KR101883521B1 - Silicon-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

(R¹ 은 하기 식 (2) 의 구조를 나타내고, R² 는 탄소 원자수 1 ∼ 5 의 알킬기를 나타낸다)
(화학식 1)

(Y¹ 은 단결합 등, Y² 는 단결합 등, Y³ 은 단결합 등, Y⁴ 는 벤젠 고리, 시클로헥실 고리, 또는 복소 고리에서 선택되는 2 가의 고리형기 등, Y⁵ 는 벤젠 고리, 시클로헥실 고리 및 복소 고리로 이루어지는 군에서 선택되는 2 가의 고리형기 등, n 은 0 ∼ 4 의 정수, Y⁶ 은 수소 원자 등을 나타낸다)

(R³ 은 아크릴기 등으로 치환된 탄소수 1 ∼ 30 의 알킬기, R⁴ 는 탄소수 1 ∼ 5 의 알킬기를 나타낸다)It is also possible to improve the response speed after UV irradiation without lowering the vertical alignment force even in a liquid crystal display element in which a liquid crystal without the addition of a polymerizable compound is used in a manner similar to the PSA method to improve the response speed after UV irradiation A liquid crystal aligning agent capable of forming a liquid crystal alignment film is provided. A liquid crystal aligning agent characterized by containing a polysiloxane (A) obtained by polycondensing an alkoxysilane represented by the following formula (1) and an alkoxysilane containing an 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)
(Formula 1)

(Y ¹ is a single bond, Y ² is a single bond, Y ³ is a single bond, Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, Y ⁵ is a benzene ring, A cyclohexyl ring and a heterocyclic ring, etc., n represents an integer of 0 to 4, and Y ⁶ represents a hydrogen atom or the like)

(R ³ is an alkyl group having 1 to 30 carbon atoms substituted with an acrylic group or the like, and R ⁴ is 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 alignment film, and a liquid crystal alignment film.

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

Among the display methods of liquid crystal display elements in recent years, liquid crystal display elements of the vertical (VA) type are widely used for a liquid crystal television of a large screen or a mobile application (a display portion of a digital camera or a cellular phone) 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 polymer sustained alignment (PSA) 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 the liquid crystal, and after the liquid crystal panel is manufactured, an electric field is applied to irradiate ultraviolet rays (UV) onto the liquid crystal panel in a state where the liquid crystal falls. As a result, the alignment direction of the liquid crystal is fixed by photopolymerization of the polymerizable compound, pretilt is generated, and the response speed is improved. A slit is formed on one of the electrodes on the opposite side of the liquid crystal panel and a slit such as MVA or PVA is not formed on the electrode pattern on the opposite side. (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 brought into contact with a liquid crystal alignment film obtained by baking is formed. While applying voltage to this liquid crystal layer, A liquid crystal display element having a high response speed can be obtained without adding a polymerizable compound to the liquid crystal by manufacturing a liquid crystal display element.

On the other hand, an inorganic liquid crystal alignment film material is known along with an organic liquid crystal alignment film material such as polyimide which has been conventionally used. For example, an orientation agent composition containing a reaction product of a tetraalkoxysilane, a trialkoxysilane, an alcohol and oxalic acid as a material of an inorganic orientation film of a coating type has been proposed. On the electrode substrate of a liquid crystal display element, (Refer to Patent Document 3). Further, a liquid crystal aligning composition containing a reaction product of tetraalkoxysilane, a specific trialkoxysilane and water and a specific glycol ether solvent has been proposed, and it has been proposed to provide a liquid crystal aligning composition capable of preventing display defects and having excellent afterimage characteristics, (Hereinafter referred to as " liquid crystal alignment layer "), and the voltage sustaining rate with respect to light and heat is reduced little (see Patent Document 4).

Japanese Laid-Open Patent Publication No. 2004-302061 Japanese Laid-Open Patent Publication No. 2011-95967 Japanese Laid-Open Patent Publication No. 09-281502 Japanese Patent Application Laid-Open No. 2005-250244

In the VA mode (mode) in which the vertical alignment is performed, a strong vertical alignment force for vertical alignment is required. However, in this method in which no polymerizable compound is used, the response speed after UV irradiation is slowed down when the vertical alignment power is improved , And when the response speed after UV irradiation is improved, the vertical orientation force is lowered. The vertical orientation power and the response speed improvement after UV irradiation are in a trade-off relationship.

It is an object of the present invention to provide a liquid crystal display device in which a liquid crystal without the addition of a polymerizable compound is used in a liquid crystal display element which is processed similarly to the PSA system to improve the 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 present invention also provides a liquid crystal display device comprising the liquid crystal alignment film.

The present invention is characterized by the following points.

