KR20160041754A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, polymer and compound - Google Patents

Abstract

Provided is a liquid crystal aligning agent of which a component has good solubility, and which can obtain a liquid crystal display device showing good afterimage properties. A compound (P) having a partial structure represented by chemical formula (1) is contained in the liquid crystal aligning agent. In the chemical formula (1), Y1 is a protection group; and an asterisk (*) symbol exhibits a binding site.

Description

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

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

Conventionally, liquid crystal display devices have been developed in various driving methods that differ in electrode structure, physical properties of liquid crystal molecules used, and manufacturing process. For example, TN (Twisted Nematic) type or STN (Super Twisted Nematic) , VA (Vertical Alignment) type, IPS (In-Plane Switching) type, FFS (Fringe Field Switching) type and the like are known. These liquid crystal display devices have a liquid crystal alignment film for aligning liquid crystal molecules. As a material of the liquid crystal alignment film, polyamic acid and polyimide are generally used in view of good heat resistance, mechanical strength, and various properties such as affinity with liquid crystal.

In recent years, various liquid crystal aligning agents have been proposed in order to further improve the display performance of liquid crystal display elements. For example, it has been proposed to form a liquid crystal alignment film using a liquid crystal aligning agent containing a polyimide having a nitrogen atom or a precursor thereof in addition to an imide for the purpose of reducing afterimage (see, for example, Patent Document 1 Reference).

Patent Document 1 discloses a process for producing a polyamic acid by reacting a tetracarboxylic acid dianhydride containing 1,2,3,4-cyclobutane tetracarboxylic dianhydride with a diamine containing a diamine having an amide bond (-NH-CO-) It is preferable that the liquid crystal alignment agent contains a polyamic acid imidized polymer obtained by reacting a polyamic acid or a tetracarboxylic acid dianhydride with a diamine and that the ratio of the number of imide rings contained in the imidized polymer in the liquid crystal aligning agent is specified It has been proposed to set the range. In Patent Document 1, such a liquid crystal aligning agent is used to improve the voltage preservation performance and the afterimage characteristic.

Japanese Patent Application Laid-Open No. 2009-294274

However, since the amide bond has high polarity and solubility in the solvent component of the liquid crystal aligning agent is not so good, the amide bond tends to deteriorate in terms of storage stability of the liquid crystal aligning agent and applicability to the substrate (printability) There is room for further improvement.

An object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal display element having good solubility of a component containing the liquid crystal aligning agent and exhibiting good afterimage characteristics.

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in order to achieve the problems of the prior art as described above, and found that the above problems can be solved by protecting the amide bond with a protecting group. Specifically, the following liquid crystal aligning agents, liquid crystal alignment films, liquid crystal display elements, polymers and compounds are provided.

In one aspect, the present invention provides a liquid crystal aligning agent containing a compound (P) having a partial structure represented by the following formula (1):

(In the formula (1), Y ¹ represents a protecting group, and "*" represents a bonding hand).

In another aspect, there is provided a liquid crystal alignment film formed using the liquid crystal aligning agent. Further, there is provided a liquid crystal display element comprising the liquid crystal alignment film.

In another aspect, there is provided a polymer having a main structure of polyamic acid, polyamic acid ester, polyimide, or polyamide as a main skeleton and having a partial structure represented by the above formula (1). Also provided are diamines having a partial structure represented by the formula (1) and tetracarboxylic dianhydrides having a partial structure represented by the formula (1).

By protecting the amide bond in the compound having an amide bond (-NH-CO-) with a protecting group and containing it in the liquid crystal aligning agent, solubility in a solvent can be improved. Thereby, a liquid crystal aligning agent having excellent storage stability and printability can be obtained. Further, the protective group introduced into the amide bond is removed by, for example, heating at the time of film formation, conditions of an acid or a base, light irradiation or the like so that a structure having a high liquid crystal orientation is regenerated after film formation, A liquid crystal display element having good afterimage characteristics can be obtained.

Fig. 1 is an explanatory view showing a pattern of a transparent conductive film in a liquid crystal cell having a patterned transparent conductive film prepared in Examples and Comparative Examples. Fig.

(Mode for carrying out the invention)

Hereinafter, each component contained in the liquid crystal aligning agent according to the present invention and other components arbitrarily blended as required will be described.

≪ Compound (P) >

The liquid crystal aligning agent according to the present invention contains a compound (P) having a partial structure represented by the following formula (1): ????????

(In the formula (1), Y ¹ represents a protecting group, and "*" represents a bonding hand).

Y ¹ in the above formula (1) is not particularly limited as long as it is a protecting group for protecting an amide group, an imide group, an ureido group or a carbamate group, and for example, a group capable of eliminating at least one of heat, light, And the like. Y ¹ is preferably a monovalent organic group which is desirably removed at least by heat, and specific examples thereof include a carbamate-based protecting group, an amide-based protecting group, an imide-based protecting group, and a sulfonamide-based protecting group. Of these, preferred are carbamate-based protecting groups, and specific examples thereof include t-butoxycarbonyl, benzyloxycarbonyl, 1,1-dimethyl-2-haloethyloxycarbonyl, 1,1-dimethyl 2-cyanoethyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, 2- (trimethylsilyl) ethoxycarbonyl group and the like. Specific examples of Y ¹ include groups represented by the following formulas (7-1) to (7-5), and the like:

(In the formulas (7-1) to (7-5), Ar ¹ is a monovalent aromatic ring having 6 to 10 carbon atoms, R ¹⁴ is an alkyl group having 1 to 12 carbon atoms, and R ¹⁵ is a monovalent organic group; &Quot; * " represents a bonding hand bonding to a nitrogen atom).

Ar ¹ in the formula (7-2) is a group in which one hydrogen atom has been removed from an aromatic ring having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^{14 in} the formula (7-4) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group and they may be linear or branched . Examples of the monovalent organic group represented by R ^{15 in} the formula (7-5) include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, . Among them, R ¹⁵ is preferably an aryl group having 6 to 10 carbon atoms, more preferably an aromatic group such as phenyl or naphthyl group. The group represented by each of the formulas (7-1) to (7-4) can be deprotected by light as well as by heat.

