KR20170117926A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device - Google Patents

Abstract

(식 (4) 중, R¹은, 메틸렌기, 탄소수 2∼30의 알킬렌기, -(C_b'H_2b'O)_c'-, 페닐렌기 또는 사이클로헥실렌기이고; b'는, 0∼20의 정수이고; c'는, 0∼10의 정수이고; 단, 이들 기의 수소 원자의 일부 또는 전부는, 치환되어 있어도 좋고; R²는, 탄소-탄소 이중 결합, 탄소-탄소 삼중 결합, 에테르 결합, 에스테르 결합 또는 아미드 결합을 포함하는 연결기이고; R³은, 적어도 2개의 단환 구조를 갖는 기이고; a는, 1이고; R⁹는, 단결합, -O-, *-COO- 또는 -OCO-이고; 단, *는 디아미노페닐기와 결합하는 부위이고; d는, 0 또는 1이고; e는, 0∼2의 정수이고; g는, 2 또는 3임)[PROBLEMS] To provide a liquid crystal aligning agent capable of producing a liquid crystal display element capable of high-speed response and excellent in voltage-holding ratio, after-image characteristic and light resistance, and having excellent uniform coating property.
[MEANS FOR SOLVING PROBLEMS] (A) A polymer composition containing at least one polymer selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and the polymer has a partial structure derived from a compound represented by the following formula (4) Liquid crystal aligning agent.

(Wherein R ¹ represents a methylene group, an alkylene group having 2 to 30 carbon atoms, - (C _{b '} H _{2 b '} O) _{c '} -, a phenylene group or a cyclohexylene group, b' And R < ² > represents a carbon-carbon double bond, a carbon-carbon triple bond R ³ is a group having at least two monocyclic structures, a is 1, R ⁹ is a single bond, -O-, -COO-, -COO-, D is 0 or 1, e is an integer of 0 to 2, g is 2 or 3, and R < 3 >

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment material, a liquid crystal alignment film, and a liquid crystal display device,

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display element.

In recent years, liquid crystal display devices have advantages such as small power consumption, small size, and ease of flattening. Therefore, they are widely used for a wide range of applications, from small liquid crystal display devices such as cellular phones to large- .

TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and the like are known as the driving mode of the liquid crystal display device in accordance with the change of the orientation have. In addition, in the VA mode, a multi-domain vertical alignment (MVA) method or a PVA (patterned vertical alignment) method is employed in order to increase the viewing angle by orientation division. Angle orientation method, a PSA (Polymer Sustained Alignment) method or the like is being considered. In any of these driving modes, the alignment state of the liquid crystal molecules is directly controlled by the liquid crystal alignment film, and the liquid crystal alignment film takes a considerable portion of the function and the control of the functional characteristics of the liquid crystal display element.

Such a liquid crystal display device is expected to be used as a moving image display device such as a cellular phone or a liquid crystal television. In view of the characteristics required for a liquid crystal display device, A further increase in time is required. With respect to this demand, there has been reported a technique for improving by giving a structure giving dielectric anisotropy to polymer side chains used in a liquid crystal alignment film (see Japanese Patent Publication No. 2007-521361 and Japanese Patent Publication No. 2007-521506). However, this patent document does not disclose electrical characteristics such as voltage holding ratio and afterimage characteristic, which are important in practical use, in addition to speeding up the electrooptical response time.

From such a situation, it is desired to develop a liquid crystal aligning agent capable of producing a liquid crystal display element having excellent performance such as a voltage holding ratio while realizing high-speed response of the liquid crystal element.

Japanese Patent Publication No. 2007-521361 Japanese Patent Publication No. 2007-521506

The object of the present invention is to provide a liquid crystal aligning agent capable of producing a liquid crystal display element capable of high-speed response and excellent in voltage-holding ratio, after-image characteristic and light resistance, and having excellent uniform coating property will be.

According to an aspect of the present invention,

[A] a liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid, polyimide and polyamic ester, and the polymer having a partial structure derived from a compound represented by the following formula (4) .

(In the formula (4)

R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, - (C _{b '} H _{2 b '} O) _{c '} -, a phenylene group or a cyclohexylene group; b 'is an integer of 0 to 20; c 'is an integer of 0 to 10; Provided that some or all of the hydrogen atoms of these groups may be substituted;

R ² is a linking group comprising a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or an amide bond;

R ³ is a group having at least two monocyclic structures;

a is 1;

R ⁹ is a single bond, -O-, * -COO- or -OCO-; Provided that * is a site bonding with a diaminophenyl group;

d is 0 or 1;

e is an integer from 0 to 2;

g is 2 or 3)

The liquid crystal aligning agent contains a [A] polymer having a specific partial structure derived from the compound represented by the formula (4), thereby realizing a high-speed response. Further, by suitably selecting at least one kind of polymer selected from the group consisting of polyamic acid, polyimide and polyamic acid ester having different polymer main chain structures, it is possible to obtain desired characteristics (voltage holding ratio, residual image characteristic, Light resistance) can be imparted.

It is preferable that R ³ is a group represented by the following formula (2).

(In the formula (2)

R ⁴ and R ⁶ are each independently a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle; Provided that some or all of the hydrogen atoms of these groups may be substituted;

R ⁵ is a linking group comprising a methylene group, an alkylene group having 2 to 10 carbon atoms, a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or a heterocycle; Provided that some or all of the hydrogen atoms of the linking group may be substituted;

R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group or an alkylcarbonyloxy group;

b is 0 or 1; c is an integer from 1 to 9; Provided that when plural R < ⁷ > s are present, plural R < ⁷ > s may be the same or different)

By introducing the structure represented by the formula (2) as the side chain of the polymer [A], the response speed of the resulting liquid crystal aligning element can be further improved.

The present invention preferably includes a liquid crystal alignment film formed of the liquid crystal display device and a liquid crystal display device having the liquid crystal alignment film. As described above, according to the liquid crystal aligning agent of the present invention, since the liquid crystal display element capable of high-speed response and excellent in the performance such as voltage holding ratio, after-image characteristic, uniform coating ability, light resistance, , STN, IPS, FFS, Ht-VA (VA-IPS), VA (including MVA, PVA, optical vertical alignment and PSA).

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a liquid crystal aligning agent capable of producing a liquid crystal display element capable of high-speed response and excellent in performances such as voltage holding ratio, afterimage characteristic, light resistance and the like and also having excellent uniform coating property. Therefore, the liquid crystal display device is suitably used in a driving mode such as TN, STN, IPS, FFS, Ht-VA (VA-IPS), VA (including MVA, PVA, optical vertical alignment and PSA) Can be applied.

(Mode for carrying out the invention)

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention contains the [A] polymer. The liquid crystal aligning agent may contain other optional components within the range not impairing the effects of the present invention. Hereinafter, each component will be described in detail.

<[A] Polymer>

The polymer [A] contains at least one polymer selected from the group consisting of polyamic acid, polyimide, (meth) acrylic polymer, polysiloxane and polyamic acid ester, and the polymer is a group represented by the following formula . The liquid crystal aligning agent contains a [A] polymer having a group of a specific structure represented by the following formula (1), whereby a high-speed response can be realized. In addition, by appropriately selecting at least one kind of polymer selected from the group consisting of polyamic acid, polyimide, (meth) acrylic polymer, polysiloxane and polyamic ester having different polymer main chain structures, desired characteristics (voltage holding ratio , Afterimage characteristic, uniform coating property, light resistance) can be imparted. Hereinafter, the groups represented by the following formula (1) and the order of the respective polymers will be described in detail.

[The group represented by the formula (1)

(In the formula (1)

R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, - (CH _2b O) _c -, a phenylene group or a cyclohexylene group; b is an integer from 0 to 20; c is an integer of 0 to 10; Provided that some or all of the hydrogen atoms of these groups may be substituted;

R ² is a linking group containing a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or an amide bond;

R ³ is a group having at least two monocyclic structures;

a is 0 or an integer of 1)

In the formula (1), R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, - (C _b H _2b O) _c -, a phenylene group or a cyclohexylene group. b is an integer of 0 to 20; and c is an integer of 0 to 10. However, some or all of the hydrogen atoms of these groups may be substituted. R ² is a linking group containing a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or an amide bond. R ³ is a group having at least two monocyclic structures. and a is an integer of 0 or 1.

The linking group represented by R ² is preferably an ether group, an ester group or an amide group.

Examples of the alkylene group having 2 to 30 carbon atoms represented by R ¹ include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, , A tetradecylene group, a hexadecylene group, an octadecylene group, a nonadecylene group, an eicosylene group, a hemexocylene group, a docosylene group, a tricoxylene group, a tetracosylene group, a pentacosylene group, A silane group, a heptacosylene group, an octacosylene group, a nonacosylene group, and a triacontylene group.