[1] A liquid crystal aligning agent comprising a polysiloxane (A) obtained by polycondensing an alkoxysilane represented by the following 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)

[Chemical Formula 1]

(Y ¹ is a single _{bond, - (CH 2) a -} . (A 1 to an integer of 15), is -O-, -CH ₂ O-, -COO- or -OCO- Y ² is a single bond, (CR ¹⁷ R ¹⁸ ) _b - (b is an integer of 1 to 15, and R ¹⁷ and R ¹⁸ are each independently a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, . an atom or an alkyl group of carbon number 1 ~ ³⁾ 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 benzene ring, a cyclohexyl ring and a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton, and any of these cyclic groups The hydrogen atom is substituted with 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, Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, wherein any hydrogen atom on the cyclic group may be substituted with 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, or a fluorine atom, and n is an integer of 0 to 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 alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

(R ³ is an alkyl group having 1 to 30 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group, and R ⁴ is an alkyl group having 1 to 5 carbon atoms)

[2] The liquid crystal alignment described in [1], wherein in the formula (3), R ³ is an alkyl group having 3 to 10 carbon atoms substituted with an acryl group, an acryloxy group, a methacrylic group, a methacryloxy group or a styryl group My.

[3] The liquid crystal aligning agent according to the above [1] or [2], further comprising a polysiloxane (B) obtained by polycondensation of an alkoxysilane containing 50% to 100% of alkoxysilane represented by the formula (5).

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

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

[5] The liquid crystal aligning agent according to the above [3] or [4], wherein the polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (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] Any one of the above-mentioned [1] to [5], wherein at least one of the polysiloxane (A) and the polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula Wherein the liquid crystal aligning agent is a liquid crystal aligning agent.

(In the formula (4), 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 is an integer of 0 to 3)

[7] The positive resist composition as described in [1], wherein the alkoxysilane represented by the formula (1) is contained in an amount of 2 to 20 mol% of the total alkoxysilane used in the polysiloxane (A), and the alkoxysilane represented by the formula (3) The liquid crystal aligning agent according to any one of [1] to [6], wherein the liquid crystal aligning agent is contained in an amount of 5 to 80 mol% of the total alkoxysilane used.

[8] A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of [1] to [7] to a substrate, followed by drying and firing.

[9] A liquid crystal display element having the liquid crystal alignment film according to the above [8].

[10] A liquid crystal display device in which a liquid crystal aligning agent according to any one of [1] to [7] above is applied and a liquid crystal cell in which liquid crystal is sandwiched by two fired substrates, .

[11] A method for manufacturing a liquid crystal display element in which the liquid crystal aligning agent according to any one of [1] to [7] above is applied, the liquid crystal is sandwiched by two fired substrates, Way.

According to the present invention, there can be provided 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 an alignment agent, and a liquid crystal display device having the liquid crystal alignment film can be provided.

≪ Polysiloxane (A) >

The polysiloxane (A) contained in the liquid crystal aligning agent of the present invention is a polysiloxane obtained by polycondensation of an alkoxysilane represented by formula (1) and an alkoxysilane containing alkoxysilane represented by formula (3). The preparation of the siloxane from the silane is described in detail as hydrolysis and polycondensation, but in the present specification, it is simply referred to as polycondensation.

R ^{1 of the} alkoxysilane represented by the formula (1) (hereinafter also referred to as a specific organic group) has a structure represented by the following formula (2) and R ² is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms .

(2)

R ³ is an alkyl group having 1 to 30 carbon atoms, preferably 3 to 10 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms .

In 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- . 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- makes it possible to easily synthesize a side chain structure . 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 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 - (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 the formula (2), Y ³ is any 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 choice 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. 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 formula (2), Y ⁴ is a 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 fluorine-containing alkoxy group of 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 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 on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, An alkoxy group, 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 an integer of 0 to 2.

In formula (2), 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 alkoxy group having 1 to 18 carbon atoms, or a fluorinated alkoxy group having 1 to 18 carbon atoms. Among them, 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 is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

Although it is not clear whether such a liquid crystal aligning agent using a polysiloxane incorporating a side chain and a photoreactive group can satisfy both the response speed characteristic and the good vertical alignment property, by using a side chain having a structure similar to a liquid crystal skeleton, It is presumed that both the response speed and the vertical orientation related to trade-off are compatible with each other.

A preferable combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula (2) is (2-1) to (2-629 ).

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

The alkoxysilane represented by the formula (1) can be synthesized by a known synthesis method (for example, JP-A-61-286393). Specific examples are given below, but the present invention is not limited thereto.

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(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 9]

(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)

[Chemical formula 10]

(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 represents -O-, 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)

(11)

(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, respectively)

[Chemical Formula 12]

(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 13]

(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 Atom or -COO- * (provided that a bonding hand having "*" is bonded to B ₃ ), B ₁ is an oxygen atom or -COO- * (provided that the bonding hand (CH ₂ ) is engaged with a _2). Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 ~ 10, a ₃ represents an integer of 0 or 1)

The alkoxysilane represented by the above-mentioned formula (1) has a property of solubility in a solvent when it is a siloxane polymer, orientation of liquid crystal in the case of a liquid crystal alignment film, pretilt angle characteristics, voltage retention rate, Accordingly, one kind or two or more kinds 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-mentioned formula (1) can be produced by a known method.

