speed is improved by forming the pretilt. A slit is formed on one of the electrodes on the side of the liquid crystal panel and a slit such as MVA is not formed on the electrode pattern on the opposite side and a slit such as PVA is not formed so that simplification of manufacturing and excellent panel transmittance can be obtained (See Patent Document 1).

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

Thus, a liquid crystal aligning agent using a polymer in which a photoreactive side chain is introduced into polymer molecules is applied to a substrate, and a liquid crystal layer in contact with a liquid crystal alignment film obtained by firing is formed, and ultraviolet rays A liquid crystal display device having a high response speed can be obtained without adding a polymerizable compound to a liquid crystal by manufacturing a liquid crystal display device.

Japanese Laid-Open Patent Publication No. 2004-302061 Japanese Laid-Open Patent Publication No. 2011-95967

In the VA mode in which the vertical alignment is performed, a strong vertical alignment force for vertical alignment is required. However, in this method using no polymerizable compound, the response speed after UV irradiation is slowed down when the vertical alignment power is improved. When the response speed is improved, the vertical orientation force is lowered. That is, there is a trade-off relationship between the vertical orientation power and the response speed improvement after UV irradiation.

It is an object of the present invention to provide a liquid crystal display device in which a liquid crystal having no polymerizable compound is used to perform the same treatment as the PSA method to improve the response speed after UV irradiation, A liquid crystal alignment film capable of forming a liquid crystal alignment film capable of improving the response speed after UV irradiation, a liquid crystal alignment film obtained from the liquid crystal alignment agent, a liquid crystal display device having the liquid crystal alignment film, and a method of manufacturing the liquid crystal display device.

The present invention provides the following.

[1] A liquid crystal aligning agent containing the following polysiloxane (A).

Polysiloxane (A): A polysiloxane obtained by reacting an alkoxysilane represented by the following formula (1) and an alkoxysilane-containing alkoxysilane represented by the following formula (3)

(R ¹ represents a structure represented by the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)

[Chemical Formula 1]

(In the formula (2), Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Y ² is a linear or branched hydrocarbon group having 3 to 8 carbon atoms containing a single bond or a double bond or - (CR ¹⁷ R ¹⁸ ) _b - (b is an integer of 1 to 15, and R ¹⁷ , .. R ¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms a) Y ³ represents a single _{bond, - (CH 2) c -} (c is an integer of 1 ~ 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a single bond, a benzene ring, a cyclohexyl ring, and a heterocyclic ring, or a divalent cyclic group having a carbon number of 12 to 25 , And any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms Substituted by fluorine atom Or may. Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring, and heterocyclic, any of the hydrogen atoms on these cyclic group, the alkyl group having a carbon number of 1 to 3, 1 to 3 carbon atoms alkoxy group, may be substituted 1 to 3 carbon atoms a fluorine-containing alkyl group, fluorine-containing alkoxy group or a fluorine atom of 1 to 3 carbon atoms in the. n1 is an integer of 0 ~ 4. Y ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms , A fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluoro-containing alkoxyl group having 1 to 18 carbon atoms.

(2)

(R ²¹ , R ²² and R ²³ each independently represent -OCH ₃ , -OC ₂ H ₅ , -OCH (CH ₃ ) ₂ , -OC (CH ₃ ) ₃ , -CH ₃ , -Ph, , -OCOCH ₃ , -OH, -H, or a combination thereof, R ²⁴ represents a hydrogen atom or a methyl group, Y ²¹ represents a single bond or a single bond which may contain a double bond, 1-8 represents a group of linear or branched hydrocarbons, Y ²² is a single bond, -O-, -CO-, -COO-, -OCO- , -NH-, -N (CH 3) -., -NPh _{-, -NHCO-, -N (CH 3} ) CO-, -NPhCO-, -NHSO 2 -, -N (CH 3) SO 2 -, -NPhSO 2 -, -S-, -SO 2 -, -NHCONH _{-., -N (CH 3)} CONH-, -NPhCONH-, -NHCOO-, and represents a bonding group selected from -OCONH- Y ²³ represents a single bond, or a linear or branched group having 1 to 8 carbon atoms Y ²⁴ represents a single bond or a linear or branched hydrocarbon group having 1 to 8 carbon atoms, Y ²⁵ represents a single bond, -O- or -NZ ₂ -, Z ₂ Is a number An aromatic cyclic group or an aliphatic cyclic group having 1 to 18 carbon atoms, Cy is a divalent cyclic group selected from the following and bonded at an arbitrary substitution position, May be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a cyano group, a fluorine atom, and a chlorine atom.

(3)

(Z ₁ represents an aromatic ring group or a linear or branched divalent hydrocarbon group of 1 to 18 carbon atoms which may contain an aliphatic ring group.)

[2] The liquid crystal aligning agent according to [1], wherein the alkoxysilane component further contains an alkoxysilane represented by the following formula (4).

(R ³ is an alkyl group having 1 to 30 carbon atoms in which a hydrogen atom is substituted with an acrylic group, an acryloxy group, a methacrylic group, a methacryloxy group or a styryl group, and R ⁴ is an alkyl group having 1 to 5 carbon atoms.)

[3] The liquid crystal aligning agent according to [1] or [2], further comprising the following polysiloxane (B).

Polysiloxane (B): A polysiloxane obtained by reacting an alkoxysilane-containing alkoxysilane component represented by the following formula (5)

(R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms)

[4] The positive resist composition according to any one of [1] to [3], wherein the polysiloxane is obtained by reacting at least one of the polysiloxane (A) and the polysiloxane (B) with an alkoxysilane-containing alkoxysilane component represented by the following formula (6) The liquid crystal aligning agent according to item 1.

(In the formula (6), R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, , R ¹⁴ is an alkyl group having 1 to 5 carbon atoms, and n 2 is an integer of 0 to 3.

[5] A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of [1] to [4] to a substrate and firing the liquid crystal aligning agent.

[6] A liquid crystal display element having the liquid crystal alignment film according to [5].

[7] A liquid crystal aligning agent as described in any one of [1] to [4], wherein the liquid crystal aligning agent is applied to a liquid crystal cell sandwiched between two fired substrates, And a liquid crystal layer.

[8] A liquid crystal cell is fabricated by applying the liquid crystal aligning agent according to any one of [1] to [4] and sandwiching liquid crystal between two fired substrates, and in a state where a voltage is applied to the liquid crystal cell A method for manufacturing a liquid crystal display element having a step of irradiating UV light.

According to the present invention, it is possible to provide a liquid crystal aligning agent capable of improving the response speed after UV irradiation without lowering the vertical alignment power by irradiating UV light similarly to the PSA method using a liquid crystal to which no polymerizable compound is added, A liquid crystal alignment film obtained from a liquid crystal aligning agent, a liquid crystal display device having the liquid crystal alignment film, and a process for producing a liquid crystal display device.