The group having at least two monocyclic structures represented by R ³ is preferably a group represented by the formula (2). By introducing the structure represented by the formula (2) as the side chain of the polymer [A], the response speed of the resulting liquid crystal aligning element can be further improved.

In the formula (2), R ⁴ and R ⁶ are each independently a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle. However, some or all of the hydrogen atoms of these groups may be substituted. R ⁵ is a linking group containing a methylene group, an alkylene group having 2 to 10 carbon atoms, a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or a heterocycle. Provided that some or all of the hydrogen atoms of the connecting group may be substituted. R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group or an alkylcarbonyloxy group. b is 0 or 1; and c is an integer of 1 to 9. However, in the case where R ⁷ is plural, plural R ⁷ may be the same or different. In the present specification, the condensed rings such as the naphthalene group and the like are included in monocyclic rings.

Examples of the heterocyclic ring represented by R ⁴ and R ⁶ include a pyridine ring, a pyridazine ring, and a pyrimidine ring. Examples of the alkylene group having 2 to 10 carbon atoms in the linking group containing an alkylene group having 2 to 10 carbon atoms represented by R ⁵ include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and an octylene group. . Examples of the heterocyclic ring represented by R ⁵ include a pyridine ring, a pyridazine ring, and a pyrimidine ring. Examples of the alkoxycarbonyl group represented by R ⁷ include a methoxycarbonyl group, ethoxycarbonyl group and propoxycarbonyl group. Examples of the alkyl group represented by R ⁷ include a linear or branched alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group and an isobutyl group. Examples of the alkoxy group represented by R ⁷ include methoxy group, ethoxy group and propoxy group. Examples of the alkylcarbonyloxy group represented by R ⁷ include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, and a propoxycarbonyloxy group.

From the viewpoint of fast response of the liquid crystal display element using the liquid crystal aligning agent, the R ⁷ is preferably an alkyl group, more preferably a linear alkyl group having 1 to 20 carbon atoms. It is preferable that at least one of R ⁴ to R ⁶ has a fluorine atom.

The group represented by the formula (2) includes, for example, groups represented by the following formulas.

In the formulas (2-1) to (2-123), R ⁸ is an alkyl group or an alkoxy group having 1 to 20 carbon atoms. Each X independently represents a hydrogen atom or a fluorine atom.

The R ⁸ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.

(2-1), (2-4), (2-6), (2-1), (2-2) and (3-2), from the viewpoint of fast response of the liquid crystal display element using the liquid crystal aligning agent, (2-41), (2-50) to (2-60), (2-64) and (2-65) A group having a fluorine atom and having an alkyl group at the terminal, a group represented by the formula (2-72), and a group represented by the formula (2-50) to (2-58) The group represented by the formula (2-90) is more preferable.

[Polyamic acid]

The polyamic acid as the [A] polymer can be obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound. A part of the diamine compound needs to be a diamine compound containing a group represented by the formula (1).

Examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aromatic tetracarboxylic acid dianhydride. These tetracarboxylic acid dianhydrides may be used alone or in combination of two or more.

Examples of the aliphatic tetracarboxylic acid dianhydride include butane tetracarboxylic dianhydride.

Examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2 , 4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6,8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- 5,8,10-tetraone, and the like.

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride and the like, and tetracarboxylic dianhydrides described in JP-A-2010-97188.

Of these tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic dianhydrides are preferable, and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride are preferable. desirable.

Examples of the diamine compound include an aliphatic diamine, an alicyclic diamine, a diaminoorganosiloxane, and an aromatic diamine. These diamine compounds may be used alone or in combination of two or more.

Examples of the aliphatic diamine include, for example, meta-xylene diamine, 1,3-propanediamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine and the like.

Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), and 1,3-bis (aminomethyl) cyclohexane.

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, as well as the diamines described in JP-A-2010-97188.

Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9- 4,4'- (m-tert-butylphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4 - diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl- , 6-diaminocarbazole, N- (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis (4-aminophenyl) -Bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecaneoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy- , 4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecanoxy- Diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy- Diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid Cholestanol, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3 , 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyl) Bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1- Methylphenyl) -4-heptylcyclohexane, 1,1-bis (4 - ((aminophenoxy) methyl) (4-aminobenzylamine) represented by the following formula (3): &quot; (4) &quot; A compound represented by the following formula (4), and the like.

In the above formula (3), R ⁹ , R ⁹ "and R ⁹ "'are each independently a single bond, -O-, * -COO- or -OCO-. However, * in R ⁹ is a moiety bonded to a diaminophenyl group. In addition, * in R ⁹ "and R ⁹ "'is a moiety bonded to the phenylene group side. R ⁹ 'is an alkanediyl group having 1 to 3 carbon atoms. d is 0 or 1; e is an integer of 0 to 2; f is 0 or 1; R ¹⁰ is a linear, branched or cyclic alkyl group. The two amino groups in the diaminophenyl group are preferably bonded at the 2,4-position or 3,5-position.

In the formula (4), R ⁹ , d and e have the same meanings as in the formula (3). R ¹ to R ³ and a have the same meanings as in the formula (1). The two amino groups in the diaminophenyl group are preferably bonded at the 2,4-position or 3,5-position. g is an integer of 1 to 5;

With respect to R ¹ to R ³ , the description of each definition and the description of the preferred group in the above-mentioned [group represented by the formula (1)] can be directly applied.

The above-mentioned g is preferably 1 to 3, and more preferably 2 or 3 from the viewpoint of high-speed response of the liquid crystal display element using the liquid crystal aligning agent.

Examples of the diamine represented by the formula (4) include diamines represented by the following formulas.

Among these diamines, when a polyamic acid is selected as the polymer [A], from the viewpoint of introducing the group represented by the formula (1) into the polymer, at least a compound represented by the formula (4) 1) is required to be used. When other diamines are used in combination, it is preferable to use the compound represented by the formula (3).

The ratio of the tetracarboxylic acid dianhydride and the diamine compound provided in the synthesis reaction of the polyamic acid is preferably 0.2 equivalents to 2 equivalents of the acid anhydride group of the tetracarboxylic acid dianhydride with respect to 1 equivalent of the amino group contained in the diamine compound, More preferably 0.3 equivalents to 1.2 equivalents.

The synthesis reaction is preferably carried out in an organic solvent. The reaction temperature is preferably -20 占 폚 to 150 占 폚, more preferably 0 占 폚 to 100 占 폚. The reaction time is preferably 0.5 hours to 24 hours, more preferably 2 hours to 12 hours.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be synthesized. Examples of the organic solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, , N, N-dimethylimidazolidinone, dimethylsulfoxide,? -Butyrolactone, tetramethylurea, hexamethylphosphoric triamide, m-cresol, xylenol, phenol, halogenated phenol, diethylene glycol ethyl methyl Ether, and the like.

The amount of the organic solvent to be used is preferably 0.1 part by mass to 50 parts by mass, more preferably 5 parts by mass to 40 parts by mass, per 100 parts by mass of the total amount of the tetracarboxylic acid dianhydride and the diamine compound.

The polyamic acid solution obtained after the reaction may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent. After the isolated polyamic acid is purified, It may be provided in the preparation of the article. Examples of the method of isolating the polyamic acid include a method of drying a precipitate obtained by pouring the reaction solution into a large amount of a poor solvent under reduced pressure, and a method of distilling off the reaction solution by distillation under reduced pressure. Examples of the method for purifying polyamic acid include a method in which an isolated polyamic acid is dissolved again in an organic solvent and then precipitated with a poor solvent, and a method in which a step of distilling off an organic solvent or the like under reduced pressure is performed once or plural times have.

[Polyimide]

The polyimide can be produced by dehydrating and cyclizing the arid acid structure of the polyamic acid to imidize it. The polyimide may be a complete imide cargo which is subjected to dehydration ring closure of all of the arboric acid structure of the polyamic acid which is the precursor thereof and may be dehydrated and ring closed only in a part of the arboric acid structure to form a partial imide cargo .

The polyimide may be synthesized by, for example, (i) a method of heating a polyamic acid (hereinafter also referred to as "method (i)"), (ii) dissolving a polyamic acid in an organic solvent, And a method of adding a ring-closing catalyst and heating as required (hereinafter also referred to as &quot; method (ii) &quot;).

The reaction temperature in the method (i) is preferably 50 ° C to 200 ° C, more preferably 60 ° C to 170 ° C. If the reaction temperature is less than 50 캜, the dehydration ring closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 캜, the molecular weight of the obtained polyimide may be lowered. The reaction time is preferably 0.5 hours to 48 hours, more preferably 2 hours to 20 hours.