The alkoxysilane represented by the above-mentioned formula (1) is preferably 1 mol% or more in the total alkoxysilane used for obtaining the polysiloxane in order to obtain good liquid crystal alignability. 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.

The R ^{3 of the} alkoxysilane represented by the formula (3) (hereinafter also referred to as the second specific organic group) is an alkyl group substituted with an acryl group, an acryloxy group, a methacryl 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 of the alkyl group has 1 to 30 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 5 to 10 carbon atoms.

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

Specific examples of the alkoxysilane represented by the formula (3) 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, 2-aminoethylamino) propyltrimethoxysilane, 3-methacryloxyhexyltrimethoxysilane, 3-methacryloxyhexyltriethoxysilane, 3-acryloxyhexyltrimethoxysilane, 3 -Acryloxyhexyltrimethoxysilane, 3-acryloxyhexyltrimethoxysilane, 3-acryloxyhexyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, to be.

The alkoxysilane represented by the formula (3) is preferably not less than 5 mol% in the total alkoxysilane used for obtaining the polysiloxane in order to obtain a good liquid crystal response speed. More preferably, it is 10 mol% or more. More preferably, it is 20 mol% or more. In addition, in order to increase the vertical alignment property, it is preferably 70 mol% or less. And more preferably 60 mol% or less.

The production of the polysiloxane (A) is not limited to the alkoxysilane represented by the formula (1) and the formula (3), but may be used for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecule, , One or more alkoxysilanes represented by the following formula (4) may be used. The alkoxysilane represented by the formula (4) can impart various properties to the polysiloxane, so that one or more kinds of alkoxysilanes can be selected depending on the required characteristics.

(In the formula (4), 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 or a ureido group R ¹⁴ is an alkyl group of 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and n represents an integer of 0 to 3, preferably 0 to 2.)

R ¹³ in the alkoxysilane represented by formula (4) is a hydrogen atom or an organic group having 1 to 10 carbon atoms (hereinafter, also referred to as a third organic group). Examples of the third organic group include an aliphatic hydrocarbon, a cyclic structure such as an aliphatic ring, an aromatic ring and a heterocyclic ring, an unsaturated bond, and a hetero atom such as an oxygen atom, a nitrogen atom and a sulfur atom, Having 1 to 6 carbon atoms. In addition, the organic group may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, an ureido group, or the like.

Specific examples of the alkoxysilane represented by the formula (4) 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 -ureidopropyltriethoxysilane, gamma -ureidopropyltriethoxysilane, gamma -butyldimethoxysilane, gamma- - ureidopropyl tri Methoxysilane, and? -Ureidopropyltripropoxysilane.

In the alkoxysilane represented by the formula (4), the alkoxysilane wherein n is 0 is tetraalkoxysilane. Tetraalkoxysilane is preferable to obtain the polysiloxane of the present invention since it is likely to polycondensate with alkoxysilanes represented by the formulas (1) and (3).

In the formula (4), as the alkoxysilane wherein n is 0, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetra Ethoxysilane is preferred.

In the present invention, the alkoxysilane represented by the formula (1) is contained in an amount of preferably 2 to 20 mol%, particularly preferably 3 to 15 mol%, in the total alkoxysilane used for producing the polysiloxane (A) 3) is contained in an amount of 5 to 80 mol%, particularly preferably 10 to 70 mol%, of the total alkoxysilane used in the production of the polysiloxane (A).

≪ Polysiloxane (B) >

The polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane containing 50 mol% to 100 mol% of an alkoxysilane represented by the formula (5).

R ¹⁵ in the alkoxysilane represented by the formula (5) represents an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms.

As specific examples of the alkoxysilane represented by the formula (5), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is more preferable, and tetramethoxysilane or tetraethoxy Silane is preferred.

The polysiloxane (B) may further contain, in addition to the alkoxysilane represented by the formula (5), an alkoxysilane represented by the formula (3), R ³ Si (OR ⁴ ) ₃ described in the production of the polysiloxane Or a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane. The description of the alkoxysilane represented by the formula (3) applies to the description of the polysiloxane (A) described above.

The polysiloxane (B) may be a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (6) in addition to the alkoxysilane represented by the formula (5).

R ¹⁶ in the alkoxysilane 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.

R ¹⁷ in the alkoxysilane represented by the formula (6) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.

Specific examples of the alkoxysilane represented by the formula (6) are shown below, but are not limited thereto. For example, methyltriethoxysilane, methyltrimethoxysilane, dimethyltrimethoxysilane, dimethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane.

Particularly, a liquid crystal aligning agent containing a polysiloxane (B) obtained by polycondensation of an alkoxysilane containing an alkoxysilane further represented by the formula (6) in addition to the alkoxysilane represented by the formula (5) is preferable because of its high vertical alignment ability.