Hereinafter, the present invention will be described in detail.

≪ Polysiloxane (A) >

The present invention relates to a liquid crystal aligning agent containing a polysiloxane (A). The polysiloxane (A) is a polysiloxane obtained by reacting an alkoxysilane represented by the above formula (1) with an alkoxysilane component containing an alkoxysilane represented by the above formula (3).

In formula (2), Y ¹ is any of a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- . Among them, it is preferable to select any one of _a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- From the viewpoint of facilitating the operation. It is more preferable to select any one of _a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

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

In formula (2), Y ³ is any one of a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- . Among them, the selection of any one of a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- From the viewpoint of facilitating the synthesis of the chain structure. It is more preferable to select any one of a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO- or -OCO- .

In formula (2), Y ⁴ is a cyclic group selected from the group consisting of a monovalent bond, a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be 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 alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Y ⁴ may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms and having a steroid skeleton. Among them, an organic group having 12 to 25 carbon atoms and having either a benzene ring, a cyclohexane ring or a steroid skeleton is preferable.

In formula (2), Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, An alkoxy group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluoro-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom.

In the formula (2), n1 is an integer of 0 to 4. Preferably, it is an integer of 0 to 2.

In the formula (2), Y ⁶ is any one of an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms. Among them, it is preferably any one of an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

R ² of the alkoxysilane represented by the formula (1) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, R ² is a methyl group or an ethyl group.

Specific examples of the alkoxysilane represented by the formula (1) below are represented by the formulas [1-1] to [1-31], but are not limited thereto. Also, R ² in the formula [1-1] - [1-31] is the same as R ² in the formula (1).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

(Formula [1-19] - formula [1-21] of, R ⁵ is _{-O-, -OCH 2 -, -CH 2} O-, -COOCH 2 - or denotes a -CH ₂ OCO-, R ⁶ is An alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

[Chemical formula 10]

(Formula [1-22] - formula [1-24] of, 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 -, and R ⁸ is an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

(11)

(Formula [1-25] and formula [1-26] of, R ⁹ is _{-COO-, -OCO-, -COOCH 2 -,} -CH 2 OCO-, -CH 2 O-, -OCH 2 -, - CH ₂ - or -O-, and R ¹⁰ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.

[Chemical Formula 12]

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

[Chemical Formula 13]

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

[Chemical Formula 14]

(In the formula [1-31], B ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, B ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group, B ₂ is an oxygen (bonds to a single, combined hand B ₃ provided with an "*".) atom or -COO- * a, B ₁ is a bond hand provided with an oxygen atom or -COO- * (However, the "*" (CH ₂ ) < / RTI > a ₂ ). 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 formula (1) is preferably selected from the group consisting of a solubility in a solvent for a siloxane polymer (polysiloxane), an alignment property of a liquid crystal in the case of a liquid crystal alignment film, a pretilt angle characteristic, a voltage holding ratio, Accordingly, one type or two or more types may be mixed and used. It is also possible to use in combination with an alkoxysilane containing 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 such as that described in, for example, JP-A-61-286393.

The alkoxysilane represented by the formula (1) is preferably at least 1 mol% in the total alkoxysilane or alkoxysilane component used for obtaining the polysiloxane (A) in order to obtain good liquid crystal alignment properties. More preferably, it is 1.5 mol% or more. More preferably, it is 2 mol% or more. Further, in order to obtain sufficient curing characteristics of the liquid crystal alignment film to be formed, it is preferably 30 mol% or less. And more preferably 25 mol% or less.

Equation (3) of an alkoxysilane R ^21, represented by R ^22, R ²³ are, each _{independently, -OCH 3, -OC 2 H 5} , -OCH (CH 3) 2, -OC (CH 3) 3, - CH ₃ , -Ph (i.e. -C ₆ H ₅ ), -Cl, -OCOCH ₃ , -OH, -H, or a combination thereof. Preferably, R ²¹ , R ²² and R ²³ are -OCH ₃ or -OC ₂ H ₅ .

R ²⁴ in the alkoxysilane represented by the formula (3) represents a hydrogen atom or a methyl group.

Y ²¹ of the alkoxysilane represented by the formula (3) is a linear or branched hydrocarbon group having 1 to 8 carbon atoms which may contain a single bond or a double bond. Preferably, Y ²¹ is a single bond or a linear hydrocarbon group having 3 to 5 carbon atoms.

Y ²² of the alkoxysilane represented by formula (3) is a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N (CH ₃ ) -, -NPh-, -NHCO- _{, -N (CH 3) CO-,} -NPhCO-, -NHSO 2 -, -N (CH 3) SO 2 -, -NPhSO 2 -, -S-, -SO 2 -, -NHCONH-, -N ( CH ₃ ) CONH-, -NPhCONH-, -NHCOO-, and -OCONH-. Preferably, Y < ²² > is a single bond.

Y ²³ is a single bond or a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and preferably Y ²³ is a single bond.

Y ²⁴ is a single bond or a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and preferably Y ²⁴ is a single bond or a linear hydrocarbon group having 1 to 3 carbon atoms.

Y ²⁵ is a single bond, -O-, or -NZ ₂ -. And Z ₂ represents a hydrogen atom, a linear or branched hydrocarbon group having 1 to 18 carbon atoms, an aromatic ring group or an aliphatic ring group. Preferably, Y ²⁵ is a single bond, -O-, or -NH-.

Cy represents a divalent cyclic group selected from the following at a random substitution position and arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a cyano group, A fluorine atom, and a chlorine atom. Preferably, Cy is a benzene ring or a biphenyl ring. Further, the "bivalent cyclic group formed by a bond at an arbitrary substitution position" means that the positions of two bonding hands of the following cyclic groups may be arbitrary.

[Chemical Formula 15]

(Z ₁ represents an aromatic ring group or a linear or branched divalent hydrocarbon group of 1 to 18 carbon atoms which may contain an aliphatic ring group.)

The alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3) may be respectively one type or two or more types.

A liquid crystal aligning agent obtained by reacting the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3), and using the polysiloxane (A) having a specific side chain and a photoreactive group introduced therein, (Tilt) from the alkoxysilane represented by the formula (1) and exhibits a high degree of homogeneity in the liquid crystal skeleton and the like, (A) having a cyclic group and a side chain having a (meth) acryloyl group derived from a side chain having a similar structure and an alkoxysilane represented by the formula (3) It is presumed that both the response speed and the vertical orientation in the film are compatible with each other.

In addition, since the polysiloxane contained in the liquid crystal aligning agent of the present invention is inexpensive as compared with an expensive polyimide system, the liquid crystal aligning agent of the present invention can be produced at a low cost and has high versatility.

The proportion of each alkoxysilane is not particularly limited, but the alkoxysilane represented by the formula (1) is preferably an alkoxysilane of 2 to 20 Mol%, particularly preferably 3 to 15 mol%. The alkoxysilane represented by the formula (3) is preferably 5 to 30 mol% of the alkoxysilane components used for obtaining the polysiloxane (A).