The polyimide obtained in the method (i) may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, after the polyimide is isolated, the polyimide may be supplied to the preparation of the liquid crystal aligning agent, And may be provided in the preparation of the liquid crystal aligning agent after purification.

Examples of the dehydrating agent in the method (ii) include acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride.

The amount of the dehydrating agent to be used is appropriately selected depending on the desired imidization rate, but is preferably 0.01 mol to 20 mol based on 1 mol of the acid structure of the polyamic acid.

Examples of the dehydration ring closure catalyst in the method (ii) include pyridine, collidine, lutidine, triethylamine, and the like.

The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 mol to 10 mol relative to 1 mol of the dehydrating agent contained. The imidization rate can be increased as the content of the dehydrating agent and the dehydration ring-closing catalyst is larger.

Examples of the organic solvent used in the method (ii) include the same organic solvents as those exemplified for the synthesis of polyamic acid.

The reaction temperature in the method (ii) is preferably 0 ° C to 180 ° C, more preferably 10 ° C to 150 ° C. The reaction time is preferably 0.5 hours to 20 hours, more preferably 1 hour to 8 hours. By setting the reaction conditions within the above range, the dehydration ring-closure reaction proceeds sufficiently, and the molecular weight of the obtained polyimide can be made appropriate.

In the method (ii), a reaction solution containing polyimide can be obtained. This reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or may be provided to the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. Alternatively, after the polyimide is isolated and provided in the preparation of the liquid crystal aligning agent After the polyimide having good or isolation is purified, it may be added to the preparation of the liquid crystal aligning agent. Examples of the method for removing the dehydrating agent and the dehydration cyclization catalyst from the reaction solution include a method of solvent substitution. Examples of the polyimide isolation and purification methods include the same methods as those exemplified as the polyamic acid isolation and purification methods.

[(Meth) acrylic polymer]

The (meth) acrylic polymer as the [A] polymer is not particularly limited as long as it is a (meth) acrylic polymer containing a group represented by the formula (1), and is obtained by polymerizing a known ethylenically unsaturated compound by a known method. (A) an ethylenically unsaturated compound containing an epoxy group (hereinafter also referred to as "(a) unsaturated compound") and (b1) an ethylenically unsaturated carboxylic acid and / or a polymerizable unsaturated polycarboxylic acid anhydride (hereinafter also referred to as &quot; b1) unsaturated compound &quot;) and a polymerizable unsaturated compound other than (a) an unsaturated compound and (b1) an unsaturated compound (hereinafter also referred to as &quot; unsaturated compound (b2) &quot;).

Examples of the unsaturated compound (a) include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α- 3,4-epoxycyclohexyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl acrylate, acrylic acid 6,7-epoxyheptyl acrylate, and 6,7-epoxy heptyl acrylate.

As the unsaturated compound (b1), for example,

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid,? - ethyl acrylic acid,? - n-propyl acrylic acid,? - n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

And unsaturated polycarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride and cis-1,2,3,4-tetrahydrophthalic anhydride.

As the unsaturated compound (b2), for example,

Esters having a (meth) acrylic acid hydroxyl group such as a (meth) acrylic acid ester having a group represented by the formula (1), 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

(Meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec- Butyl (meth) acrylate and t-butyl (meth) acrylate;

(Meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan- (Meth) acrylic acid alicyclic esters such as dicyclopentanyloxyethyl, isobornyl (meth) acrylate and cholestanyl (meth) acrylate;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Unsaturated dicarbonylimide derivatives such as N-succinimidyl-3-maleimidopropionate and N- (9-acridyl) maleimide;

(Meth) acrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide;

Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide;

Aromatic vinyl compounds such as styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene;

Indene derivatives such as indene and 1-methylindene;

Vinylidene chloride, vinylidene chloride, and vinyl acetate, in addition to conjugated diene compounds such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

As the unsaturated compound, glycidyl (meth) acrylate is preferable, and (b1) unsaturated compound is preferably (meth) acrylic acid, and (b2) unsaturated compound is preferably cholestanyl (meth) acrylate. When the (meth) acrylic polymer as the polymer (A) is synthesized by, for example, radical polymerization, from the viewpoint of introducing the group represented by the formula (1) into the polymer, at least one of the unsaturated compounds ) Is required to be used. On the other hand, a group represented by the formula (1) may be introduced by a conventionally known polymer reaction using, for example, an epoxy group in a polymer having no group represented by the formula (1).

As a method for synthesizing a (meth) acrylic polymer, it is convenient to synthesize each unsaturated compound by, for example, radical polymerization in the presence of an appropriate solvent and polymerization initiator. Examples of the organic solvent include the same organic solvents as those exemplified for the synthesis of polyamic acid.

As the polymerization initiator, for example,

(2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethyl Azo compounds such as valeronitrile);

Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane;

Hydrogen peroxide;

And a redox-type initiator comprising these peroxides and a reducing agent. These polymerization initiators may be used alone or in combination of two or more.

[Polysiloxane]

The polysiloxane as the polymer [A] is not particularly limited as long as it is a polysiloxane containing a group represented by the above formula (1), and examples thereof include at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound Quot; raw silane compound &quot;), preferably in an appropriate organic solvent, in the presence of water and a catalyst, by hydrolysis or hydrolysis / condensation.

As the raw material silane compound, for example,

Tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, Tetrachlorosilane and the like;

Methyltriethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-sec Butoxysilane, methyltri-butoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso Butoxy silane, ethyl tri-sec-butoxysilane, ethyl tri-tert-butoxysilane, ethyl trichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyl Trichlorosilane and the like;

Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane and the like;

Trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane and the like;

And silane having a group represented by the above formula (1).

Of these raw material silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Trimethyl methoxysilane, trimethylethoxysilane, octadecyltriethoxysilane, and silane having a group represented by the above formula (1) are preferable. In the case of selecting polysiloxane as the polymer [A], it is necessary to use at least silane having a group represented by the formula (1) as one of the raw material silane compounds from the viewpoint of introducing the group represented by the formula (1) into the polymer .

Examples of the organic solvent that can optionally be used in the synthesis of the polysiloxane include an alcohol compound, a ketone compound, an amide compound, an ester compound, or other non-protonic compounds. These may be used alone or in combination of two or more.

The reaction temperature for synthesizing the polysiloxane is preferably 0 deg. C to 100 deg. C, more preferably 15 deg. C to 80 deg. The reaction time is preferably 0.5 hours to 24 hours, more preferably 1 hour to 8 hours.

[Polyamic acid ester]

The polyamic acid ester is a polymer obtained by reacting the above-described polyamic acid with an organic halide, an alcohol or a phenol.

The polymer [A] is at least one polymer selected from the group consisting of polyamic acid, polyimide, (meth) acrylic polymer, polysiloxane and polyamic acid ester. [A] , When at least one kind of polymer has a group represented by the above formula (1), high-speed responsiveness, which is a desired effect of the present invention, can be realized.

The weight average molecular weight (Mw) in terms of styrene by gel permeation chromatography of the polymer [A] is not particularly limited, but is preferably 1,000 to 500,000, more preferably 2,000 to 300,000 in the case of polyamic acid, polyimide or polyamic acid ester Is more preferable. (Meth) acrylic polymer is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000. In the case of polysiloxane, 1,000 to 200,000 is preferable, and 2,000 to 100,000 is more preferable. Within this molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

&Lt; Other optional components &gt;

The liquid crystal aligning agent may contain other optional components such as a curing agent, a curing catalyst, a curing accelerator, an epoxy compound, a surfactant and the like, so long as the effect of the present invention is not impaired. These other optional components may be used alone or in combination of two or more. The blending amount of other optional components can be appropriately determined in accordance with the purpose. Hereinafter, each component will be described in detail.

[Curing agent, curing catalyst and curing accelerator]

The curing agent and the curing accelerator may be contained in the liquid crystal aligning agent for the purpose of enhancing the crosslinking reaction of the [A] polymer. The curing accelerator may be contained in the liquid crystal aligning agent for the purpose of accelerating the curing reaction which is carried out by the curing agent.

As the curing agent, a curing agent generally used for curing a curable compound having an epoxy group or a compound containing an epoxy group can be used. Examples of such a curing agent include polyvalent amines and polyvalent carboxylic acid anhydrides.

Examples of the polyvalent carboxylic acid anhydride include anhydrides of cyclohexanetricarboxylic acid and other polyvalent carboxylic acid anhydrides. Examples of the cyclohexanetricarboxylic acid anhydrides include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic-3,5- Hexane-1,2,3-tricarboxylic acid-2,3-anhydride and the like. Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride and the like.