In order to improve the response speed of the liquid crystal display element by applying UV light while applying a voltage by using a liquid crystal to which no polymerizable compound is added, the alkoxysilane represented by the formula (3) having the second specific organic group is preferably obtained by obtaining a polysiloxane Is preferably 10 mol% or more based on the total alkoxysilane used. More preferably, it is 20 mol% or more. More preferably, it is at least 30 mol%. Further, in order to sufficiently cure the liquid crystal alignment film to be formed, it is preferably 75 mol% or less.

The polysiloxane (B) can be produced by using the alkoxysilane represented by the formula (3), the formula (5) and the formula (6) for the purpose of improving the adhesion with the substrate and the affinity with the liquid crystal molecules. in one that does not inhibit, in the production of the above-mentioned polysiloxane (a) described above, expression (4) an alkoxysilane represented by, (R ¹³⁾ _n Si (oR ¹⁴⁾ _4-n, one or plural kinds of use It is possible. The description of the alkoxysilane represented by the formula (4) applies to the description of the polysiloxane (A) described above.

Since the alkoxysilane represented by the formula (4) can impart various properties to the polysiloxane, one or more kinds of alkoxysilanes can be selected depending on the required characteristics.

When the liquid crystal aligning agent is mixed with the polysiloxane (A) and the polysiloxane (B), the mixing ratio of the polysiloxane (A) and the polysiloxane (B) is preferably 10: 90 to 50:50, and particularly preferably 20:80 to 40:60.

≪ Process for producing polysiloxane >

The method for obtaining the polysiloxane used in the present invention is not particularly limited. In the polysiloxane (A), alkoxysilane containing the above-described formulas (1) and (3) as essential components and polysiloxane (B) containing the above formula (5) as essential components, Is obtained by condensing an alkoxysilane containing an optional component of the formula (3) and the formula (6) in an organic solvent. Generally, polysiloxane is obtained as a solution in which such alkoxysilane is polycondensed and uniformly dissolved in an organic solvent.

As a method for polycondensation of the polysiloxane, for example, a method of hydrolyzing and condensing an alkoxysilane in a solvent such as an alcohol or glycol can 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-fold molar amount.

In the present invention, the amount of water used in the reaction may be appropriately selected according to the desired amount, and is preferably 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 Alkali metal such as hydrochloric acid, sulfuric acid, nitric acid and the like. In addition, it is also common to accelerate the hydrolysis / condensation reaction by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected according to the desired one. For example, heating and stirring at 50 占 폚 for 24 hours 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 solution is heated to mix the alkoxysilane. At this time, the amount of oxalic acid to be used is preferably 0.2 to 2 mol based on 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 heating for several tens of minutes to several tens of hours under reflux so as not to evaporate or volatilize the liquid.

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

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

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 pentanediol, 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 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 mono Butyl ether, di Diethylene glycol diisopropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl 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 polymerization solvents may be used in combination.

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

≪ Solution of polysiloxane >

In the present invention, the polymerization solution obtained by the above method may be used as it is as a solution of polysiloxane. If necessary, the solution obtained by the above method may be concentrated or diluted with a solvent or replaced with another solvent to obtain a polysiloxane Solution.

At this time, the solvent to be used (hereinafter also referred to as an addition solvent) may be the same as or different from the polymerization solvent. This addition solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and even a single kind or plural kinds of solvents can be arbitrarily selected and used.

Specific examples of such an addition solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate and ethyl lactate, have.

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.

≪ Other components >

In the present invention, as long as the effect of the present invention is not impaired, components other than the polysiloxane such as inorganic microfine particles, metaloxyl oligomer, metaloxyl polymer, leveling agent and further surfactant May be included.

As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, or magnesium fluoride fine particles are preferable, and in particular, they are preferably in a colloidal solution state. The colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a colloidal solution of a commercial product. In the present invention, by containing the inorganic fine particles, the surface shape and other functions of the formed cured coating can be imparted. The 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.

The dispersion medium of the inorganic fine particles may be water or 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 for use in the dispersion medium of the colloid solution include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexyleneglycol, diethylene glycol, dipropylene glycol and ethylene glycol monopropyl ether Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; ethyl acetate, butyl acetate, Ethers such as tetrahydrofuran and 1,4-dioxane, and the like. 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 oxalic oligomer and the metal oxalic polymer, a single or complex oxide precursor such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium and zinc is used. The metaloxyl oligomer and the metaloxane polymer may be commercially available products or may be obtained by a conventional method such as hydrolysis from monomers such as metal alkoxides, nitrates, hydrochlorides and carboxylates.

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

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

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

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is a solution containing the above-mentioned polysiloxane and, if necessary, other components. 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 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 possible to easily obtain a desired film thickness by one application and easily obtain a sufficient pot life of the solution.

The method for preparing the liquid crystal aligning agent of the present invention is not particularly limited. The polysiloxane used in the present invention and other components to be added as required may be uniformly mixed. Since the polysiloxane is usually polycondensed in a solvent, it is convenient to use the solution of the polysiloxane as it is or to add other components as needed to the polysiloxane solution. The most convenient method is to use the polymerization solution of polysiloxane as it is.