In addition to the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3), the alkoxysilane represented by the formula (4) may also be used as the raw material for producing the polysiloxane (A). That is, as the alkoxysilane component used for obtaining the polysiloxane (A), the alkoxysilane represented by the formula (4) may also be used.

R ³ in the alkoxysilane represented by the formula (4) is an alkyl group in which a hydrogen atom is substituted with an acrylic group, an acryloxy group, a methacrylic group, a methacryloxy group or a styryl group. The number of hydrogen atoms to be substituted is one or more, preferably one. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. More preferably from 1 to 10.

R ⁴ of the alkoxysilane represented by formula (4) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

Specific examples of the alkoxysilane represented by the formula (4) include, but are not limited to, the following. For example, there may be mentioned 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-acryloxypropyl tri Acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltriethoxysilane, 3- (N (meth) acryloxypropyltriethoxysilane, -Styrylmethyl-2-aminoethylamino) propyltrimethoxysilane.

The alkoxysilane represented by the formula (4) is preferably 5 to 80 mol%, and particularly preferably 10 to 70 mol%, of the alkoxysilane components used for obtaining the polysiloxane (A). The alkoxysilane represented by the formula (4) may be one kind or two or more kinds.

In addition to the alkoxysilane represented by the formula (1) and the alkoxysilane represented by the formula (3), the polysiloxane (A) can be produced by the method of the present invention for the purpose of improving the adhesion with the substrate, The alkoxysilane represented by the above formula (6) can also be used as a raw material. That is, as the alkoxysilane component used for obtaining the polysiloxane (A), an alkoxysilane represented by the above formula (6) may also be used. The alkoxysilane represented by the formula (6) can impart various properties to the polysiloxane, so that one or more kinds of alkoxysilanes can be selected depending on the required characteristics. The alkoxysilane represented by the formula (6) is preferably 1 to 20 mol% of the alkoxy component used for obtaining the polysiloxane.

R ¹³ in the alkoxysilane represented by the formula (6) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, , And is preferably an amino group, a glycide group or a ureide group. R ¹⁴ is an alkyl group of 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and n 2 represents an integer of 0 to 3, preferably 0 to 2.

Specific examples of the alkoxysilane represented by the formula (6) are shown below, but the invention is not limited thereto. (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2- aminoethylaminomethyltrimethoxysilane, 2- Aminoethylthioethyl) triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, trifluoropropyltrimethoxy Silane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, di 3-aminopropyldimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, gamma -oleadpropyltriethoxysilane, gamma -methylpropyltriethoxysilane, gamma -butyldimethoxysilane, gamma- - Ureid profile tree Methoxysilane and? -Ureidopropyltripropoxysilane, and the like.

In the alkoxysilane represented by the formula (6), the alkoxysilane wherein n2 is 0 is tetraalkoxysilane. Tetraalkoxysilane is preferable for obtaining the polysiloxane (A) contained in the liquid crystal aligning agent of the present invention since it is likely to undergo a polycondensation reaction with the alkoxysilane represented by the formula (1), (3) or (4).

As the alkoxysilane in which n2 is 0 in the formula (6), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxy Silane is preferred.

The alkoxysilane represented by the formula (6) in which n2 is 1 to 3 is preferably 1 to 20 mol%, and particularly preferably 1 to 10 mol%, of the alkoxysilane components used for obtaining the polysiloxane (A). The alkoxysilane represented by the formula (6) in which n2 is 0 is preferably 1 to 50 mol%, and particularly preferably 5 to 40 mol%, of the alkoxysilane components used for obtaining the polysiloxane (A). The alkoxysilane represented by the formula (6) may be one kind or two or more kinds.

≪ Other polysiloxane >

The liquid crystal aligning agent of the present invention may contain other polysiloxane together with the polysiloxane (A). Other examples of the polysiloxane include a polysiloxane (B) which is a polysiloxane obtained by reacting an alkoxysilane-containing alkoxysilane component represented by the formula (5). The polysiloxane component as the raw material of the polysiloxane (B) preferably contains 20 to 100 mol%, more preferably 50 to 100%, of the polysiloxane represented by the formula (5).

As the alkoxysilane represented by the formula (5), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.

The polysiloxane (B) may also be a polysiloxane obtained by reacting an alkoxysilane component containing an alkoxysilane represented by the formula (7) in addition to the alkoxysilane represented by the formula (5). The liquid crystal aligning agent containing the polysiloxane (B) obtained by reacting the alkoxysilane-containing alkoxysilane component represented by the formula (7) is particularly preferable because of its high vertical orientation power.

R¹⁶Si (OR¹⁷)₃ (7)

R ¹⁶ in the alkoxysilane represented by the formula (7) is an alkyl group having 1 to 5 carbon atoms. The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.

R ¹⁷ in the alkoxysilane represented by the formula (7) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

Specific examples of the alkoxysilane represented by the formula (7) include, but are not limited to, the following. For example, methyltriethoxysilane, methyltrimethoxysilane, dimethyltrimethoxysilane, dimethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane.

The polysiloxane (B) may also be a polysiloxane obtained by reacting an alkoxysilane component containing an alkoxysilane represented by the above formula (4) in addition to the alkoxysilane represented by the formula (5).

In order to further improve the response speed of the liquid crystal display element by irradiating UV (ultraviolet rays) while applying a voltage using a liquid crystal to which no polymerizable compound is added, the alkoxysilane represented by the formula (4) Is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more, of the alkoxysilane component used to obtain the alkoxysilane. Further, in order to sufficiently cure the liquid crystal alignment film to be formed, it is preferably 75 mol% or less.

The polysiloxane (B) is preferably a polysiloxane having an alkoxy group represented by the formula (6) as long as it does not impair the effect of the present invention, for the purpose of imparting various properties such as adhesion with a substrate and improvement in affinity with a liquid crystal molecule. Or a polysiloxane obtained by reacting an alkoxysilane component containing silane.

The alkoxysilane represented by the formula (6) is preferably from 1 to 20 mol%, and particularly preferably from 1 to 10 mol%, of the alkoxysilane components used for obtaining the polysiloxane (B).

The alkoxysilane represented by the formula (5), the alkoxysilane represented by the formula (6), the alkoxysilane represented by the formula (7), and the alkoxysilane represented by the formula (4), which are the raw materials of the polysiloxane (B) Two or more types may be used.

The compounding ratio of the polysiloxane (A) and the polysiloxane of the liquid crystal aligning agent containing other polysiloxane such as polysiloxane (B) is not particularly limited, but the amount of the polysiloxane (A) is preferably 10 mass% % Or more. For example, the polysiloxane (A): polysiloxane (B) = 10: 90 to 50: 50 is preferable as the mass ratio.