As the curing catalyst, for example, an antimony hexafluoride compound, a hexafluorophosphate compound, and aluminum trisacetylacetonate can be given. These catalysts can accelerate the cationic polymerization of the epoxy group by heating.

As the curing accelerator, for example, an imidazole compound; A quaternary compound; Quaternary amine compounds; Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; Organometallic compounds such as zinc octylate, tin octylate and aluminum acetyl acetone complex; Boron compounds such as boron trichloride and triphenyl borate; Metal halide compounds such as zinc chloride and stannic chloride; A high melting point dispersing latent curing accelerator such as dicyandiamide, an amine addition type accelerator such as an adduct of an amine and an epoxy resin; A microcapsulated latent curing accelerator in which a surface of a quaternary phosphonium salt or the like is coated with a polymer; Amine salt type latent curing accelerator; High-temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Brensted acid salts, and the like.

[Epoxy Compound]

The epoxy compound may be contained in the liquid crystal aligning agent from the viewpoint of improving the adhesion to the substrate surface of the liquid crystal alignment layer to be formed.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglyl N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane , N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N, -diglycidylbenzylamine, N, N-diglycidylaminomethyl Cyclohexane is preferred.

[Surfactants]

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants.

&Lt; Preparation method of liquid crystal aligning agent &gt;

As described above, the liquid crystal aligning agent may contain a polymer [A] as an essential component and, if necessary, other optional components. Preferably, the liquid crystal aligning agent is a solution composition in which each component is dissolved in an organic solvent It is prepared.

As the organic solvent that can be used for preparing the liquid crystal aligning agent, it is preferable that the polymer [A] and other optional components are dissolved and not reacted with the polymer. Examples of the organic solvent include the organic solvents exemplified above, which are used for the synthesis of the polyamic acid. The poor solvent exemplified for use in the synthesis of polyamic acid may also be used in combination. These organic solvents may be used alone or in combination of two or more.

As a preferable solvent to be used for preparing the liquid crystal aligning agent, it is preferable that each component contained in the liquid crystal aligning agent is not precipitated at a preferable solid concentration to be described later and that the surface tension of the liquid crystal aligning agent is 25 mN / m to 40 mN / m Range.

The ratio of the solid content of the liquid crystal aligning agent, that is, the mass of all the components other than the solvent in the liquid crystal aligning agent, to the total mass of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc., Mass%. The liquid crystal aligning agent is applied to the surface of the substrate to form a coating film which becomes a liquid crystal alignment film. However, when the solid concentration is 1% by mass or more, the film thickness of the coating film is less likely to be unduly low, and a good liquid crystal alignment film can be obtained. On the other hand, when the solid content concentration is 10% by mass or less, it is possible to suppress an excessive film thickness of the coating film and obtain a good liquid crystal alignment film. Further, it is possible to prevent the viscosity of the liquid crystal aligning agent from being increased, and to improve the coating property. The range of the solid content concentration is more preferably 1.5% by mass to 4.5% by mass, for example, by the spinner method. And 3% by mass to 9% by mass in the case of the printing method. And is from 1% by mass to 5% by mass in the case of the inkjet method.

<Liquid crystal display element>

The driving method of the liquid crystal display of the present invention is not particularly limited, and TN, STN, IPS, FFS, Ht-VA (VA-IPS), VA (including VA-MVA method, VA- And the liquid crystal alignment layer formed of the liquid crystal aligning agent. As described above, according to the liquid crystal aligning agent, it is possible to produce a liquid crystal display element which is capable of high-speed response and excellent in performances such as voltage-holding ratio, after-image characteristic, uniform coating property, light resistance and the like. Generally, a liquid crystal display device has a pair of substrates on which a transparent electrode and a liquid crystal alignment film are laminated in this order, and the pair of substrates are disposed inside to face each other, and liquid crystal is charged And the peripheral portion is sealed with a sealant.

<Manufacturing Method of Liquid Crystal Display Element>

The liquid crystal display element of the present invention can be produced, for example, as follows. The liquid crystal alignment film included in the liquid crystal display element is formed on the substrate by applying the liquid crystal aligning agent on the substrate and then heating the coated surface. Examples of the substrate include glass such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and alicyclic polyolefin can be used. Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is arranged between the two substrates to manufacture a liquid crystal cell. Examples of the method for producing the liquid crystal cell include the following methods.

As a first method, two substrates are opposed to each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded to each other using a sealant, A liquid crystal is injected and filled in the cell gap defined by the liquid crystal cell, and then the injection port is sealed.

As a second method, there is a method called ODF (One Drop Fill) method. For example, an ultraviolet curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, the liquid crystal is further dropped on the liquid crystal alignment film surface, A liquid crystal cell can be manufactured by bonding one of the substrates and then curing the sealing agent by irradiating ultraviolet light to the entire surface of the substrate.

In either case, it is preferable to remove the flow orientation at the time of injection by heating the liquid crystal using the liquid crystal cell to a temperature at which the liquid crystal takes an isotropic phase (isotropic phase), and gradually cooling to room temperature. Then, the polarizing plate is bonded to the outer surface of the liquid crystal cell to obtain the liquid crystal display element.

Examples of the sealant include an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent.

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal or the like can be used. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, it is preferable to have a positive dielectric anisotropy for forming a nematic liquid crystal. Examples of such liquid crystals include biphenyl-based liquid crystal, phenylcyclohexane-based liquid crystal, ester-based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane- Quartz liquid crystal or the like is used. Further, it is also possible to add a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonanoate or cholesteryl carbonate to the liquid crystal; Chiral agents such as those sold under the trade names C-15 and CB-15 (Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, and the like.

On the other hand, in the case of the vertical alignment type liquid crystal cell, it is preferable to have a negative dielectric anisotropy for forming a nematic liquid crystal. As such a liquid crystal, for example, a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, a cypher base-based liquid crystal, an agglutinative liquid crystal, a biphenyl-based liquid crystal, a phenylcyclohexane-based liquid crystal and the like are used.

The polarizing plate used for the outside of the liquid crystal cell is not particularly limited, but a polarizing plate in which a polarizing film called an &quot; H film &quot;, in which a polyvinyl alcohol film is oriented in a stretched state while absorbing iodine is sandwiched by a cellulose acetate protective film or a polarizing plate And the like.

[Example]

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples.

The weight average molecular weight (Mw) of the polymer [A] obtained in the following Examples is the polystyrene equivalent measured by GPC in the following specification.

Column: TSKgelGRCXLII, Toso K.K.

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

[Synthesis Example 1]

Compounds 1, 2 and 3 were synthesized according to the following reaction formula.

(0.0645 mole) of 4-cyano-4'-hydroxybiphenyl, 17.0 g (0.0717 mole) of 10-bromo-1-decanol and 28.4 g of potassium carbonate were added to a 500 ml three- And 350 mL of N, N-dimethylformamide were added and the mixture was heated and stirred at 160 DEG C for 5 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 1,000 mL of water and mixed and stirred. The precipitated white solid was filtered off and further washed with water. The obtained solid was vacuum-dried at 80 占 폚 to obtain 20.6 g of the compound 1. Next, 20 g (0.0569 mol) of Compound 1 obtained was dissolved in 150 mL of dehydrated tetrahydrofuran (THF), 7.49 g (0.0740 mol) of triethylamine was added, and then 3,5-dinitrobenzoyl 14.4 g (0.0625 mol) of chloride were slowly added dropwise over 30 minutes under ice-cooling (ice cooling), and then stirred at room temperature for 3 hours. After completion of the reaction, triethylamine hydrochloride was removed by filtration, and THF was removed by distillation under reduced pressure, and 400 mL of chloroform was added. This solution was washed with water and the organic layer was dried over magnesium sulfate, and then chloroform was removed by distillation under reduced pressure. Thereafter, recrystallization was performed with ethanol, and vacuum drying was performed at 80 캜 to obtain 23.8 g of the compound 2. 20 g (0.0367 mol) of the compound 2 and 1 g (5 wt.% Of the compound 2) of 5% Pd / C were added to 500 mL of ethanol under a nitrogen stream, and further 4.2 g of 28% ammonia water Mol) was added. 21 g of hydrazine monohydrate (80% purity) was slowly added dropwise while keeping the solution at 15 5 캜, and the mixture was reacted for about 20 hours with stirring. Thereafter, the reaction solution was added dropwise to distilled water while being filtered while being heated (when heated), stirred and washed at room temperature, and filtered to obtain a white to pale yellow solid. This was vacuum-dried at 35 캜 to obtain 16.8 g of the compound 3.

[Synthesis Example 2]

Compound 4 was synthesized according to the following reaction formula.