A compound derived from a Y ¹ desorbed by heating at the time point or a film-forming high desorption property by heat in a point that can be a film discharged from a gas, Y ¹ is inter alia and preferably a carbamate protecting group, a t-butoxycarbonyl group is more preferable.

The atom to which the bonding hand "*" in the formula (1) is bonded is preferably a carbon atom.

The compound (P) may constitute at least a part of the polymer component of the liquid crystal aligning agent, or may be contained in the form of an additive separately from the polymer component serving as the base.

[Polymer (P)]

When the compound (P) is a polymer having a partial structure represented by the above formula (1) (hereinafter also referred to as "polymer (P)"), the main skeleton thereof is not particularly limited and examples thereof include polyamic acid, (Meth) acrylates, azobenzene derivatives, etc., and the like can be used as the main component in the present invention. Examples of the polymer include, but are not limited to, polyacrylic acid esters, polysiloxanes, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) . The polymer (P) is preferably a polymer having a partial structure represented by the formula (1) in the main chain from the viewpoint of improving the solubility of the polymer and the after-image characteristics of the obtained liquid crystal display element.

Among these polymers, at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyamide (hereinafter referred to as " polyimide polymer ") is preferable from the viewpoints of heat resistance, mechanical strength, Specific polymer "), and it is more preferable that the specific polymer is a polymer having a partial structure represented by the formula (1) in its main chain. Further, (meth) acrylate means that it includes acrylate and methacrylate.

(Polyamic acid)

When the polymer (P) is a polyamic acid, the polyamic acid can be obtained by reacting a tetracarboxylic acid dianhydride with a diamine. More specifically, the present invention relates to: (i) a method of synthesizing tetracarboxylic dianhydride having a partial structure represented by the above formula (1) by polymerization involving the monomer composition; (ii) (Iii) a method of synthesizing a tetracarboxylic acid dianhydride having a partial structure represented by the formula (1) and a diamine having a partial structure represented by the formula (1) in a monomer composition And a method of synthesizing by the polymerization which is contained. Hereinafter, the tetracarboxylic acid dianhydride having the partial structure represented by the above formula (1) is referred to as "specific tetracarboxylic dianhydride", and the diamine having the partial structure represented by the above formula (1) is also referred to as "specific diamine" .

(Tetracarboxylic acid dianhydride)

The specific tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid is not particularly limited as long as it has a partial structure represented by the above formula (1). Specific tetracarboxylic acid dianhydrides preferably contain a partial structure represented by the formula (1) in the main chain in the case where the structural part connecting the two acid anhydride groups is the main chain, and specific examples thereof include Include compounds represented by the following formula (2) and the like:

(Formula (2) of, R ^1, R ² and R ⁴ are each independently a divalent organic group, and; R ³ is a single bond or a divalent organic group, and; Y ¹ is a protecting group; Z ¹ and Z ² is , M is an integer of 1 to 3, and k is 0 or 1).

Examples of the divalent organic group represented by R ¹ to R ⁴ in the formula (2) include a divalent hydrocarbon group having 1 to 20 carbon atoms; A methylene group of the hydrocarbon group -O-, -S-, -CO-, -COO-, -COS-, -NR a -, -CO-NR a -, -NR a -CO-NR a -, -Si ( R ^a ) ₂ - (wherein R ^a is ^a monovalent hydrocarbon group having 1 to 12 carbon atoms or a protecting group), -N = N-, -SO ₂ -, or the like; A divalent group formed by replacing at least one hydrogen atom bonded to a carbon atom of a hydrocarbon group with a halogen atom (fluorine, chlorine, bromine, iodine, etc.), hydroxyl, cyano or the like; And a bivalent group having a heterocyclic ring.

In the present specification, the term "hydrocarbon group" is meant to include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these, "chain hydrocarbon group" means a straight chain hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain and are composed of only a chain structure. However, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only a structure of an alicyclic hydrocarbon and not containing an aromatic ring structure as the ring structure. However, it need not be composed of only the structure of an alicyclic hydrocarbon, and a part thereof may also have a chain structure. The term "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not always necessary to be constituted only of an aromatic ring structure, and a part thereof may contain a chain structure or a structure of an alicyclic hydrocarbon.

Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ⁴ include linear hydrocarbon groups such as a methylene group, an ethylene group, a propanediyl group, a butane diyl group, a pentanediyl group, , Heptanediyl group, octanediyl group, nonanediyl group, decanediyl group, vinylene group, propanediyl group, butenediyl group and the like; As the alicyclic hydrocarbon group, for example, cyclohexylene group and the like; Examples of the aromatic hydrocarbon group include phenylene group, biphenylene group and the like; Respectively.

The trivalent organic group of Z ¹ and Z ² is preferably a trivalent chain hydrocarbon group, an alicyclic hydrocarbon group or an aromatic ring group, and is preferably a benzene ring, a naphthalene ring, a cyclopentane ring and a cyclohexane ring. More preferably a cyclic group in which three hydrogen atoms have been removed from the ring of the species.

m is preferably 1.

Specific examples of the specific tetracarboxylic acid dianhydride include compounds represented by the following formulas (2-1) to (2-3), and the like:

(Wherein TMS represents a trimethylsilyl group).

In the synthesis of polyamic acid, specific tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

The specific tetracarboxylic acid dianhydrides can be synthesized by appropriately combining the stereochemistry of organic chemistry. For example, by reacting tetracarboxylic acid dianhydride having "-NH-CO-" with di-tert-butyl dicarbonate in the presence of a strong base such as dimethylaminopyridine, Y ¹ is a t-butoxycarbonyl group A specific tetracarboxylic acid dianhydride can be synthesized. However, the method of synthesizing the specific tetracarboxylic acid dianhydride is not limited to the above.

The tetracarboxylic acid dianhydrides used in the methods of [i] and [iii] may be only specific tetracarboxylic dianhydrides, but other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydrides may be used in combination. In the method [ii], tetracarboxylic acid dianhydride is used as the tetracarboxylic acid dianhydride in the synthesis of the polyamic acid.