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.

&Lt; Liquid crystal alignment film &

The liquid crystal alignment film of the present invention is obtained by using the liquid crystal aligning agent of the present invention. For example, a cured film obtained by applying the liquid crystal aligning agent of the present invention to a substrate, followed by drying and firing, may be used as the liquid crystal alignment film as it is. It is also possible to rub the cured film, irradiate polarized light, light of a specific wavelength, or the like, or irradiate UV with a treatment such as ion beam or a voltage applied to the liquid crystal display element after liquid crystal charge.

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 having a transparent electrode for driving the liquid crystal on the substrate is preferable.

Specific examples thereof include glass plates, polycarbonates, poly (meth) acrylates, polyethersulfones, polyarylates, polyurethanes, polysulfones, polyethers, polyether ketones, trimethylpentens, polyolefins, polyethylene terephthalates, A substrate on which a transparent electrode is formed on a plastic plate such as acrylonitrile, triacetylcellulose, diacetylcellulose, and acetate butyrate cellulose.

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 also preferably used.

The step of drying after application of the liquid crystal aligning agent is not necessarily required. However, if the time from the application to the firing is not constant for each substrate, or if the firing is not carried out immediately after the application, it is preferable to include a drying step. The drying may be carried out as long as the solvent is removed to such an extent that the coating film shape is not deformed by, for example, conveyance of the substrate, and the drying means is not particularly limited. For example, a method of drying on a hot plate at a temperature of 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C for 0.5 to 30 minutes, preferably for 1 to 5 minutes.

The coating film formed by applying the liquid crystal aligning agent by the above method can be fired to form a cured film. In this case, the firing temperature may be any temperature of 100 ° C to 350 ° C, preferably 140 ° C to 300 ° C, more preferably 150 ° C to 230 ° C, and more preferably 160 ° C to 220 ° C to be. The firing time can be fired at any time between 5 minutes and 240 minutes. Preferably 10 to 90 minutes, and more preferably 20 to 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, the polycondensation does not need to be carried out completely unless the effect of the present invention is impaired. However, it is preferable to carry out the firing at a temperature higher by 10 ° C or more than the heat treatment temperature such as seal hardening which is required in the production process of the liquid crystal cell.

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

The method of injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which the 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.

When a voltage is applied between the electrodes of both substrates of the liquid crystal cell into which liquid crystal has been introduced, the cross-linking group such as an acrylic group or a methacryl group is polymerized and cross-linked in the liquid crystal alignment layer, Faster. Here, the applied voltage is 5 to 50 Vp-p, but preferably 5 to 30 Vp-p. The amount of irradiated UV light is 1 to 60 J, preferably 40 J or less. When the amount of UV irradiation is small, it is possible to suppress the reliability degradation due to breakage of members constituting the liquid crystal display, Of the tact is increased.

The substrate used for the liquid crystal display element is not specifically limited as long as it is a substrate having high transparency, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. A specific example is the same as the substrate described in [liquid crystal alignment film]. It can also be used in electrode patterns or protruding patterns such as standard PVA or MVA. 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, a substrate such as the one described above is generally used. In a reflective liquid crystal display device, a material such as aluminum that reflects light only on one side can be used, and an opaque substrate such as a silicon wafer is also used It is possible to do.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not construed as being limited thereto.

[Chemical Formula 14]

&Lt; Synthesis Example 1 of Compound 8 &

In a 500 ml four-necked flask equipped with a magnetic stirrer, 1.71 g of metal magnesium was charged, and the inside of the vessel was purged with nitrogen and sealed. 2 ml of THF (dehydrated) was added, and a solution of 20.68 g of Compound 7 dissolved in 155 ml of THF (dehydrated) was added dropwise over 1 hour under strong stirring. Thereafter, the temperature was raised to 55 占 폚, and the mixture was stirred for 2 hours to confirm that the metal magnesium disappeared. Subsequently, 30.53 g of tetramethoxysilane was added in an ice bath (inner temperature: 4 ° C), and the mixture was heated to reflux and stirred for 3 hours. After the reaction solution was cooled to room temperature, 210 ml of a saturated ammonium chloride aqueous solution was added, and the resulting insoluble matter was removed by filtration under reduced pressure. Further, the filtrate was washed with 260 ml of n-hexane. The aqueous phase 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 21.65 g of crude product. The residue was distilled under reduced pressure and distilled under the conditions of an external temperature of 220 to 230 DEG C / pressure of 0.8 torr to obtain 5.74 g (yield: 25%) of Compound 8.

[Chemical Formula 15]

&Lt; Synthesis Example 2 of Compound 10 &

To a 500 ml four-necked flask equipped with a magnetic stirrer were added 30.00 g of Compound 9, 25.24 g of potassium carbonate and 120 g of DMF, 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 of compound 10 (100% yield).