20 g (0.0569 mole) of Compound 1 obtained by the same procedure as in Synthesis Example 1 was dissolved in 300 ml of THF, and 7.49 g (0.0740 mole) of triethylamine was added. Then, 6.53 g (0.0625 mole) of methacryloyl chloride The mixture was gradually added dropwise over 30 minutes under ice-cooling, and then stirred at room temperature for 3 hours. After completion of the reaction, triethylamine hydrochloride was removed by filtration, and THF was removed by distillation under reduced pressure, and 400 mL of chloroform was added. This solution was washed with water and the organic layer was dried over magnesium sulfate, and then chloroform was removed by distillation under reduced pressure. Thereafter, recrystallization was performed with ethanol, and vacuum drying was performed at 80 캜 to obtain 17.7 g of the compound 4.

[Synthesis Example 3]

Compounds 5 and 6 were synthesized according to the following reaction formula.

(0.0645 mol) of 4-cyano-4'-hydroxybiphenyl, 16.7 g (0.0717 mol) of 11-bromo-1-undecene and 28.4 g And 350 mL of N, N-dimethylformamide were added and the mixture was heated and stirred at 160 DEG C for 5 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 1,000 mL of water and mixed and stirred. The precipitated white solid was filtered off and further washed with water. The obtained solid was vacuum-dried at 80 占 폚 to obtain 19.8 g of the compound 5. (0.0250 mol) of Compound 5, 15 g of trimethoxysilane, and 40 쨉 l of an isopropanol solution of 0.2 M chloroplatinic acid hexahydrate were placed in a 100 mL three-necked flask equipped with a stirrer, a reflux tube and a nitrogen inlet tube, , And the reaction was carried out under reflux for 10 hours under nitrogen. The reaction mixture was passed through a short column of silica gel, purified with a silica column, and furthermore, the solvent was removed to obtain 3.5 g of the compound 6.

[Synthesis Example 4]

Compounds 7 to 11 were synthesized according to the following reaction formula.

To a 500 mL three-necked flask equipped with a condenser tube were added 12.5 g of 4- [difluoro (4-pentylcyclohexyl) methoxy] -2,3-difluorophenol, 10 g of methyl 11-bromododecanoate, And 200 mL of N, N-dimethylformamide were added and the mixture was heated and stirred at 160 占 폚 for 5 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water, followed by mixing and stirring. The precipitated white solid was filtered off and further washed with water. The resulting solid was vacuum-dried at 80 占 폚 to obtain 14.8 g of Compound 7.

10 g of Compound 7, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was heated and stirred at 80 캜 for 4 hours. After completion of the reaction was confirmed by TLC, the reaction solution was cooled to room temperature. With stirring the reaction solution, diluted hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered, washed with water and then with ethanol in this order. The obtained solid was vacuum-dried at 80 占 폚 to obtain 6 g of Compound 8.

In a 100 mL three-necked flask equipped with a cooling tube, 5 g of compound 8 and 5 mL of thionyl chloride were mixed and reacted by heating at 80 DEG C for 1 hour with stirring. The thionyl chloride was removed by decompression with a water jet type aspirator and then mixed with 50 mL of tetrahydrofuran to obtain solution (1). Then, 8.9 g of ethylene glycol, 20 ml of tetrahydrofuran and 2.2 g of triethylamine were mixed in a 200 ml three-necked flask equipped with a dropping funnel and stirred in an ice bath. The solution (1) was added dropwise thereto, and the mixture was reacted at room temperature for 3 hours with stirring. After the reaction, 300 mL of ethyl acetate was added, and the mixture was subjected to liquid separation. Thereafter, the organic layer was concentrated to obtain a solid. The obtained solid was recrystallized in ethanol / distilled water, and the precipitated solid was filtered and dried to obtain 4.3 g of Compound 9.

In a 100 mL three-necked flask equipped with a dropping funnel, 4.0 g of Compound 9, 35 mL of tetrahydrofuran, and 1.0 g of triethylamine were stirred in an ice bath. Then, 1.8 g of 3,5-dinitrobenzoyl chloride was slowly added dropwise thereto, and the mixture was reacted at room temperature for 3 hours with stirring. After the reaction, 300 mL of ethyl acetate was added, and water was purified by separating. Thereafter, the organic layer was concentrated to obtain a solid. The resulting solid was recrystallized from ethanol, and the precipitated solid was filtered and dried to obtain 4.8 g of Compound 10.

In a 100 mL three-necked flask equipped with a dropping funnel, 4 g of compound 10, 7 g of zinc and 1.1 g of ammonium chloride were mixed and vacuum degassed and purged with nitrogen. Then, 10 mL of tetrahydrofuran and 10 mL of ethanol were added, followed by stirring and mixing in an ice bath. Subsequently, 5 mL of distilled water was slowly added dropwise. The solvent used in the reaction was previously bubbled with nitrogen. During the dropwise addition, the mixture was stirred while cooling in an ice bath, and then reacted at room temperature for 4 hours. Then, the reaction solution was filtered to remove the catalyst. Subsequently, 300 mL of ethyl acetate was added, and the liquid separation and purification were performed with distilled water. Subsequently, the organic layer was concentrated and the solvent was removed to obtain a solid. Ethanol, and the solid was filtered, dried under reduced pressure, filtered, and vacuum-dried at 35 캜 to obtain 2.4 g of Compound 11.

[Synthesis Example 5]

Compounds 12 to 14 were synthesized according to the following reaction formula.

In a 500 mL three-necked flask equipped with a cooling tube, 18.6 g of 3,5-dinitrofluorobenzene, 24.4 g of 11-bromododecanol, 20 g of triethylamine and 100 mL of tetrahydrofuran were mixed, For 30 hours. After the reaction, 200 mL of ethyl acetate was added, and the liquid separation was performed four times with 50 mL of distilled water. The organic layer was then concentrated to remove the solvent to obtain a yellowish brown liquid. A small amount of ethanol was added to the solution, and the solution was cooled at 0 DEG C or lower to precipitate a solid. Subsequently, the precipitated solid was filtered and dried to obtain 30 g of Compound 12.

8.3 g of Compound 12, 6 g of 2,3-difluoro-4- (4-pentylcyclohexyl) phenol, 6 g of potassium carbonate and 100 mL of dimethylformamide were mixed in a 300 mL three-necked flask equipped with a cooling tube, Lt; 0 &gt; C for 5 hours. After confirming the completion of the reaction, 200 mL of ethyl acetate was added, and the liquid separation was carried out four times with 50 mL of distilled water. The organic layer was then concentrated and the solvent removed to obtain a yellowish brown liquid. A small amount of ethanol was added to the mixture and the mixture was cooled to 0 deg. C or less to precipitate a solid. Subsequently, the precipitated solid was filtered and dried to obtain 10 g of Compound 13.

9.8 g of Compound 13, 20 g of zinc and 3.4 g of ammonium chloride were mixed in a 200-mL three-necked flask equipped with a dropping funnel, followed by vacuum degassing and nitrogen substitution. Subsequently, 30 mL of tetrahydrofuran and 30 mL of ethanol were added, followed by stirring and mixing in an ice bath. Then, 10 mL of distilled water was slowly added dropwise. The solvent used in the reaction was previously bubbled with nitrogen. During the dropwise addition, the mixture was stirred while cooling in an ice bath, and then reacted at room temperature for 6 hours. Then, the reaction solution was filtered to remove the catalyst. Subsequently, 300 mL of ethyl acetate was added, and liquid separation was performed with distilled water. Subsequently, the organic layer was concentrated and the solvent was removed to obtain a solid. The solid was filtered and dried under reduced pressure to obtain 5 g of Compound 14.

[Synthesis Example 6]

Compounds 15 to 17 were synthesized according to the following reaction formula.

, 3.48 g of 2- [2- (2-chloroethoxy) ethoxy] ethanol, 8.3 g of potassium carbonate, 100 mL of dimethylformamide And the mixture was allowed to react at 85 占 폚 under a nitrogen atmosphere for 24 hours. Subsequently, 200 mL of ethyl acetate was added, and the liquid separation and purification were performed with distilled water. The organic layer was concentrated and the solvent was removed to obtain 6 g of Compound 15 (light yellow liquid).

5 g of Compound 15, 2.9 g of 2,4-dinitrofluorobenzene, 50 mL of tetrahydrofuran and 1.9 g of triethylamine were mixed and reacted at 80 ° C for 10 hours. 200 mL of ethyl acetate was added, and the liquid separation and purification were carried out with distilled water. The organic layer was concentrated to remove the solvent to obtain 4.8 g of Compound 16.