Examples of other tetracarboxylic acid dianhydrides include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and the like. Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic acid dianhydride, for example, 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, Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-2 anhydride, bicyclo [2.2.1] heptane-2,3,5,6- Acid 2: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5- Cyclohexane tetracar Acid dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, ethylenediamine tetraacetic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, ethylene glycol bis Anhydrotrimellitate), 1,3-propylene glycol bis (anhydrotrimellitate), p-phenylenebis (trimellitic acid monoester anhydride), 5- (2,5-dioxotetrahydrofuran- -Yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran- Methyl-3a, 4,5,9b-tetrahydronaphtho [l, 2-c] furan-l, 3-dione and the like;

As the aromatic tetracarboxylic acid dianhydride, for example, pyromellitic dianhydride and the like; The tetracarboxylic acid dianhydride described in JP-A-2010-97188 can be used. The other tetracarboxylic acid dianhydrides may be used alone or in combination of two or more.

As other tetracarboxylic acid dianhydrides, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5- (2 Dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- Tetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, bicyclo [3.3.0] , 4,6,8-tetracarboxylic acid 2: 4,6: 8-2 anhydride, cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, p-phenylenebis (Trimellitic acid monoester anhydride), and pyromellitic acid dianhydride. In addition, it is preferable to use at least one compound selected from the group consisting of trimellitic acid anhydride (trimellitic acid monoester anhydride) and pyromellitic dianhydride. The amount of these other tetracarboxylic acid dianhydrides to be used (the total amount thereof when two or more of them are used) is preferably at least 5 mol% based on the total amount of the tetracarboxylic acid dianhydrides used for the synthesis of the polyamic acid , More preferably 10 mol% or more, and still more preferably 20 mol% or more.

(Diamine)

When the specific diamine has the partial structure represented by the above formula (1), the remaining structure is not particularly limited. However, when the structural part connecting two primary amino groups is the main chain, ) Are preferred. Specific preferred examples thereof include, for example, a compound represented by the following formula (3), a compound represented by the following formula (3A) and a compound represented by the following formula (3B)

(Wherein R ⁵ , R ⁶ and R ⁸ are each independently a divalent organic group; R ⁷ is a single bond or a divalent organic group; Y ¹ is a protecting group; t is an integer of ¹ to 3 And s is 0 or 1;

(Formula (3A) of the, Y ² and Y ³ are, each independently, a hydrogen atom, an alkyl group or a protective group of a carbon number of 1 to 3 and, at least one side of the stage, Y ² and Y ³ is a protecting group; R ^11, R ¹² And R ¹⁴ are each independently a divalent organic group and R ¹³ is a single bond or a divalent organic group; v is an integer of 1 to 3, and u is 0 or 1;

(Wherein R ²¹ , R ²² and R ²⁴ are each independently a divalent organic group, R ²³ is a single bond or a divalent organic group, Y ⁴ is a protecting group, x is 1 to 3 Integer).

The divalent organic groups represented by R ⁵ to R ⁸ in the formula (3), the divalent organic groups represented by R ¹¹ to R ¹⁴ in the formula (3A), and R ²¹ to R ^{As for} the divalent organic group of ²⁴ , the description of the divalent organic groups R ¹ to R ^{4 in} the above formula (2) can be applied. R ⁵ , R ⁸ , R ¹¹ , R ¹⁴ , R ²¹ and R ²⁴ are preferably a phenylene group or a substituted phenylene group. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom.

t, v, and x are preferably 1, respectively.

Specific examples of the specific diamine include compounds represented by each of the following formulas (3-1) to (3-20) and (ADA1) to (ADA8)

(Wherein TMS represents a trimethylsilyl group).

(Wherein R ¹⁵ and R ¹⁶ are each independently a halogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 2 to 12, and a 1 and a 2 are each independently 0 to 4 And p is an integer of 1 to 12).

In the synthesis of polyamic acid, specific diamines may be used singly or in combination of two or more.

When Y ¹ in the formula (1) is a group deprotecting by light, for example, it is used as a liquid crystal aligning agent for photo alignment by irradiation with polarized light or unpolarized light, using the reaction of the following reaction formula It may be:

(In Scheme A, " * " indicates a binding hand).

Specific diamines can be synthesized by appropriately combining the stereochemistry of organic chemistry. For example, by reacting a diamine having "-NH-CO-" and di-tert-butyl dicarbonate in the presence of a strong base such as dimethylaminopyridine, Y ¹ is a specific diamine of t-butoxycarbonyl group Can be synthesized. However, the method of synthesizing a specific diamine is not limited to the above.

The diamines used in the methods [ii] and [iii] may be only specific diamines, but other diamines other than the specific diamines may be used in combination. In the method of [i], other diamines are used as diamines in the synthesis of polyamic acid.

Other diamines include, for example, aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane and the like;

As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine) and the like;

As the aromatic diamine, there may be mentioned, for example, dodecanoxydiaminobenzene, tetradecanoxydiaminobenzene, pentadecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminobenzoyloxy) cholestane, diaminobenzoic acid cholestearyl, diaminobenzoic acid lanostanyl, Bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1- Heptylcyclohexane, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4- ( (4-heptylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -4-

^Wherein X ^I and X ^II each independently represents a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, R ^ⅱ is an alkanediyl group of a single bond or a carbon number of 1~3, a is 0 or 1, b is an integer of 0~2, c is an integer of 1~20, d is 0 or 1; stage, a And b are not 0 at the same time)

Containing diamines such as compounds represented by the following formula:

p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzoate, 4,4'- Bis (4-aminophenoxy) pentane, bis [2- (4-aminophenyl) ethyl] hexane diacid, N, -Aminophenyl) methylamine, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 ' - (p-phenylenediisopropylidene) bisaniline, 4,4 '- (m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, (4-aminophenoxy) biphenyl, 2,6-diaminopyridine , 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl- N, N'-bis (4-aminophenyl) benzidine, N, N'-bis Phenyl) -N, N'-dimethylbenzidine, 1,4-bis (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid and the like;

As the diaminoorganosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like; The diamine described in JP-A-2010-97188 can be used.