≪ Process for producing polysiloxane >

The method for obtaining the polysiloxane used in the present invention is not particularly limited, and the alkoxysilane component may be reacted. For example, in the polysiloxane (A), the alkoxysilane represented by the above formula (1) and the alkoxysilane component containing the alkoxysilane represented by the formula (3) as an essential component are reacted in an organic solvent (for example, Reaction). Usually, the polysiloxane is obtained as a solution in which such an alkoxysilane component is polycondensed and uniformly dissolved in an organic solvent.

As a method for polycondensation of an alkoxysilane to obtain a polysiloxane, 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, 0.5-fold molar water of the total alkoxy group in the alkoxysilane may be added in theory, but it is usually preferable to add an excess amount of water in excess of 0.5-molar mol.

In the present invention, the amount of water used in the reaction can be appropriately selected in accordance with the desired amount, but is usually 0.5 to 2.5 times the total alkoxy group in the alkoxysilane.

For the purpose of accelerating the hydrolysis and condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid, ammonia, methylamine, ethylamine, ethanolamine, triethylamine And alkali metal salts such as hydrochloric acid, sulfuric acid and nitric acid. In addition, it is also common to further accelerate the hydrolysis / condensation reaction by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected according to the desired one. For example, heating and stirring at 50 ° C for 24 hours, or heating and stirring for 1 hour under reflux.

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

In the present invention, a plurality of alkoxysilanes are used in obtaining the polysiloxane, but they may be mixed as a premixed mixture of alkoxysilanes, or a plurality of alkoxysilanes may be sequentially mixed. That is, the order of reacting the alkoxysilane component is not limited. For example, the alkoxysilane component may be reacted at one time, or a part of the alkoxysilane may be reacted, followed by the addition of another alkoxysilane. Specifically, for example, the alkoxysilane represented by the formula (1), the alkoxysilane represented by the formula (3) and the alkoxysilane represented by the formula (4) may be mixed to effect a polycondensation reaction, and the alkoxysilane represented by the formula Silane and the alkoxysilane represented by the formula (4) may be subjected to a polycondensation reaction, followed by the addition of the alkoxysilane represented by the formula (3).

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

Specific examples of such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol and diacetone alcohol, alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, Butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, Glycols such as diol, 2,4-pentanediol, 2,3-pentanediol, and 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, di Propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, and the like; glycol ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether; Dimethylacetamide,? -Butyrolactone, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, and m-cresol.

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

(Hereinafter also referred to as polymer solution) polymerization solution of the polysiloxane obtained by the above method, (hereinafter referred to as, SiO ₂ in terms of concentration) the silicon atom of the whole alkoxysilane injection as a raw material, the concentration in terms of SiO ₂ a More preferably 20 mass% or less, further preferably 5 to 15 mass%. By selecting an arbitrary concentration in this concentration range, generation of gel can be suppressed and a homogeneous solution can be obtained.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is a solution containing the above-mentioned polysiloxane (A) and, if necessary, other polysiloxane and other components. Other polysiloxane such as polysiloxane (A) and polysiloxane (B) added as needed, and other components may be uniformly mixed. For example, the reaction solution such as the polymerization solution of the polysiloxane obtained by the above method may be used as it is as a liquid crystal aligning agent, and if necessary, the reaction solution such as the polymerization solution of the polysiloxane obtained by the above- It may be diluted or replaced with another solvent to form a liquid crystal aligning agent. At this time, as the solvent, a solvent selected from the group consisting of a polymerization solvent of the above-mentioned polysiloxane and an addition solvent is used. The addition solvent is not particularly limited as long as the polysiloxane is dissolved uniformly, and one or more kinds of solvents may be arbitrarily selected and used. Specific examples of such an addition solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and esters such as methyl acetate, ethyl acetate and ethyl lactate. These solvents can improve the applicability when the liquid crystal aligning agent is applied onto the substrate by adjusting the viscosity of the liquid crystal aligning agent, or by spin coating, flexographic printing, inkjet or the like.

The content of the polysiloxane in the liquid crystal aligning agent is preferably 0.5 to 15% by mass, more preferably 1 to 6% by mass in terms of SiO ₂ . With such a SiO ₂ -converted concentration range, it is easy to obtain a desired film thickness by one application, and it is easy to obtain a sufficient pot life of the solution.

When adjusting the content of the polysiloxane in the liquid crystal aligning agent, a solvent selected from the group consisting of a polymerization solvent of the above-mentioned polysiloxane and an additive solvent may be used.

In the liquid crystal aligning agent of the present invention, other components other than polysiloxane such as an inorganic microfine particle, a metalic acid oligomer, a metalic acid polymer, a leveling agent, a surfactant Or the like may be contained.

As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, or magnesium fluoride fine particles are preferable, and it is particularly preferable to be a colloid solution. The colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a colloidal solution of a commercial product. In the present invention, by containing the inorganic fine particles, the surface shape and other functions of the formed cured coating can be imparted. The average particle diameter of the inorganic fine particles is preferably 0.001 to 0.2 탆, more preferably 0.001 to 0.1 탆. When the average particle size of the inorganic fine particles exceeds 0.2 탆, the transparency of the cured coating formed using the coating liquid to be prepared may be lowered.

Examples of the dispersion medium of the inorganic fine particles include water and an organic solvent. As the colloid solution, it is preferable that the pH or the pKa is adjusted to 1 to 10 from the viewpoint of the stability of the film-forming coating liquid. And more preferably 2 to 7.

Examples of the organic solvent used in the dispersion medium of the colloid solution include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexyleneglycol, diethyleneglycol, dipropyleneglycol and ethylene glycol monopropylether, Ketones such as methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene and xylene, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, ethyl acetate, butyl acetate, Esters such as tetrahydrofuran and lactone, and ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols or ketones are preferred. These organic solvents may be used alone or as a dispersion medium by mixing two or more kinds thereof.

As the metal oxal oligomer and the metal acid polymer, a single or composite oxide precursor such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium or zinc is used. Examples of the metal acid oligomer and the metal acid polymer are commercially available products or monomers such as metal alkoxides, nitrates, hydrochlorides, and carboxylates, and those obtained by a conventional method such as hydrolysis.

Specific examples of the commercially available metal hydroxyanide oligomer and the metal oxal polymer include siloxane oligomers or siloxane polymers such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485 and SS-101, And titanoxane oligomers such as titanium-n-butoxide tetramer manufactured by Kanto Chemical. These may be used alone or in combination of two or more.

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

The method of mixing the above other components with the polysiloxane may be simultaneous with or after the polysiloxane, and is not particularly limited.

&Lt; Liquid crystal alignment film &

The liquid crystal alignment film of the present invention is obtained using the liquid crystal aligning agent of the present invention. Since the liquid crystal aligning agent of the present invention contains the above polysiloxane (A), the resulting liquid crystal alignment film of the present invention is processed in the same manner as the PSA system using a liquid crystal to which no polymerizable compound is added, It is possible to improve the response speed after UV irradiation without lowering the vertical alignment power.