4 g of Compound 16, 10 g of zinc, and 1.6 g of ammonium chloride were mixed in a 100 mL three-necked flask equipped with a dropping funnel, followed by vacuum degassing and nitrogen substitution. Then, 10 ml of tetrahydrofuran and 10 ml of ethanol were added in a stream of nitrogen, followed by stirring and mixing in an ice bath. Subsequently, 5 ml of distilled water was slowly added dropwise. The solvent used in the reaction was previously bubbled with nitrogen. During the dropwise addition, the mixture was stirred while cooling in an ice bath, and then reacted at room temperature for 2 hours. Then, the reaction solution was filtered to remove the catalyst. Subsequently, 300 ml of ethyl acetate was added, and the liquid separation and purification were carried out with distilled water. Subsequently, the organic layer was concentrated and the solvent was removed to obtain a solid. The solid was filtered and dried under reduced pressure by filtration, followed by drying, thereby obtaining 3.3 g of Compound 17.

[Synthesis Example 7]

Compounds 18 and 19 were synthesized according to the following reaction formula.

50 g of 4- [difluoro (4-pentylcyclohexyl) methoxy] -2,3-difluorophenol, 38 g of 11-bromododecanol, 60 g of potassium carbonate and 100 ml of dimethylformamide were mixed, Followed by reaction at 85 ° C for 24 hours. Subsequently, 200 mL of ethyl acetate was added, and the liquid separation and purification were performed with distilled water. The organic layer was concentrated to remove the solvent to obtain 38.7 g of Compound 18.

A solution of 10 g of the compound 18 and 20 ml of tetrahydrofuran and adding 3.9 g of triethylamine and then dropwise adding a solution of 2.6 g of acrylic acid chloride in 10 ml of tetrahydrofuran over 15 minutes under ice cooling, And stirred for 2 hours. After completion of the reaction, the triethylamine hydrochloride was removed by filtration, the solvent was removed by distillation under reduced pressure, and 400 mL of chloroform was added. This solution was washed with water and the organic layer was dried over magnesium sulfate, and then chloroform was removed by distillation under reduced pressure. Thereafter, recrystallization was performed with ethanol, and vacuum drying was performed at 80 캜 to obtain 11 g of Compound 19.

<Synthesis of [A] Polymer>

[Synthesis of polyamic acid]

[Synthesis Example 8]

26.8 g of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 7.90 g of the diamine (G-1) represented by the following formula and 66.0 g of the diamine of the above compound 3 were dissolved in 400 g of NMP and reacted at room temperature for 6 hours . The reaction mixture was then poured into a large excess of methanol and the reaction product was precipitated. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 78.5 g of polyamic acid (PA-1).

[Synthesis Example 9]

(PA-2) was obtained in the same manner as in Synthesis Example 8, except that 96.6 g of the compound 11 was used instead of the compound 3.

[Synthesis of polyimide]

[Synthesis Example 10]

13.45 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, 3.72 g of 3,5-diaminobenzoic acid as a diamine compound, 3.02 g of a diamine (G-2) Of diamine were dissolved in 140 g of NMP and reacted at 60 DEG C for 4 hours. The viscosity of this polymer solution was measured and found to be 2,200 mPa · s. The reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol, and dried under reduced pressure at 40 DEG C for 24 hours to obtain a polyamic acid. All of the obtained polyamic acids were redissolved in 465 g of NMP, and 7.12 g of pyridine and 9.19 g of acetic anhydride were added and subjected to dehydration cyclization at 110 占 폚 for 4 hours. After the precipitation, washing and drying under reduced pressure were carried out in the same manner as above, 21.5 g of 68% polyimide (PI-1) was obtained.

[Synthesis Example 11]

10.89 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, 7.33 g of the above diamine (G-2) as a diamine compound and 16.78 g of a diamine of the compound 3 were dissolved in NMP, And reacted for 4 hours. The viscosity of this polymerization solution was measured and found to be 1,250 mPa · s. The reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol, and dried under reduced pressure at 40 DEG C for 24 hours to obtain a polyamic acid. All of the obtained polyamic acids were redissolved in 465 g of NMP, and 3.84 g of pyridine and 4.96 g of acetic anhydride were added, followed by dehydration cyclization at 110 占 폚 for 4 hours, followed by precipitation, washing and vacuum drying in the same manner as above, 23.1 g of 49% polyimide (PI-2) was obtained.

[Synthesis Example 12]

15.17 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as the tetracarboxylic acid dianhydride, 3.60 g of the diamine (G-1) as the diamine compound, 6.68 g of the diamine of the compound 3 and 4,4'- 9.55 g of phenylmethane was dissolved in 140 g of NMP and reacted at 60 DEG C for 4 hours. The viscosity of this polymerization solution was measured and found to be 2,700 mPa s. The reaction solution was poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol, and dried under reduced pressure at 40 DEG C for 24 hours to obtain a polyamic acid. All the obtained polyamic acid was redissolved in 465 g of NMP, and 10.70 g of pyridine and 13.82 g of acetic anhydride were added and subjected to dehydration ring closure at 110 占 폚 for 4 hours. The mixture was subjected to precipitation, washing and vacuum drying in the same manner as above, 22.4 g of 76% polyimide (PI-3) was obtained.

[Synthesis Example 13]

By operating in the same manner as in Synthesis Example 12 except that 7.69 g of Compound 14 was used instead of Compound 3, 22.9 g of a polyimide (PI-4) having an imidization rate of 76% was obtained.

[Synthesis Example 14]

21.9 g of a polyimide (PI-5) having an imidization rate of 76% was obtained by operating in the same manner as in Synthesis Example 12 except that 6.36 g of Compound 17 was used instead of Compound 3.

[Synthesis of methacrylic polymer]

[Synthesis Example 15]

Cholestanyl methacrylate was synthesized according to the following reaction formula.

80 g of? -cholestanol was dissolved in 800 mL of THF, and 27.2 g of triethylamine was added thereto. Then, 35.6 g of methacryloyl chloride was slowly added dropwise, followed by stirring at room temperature for 3 hours. After completion of the reaction, triethylamine hydrochloride was removed by filtration, and THF was removed by distillation under reduced pressure, and 400 mL of chloroform was added. This solution was washed with water and the organic layer was dried over magnesium sulfate, and then chloroform was removed by distillation under reduced pressure. Thereafter, recrystallization with ethanol was carried out to obtain 54 g (yield: 57.4%) of white solid colestanyl methacrylate shown in the above reaction formula. (0.033 mole) of the cholestanyl methacrylate, 12.8 g (0.09 mole) of glycidyl methacrylate, and 7.2 g (0.09 mole) of methacrylic acid as a monomer were added to a four-necked flask equipped with a stirrer, (0.109 mole) of the above compound 4, 52.8 g of diethylene glycol ethyl methyl ether as a solvent, 2.24 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, 0.96 g of? -Methasystene dimer was added as a chain transfer agent. This was bubbled through a nitrogen stream for about 10 minutes to perform nitrogen substitution in the system and then reacted at 70 DEG C for 5 hours under a nitrogen atmosphere to obtain a methacrylic polymer (PM-1). The molecular weight of the methacrylic polymer (PM-1) was measured by GPC to find that Mw = 96,000, Mw / Mn = 7.87, and no peak due to the residual monomer was confirmed. It was also assumed that the injected monomer in the polymer solution was converted into the total amount of the methacrylic polymer (PM-1), and the monomer was diluted as it was and used in the liquid crystal aligning agent preparation of the present invention.

[Synthesis Example 16]

(0.0219 mole) of cholestanyl methacrylate, 15.0 g (0.1055 mole) of glycidyl methacrylate, 9.0 g (0.1045 mole) of methacrylic acid, and 19.3 g (0.046 mole) of Compound 4 were charged, The same procedure as in Synthesis Example 15 was carried out except that 43.0 g of ethylene glycol ethyl methyl ether, 1.83 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 0.78 g of α-metastyrene dimer as a chain transfer agent were used. To obtain a methacrylic polymer (PM-2). The measurement of the molecular weight of the methacrylic polymer (PM-2) by GPC revealed that Mw = 125,000 and Mw / Mn = 9.54, and no peak due to the residual monomer was confirmed. Furthermore, assuming that the injected monomer in the present polymer solution was converted into the total amount of the methacrylic polymer (PM-2), it was diluted as it was and used in the preparation of the liquid crystal aligning agent of the present invention.