Examples of the divalent group represented by "-X ^I - (R ^I -X ^II ) _d -" in the above formula (E-1) include an alkanediyl group having 1 to 3 carbon atoms, * -O-, Or * -OC ₂ H ₄ -O- (provided that a bonding hand having "*" attached thereto is bonded to a diaminophenyl group). Examples of the group -C _c H _{2c + 1} include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, A tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group, and they are preferably linear. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or the 3,5-position with respect to the other groups.

Specific examples of the compound represented by the formula (E-1) include compounds represented by the following formulas (E-1-1) to (E-1-4).

As other diamines, one of these compounds may be used alone or two or more of them may be appropriately selected and used.

When applied to liquid crystal aligning agents for liquid crystal display elements of TN type, STN type or vertical alignment type, a group (aligning group) capable of imparting liquid crystal aligning ability to the coating film may be introduced into the side chain of the polyamic acid. Examples of the aligning group include an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, . The polyamic acid having an oriented group can be obtained, for example, by polymerization containing an orientable group-containing diamine in the monomer composition. When an aromatic group-containing diamine is used, the blending amount thereof is preferably 3 mol% or more, more preferably 5 to 70 mol%, based on the total diamine used in the synthesis.

When the liquid crystal aligning ability is imparted to the coating film formed by the liquid crystal aligning agent by the photo alignment method, at least a part of the polyamic acid as the polymer (P) may be a polymer having a photo-orientable structure. As specific examples of the photo-alignment structure, a group capable of photo-orientation by photo-isomerization, photo-dimerization, photodegradation, or the like can be employed. Specifically, there may be mentioned, for example, an azo compound containing an azo compound or a derivative thereof as a basic skeleton, a cinnamic acid-containing group containing a cinnamic acid or a derivative thereof as a basic skeleton, a chalcone compound containing a chalcone or a derivative thereof as a basic skeleton Containing structure containing a benzophenone-containing group containing a benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing a coumarin or a derivative thereof as a basic skeleton, a cyclobutane-containing structure containing as a basic skeleton a cyclobutane or a derivative thereof, [2.2.2] octene or a derivative thereof as a basic skeleton, a structure containing bicyclo [2.2.2] octene represented by the following formula (4):

(In the formula (4), X ³ represents a sulfur atom, an oxygen atom or -NH-; "*" represents a bonding bond, provided that at least one of the two "*"

As a basic skeleton, and the like.

The polyamic acid having a photo-alignment structure can be obtained, for example, by polymerization containing at least one of a tetracarboxylic acid dianhydride having a photo-aligning structure and a diamine having a photo-orientable structure in the monomer composition. In this case, the use ratio of the monomer having a photo-orientable structure is preferably 20 mol% or more, more preferably 30 to 80 mol%, based on the total amount of the monomers used in the synthesis of the polymer from the viewpoint of photoreactivity More preferable.

(Synthesis of polyamic acid)

The polyamic acid can be obtained by reacting a tetracarboxylic acid dianhydride and a diamine as described above together with a molecular weight modifier, if necessary. The ratio of the tetracarboxylic acid dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid is preferably 0.2 to 2 equivalents of the tetracarboxylic acid dianhydride relative to 1 equivalent of the amino group of the diamine, To 1.2 equivalents is more preferable.

In the synthesis of the polyamic acid as the polymer (P), from the viewpoint of sufficiently improving the solubility of the polyamic acid and the effect of reducing the afterimage, the ratio of the specific tetracarboxylic acid dianhydride to the specific diamine , The total amount of the specific tetracarboxylic acid dianhydride and the specific diamine is preferably 10 mol% or more, more preferably 20 to 80 mol%, further preferably 25 to 70 mol% desirable.

Examples of the molecular weight regulator include acid anhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, and monoisocyanate compounds such as phenylisocyanate and naphthylisocyanate And the like. The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of tetracarboxylic acid dianhydride and diamine to be used.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 캜 to 150 캜, more preferably 0 to 100 캜. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like. Among these organic solvents, at least one kind selected from the group consisting of an aprotic polar solvent and a phenol type solvent (first group of organic solvents), or at least one kind selected from an organic solvent of the first group, It is preferable to use a mixture of at least one member selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less, relative to the total amount of the organic solvent of the first group and the organic solvent of the second group By weight, and more preferably 30% by weight or less.

Particularly preferred organic solvents are N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, The use of at least one member selected from the group consisting of triamide, m-cresol, xylenol and halogenated phenol as a solvent, or a mixture of at least one of them with other organic solvent in the above- desirable. The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50 wt% with respect to the total amount (a + b) of the reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution 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, or after the isolated polyamic acid is purified, . The polyamic acid can be isolated and purified by a known method.

(Polyamic acid ester)

The polyamic acid ester as the polymer (P) can be obtained by, for example, a method of reacting a tetracarboxylic acid diester dihalide with a diamine.

In the present specification, the term "tetracarboxylic acid diester dihalide" means a compound in which two of four carboxyl groups possessed by tetracarboxylic acid are esterified and the remaining two are halogenated. "Tetracarboxylic acid diester" means a compound in which two of four carboxyl groups possessed by tetracarboxylic acid are esterified, and the remaining two are carboxyl groups.

The tetracarboxylic acid diester dihalide used can be obtained by reacting a tetracarboxylic acid diester with a suitable chlorinating agent such as thionyl chloride. The tetracarboxylic acid diester can be prepared by, for example, reacting tetracarboxylic acid dianhydrides (specific tetracarboxylic dianhydrides and other tetracarboxylic dianhydrides) exemplified in the synthesis of polyamic acid with alcohols such as methanol and ethanol Can be obtained.

Examples of the diamine to be reacted with the tetracarboxylic acid diester dihalide include a specific diamine and other diamines exemplified in the description of the synthesis of the polyamic acid, a compound in which a primary amino group of a specific diamine and other diamines is protected with a protecting group (Also referred to as " diamine compound (CA1) "). Specific examples of the diamine compound (CA1) in which the primary amino group is protected include compounds represented by the following formula (5) and the like:

(In the formula (5), R ⁹ is a divalent organic group and Y ¹ is a protecting group; plural Y ^{1 s} may be the same or different).