In the present invention, for example, a cured film obtained by applying the liquid crystal aligning agent of the present invention to a substrate, drying it if necessary, and baking it may be used as a liquid crystal alignment film as it is. The cured film may be subjected to alignment treatment, specifically, rubbing, irradiation with polarized light or light of a specific wavelength, treatment with an ion beam, etc., or with application of a voltage to a liquid crystal display element after liquid crystal charging It is also possible to do.

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

Specific examples thereof include glass plates, polycarbonates, poly (meth) acrylates, polyethersulfones, polyarylates, polyurethanes, polysulfones, polyethers, polyetherketones, trimethylpentens, polyolefins, polyethylene terephthalates, Plastic plates such as acrylonitrile, triacetylcellulose, diacetylcellulose, and acetate butyrate cellulose, and substrates on which transparent electrodes are formed.

Examples of the application method of the liquid crystal aligning agent include a spin coating method, a printing method, an ink jet method, a spraying method, a roll coating method and the like. However, in terms of productivity, a transfer printing method is widely used industrially. Is preferably used.

The drying step after the application of the liquid crystal aligning agent is not necessarily required, but it is preferable that the drying step is included when the time from the application to the baking is not constant for each substrate or when the baking is not performed immediately after the application. This drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coated film is not deformed by conveyance of the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C for 0.5 to 30 minutes, preferably 1 to 5 minutes.

The coating film formed by applying the liquid crystal aligning agent by the above method can be fired to form a cured film. In this case, the firing temperature can be any temperature of 100 to 350 DEG C, but is preferably 140 to 300 DEG C, more preferably 150 to 230 DEG C, and even more preferably 160 to 220 DEG C to be. The firing can be performed at an arbitrary time of 5 minutes to 240 minutes. Preferably 10 to 90 minutes, and more preferably 20 to 80 minutes. The heating can be carried out by a commonly known method, for example, a hot plate, a hot air circulating oven, an IR oven, a belt furnace or the like.

The polycondensation of the polysiloxane in the liquid crystal alignment film proceeds in the firing step. However, in the present invention, polycondensation is not required to be complete unless the effect of the present invention is impaired. However, it is preferable that the baking is performed at a temperature of 10 ° C or more higher than the heat treatment temperature such as seal hardening, which is required in the liquid crystal cell manufacturing process.

The thickness of the cured film can be selected as required, but preferably 5 nm or more, and more preferably 10 nm or more, because it is easy to obtain reliability of the liquid crystal display element. When the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element is not extremely increased, which is preferable.

<Liquid crystal display element>

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

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

The UV irradiation of the liquid crystal cell in which the liquid crystal is introduced with the voltage applied between the electrodes of the both side substrates immediately polymerizes and crosslinks the acrylic group and the methacrylic group in the liquid crystal alignment film, thereby accelerating the response speed of the liquid crystal display. Here, the applied voltage is 5 to 50 Vp-p, but preferably 5 to 30 Vp-p. The amount of UV irradiation to be irradiated is 1 to 60 J, preferably 40 J or less. When the amount of UV irradiation is small, deterioration in reliability due to breakage of members constituting the liquid crystal display can be suppressed, It is preferable since the manufacturing tact is improved.

The substrate used for the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency, but is usually a substrate on which a transparent electrode for driving a liquid crystal is formed. A specific example is the same as the substrate described in the above &lt; liquid crystal alignment film &gt;. Electrode patterns or protrusion patterns such as standard PVA or MVA can be used. It is possible to operate in a structure in which a line / slit electrode pattern of 1 to 10 mu m is formed on a unilateral substrate and a slit pattern or a projection pattern is not formed on the opposing substrate, similarly to the PSA type liquid crystal display, The process at the time of production can be simplified, and a high transmittance can be obtained.

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

In the case of a transmissive liquid crystal device, it is common to use a substrate as described above. In a reflective liquid crystal display device, however, it is possible to use a material such as aluminum that reflects light only on one substrate, It is also possible to use an opaque substrate.

Example

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples. The abbreviations used in this embodiment are as follows. In the formulas, Me represents a methyl group, and Et represents an ethyl group.

TEOS: tetraethoxysilane

C18: octadecyltriethoxysilane

MPMS: 3-methacryloxypropyltrimethoxysilane

M8MS: 3-methacryloxyoxytitrimethoxysilane

MTES: methyltriethoxysilane

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

BCS: 2-butoxyethanol

UPS: 3-ureidopropyltriethoxysilane

THF: tetrahydrofuran

DMF: N, N-dimethylformamide

Compound Synthesis Example 1 Synthesis of the following compound (c)

[Chemical Formula 16]

30.00 g of the compound (a), 25.24 g of potassium carbonate and 120 g of DMF were introduced into a 500 ml four-necked flask equipped with a magnetic stirrer and 22.10 g of allyl bromide was added dropwise at room temperature. Thereafter, the mixture was stirred at 50 占 폚 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, filtered and the filtrate was concentrated to dryness to give 34.80 g (yield 100%) of compound (b). The result of the measurement of the obtained compound (b) by ¹ H-NMR is shown below.

20.00 g of the compound (b) and 120 g of toluene were charged into a 300 ml four-necked flask equipped with a magnetic stirrer and stirred at room temperature. Next, 700 ㎕ of a karstedt catalyst (0.1 mol / l xylene solution of platinum (0) -1,1,3,3-tetramethyldisiloxane complex) was added, and 12.4 ml of trimethoxysilane was added dropwise. After stirring at room temperature for 29 hours, the reaction solution was concentrated to dryness to obtain crude product. This was distilled under reduced pressure and distilled off under the conditions of an external temperature of 245 DEG C / pressure of 0.8 torr to obtain 12.15 g of a compound (c) (yield: 43%). The result of the measurement of the obtained compound (c) by ¹ H-NMR is shown below.

&Lt; Synthesis Example 2 of Compound &gt; Synthesis of the following compound (e)

[Chemical Formula 17]

Compound (d) (20.01 g), toluene (120 g), karstedt catalyst (platinum (0) -1,1,3,3-tetramethyldisiloxane complexing agent (Platinum concentration 2%)) (1.36 g) was injected. While stirring at room temperature, trimethoxysilane (14.15 g) was added dropwise and the reaction was carried out for 1 hour. Next, the solution was cooled to 5 to 10 ° C, and triethylamine (13.57 g) was added to the reaction solution. While stirring at 5 to 10 占 폚, a solution of methacrylic acid chloride (13.38 g) dissolved in toluene (40 g) was added dropwise and reacted for 1 hour. The precipitated solid was subjected to vacuum filtration under reduced pressure, and the filtrate was diluted with ethyl acetate (500 g). The ethyl acetate phase was washed with pure water (200 g) three times, and then concentrated under reduced pressure to obtain crude (39.63 g) of the compound (e). This crude product was distilled off under reduced pressure distillation at an external temperature of 226 ° C / pressure of 0.8 torr to obtain compound (e) (5.99 g) (yield: 14%). The result of the measurement of the obtained compound (e) by ¹ H-NMR is shown below.