&Lt; Synthesis Example 3 of Compound 11 &

To a 300 ml four-necked flask equipped with a magnetic stirrer, 20.00 g of Compound 10 and 120 g of toluene were charged 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 subjected to distillation under reduced pressure, and the reaction was carried out under the conditions of an external temperature of 245 DEG C / pressure of 0.8 torr to obtain 12.15 g (yield: 43%) of Compound 11.

The abbreviations of the compounds used in this embodiment are as follows.

TEOS: tetraethoxysilane

C18: octadecyltriethoxysilane

ACPS: 3-acryloxypropyltrimethoxysilane

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

&Lt; Example 1 &gt;

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 in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube to obtain an alkoxysilane monomer Was prepared. To this solution, a solution prepared by previously 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 added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, 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. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO ₂ -conversion concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of the concentration to obtain a first [K1] of 4% by weight of the liquid crystal alignment.

&Lt; Example 2 &gt;

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 19.9 g of MPMS were mixed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, A solution of silane monomer was prepared. To this solution, a solution prepared by previously 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 added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, 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. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO ₂ -conversion concentration of 12% by weight.

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

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. To this solution, 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 at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, 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. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO ₂ -conversion concentration of 12% by weight.

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

A liquid crystal aligning agent intermediate (S2) and the liquid crystal aligning agent intermediate (U1) obtained 2 mixed in a ratio of 8, in terms of SiO ₂ concentration to obtain the [K2] of 4% by weight of the liquid crystal alignment.

&Lt; Example 3 &gt;

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 in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube to obtain an alkoxysilane monomer Solution. To this solution, a solution prepared by previously mixing 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 added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, 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. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO ₂ -conversion concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal orientation to obtain a second intermediate (S3).

A liquid crystal aligning agent intermediate (U1) obtained in the embodiment and the liquid crystal aligning agent obtained intermediate (S3) Example 22: a mixture in a ratio of 8, SiO ₂ in terms of the concentration to obtain a first [K3] it is 4% by weight of the liquid crystal alignment.

<Example 4>

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 in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube to obtain an alkoxysilane monomer Solution. To this solution, a solution prepared by previously mixing 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 added dropwise at room temperature over 30 minutes and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, 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. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO ₂ -conversion concentration of 12% by weight.

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

A liquid crystal aligning agent intermediate (U1) obtained in the embodiment and the liquid crystal aligning agent thus obtained intermediate (S4) Example 22: a mixture in a ratio of 8, SiO ₂ in terms of the concentration to obtain the [K4] is 4% by weight of the liquid crystal alignment.

&Lt; Example 5 &gt;

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 in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube to obtain an alkoxysilane monomer Was prepared. To this solution, a solution prepared by previously mixing 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 added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Then after that it was heated to reflux for 60 minutes using an oil bath to obtain a polysiloxane solution bangraeng SiO ₂ in terms of a concentration of 12% by weight.

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

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. To this solution, 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 at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, 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. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO ₂ -conversion concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal orientation to obtain a second intermediate (U2).

A liquid crystal aligning agent intermediate (S5) and the liquid crystal aligning agent intermediate (U2) obtained 2 mixed in a ratio of 8, in terms of SiO ₂ concentration to obtain the [K5] 4% by weight of the liquid crystal alignment.

&Lt; Example 6 &gt;

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 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 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 added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, 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. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO ₂ -conversion concentration of 12% by weight.

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

A liquid crystal aligning agent intermediate (U2) obtained in the embodiment and the liquid crystal aligning agent obtained intermediate (S6) Example 52: a mixture in a ratio of 8, SiO ₂ in terms of the concentration to obtain a first [K6] 4% by weight of the liquid crystal alignment.

&Lt; Comparative Example 1 &

A solution of an alkoxysilane monomer was prepared by mixing 22.1 g of HG, 7.3 g of BCS, 35.0 g of TEOS, 4.2 g of C18 and 5.0 g of MPMS in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. To this solution, a solution prepared by previously mixing 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 added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, 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. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO ₂ -conversion concentration of 12% by weight.

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

&Lt; Comparative Example 2 &

A solution of an 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. To this solution, a solution prepared by previously mixing 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 added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, 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. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO ₂ -conversion concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal alignment was obtained the intermediate (S5).

A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S5) of Synthetic Example 2 obtained 2 mixed in a ratio of 8, in terms of SiO ₂ concentration to obtain the [L2] of 4% by weight of the liquid crystal alignment.

&Lt; Comparative Example 3 &

A solution of alkoxysilane monomer was prepared by mixing 20.5 g of HG, 6.8 g of BCS, 22.5 g of BOS, 4.2 g of C18 and 19.9 g of MPMS in a 200 ml four-neck reaction flask equipped with a thermometer and reflux tube. To this solution, a solution prepared by previously mixing 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 added dropwise at room temperature over 30 minutes, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Thereafter, 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. The mixture was further refluxed for 30 minutes and then cooled to obtain a polysiloxane solution having a SiO ₂ -conversion concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 10.0 g, 20.0 g and BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal orientation to obtain a second intermediate (L3).