The description of the divalent organic group of R ⁹ in the formula (5) can be applied to the description of the divalent organic groups R ¹ to R ⁴ in the formula (2). Specific examples of the compound represented by the formula (5) include compounds represented by the following formulas (5-1) to (5-16), and the like.

The ratio of the tetracarboxylic acid diester dihalide to the diamine used in the synthesis reaction of the polymer (P) is such that the ratio of the tetracarboxylic acid diester dihalide group "-COX (X is Halogen atom) "is preferably 0.2 to 2 equivalents, more preferably 0.8 to 1.2 equivalents.

The ratio of the tetracarboxylic acid diester dihalide having a partial structure represented by the above formula (1), the specific diamine and the diamine compound (CA1) (when a plurality of species are used, the total amount thereof) Is preferably 10 mol% or more, more preferably 20 mol% to 80 mol%, still more preferably 25 mol% to 70 mol% based on the total amount of the monomers used in the synthesis from the viewpoint of sufficiently improving the effect of improving the residual image, Is more preferable.

The reaction of the tetracarboxylic acid diester dihalide with the diamine is preferably carried out in an organic solvent in the presence of a base. The reaction temperature at this time is preferably -30 ° C to 150 ° C, more preferably -10 to 100 ° C. The reaction time is preferably 0.1 to 48 hours, more preferably 0.5 to 36 hours. As the organic solvent used in the reaction, an explanation of an organic solvent that can be used for the synthesis reaction of polyamic acid can be applied. The amount of the organic solvent used is preferably such that the total amount of the tetracarboxylic acid diester dihalide and the diamine is 0.1 to 50% by weight based on the total amount of the reaction solution. Examples of the base used in the above reaction include tertiary amines such as pyridine, triethylamine and N-ethyl-N, N-diisopropylamine; Alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium and potassium can be preferably used. The amount of the base to be used is preferably 2 to 4 mol, more preferably 2 to 3 mol, per 1 mol of the diamine.

In this way, a reaction solution obtained by dissolving a polyamic acid ester is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, after the polyamic acid ester contained in the reaction solution is isolated, the reaction solution may be provided in the preparation of the liquid crystal aligning agent, or after the isolated polyamic acid ester is purified, May be provided to the preparation of The polyamic acid ester can be isolated and purified by a known method. The polyamic acid ester may have only an amide ester structure, or may be a partial esterified product in which an amide structure and an amide ester structure coexist.

The polyamic acid ester as the polymer (P) is not limited to the above-mentioned synthesis method. For example, a method of reacting a polyamic acid as the polymer (P) with an alcohol, a method of reacting a tetracarboxylic acid diester with a diamine Or the like.

(Polyimide)

The polyimide as the polymer (P) can be obtained, for example, by imidizing the polyamic acid synthesized as described above by dehydration ring closure. When the polyamic acid is subjected to dehydration ring closure to form polyimide, the reaction solution of the polyamic acid may be directly supplied to the dehydration ring-closing reaction, or the polyamic acid contained in the reaction solution may be isolated and then subjected to dehydration ring- The polyamic acid may be purified and then subjected to a dehydration ring-closing reaction.

The polyimide may be a completely imidized product obtained by dehydrating and ring closure of the entire acid structure of the polyamic acid which is a precursor of the polyimide and may be a partially imidized product in which only a part of the acid structure is subjected to dehydration ring closure, good. The imide ratio of the polyimide used in the reaction is preferably 20% or more, more preferably 30 to 99%, and even more preferably 40 to 99%. The imidization rate is a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating a polyamic acid, or a method of dissolving a polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and optionally heating . Of these, the latter method is preferable.

In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to a polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyimide is obtained. This reaction solution may be provided as it is in the preparation of a liquid crystal aligning agent, or may be supplied to the preparation of a 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, Or may be added to the preparation of a liquid crystal aligning agent after purification of the isolated polyimide. These purification operations can be carried out according to a known method.

(Polyamide)

The polyamide of the polymer (P) can be obtained by, for example, a method of reacting a dicarboxylic acid with a diamine. Here, it is preferable that the dicarboxylic acid is provided for the reaction with the diamine after acid chloridation using a suitable chlorinating agent such as thionyl chloride. In the present specification, the term "dicarboxylic acid dihalide" means a compound in which two carboxyl groups of the dicarboxylic acid are halogenated.

The dicarboxylic acid used for the synthesis of the polyamide is not particularly limited, and examples thereof include oxalic acid, malonic acid, dimethyl malonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, Aliphatic dicarboxylic acids such as pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, fumaric acid and muconic acid;

Dicarboxylic acids having an alicyclic structure such as cyclobutanedicarboxylic acid, 1-cyclobutenedicarboxylic acid, cyclopentanedicarboxylic acid, and cyclohexanedicarboxylic acid;

Examples of the organic acid include phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 2,5-dimethylterephthalic acid, naphthalenedicarboxylic acid, 4,4'- Dicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-carbonylbenzoic acid, 4-carboxycinnamic acid, (4,4 '- (oxydi-p-phenylene)] 2-butyric acid, 3,4-di Phenyl-1,2-cyclobutanedicarboxylic acid, and azobenzene-4,4'-dicarboxylic acid; And the like. The dicarboxylic acid dihalides may be used singly or in combination of two or more.

Examples of the diamine used for the synthesis of the polyamide include the compounds represented by the above formula (5) in addition to the specific diamines and other diamines exemplified in the description of the synthesis of the polyamic acid. At this time, polyamide as the polymer (P) can be obtained by using a specific diamine or diamine compound (CA1) for at least a part of the monomer. The diamines may be used singly or in combination of two or more.

The proportion of the diamine to be used in the synthesis reaction of the polymer (P) and the diamine is preferably such that the ratio of the group " -COX (X is a halogen atom) " of the dicarboxylic acid dihalide is 0.2 To 2 equivalents, and more preferably 0.8 to 1.2 equivalents.