[Synthesis Example 17]

A methacrylic polymer (PM-3) was obtained in the same manner as in Synthesis Example 16 except that 25.6 g (0.046 mole) of Compound 19 was used instead of the compound 4. The measurement of the molecular weight of the methacrylic polymer (PM-3) by GPC revealed that Mw = 131,000 and Mw / Mn = 9.43, and no peak due to the residual monomer was observed. Further, in the present polymer solution, it was assumed that the device monomer was converted into the total amount of the methacrylic polymer (PM-3), and it was diluted as it was and used in the preparation of the liquid crystal aligning agent of the present invention.

[Synthesis of polysiloxane]

[Synthesis Example 18]

12.4 g of oxalic acid and 22.2 g of ethanol were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and stirred to prepare an ethanol solution of oxalic acid. Subsequently, this solution was heated to 70 deg. C in a nitrogen atmosphere, and then a mixture of 11.1 g of tetraethoxysilane and 10.6 g of compound 6 as a raw silane compound was added dropwise thereto. After completion of the dropwise addition, the temperature was maintained at 70 캜 for 6 hours and then cooled to 25 캜. Then, 40.0 g of butyl cellosolve was added to prepare a solution containing the polyorganosiloxane (PS-1). The Mw of the polyorganosiloxane (PS-1) contained in this solution was 9,000.

[Synthesis Example 19]

A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser was charged with 13.9 g of oxalic acid and 19.5 g of ethanol, and stirred to prepare an ethanol solution of oxalic acid. Subsequently, this solution was heated to 70 deg. C in a nitrogen atmosphere, and then a mixture composed of 15.1 g of tetraethoxysilane and 3.95 g of compound 6 as a raw silane compound was added dropwise thereto. After completion of the dropwise addition, the temperature was maintained at 70 캜 for 6 hours and then cooled to 25 캜. Subsequently, 40.0 g of butyl cellosolve was added to prepare a solution containing the polyorganosiloxane (PS-2). The Mw of the polyorganosiloxane (PS-2) contained in this solution was 12,000.

[Synthesis Example 20]

10.2 g of oxalic acid and 26.3 g of ethanol were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and stirred to prepare an ethanol solution of oxalic acid. Subsequently, this solution was heated to 70 deg. C in a nitrogen atmosphere, and then a mixture composed of 5.54 g of tetraethoxysilane, 12.49 g of compound 6 and 2.5 g of octadecyltriethoxysilane as a silane compound as a starting material was added dropwise thereto . After completion of the dropwise addition, the temperature was maintained at 70 캜 for 6 hours and then cooled to 25 캜. Subsequently, 40.0 g of butyl cellosolve was added to prepare a solution containing the polyorganosiloxane (PS-3). The Mw of the polyorganosiloxane (PS-3) contained in this solution was 6,000.

[Synthesis Example 21]

19.88 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride, 6.83 g of p-phenylenediamine as a diamine compound, 3.58 g of diaminodiphenylmethane and 4.72 g of the above diamine (G-1) Was dissolved in 140 g of NMP and allowed to react at 60 占 폚 for 4 hours. The viscosity of this polymer solution was measured and found to be 2,100 mPa · s. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, the resultant was washed with methyl alcohol, and dried at 40 DEG C for 24 hours under reduced pressure to obtain 32.8 g of polyamic acid. 30 g of the obtained polyamine was dissolved in 400 g of NMP and 12.0 g of pyridine and 15.5 g of acetic anhydride were added and subjected to dehydration ring closure at 110 占 폚 for 4 hours. After precipitation, washing and drying under reduced pressure, the imidization rate was 79% Of polyimide (PI-6) was obtained.

[Synthesis Example 22]

(0.0332 mol) of cholestanyl methacrylate, 12.8 g (0.09 mol) of glycidyl methacrylate, and 7.2 g (0.0836 mol) of methacrylic acid as a monomer were added to a four-necked flask equipped with a stirrer, a three- 7.2 g (0.0691 mol) of styrene and 7.2 g (0.0402 mol) of N-cyclohexylmaleimide were placed, and furthermore, 52.8 g of diethylene glycol ethyl methyl ether as a solvent, and 2,2'-azobis 2,4-dimethylvaleronitrile) and 0.96 g of? -Methylstyrene dimer as a chain transfer agent were added. This was bubbled with a nitrogen stream for about 10 minutes to carry out nitrogen substitution in the system, and then reacted at 70 DEG C for 5 hours under a nitrogen atmosphere to obtain a methacrylic polymer (PM-4) having a pretilt angular expression component. Molecular weight of the methacrylic polymer (PM-4) was measured by GPC. As a result, Mw = 96,000 and Mw / Mn = 7.87, and no peak due to the residual monomer was confirmed. Further, in the present polymer solution, it was assumed that the device monomer was converted into the total amount of the methacrylic polymer (PM-4), and it was diluted as it was and used in the liquid crystal aligning agent preparation of the present invention.

[Synthesis Example 23]

10.2 g of oxalic acid and 26.3 g of ethanol were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and stirred to prepare an ethanol solution of oxalic acid. Subsequently, this solution was heated to 70 deg. C in a nitrogen atmosphere, and then a mixture of 11.1 g of tetraethoxysilane and 2.5 g of octadecyltriethoxysilane as a raw silane compound was added dropwise thereto. After completion of the dropwise addition, the temperature was maintained at 70 캜 for 6 hours, and then cooled to 25 캜. Subsequently, 40.0 g of butyl cellosolve was added to prepare a solution containing the polyorganosiloxane (PS-4). The Mw of the polyorganosiloxane (PS-4) contained in this solution was 6,900.

&Lt; Preparation of liquid crystal aligning agent &

[Example 1]

NMP and butyl cellosolve were added to the polyamic acid (PA-1) so that the solvent composition was NMP: butyl cellosolve = 50: 50 (mass ratio), and the solid concentration was 3.5 mass% And a concentration of 7.0% by mass (for evaluation of uniform coating property). These solutions were thoroughly stirred, and then filtered through a filter having a pore diameter of 0.2 mu m to prepare a liquid crystal aligning agent (S-1).

[Example 2]

A liquid crystal aligning agent (S-2) was prepared in the same manner as in Example 1 except that the polyamic acid (PA-2) was used instead of the polyamic acid (PA-1).

[Example 3]

NMP and butyl cellosolve were added to the polyimide (PI-1) so that the solvent composition was NMP: butyl cellosolve = 50: 50 (mass ratio), and the solid concentration was 3.5 mass% And a concentration of 7.0% by mass (for evaluation of uniform coating property). These solutions were thoroughly stirred, and then filtered through a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (S-3).

[Example 4]

NMP and butyl cellosolve were added to the polyimide (PI-2) such that the solvent composition was NMP: butyl cellosolve = 50: 50 (mass ratio), and a solid content concentration of 3.5 mass% And a concentration of 7.0% by mass (for evaluation of uniform coating property). These solutions were thoroughly stirred and then filtered through a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (S-4).

[Example 5]

NMP and butyl cellosolve were added to the polyimide (PI-3) so that the solvent composition was NMP: butyl cellosolve = 70: 30 (mass ratio) to obtain a solid content concentration of 3.5 mass% And a concentration of 7.0% by mass (for evaluation of uniform coating property). These solutions were thoroughly stirred and then filtered through a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (S-5).

[Example 6]

A liquid crystal aligning agent (S-6) was prepared in the same manner as in Example 3 except that the polyimide (PI-4) was used instead of the polyimide (PI-1).

[Example 7]

A liquid crystal aligning agent (S-7) was prepared in the same manner as in Example 3 except that the polyimide (PI-5) was used instead of the polyimide (PI-1).

[Example 8]

Diethylene glycol methyl ethyl ether was further added to the methacrylic polymer (PM-1) solution to prepare a solution having a solid content concentration of 3.5 mass% (for liquid crystal cell preparation) and a solid content concentration of 7.0 mass% (for evaluation of uniform application property) Solution. These solutions were thoroughly stirred, and then filtered using a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (S-8).

[Example 9]

Diethylene glycol methyl ethyl ether was further added to the methacrylic polymer (PM-2) solution to prepare a solution having a solid content concentration of 3.5 mass% (for liquid crystal cell preparation) and a solid content concentration of 7.0 mass% (for evaluation of uniform application property) Solution. These solutions were sufficiently stirred, and then filtered using a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (S-9).

[Example 10]

A liquid crystal aligning agent (S-10) was prepared in the same manner as in Example 8 except that the methacrylic polymer (PM-3) was used in place of the methacrylic polymer (PM-1).

[Example 11]

Butyl cellosolve was added to the solution containing the polyorganosiloxane (PS-1) to prepare a solution having a solid content concentration of 5% by mass (for preparing a liquid crystal cell) and a solid content concentration of 10.0% by mass (for evaluation of uniform coating property) did. These solutions were sufficiently stirred, and then filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent (S-11).