&Lt; Synthesis Example 1 &

&Lt; Synthesis of polysiloxane (A) &gt;

15.9 g of HG, 7.9 g of BCS, 17.50 g of TEOS, 3.5 g of the compound (c) obtained in the Synthesis Example 1, 19.9 g of MPMS, And 3.5 g of the compound (e) obtained in Synthesis Example 2 were mixed to prepare a solution of the alkoxysilane monomer. A solution prepared by previously mixing 7.9 g of HG, 4.0 g of BCS, 10.8 g of water and 1.8 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Then, a mixed solution of 0.6 g of a methanol solution having a UPS content of 92 mass%, 0.3 g of HG and 0.1 g of BCS was added. After refluxing for 30 minutes, the solution was allowed to cool to obtain a polysiloxane solution having a SiO ₂ concentration of 12 mass%.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of the concentration to obtain a liquid crystal aligning agent intermediate (S1) of 4% by mass.

&Lt; Synthesis of polysiloxane (B) &gt;

A solution of an alkoxysilane monomer was prepared by mixing 23.8 g of HG, 7.9 g of BCS, 37.1 g of TEOS and 3.6 g of MTES in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. A solution prepared by previously mixing 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 added dropwise to this solution over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Then, a mixed solution of 0.6 g of a methanol solution having a UPS content of 92 mass%, 0.3 g of HG and 0.1 g of BCS was added. After refluxing for 30 minutes, the solution was allowed to cool to obtain a polysiloxane solution having a SiO ₂ concentration of 12 mass%.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of the concentration of liquid crystal alignment of 4% to give a second intermediate (U1).

&Lt; Preparation of liquid crystal aligning agent &

A liquid crystal aligning agent intermediate (S1) and the liquid crystal aligning agent intermediate (U1) obtained, in a mass ratio of 3: 7 mixed in a ratio of, in terms of SiO ₂ concentration of 4% by mass to obtain a liquid crystal aligning the [K1].

&Lt; Synthesis Example 2 &

15.4 g of HG, 7.7 g of BCS, 17.50 g of TEOS, 9.8 g of the compound (c) obtained in the Synthesis Example of Compound (1), 17.4 g of MPMS, And 7.1 g of the compound (e) obtained in the Synthesis Example 2 of the compound were mixed to prepare a solution of the alkoxysilane monomer. A solution prepared by previously mixing 7.7 g of HG, 3.8 g of BCS, 10.8 g of water and 1.8 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes. After heating using an oil bath and bangraeng then refluxed 60 minutes in terms of SiO ₂ concentration to obtain a polysiloxane solution of 12% by mass.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of the concentration to obtain a liquid crystal aligning agent intermediate (S2) of 4% by mass.

A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S2) of Synthetic Example 1 thus obtained, in a mass ratio of 3: a mixture in a ratio of 7, SiO ₂ in terms of the concentration of the first [K2] the liquid crystal of 4% by mass orientation .

&Lt; Synthesis Example 3 &

14.5 g of HG, 7.2 g of BCS, 17.50 g of TEOS, 9.8 g of the compound (c) obtained in the Synthesis Example of Compound (1), 12.4 g of MPMS, And 14.2 g of the compound (e) obtained in Synthesis Example 2 were mixed to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 7.2 g of HG, 3.6 g of BCS, 10.8 g of water and 1.8 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes and further stirred at room temperature for 30 minutes. After heating using an oil bath and bangraeng then refluxed 60 minutes in terms of SiO ₂ concentration to obtain a polysiloxane solution of 12% by mass.

10.0 g of the obtained polysiloxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal aligning intermediate (S3) having a SiO ₂ concentration of 4% by mass.

A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S3) in Synthesis Example 1 is obtained, the weight ratio of 3: 7 with a ratio, the SiO ₂ in terms of the concentration of liquid crystal aligning agent [K3] of 4% by weight of .

&Lt; Synthesis Example 4 &

13.5 g of HG, 6.8 g of BCS, 17.50 g of TEOS, 9.8 g of the compound (c) obtained in Synthesis Example 1 of Compound (1), 7.25 g of MPMS, And 21.3 g of the compound (e) obtained in Synthesis Example 2 were mixed to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 6.7 g of HG, 3.4 g of BCS, 10.8 g of water and 1.8 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes and further stirred at room temperature for 30 minutes. After heating using an oil bath and bangraeng then refluxed 60 minutes in terms of SiO ₂ concentration to obtain a polysiloxane solution of 12% by mass.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of the concentration to obtain a liquid crystal aligning agent intermediate (S4) of 4% by mass.

A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S4) of Synthetic Example 1 thus obtained, in a mass ratio of 3: a mixture in a ratio of 7, SiO ₂ in terms of the concentration of the first [K4] crystal of 4% by mass orientation .

&Lt; Synthesis Example 5 &

15.8 g of HG, 5.3 g of BCS, 23.8 g of TEOS, 9.8 g of the compound (c) obtained in the Synthesis Example of Compound (1) and 9.8 g of the compound (c) in Synthesis Example 2 were added to a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. 21.3 g of the obtained compound (e) was mixed to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 7.9 g of HG, 2.6 g of BCS, 10.8 g of water and 1.8 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred at room temperature for 30 minutes. After heating using an oil bath and bangraeng then refluxed 60 minutes in terms of SiO ₂ concentration to obtain a polysiloxane solution of 12% by mass.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of the concentration to obtain a liquid crystal aligning agent of claim 4% by mass [K5].

&Lt; Synthesis Example 6 &

16.1 g of HG, 5.4 g of BCS, 21.7 g of TEOS, 9.8 g of the compound (c) obtained in Synthesis Example 1 of Compound (1), 5.0 g of MPMS, And 17.7 g of the compound (e) obtained in the Synthesis Example 2 were mixed to prepare a solution of the alkoxysilane monomer. To this solution, a solution prepared by previously mixing 8.1 g of HG, 2.6 g of BCS, 10.8 g of water and 1.8 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred at room temperature for 30 minutes. After heating using an oil bath and bangraeng then refluxed 60 minutes in terms of SiO ₂ concentration to obtain a polysiloxane solution of 12% by mass.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of the concentration of liquid crystal alignment of 4% by mass to obtain a first [K6].