The reaction of the dicarboxylic acid dihalide with the diamine is preferably carried out in an organic solvent in the presence of a base. The reaction temperature at this time is preferably 0 to 200 캜, more preferably 10 to 100 캜. The reaction time is preferably 0.5 to 48 hours, more preferably 1 to 36 hours.

As the organic solvent used in the reaction, for example, tetrahydrofuran, dioxane, toluene, chloroform, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone and the like can be preferably used . The amount of the organic solvent used is preferably 400 to 900 parts by weight, more preferably 500 to 700 parts by weight, based on 100 parts by weight of the total amount of the dicarboxylic acid dihalide and the diamine.

Examples of the base used in the above reaction include tertiary amines such as pyridine, triethylamine and N-ethyl-N, N-diisopropylamine; (Trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, lithium diisopropylamide, sodium diisopropylamide, potassium diisopropylamide, sodium diisopropylamide, , and t-butyllithium, can be preferably used. The amount of the base to be used is preferably 2 to 4 mol, more preferably 2 to 3 mol, per 1 mol of the diamine.

As described above, a reaction solution obtained by dissolving polyamide is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or may be supplied to the preparation of the liquid crystal aligning agent after the polyamide contained in the reaction solution is isolated, or after the isolated polyamide is purified, . The polyamide may be isolated and purified by a known method.

The solution viscosity and weight average molecular weight (Mw) of the polymer (P) can be appropriately selected in accordance with the main skeleton. For example, in the case of polyamic acids, polyamic acid esters, polyimides and polyamides, the solution viscosity of the polymer is preferably 10 to 800 mPa · s when the solution has a concentration of 10 wt% , And more preferably 15 to 500 mPa · s. The solution viscosity (mPa 占 퐏) of the polymer (P) can be measured by using a good solvent (e.g.? -Butyrolactone, N-methyl-2-pyrrolidone or the like) Measured at 25 캜 using an E-type rotational viscometer for a polymer solution having a prepared concentration of 10% by weight.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less.

[Compound (P) as an additive]

When the compound (P) is used as an additive, a compound having a plurality of photopolymerizable groups (hereinafter also referred to as " photopolymerizable compound (P) ") can be preferably used as the compound having a partial structure represented by the formula have. Specific preferred examples thereof include compounds represented by the following formula (6) and the like:

(Wherein, X ⁴ and X ⁵ are a photopolymerizable group; R ¹⁰ , R ¹¹ and R ¹³ are each independently a divalent organic group; R ¹² is a single bond or a divalent organic group; Y ¹ F is an integer of 1 to 3, and g is 0 or 1).

In the formula (6), examples of the photopolymerizable group of X ⁴ and X ⁵ include a group having a polymerizable unsaturated bond. (Meth) acryloyloxy group, styryl group, (meth) acrylamide group, vinyl group, CH ₂ ═C (CH ₃ ) -, vinyloxy group (CH ₂ ═CH-O-) , A group represented by the following formula (x-1) or (x-2), and the like:

(In the formula (x-1), X ⁶ is an oxygen atom or -NH-;

The photopolymerizable group is preferably a (meth) acryloyloxy group in view of high photoreactivity. In addition, (meth) acryloyloxy group means "acryloyloxy group" and "methacryloyloxy group". (Meth) acrylamide group means " acrylamide group " and " methacrylamide group ".

The description of the divalent organic groups represented by R ¹⁰ to R ¹³ is applicable to the divalent organic groups represented by R ¹ to R ^{4 in} the above formula (2). As R ¹⁰ to R ¹³ , it is preferable that at least one of them is a phenylene group, a cyclohexylene group or a biphenylene group from the viewpoint of affinity with a liquid crystal, and at least two of R ¹⁰ to R ¹³ are a phenylene group, More preferably a cyclohexylene group or a biphenylene group. From the viewpoint of the solubility of the compound (P), it is preferable that at least one of R ¹⁰ to R ¹³ is a cyclohexylene group.

f is preferably 1.

Specific examples of the photopolymerizable compound (P) include compounds represented by the following formulas (6-1) to (6-30), and the like:

(In the formulas (6-1) to (6-20), R is a hydrogen atom or a methyl group, n is an integer of 1 to 20, and Boc represents a tert-butoxycarbonyl group);

(In the formulas (6-21) to (6-24), n is an integer of 1 to 20; Boc represents a tert-butoxycarbonyl group);

(Wherein R is a hydrogen atom or a methyl group, m and n are each independently an integer of 1 to 20, and Boc is a tert-butoxycarbonyl group) .

In the liquid crystal aligning agent, the compounding ratio of the compound (P) as an additive is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the total weight of the polymer components. The above-mentioned compounds (P) can be used singly or in combination of two or more kinds. The molecular weight of the compound (P) is preferably 1,500 or less, more preferably 1,200 or less, and even more preferably 1,000 or less.

<Other components>

The liquid crystal aligning agent according to the present invention may contain other components other than the compound (P), if necessary. Other components include, for example, other polymers other than the polymer (P), a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound"), and a functional silane compound.

[Other Polymers]

The other polymer can be used for the purpose of improving various characteristics such as solution characteristics, electric characteristics, heat resistance, mechanical strength, etc., or for lowering the cost. Such another polymer is a polymer having no partial structure represented by the above formula (1), and examples thereof include polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polyester, polyamide, cellulose derivative, A polystyrene derivative, a poly (styrene-phenylmaleimide) derivative, or a polymer having a poly (meth) acrylate as a main skeleton and having no specific structure as described above. As the other polymer, at least one polymer selected from the group consisting of polyamic acid, polyimide, polyamic acid ester and polyamide can be preferably used.

When the other polymer is compounded in the liquid crystal aligning agent, the blending ratio thereof is preferably selected appropriately according to the kind of the compound (P). For example, when the compound (P) is a polymer, the blending ratio of the other polymer is preferably 50 to 50 parts by weight based on 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent (the sum of the polymer (P) More preferably 0.1 to 40 parts by weight, still more preferably 0.1 to 30 parts by weight.