<Cell Example 1>

The liquid crystal aligning agent [K1] obtained in Example 1 was spin-coated on the ITO surface of the ITO electrode substrate on which the beta ITO electrode was formed. After drying for 2 minutes on a hot plate at 80 DEG C, firing was performed in a hot air circulating oven at 200 DEG C or 220 DEG C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. Two sheets of the substrates were prepared, and a bead spacer of 4 mu m or 6 mu m was scattered on the liquid crystal alignment film surface of one of the substrates, and then the sealant was printed thereon. The other substrate was adhered with the liquid crystal alignment film face inward, and then the sealant was cured to prepare a blank cell. A liquid crystal cell was prepared by injecting liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) into the empty cell by a low pressure injection method.

Thereafter, the resulting liquid crystal cell was annealed in a circulating oven at 100 캜 for 30 minutes. The removed cell was observed under a microscope with the polarizing plate being Cross-Nicol, and the state of the domain which was the alignment disorder of the liquid crystal was observed. The results are shown in Table 43.

<Cell Example 2>

The liquid crystal aligning agent [K2] obtained in Example 2 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 x 300 microns and a line / space of 5 microns each was formed. After drying for 2 minutes on a hot plate at 80 DEG C, firing was performed in a hot air circulating oven at 200 DEG C or 220 DEG C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. The liquid crystal aligning agent [K2] obtained in Synthesis Example 2 was spin-coated on an ITO surface on which no electrode pattern was formed and dried for 2 minutes on a hot plate at 80 DEG C, and hot air of 200 DEG C or 220 DEG C And fired in a circulating oven for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm. These two substrates were prepared, a 4-μm bead spacer was scattered on the liquid crystal alignment film surface of one of the substrates, and then a sealant was printed thereon. The other substrate was adhered with the liquid crystal alignment film face inward, and then the sealant was cured to prepare a blank cell. A liquid crystal cell was prepared by injecting liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) into the empty cell by a low pressure injection method.

The response time characteristics of these liquid crystal cells were represented by an oscilloscope with respect to the time change of the brightness of the liquid crystal panel when a square wave of AC voltage of ± 5 V and frequency of 1 kHz was applied to the liquid crystal cell. A voltage of 0% and a voltage of 5 V was applied to the luminance when the voltage was not applied, and the time at which the luminance varied from 10% to 90% with the value of the saturated luminance as 100% was set as the rising response speed .

Was measured by a method described later.

Thereafter, with the DC voltage of 20 V applied to the liquid crystal cell, 20 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 44.

Thereafter, the resulting liquid crystal cell was annealed in a circulating oven at 100 캜 for 30 minutes. The removed cell was observed under a microscope in the state of a polarizing plate made of Cross-Nicol, and the state of the domain which was the alignment disorder of the liquid crystal was observed. The results are also shown in Table 44.

<Cell Example 3>

A liquid crystal cell was prepared in the same manner as in the cell example 2 except that the liquid crystal aligning agent [K2] was changed to the liquid crystal aligning agent [K3] obtained in Example 3, and the response speed was measured. Respectively. The results are shown in Table 44.

<Cell Example 4>

A liquid crystal cell was prepared in the same manner as in the cell example 2 except that the liquid crystal aligning agent [K2] was changed to the liquid crystal aligning agent [K4] obtained in Example 4, and the response speed was measured. Respectively. The results are shown in Table 44.

<Cell Example 5>

A liquid crystal cell was prepared in the same manner as in the cell example 2 except that the liquid crystal aligning agent [K2] was changed to the liquid crystal aligning agent [K5] obtained in Example 5, and the response speed was measured. Respectively. The results are shown in Table 44.

<Cell Example 6>

A liquid crystal cell was prepared in the same manner as in the cell example 2 except that the liquid crystal aligning agent [K2] was changed to the liquid crystal aligning agent [K6] obtained in Example 6, and the response speed was measured. Respectively. The results are shown in Table 44.

<Cell Comparative Example 1>

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 [L1] obtained in Comparative Example 1. Thereafter, the resulting liquid crystal cell was annealed in a circulating oven at 100 캜 for 30 minutes. The removed cell was observed under a microscope in the state of a polarizing plate made of Cross-Nicol, and the state of the domain which was the alignment disorder of the liquid crystal was observed. The results are shown in Table 43.

<Cell Comparative Example 2>

A liquid crystal cell was fabricated in the same manner as in the cell example 2 except that the liquid crystal aligning agent [K2] was changed to the liquid crystal aligning agent [L2] obtained in the comparative example 2, and the response speed was measured. Respectively. The results are shown in Table 44.

<Cell Comparative Example 3>

A liquid crystal cell was prepared in the same manner as in the cell example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L3] obtained in the comparative example 3, and the response speed was measured. Respectively. The results are shown in Table 44.