<Comparative Synthesis Example 1>

16.3 g of HG, 8.2 g of BCS, 17.50 g of TEOS, 9.8 g of the compound (c) obtained in the Synthesis Example of Compound 1, and 22.4 g of MPMS in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube To prepare a solution of an alkoxysilane monomer. To this solution, a solution prepared by previously mixing 8.2 g of HG, 4.1 g of BCS, 10.8 g of water and 1.8 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Then, a mixed solution of 0.6 g of a methanol solution having a UPS content of 92 mass%, 0.3 g of HG and 0.1 g of BCS was added. After refluxing for 30 minutes, the solution was allowed to cool to obtain a polysiloxane solution having a SiO ₂ concentration of 12 mass%.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of the concentration to obtain a liquid crystal aligning agent intermediate (S5) of 4% by mass.

A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S5) of Synthetic Example 1 thus obtained, the weight ratio of 3: 7 with a ratio, SiO ₂ in terms of a concentration of a liquid crystal aligning agent [L1] of the 4% by weight of .

&Lt; Comparative Synthesis Example 2 &

A solution of alkoxysilane monomer was prepared by mixing 22.6 g of HG, 7.5 g of BCS, 39.2 g of TEOS and 4.2 g of C18 in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. A solution prepared by previously mixing 11.3 g of HG, 3.8 g of BCS, 10.8 g of water and 0.2 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Then, a mixed solution of 0.6 g of a methanol solution having a UPS content of 92 mass%, 0.3 g of HG and 0.1 g of BCS was added. After refluxing for 30 minutes, the solution was allowed to cool to obtain a polysiloxane solution having a SiO ₂ concentration of 12 mass%.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of the concentration to obtain a liquid crystal aligning agent intermediate (S6) of 4% by mass.

A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S6) as in Synthesis Example 1 is obtained, in a mass ratio of 3: a mixture in a ratio of 7, SiO ₂ in terms of the concentration of the first [L2] the liquid crystal of 4% by mass orientation .

&Lt; Comparative Synthesis Example 3 &gt;

20.4 g of HG, 6.8 g of BCS, 22.5 g of TEOS, 4.2 g of C18 and 19.9 g of MPMS were mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube to prepare a solution of alkoxysilane monomer . To this solution, a solution prepared by previously mixing 10.2 g of HG, 3.4 g of BCS, 10.8 g of water and 1.3 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Then, a mixed solution of 0.6 g of a methanol solution having a UPS content of 92 mass%, 0.3 g of HG and 0.1 g of BCS was added. After refluxing for 30 minutes, the solution was allowed to cool to obtain a polysiloxane solution having a SiO ₂ concentration of 12 mass%.

By mixing the resulting polysiloxane solution, 10.0 g, BCS 20.0 g, SiO 2 in terms of the concentration to obtain a liquid crystal aligning agent intermediate (S7) of 4% by mass.

A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S7) as in Synthesis Example 1 is obtained, the weight ratio of 3: 7 with a ratio, the SiO ₂ in terms of the concentration of liquid crystal aligning agent [L3] of 4% by weight of .

&Lt; Comparative Synthesis Example 4 &gt;

16.3 g of HG, 8.2 g of BCS, 17.50 g of TEOS, 9.8 g of the compound (c) obtained in the Synthesis Example of Compound 1, and 22.4 g of MPMS in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube To prepare a solution of an alkoxysilane monomer. To this solution, a solution prepared by previously mixing 8.2 g of HG, 4.1 g of BCS, 10.8 g of water and 1.8 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Then, a mixed solution of 0.6 g of a methanol solution having a UPS content of 92 mass%, 0.3 g of HG and 0.1 g of BCS was added. After refluxing for 30 minutes, the solution was allowed to cool to obtain a polysiloxane solution having a SiO ₂ concentration of 12 mass%.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of the concentration of liquid crystal alignment of 4% by mass to obtain a first [L4].

&Lt; Example 1 &gt;

The liquid crystal aligning agent [K1] obtained in Synthesis Example 1 was spin-coated on the ITO surface of an ITO electrode substrate having a pixel size of 100 x 300 microns and an ITO electrode pattern having a line / space of 5 microns each formed therein. After drying for 2 minutes on a hot plate at 80 占 폚, firing was performed for 30 minutes in a hot air circulating oven at 200 占 폚 to form a liquid crystal alignment film having a film thickness of 100 nm. The liquid crystal aligning agent [K1] obtained in Synthesis Example 1 was spin-coated on an ITO surface on which no electrode pattern was formed, and dried on a hot plate at 80 DEG C for 2 minutes. Thereafter, And fired in a circulating oven for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. These two substrates were prepared, a bead spacer of 4 mu m was sprayed on the liquid crystal alignment film surface of one of the substrates, and then a sealant was printed thereon. The liquid crystal alignment film surface of the other substrate was inwardly bonded, and then the sealant was cured to prepare an empty cell. A liquid crystal cell 1 in which the above liquid crystal was injected was manufactured by liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) by vacuum injection into an empty cell. The response speed characteristic of the liquid crystal cell 1 was measured by a method described later.

Thereafter, with a DC voltage of 20 V applied to this liquid crystal cell 1, 5 J of UV was irradiated from the outside of the liquid crystal cell. Thereafter, the response speed characteristics were measured again, and the response speeds before and after the UV irradiation were compared. The results are shown in Table 1.

On the other hand, the above liquid crystal cell 1 (that is, a liquid crystal cell in which 5 V of UV was not irradiated from the outside of the liquid crystal cell in a state where a DC voltage of 20 V was applied) was annealed in a circulating oven at 100 캜 for 30 minutes did. The liquid crystal cell taken out was observed under a microscope in a state where the polarizing plate was made of Cross-Nicol, and the state of the domain where the orientation of the liquid crystal was disturbed was observed. The results are also shown in Table 1. Further, when the liquid crystal aligning force is low, a large number of domains are observed after the annealing, and when the liquid crystal aligning property is high, no domain is observed after the annealing.

&Lt; Example 2 &gt;

A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [K2] obtained in Synthesis Example 2, and the response speed was measured to determine the domain Observed. The results are shown in Table 1.

&Lt; Example 3 &gt;

A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [K3] obtained in Synthesis Example 3, and the response speed was measured to determine the domain Observed. The results are shown in Table 1.

<Example 4>

A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [K4] obtained in Synthesis Example 4, and the response speed was measured to determine the domain Observed. The results are shown in Table 1.

&Lt; Example 5 &gt;

A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [K5] obtained in Synthesis Example 5, and the response speed was measured to determine the domain Observed. The results are shown in Table 1.

&Lt; Example 6 &gt;

A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [K6] obtained in Synthesis Example 6, and the response speed was measured to determine the domain Observed. The results are shown in Table 1.

&Lt; Comparative Example 1 &

A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L1] obtained in Comparative Synthesis Example 1, and the response speed was measured to determine the domain . The results are shown in Table 1.

&Lt; Comparative Example 2 &

A liquid crystal cell was fabricated in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L2] obtained in Comparative Synthesis Example 2, and the response speed was measured, . The results are shown in Table 1.