When the liquid crystal aligning agent of the present invention contains the compound (P) as an additive, the liquid crystal aligning agent may contain at least one polymer selected from the group consisting of the polymer (P) and other polymers as the polymer component . In this case, the blending ratio of the other polymer can be arbitrarily set within a range of not more than 100% by weight based on the total amount of the polymer contained in the liquid crystal aligning agent. Preferably 10 to 100% by weight, and more preferably 30 to 90% by weight.

[Epoxy group-containing compound]

The epoxy group-containing compound can be used for improving the adhesion to the substrate surface and electric characteristics in the liquid crystal alignment film. Examples of such epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether , Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, , N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidylaminomethylcyclohexane, N, N- Diglycidyl-cyclohexylamine, and the like can be preferably used. As other examples of the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used.

When the epoxy group-containing compound is compounded in the liquid crystal aligning agent, the blending ratio thereof is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight per 100 parts by weight of the total amount of the polymers contained in the liquid crystal aligning agent desirable.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the printing property of the liquid crystal aligning agent. Examples of such a functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyl triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-tri Methoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, Trimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like, Can.

When other functional silane compounds are compounded in the liquid crystal aligning agent, the blending ratio thereof is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight per 100 parts by weight of the total amount of the polymers contained in the liquid crystal aligning agent .

In addition to the above, other components may include a compound having at least one oxetanyl group in the molecule, an antioxidant, a metal chelate compound, a curing accelerator, a surfactant, a filler, a dispersant, and a photosensitizer.

The liquid crystal aligning agent according to the present invention may contain only one kind of polymer as a polymer component, or may contain two or more kinds of polymers. Preferable examples of the case of containing two or more kinds of polymers include, for example, the following [1] to [3] and the like.

[1] The sun, which contains the polymer (P) and the other polymer, wherein the polymer (P) and the other polymer are at least one selected from polyamic acid, polyamic acid ester, polyimide and polyamide.

[2] The sun having at least one polymer (P) and at least one polymer (P) thereof selected from polyamic acid, polyamic acid ester, polyimide and polyamide.

[3] The polymerizable composition according to any one of [1] to [4], wherein the polymer contains at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and polyamide, .

Among them, in the embodiment of [1], the amino group in the amide bond in the polymer (P) is protected with Y ¹ , so that the polarity difference between the polymer (P) and the other polymer becomes large, Can be sufficiently generated.

The compounding ratio of the compound (P) to the solid content (component other than the solvent of the liquid crystal aligning agent) in the liquid crystal aligning agent is preferably selected appropriately according to the kind of the compound (P). For example, when the compound (P) is a polymer, the compounding ratio of the polymer (P) is preferably 40 parts by weight or more, more preferably 50 parts by weight or less, And more preferably not less than 60 parts by weight.

The blending ratio of the polymer (P) in the embodiment of [1] above is preferably 100 parts by weight or more, more preferably 100 parts by weight or less, more preferably 100 parts by weight or less, Is preferably 1 to 99 parts by weight, more preferably 10 to 90 parts by weight, and still more preferably 20 to 80 parts by weight.

When the compound (P) is an additive, the compounding ratio of the compound (P) is preferably 0.5 to 50 parts by weight, preferably 2 to 30 parts by weight, based on 100 parts by weight of the total solid weight of the liquid crystal aligning agent And more preferably 5 to 25 parts by weight.

<Solvent>

The liquid crystal aligning agent according to the present invention is prepared as a liquid composition in which the compound (P) and other components that are optionally used are dispersed or dissolved in an appropriate solvent.

Examples of the organic solvent to be used include organic solvents such as N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol- propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamylphosphate Propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate, and the like. These may be used alone or in combination of two or more.

The solid concentration in the liquid crystal aligning agent (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., 10% by weight. That is, the liquid crystal aligning agent is applied to the surface of the substrate as described later, and preferably heated to form a coating film which is a liquid crystal alignment film or a liquid crystal alignment film. At this time, when the solid concentration is less than 1% by weight, the film thickness of the coating film becomes too small, and it becomes difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large, so that a good liquid crystal alignment film tends to be difficult to obtain, and the viscosity of the liquid crystal aligning agent tends to be increased.

A particularly preferable range of the solid concentration is different depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, when the coating liquid is applied to a substrate by the spinner method, the solid concentration (the ratio of the total weight of all the components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is in the range of 1.5 to 4.5 wt% Particularly preferred. In the case of the printing method, it is particularly preferable that the solid concentration is in the range of 3 to 9% by weight, whereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, whereby the solution viscosity is in the range of 3 to 15 mPa · s. The temperature for preparing the liquid crystal aligning agent is preferably 10 to 50 캜, more preferably 20 to 30 캜.

<Liquid crystal display element>

The liquid crystal display element according to the present invention comprises a liquid crystal alignment film formed using the above-described liquid crystal aligning agent. The operation mode of the liquid crystal display element is not particularly limited and may be, for example, TN type, STN type, VA type (including VA-MVA type and VA-PVA type), IPS type, FFS type, OCB (Optically Compensated Bend ) Type and the like.

The liquid crystal display element can be produced, for example, by a process including the following steps (1) to (3). In the step (1), the substrate to be used differs depending on a desired operation mode. Processes (2) and (3) are common to each operation mode.

[Process (1): Formation of coating film]

First, a liquid crystal aligning agent is applied onto a substrate, and then a coated film is formed on the substrate by heating the coated surface.

(1-A) For example, in the case of producing a liquid crystal display element of TN type, STN type or VA type, two substrates on which a patterned transparent conductive film is formed are formed as a pair, The liquid crystal aligning agent is preferably applied on the surface by the offset printing method, the spin coating method, the roll coating method, or the ink jet printing method. 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 poly (alicyclic olefin) can be used. As the transparent conductive film to be formed on one surface of the substrate, an ITO film made of NESA film (a registered trademark of PPG Corporation of the US) or indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) . The patterned transparent conductive film can be obtained, for example, by forming a transparent conductive film without a pattern and then forming a pattern by photoetching; A method using a mask having a desired pattern when forming a transparent conductive film; And so on. In the application of the liquid crystal aligning agent, a functional silane compound, a functional titanium compound or the like is added to the surface of the substrate surface on which the coating film is to be formed in advance in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film The pre-treatment for coating may be performed.