[Example 12]

Butyl cellosolve was added to the solution containing the polyorganosiloxane (PS-2) to prepare a solution having a solid content concentration of 5 mass% (for forming a liquid crystal cell) and a solid content concentration of 10.0 mass% (for evaluating uniform coating property) did. These solutions were sufficiently stirred, and then filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent (S-12).

[Example 13]

Butyl cellosolve was added to the solution containing the polyorganosiloxane (PS-3) to prepare a solution having a solid content concentration of 5 mass% (for forming a liquid crystal cell) and a solid content concentration of 10.0 mass% (for evaluating uniform coating property) did. These solutions were thoroughly stirred, and then filtered using a filter having a pore size of 1 m each to prepare a liquid crystal aligning agent (S-13).

[Comparative Example 1]

NMP and butyl cellosolve were added to the polyimide (PI-6) so that the solvent composition was NMP: butyl cellosolve = 50: 50 (mass ratio), and the solid concentration was 3.5% by mass And a solid content concentration of 7.0% by mass (for evaluating uniform coating property). These solutions were thoroughly stirred, and then filtered through a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (CS-1).

[Comparative Example 2]

Diethylene glycol methyl ethyl ether was further added to the methacrylic polymer (PM-4) solution to prepare a solution having a solid content concentration of 3.5% by mass (for liquid crystal cell preparation) and a solid content concentration of 7.0% by mass (for evaluation of uniform application property) Solution. These solutions were thoroughly stirred and then filtered using a filter having a pore size of 0.2 탆 to obtain a liquid crystal aligning agent (CS-2).

[Comparative Example 3]

Butyl cellosolve was added to the solution containing the polyorganosiloxane (PS-4) to prepare a solution having a solid content concentration of 5 mass% (for preparing a liquid crystal cell) and a solid content concentration of 10.0 mass% (for evaluating uniform coating property) did. These solutions were thoroughly stirred, and then filtered using a filter having a pore size of 1 mu m to prepare a liquid crystal aligning agent (CS-3).

&Lt; Production of liquid crystal display element &

Each of the prepared liquid crystal aligning agents was coated on a transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film by using a spinner and prebaked with a hot plate at 80 DEG C for 1 minute, The solvent was removed by heating at 200 DEG C for 1 hour to form a coating film (liquid crystal alignment film) having a thickness of 0.08 mu m. This operation was repeated to prepare a pair of substrates (two substrates) each having a liquid crystal alignment film. An epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 3.5 mu m was applied to the periphery of the surface having one liquid crystal alignment film of the above substrate by screen printing and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other And the adhesive was thermally cured by heating at 150 DEG C for 1 hour. Subsequently, a negative-type liquid crystal (MLC-6608, manufactured by Merck Ltd.) was charged into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. In order to further eliminate the flow alignment during liquid crystal injection, After being heated at 150 占 폚 for 10 minutes, it was slowly cooled to room temperature. A polarizing plate was bonded to both sides of the substrate so that the polarizing directions of the two polarizing plates were orthogonal to each other, thereby producing a liquid crystal display device.

<evaluation>

The liquid crystal display device manufactured was evaluated as follows. The results are shown in Table 1.

[Response time (msec.)]

The response speed (start time of liquid crystal response) was measured with a device including a polarization microscope, a photodetector, and a pulse generator. Here, the liquid crystal response speed is a time (msec.) Required for the transmittance to change from 10% to 90% when a voltage of 5 V is applied for a maximum of 1 second from the voltage unapplied state to the produced liquid crystal display element.

[Voltage Conservation Rate (%)]

A voltage of 5 V was applied to the liquid crystal display device manufactured in the above manner at an application time of 60 microseconds and a span of 167 milliseconds, and the voltage maintenance ratio (%) after 167 milliseconds after the application was released was measured. The measurement apparatus used was VHR-1 manufactured by Toyo Technica Co., Ltd.

[Characteristics of afterimage (mV)]

A voltage of DC 17V was applied for 20 hours at an environmental temperature of 100 ° C and the voltage (residual DC voltage (mV)) remaining in the liquid crystal cell immediately after the DC voltage was cut was applied to the liquid crystal display device manufactured by the same operation as described above. Was obtained by the flicker erase method.

[Uniform application property]

A resin spacer (Micropearl EX-0041-AC4, manufactured by Sekisui Chemical Co., Ltd.) having a diameter of about 4.1 탆 was sprayed on a 6-inch silicon wafer and heated on a hot plate set at 120 캜 for 10 minutes And a silicon wafer having a fixing spacer was prepared. Further, in the above liquid crystal aligning composition, a liquid crystal aligning agent (solids concentration: 7.0% by mass to 10.0% by mass) adjusted for printing was applied to the surface of the silicon wafer with the fixed spacer And the resultant was prebaked on a hot plate at 80 DEG C for 1 minute to remove the solvent and then post baked on a hot plate at 200 DEG C for 10 minutes to form a coating film having an average thickness of 800 ANGSTROM. This coating film was observed with a microscope having a magnification of 20 times to evaluate the uniform coating property. The evaluation was carried out according to the printing unevenness and the presence or absence of looseness in the fixing spacer portion. The printing unevenness and the peeling of the fixing spacer portion were not observed at all, and "A" (judged as good) "C" (judged to be defective) was determined to be "B" (judged as good), and "C" to judge that there was no coating failure.

[Light Resistance]

"A" (judged to be excellent) when the voltage maintenance rate after irradiation with a weather meter using a carbon arc as a light source was measured by operating in the same manner as described above and the change amount of the voltage maintenance rate was 0.5% "B" (judged as being good) exceeding 0.5% and less than 1% is referred to as "C" (slightly judged good), and "D" It is judged as bad).

As is clear from the results in Table 1, the liquid crystal display device comprising the liquid crystal alignment film formed using the liquid crystal aligning agents of Examples 1 to 13 exhibited a good liquid crystal response speed. A liquid crystal display element comprising a liquid crystal alignment layer formed of the liquid crystal aligning agent containing polyimide or polysiloxane exhibited a high voltage holding ratio. In addition, the liquid crystal aligning agent containing polyamic acid or methacrylic polymer exhibited excellent uniform coverage. In addition, a liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal aligning agent containing polysiloxane or polyamic acid exhibited excellent afterimage characteristics. A liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal aligning agent containing a polysiloxane exhibited excellent light resistance. Accordingly, the liquid crystal aligning agent enables a high-speed response of the liquid crystal display element, and by appropriately selecting the polymer main chain structure, desired characteristics (voltage holding ratio, residual image characteristic, uniform coating property, light resistance) have.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a liquid crystal aligning agent capable of producing a liquid crystal display element which is capable of high-speed response and excellent in performances such as voltage holding ratio, afterimage characteristic, light resistance and the like. Therefore, the liquid crystal display device is suitably used in a driving mode such as TN, STN, IPS, FFS, Ht-VA (VA-IPS), VA (including MVA, PVA, optical vertical alignment and PSA) Can be applied.

Claims (4)

[A] a liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and having a partial structure derived from a compound represented by the following formula (4)

(In the formula (4)
R ¹ is a methylene group, an alkylene group having 2 to 30 carbon atoms, - (C _{b '} H _{2 b '} O) _{c '} -, a phenylene group or a cyclohexylene group; b 'is an integer of 0 to 20; c 'is an integer of 0 to 10; Provided that some or all of the hydrogen atoms of these groups may be substituted;
R ² is a linking group comprising a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or an amide bond;
R ³ is a group having at least two monocyclic structures;
a is 1;
R ⁹ is a single bond, -O-, * -COO- or -OCO-; Provided that * is a site bonding with a diaminophenyl group;
d is 0 or 1;
e is an integer from 0 to 2;
g is 2 or 3). The method according to claim 1,
The liquid crystal aligning agent wherein R ³ is a group represented by the following formula (2)

(In the formula (2)
R ⁴ and R ⁶ are each independently a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group or a heterocycle; Provided that some or all of the hydrogen atoms of these groups may be substituted;
R ⁵ is a linking group comprising a methylene group, an alkylene group having 2 to 10 carbon atoms, a carbon-carbon double bond, a carbon-carbon triple bond, an ether bond, an ester bond or a heterocycle; Provided that some or all of the hydrogen atoms of the linking group may be substituted;
R ⁷ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, a trifluoromethoxy group or an alkylcarbonyloxy group;
b is 0 or 1; c is an integer from 1 to 9; Provided that when plural R &lt; ⁷ &gt; s are present, plural R &lt; ⁷ &gt; s may be the same or different). A liquid crystal alignment film formed by the liquid crystal aligning agent according to claim 1 or 2. A liquid crystal display element comprising the liquid crystal alignment film according to claim 3.