&Lt; Comparative Example 3 &

A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L3] obtained in Comparative Synthesis Example 3, and the response speed was measured to determine the domain . The results are shown in Table 1.

&Lt; Comparative Example 4 &

A liquid crystal cell was fabricated in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L4] obtained in Comparative Synthesis Example 4, and the response speed was measured to determine the domain . The results are shown in Table 1.

[Measurement of response speed characteristics]

A time change of the luminance of the liquid crystal panel when an AC (alternating current) voltage of ± 5 V and a rectangular wave of 1 kHz frequency was applied to the liquid crystal cell was input to the oscilloscope. The time when the luminance changes from 10% to 90% is set to the rising response speed with a voltage of 0% and a voltage of 5 V applied to the luminance when the voltage is not applied and the saturated luminance value to 100% did.

As shown in Table 1, in Examples 1 to 4 using the liquid crystal aligning agent containing the polysiloxane (A) and the polysiloxane (B), the response speed after UV irradiation was less than 20 ms and very fast, The results were also very good. Even in Examples 5 to 6 using the liquid crystal aligning agent containing the polysiloxane (A), the response speed after UV irradiation was extremely short, less than 20 ms, and the results of the domain observation after annealing showed very good results. On the other hand, in Comparative Examples 1 to 4 using the liquid crystal aligning agent containing no polysiloxane (A), both the response speed and the domain observation result could not be improved.

Industrial availability

The liquid crystal display element manufactured by using the liquid crystal aligning agent of the present invention can be used in a liquid crystal display element which is processed in the same manner as the PSA system and improves the response speed after UV irradiation by using a liquid crystal to which no polymerizable compound is added , It is possible to improve the response speed after UV irradiation without lowering the vertical orientation force. Therefore, it is useful for a TFT (thin film transistor) liquid crystal display device, a TN (Twisted Nematic) liquid crystal display device, a VA liquid crystal display device and the like manufactured by the above method.

Claims (8)

A liquid crystal aligning agent characterized by containing the following polysiloxane (A).
Polysiloxane (A): A polysiloxane obtained by reacting an alkoxysilane represented by the following formula (1) and an alkoxysilane-containing alkoxysilane represented by the following formula (3)

(R ¹ represents a structure represented by the following formula (2), and R ² represents an alkyl group having 1 to 5 carbon atoms.)
[Chemical Formula 1]

(In the formula (2), Y ¹ represents a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Y ² is a single bond, a carbon number of 3 to 8 linear or branched in containing a double bond, a hydrocarbon group, ^{or, - (CR 17 R 18)} b - (b is an integer of 1 ~ 15, R ^17, .. R ¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms a) Y ³ represents a single _{bond, - (CH 2) c -} (c is an integer of 1 ~ 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a single bond, a benzene ring, a cyclohexyl ring, and a heterocyclic ring, or a divalent cyclic group having a carbon number of 12 to 25 , And any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms Substituted by fluorine atom Or may. Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring, and heterocyclic, any of the hydrogen atoms on these cyclic group, the alkyl group having a carbon number of 1 to 3, 1 to 3 carbon atoms alkoxy group, may be substituted 1 to 3 carbon atoms a fluorine-containing alkyl group, fluorine-containing alkoxy group or a fluorine atom of 1 to 3 carbon atoms in the. n1 is an integer of 0 ~ 4. Y ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms , A fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluoro-containing alkoxyl group having 1 to 18 carbon atoms.
(2)

(R ²¹ , R ²² and R ²³ each independently represent -OCH ₃ , -OC ₂ H ₅ , -OCH (CH ₃ ) ₂ , -OC (CH ₃ ) ₃ , -CH ₃ , -Ph, , -OCOCH ₃ , -OH, -H, or a combination thereof, R ²⁴ represents a hydrogen atom or a methyl group, Y ²¹ represents a single bond or a single bond which may contain a double bond, 1-8 represents a group of linear or branched hydrocarbons, Y ²² is a single bond, -O-, -CO-, -COO-, -OCO- , -NH-, -N (CH 3) -., -NPh _{-, -NHCO-, -N (CH 3} ) CO-, -NPhCO-, -NHSO 2 -, -N (CH 3) SO 2 -, -NPhSO 2 -, -S-, -SO 2 -, -NHCONH _{-., -N (CH 3)} CONH-, -NPhCONH-, -NHCOO-, and represents a bonding group selected from -OCONH- Y ²³ represents a single bond, or a linear or branched group having 1 to 8 carbon atoms Y ²⁴ represents a single bond or a linear or branched hydrocarbon group having 1 to 8 carbon atoms, Y ²⁵ represents a single bond, -O- or -NZ ₂ -, Z ₂ Is a number An aromatic cyclic group or an aliphatic cyclic group having 1 to 18 carbon atoms, Cy is a divalent cyclic group selected from the following and bonded at an arbitrary substitution position, May be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a cyano group, a fluorine atom, and a chlorine atom.
(3)

(Z ₁ represents an aromatic ring group or a linear or branched divalent hydrocarbon group of 1 to 18 carbon atoms which may contain an aliphatic ring group.) The method according to claim 1,
Wherein the alkoxysilane component further contains an alkoxysilane represented by the following formula (4).

(R ³ is an alkyl group having 1 to 30 carbon atoms in which a hydrogen atom is substituted with an acrylic group, an acryloxy group, a methacrylic group, a methacryloxy group or a styryl group, and R ⁴ is an alkyl group having 1 to 5 carbon atoms.) 3. The method according to claim 1 or 2,
The liquid crystal aligning agent further contains the following polysiloxane (B).
Polysiloxane (B): A polysiloxane obtained by reacting an alkoxysilane-containing alkoxysilane component represented by the following formula (5)

(R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms) 4. The method according to any one of claims 1 to 3,
Wherein at least one of the polysiloxane (A) and the polysiloxane (B) is a polysiloxane obtained by reacting an alkoxysilane component containing an alkoxysilane represented by the following formula (6).

(In the formula (6), R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, , R ¹⁴ is an alkyl group having 1 to 5 carbon atoms, and n 2 is an integer of 0 to 3. A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of claims 1 to 4 to a substrate and firing the liquid crystal alignment agent. A liquid crystal display element having the liquid crystal alignment film according to claim 5. A liquid crystal display device comprising the liquid crystal aligning agent according to any one of claims 1 to 4 applied thereto and irradiating UV with a voltage applied to a liquid crystal cell in which liquid crystal is sandwiched between two fired substrates Wherein the liquid crystal display element is a liquid crystal display element. A liquid crystal cell is fabricated by applying the liquid crystal aligning agent according to any one of claims 1 to 4 and sandwiching the liquid crystal between two fired substrates, applying a voltage to the liquid crystal cell, Wherein the liquid crystal display element is a liquid crystal display element.