[Response speed characteristics]

Time changes of the luminance of the liquid crystal panel when an AC voltage of ± 5 V and a square wave of frequency 1 kHz were applied to the liquid crystal cell were taken by the oscilloscope. A voltage of 0% and a voltage of 5 V was applied to the luminance when the voltage was not applied, and the time for which the luminance varied from 10% to 90% was taken as the rising response speed with the saturation luminance value being 100% .

As can be seen from Table 43, in the liquid crystal cell of the cell example 1, no domain which is disordered after annealing was observed at all. On the other hand, in the liquid crystal cell of the cell comparative example 1, a large number of domains which are disordered after annealing were observed.

Judgment of response speed O: Fast (good) X: Slow (bad)

Domain observation after annealing

 X: A large number of domains are observed

 ○: Good

 ◎: Very good

As can be seen from Table 44, in Cell Example 2, the response speed after UV irradiation was fast, and also good results were obtained in the domain observation results after annealing. On the other hand, in the cell comparison example 2, the result of observation of the domain after annealing was very good, but the response speed was slow. In Cell Comparative Example 3, although the response rate was fast, many domains were observed after annealing. In the cell examples 3 and 4 using the compound 11, the response speed after the UV irradiation was fast, and the results of the domain observation after the annealing showed very good results.

Also, in Cell Examples 5 and 6, the response speed after UV irradiation was fast, and the results of domain observation after annealing showed very good results.

Industrial availability

The liquid crystal display device manufactured by using the liquid crystal aligning agent of the present invention can be used in a liquid crystal display device in which a liquid crystal to which no polymerizable compound is added is used in a manner similar to the PSA method to improve the response speed after UV irradiation, There is provided a liquid crystal aligning agent capable of forming a liquid crystal alignment film capable of improving the response speed after UV irradiation without lowering the vertical aligning power, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal alignment film . Therefore, it is useful for TFT liquid crystal display elements, TN liquid crystal display elements, and VA liquid crystal display elements manufactured by the above method.

The entire contents of Japanese Patent Application No. 2011-118824 filed on May 27, 2011 and Japanese Patent Application No. 2011-251377 filed on November 17, 2011 are hereby incorporated by reference herein. Quot ;, which is incorporated herein by reference in its entirety.

Claims (11)

A liquid crystal aligning agent characterized by containing a polysiloxane (A) obtained by polycondensing an alkoxysilane represented by the following formula (1) and an alkoxysilane containing an 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]

(Y ¹ is a single _{bond, - (CH 2) a -} . (A 1 to an integer of 15), is -O-, -CH ₂ O-, -COO- or -OCO- Y ² is a single bond, (CR ¹⁷ R ¹⁸ ) _b - (b is an integer of 1 to 15, and R ¹⁷ and R ¹⁸ are each independently a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, . an atom or an alkyl group of carbon number 1 ~ ³⁾ 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 benzene ring, a cyclohexyl ring and a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton, and any of these cyclic groups The hydrogen atom is substituted with 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, Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, wherein any hydrogen atom on the cyclic group may be substituted with 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, or a fluorine atom, and n is an integer of 1 to 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 alkoxy group having 1 to 18 carbon atoms, or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.

(R ³ is an alkyl group having 1 to 30 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group, and R ⁴ is an alkyl group having 1 to 5 carbon atoms) The method according to claim 1,
Wherein R ³ is an alkyl group of 3 to 10 carbon atoms substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group or a styryl group in the above formula (3). The method according to claim 1,
(B) obtained by polycondensing an alkoxysilane containing 50% to 100% of an alkoxysilane represented by the following formula (5).

(R &lt; ¹⁵ &gt; represents an alkyl group having 1 to 5 carbon atoms) The method of claim 3,
Wherein the polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the formula (3). The method of claim 3,
Wherein the polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane represented by the following formula (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 method of claim 3,
Wherein at least one of the polysiloxane (A) and the polysiloxane (B) is a polysiloxane obtained by polycondensation of an alkoxysilane containing an alkoxysilane further represented by the following formula (4).

(In the formula (4), 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 is an integer of 0 to 3) The method according to claim 1,
Wherein the alkoxysilane represented by the formula (1) is contained in an amount of 2 to 20 mol% of the total alkoxysilane used in the polysiloxane (A), and the alkoxysilane represented by the formula (3) A liquid crystal aligning agent containing 5 to 80 mol% of alkoxysilane. A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to any one of claims 1 to 7 to a substrate, followed by drying and firing. 9. A liquid crystal display element having the liquid crystal alignment film according to claim 8. A liquid crystal display device comprising the liquid crystal aligning agent according to any one of claims 1 to 7 applied thereto and irradiating UV with a voltage applied to a liquid crystal cell in which liquid crystal is held between two sintered substrates.  A method for producing a liquid crystal display element, comprising applying the liquid crystal aligning agent according to any one of claims 1 to 7, sandwiching the liquid crystal by two fired substrates, and irradiating UV with applying voltage.