Preheating (prebaking) is preferably performed for the purpose of preventing the liquid flow of the applied liquid crystal aligning agent after application of the liquid crystal aligning agent. The prebaking temperature is preferably 30 to 200 캜, more preferably 40 to 150 캜, particularly preferably 40 to 100 캜. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, the solvent is completely removed, and a firing (post-baking) process is carried out in order to thermally modify the structure of the acid in the polymer as required. The firing temperature (post-baking temperature) at this time is preferably 80 to 300 占 폚, more preferably 120 to 250 占 폚. The post baking time is preferably 5 to 200 minutes, and more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 mu m, more preferably 0.005 to 0.5 mu m.

(1-B) In the case of manufacturing an IPS or FFS type liquid crystal display element, the electrode formation surface of the substrate on which the electrodes made of the transparent conductive film or the metal film patterned in the comb shape are provided, A liquid crystal aligning agent is coated on one surface of the counter substrate, and then each coated surface is heated to form a coated film. A preferable film thickness of the substrate and the transparent conductive film to be used at this time, the coating method, the heating condition after coating, the method of patterning the transparent conductive film or the metal film, the pretreatment of the substrate, and the coating film to be formed are the same as in the above (1-A) Do. As the metal film, for example, a film made of a metal such as chromium can be used.

In any of the cases (1-A) and (1-B), a liquid crystal alignment film or a coating film to be a liquid crystal alignment film is formed by removing the organic solvent after coating the liquid crystal alignment agent on the substrate. At this time, when the polymer contained in the liquid crystal aligning agent is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imidazole ring structure and an arboric acid structure, the dehydration ring-closure reaction proceeds by further heating after forming the film , Or a more imaged coating film may be used.

[Process (2): orientation treatment]

In the case of producing a liquid crystal display element of TN type, STN type, IPS type or FFS type, a treatment (alignment treatment) for imparting a liquid crystal aligning ability to the coating film formed in the above step (1) is performed. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Examples of the alignment treatment include rubbing treatment in which the coating film is rubbed in a predetermined direction with a roll formed of fibers such as nylon, rayon, and cotton to give a liquid crystal aligning ability to the coating film, and a coating film formed on the substrate is irradiated with light, And a photo alignment treatment for imparting a liquid crystal aligning ability to the substrate. On the other hand, in the case of producing a vertically aligned liquid crystal display element, the coating film formed in the above step (1) can be directly used as a liquid crystal alignment film, but the coating film may be subjected to alignment treatment.

(2a) a method of irradiating the coated film after pre-baking and post-baking, (3a) a method of irradiating the coated film after post-baking, and Or a method in which the coating film is irradiated to the coating film during heating of the coating film.

The light irradiated onto the coating film may be polarized or unpolarized radiation. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. When the radiation to be used is linearly polarized light or partial polarized light, the irradiation may be performed in a direction perpendicular to the substrate surface, in an oblique direction, or in combination thereof. In the case of irradiating non-polarized radiation, the irradiation direction is set to an oblique direction.

As the light source to be used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp and an excimer laser can be used. The ultraviolet rays in the preferable wavelength range can be obtained by a means for using a light source in combination with, for example, a filter or a diffraction grating. The dose of light is preferably 100 to 50,000 J / m 2, and more preferably 300 to 20,000 J / m 2. The light irradiation to the coating film may be performed while heating the coating film to enhance the reactivity. The temperature at the time of heating is usually 30 to 250 占 폚, preferably 40 to 200 占 폚, and more preferably 50 to 150 占 폚.

Further, it is also possible to use a process of changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film to the rubbed liquid crystal alignment film, or a process of forming a resist film on a part of the surface of the liquid crystal alignment film, After the rubbing treatment is performed in a direction different from the rubbing treatment, a treatment for removing the resist film may be performed so that the liquid crystal alignment film has a liquid crystal aligning ability different for each region. In this case, it is possible to improve the visual field characteristic of the obtained liquid crystal display element.

When a PSA (Polymer Sustained Alignment) type liquid crystal display element is produced, or when a coating film is formed using a liquid crystal aligning agent containing a polymerizable group-containing component, the coating film formed in the above step (1) The following step (3) may be carried out. However, alignment treatment such as weak rubbing treatment may be performed for the purpose of controlling the inclination of liquid crystal molecules and performing alignment division in a simple manner. A liquid crystal alignment film suitable for VA type liquid crystal display elements can be suitably used for liquid crystal display devices of the PSA type.

[Process (3): Construction of liquid crystal cell]

(3-A) A liquid crystal cell is prepared by preparing two substrates on which a liquid crystal alignment film is formed as described above, and arranging liquid crystals between two substrates opposed to each other. To produce a liquid crystal cell, for example, the following two methods can be used. The first method is a conventionally known method. First, 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. The peripheral portions of the two substrates are bonded together using a sealant, After the liquid crystal is filled and filled in the cell gap, the liquid crystal cell is manufactured by sealing the injection port. The second method 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, and liquid crystal is further dripped onto a predetermined number of places on the liquid crystal alignment film surface, The liquid crystal cell is manufactured by joining the other substrate so that the alignment film is opposed to the substrate, spreading the liquid crystal on the entire surface of the substrate, and then irradiating ultraviolet light to the entire surface of the substrate to cure the sealant. Regardless of the method, it is preferable to further heat the liquid crystal cell manufactured as described above to a temperature at which the liquid crystal used becomes an isotropic phase, and then gradually cool to room temperature to remove the flow alignment at the time of filling the liquid crystal Do.

As the sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Of these, nematic liquid crystals are preferable, and examples thereof include a cypher base liquid crystal, an agar watch liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexane liquid crystal, Based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, quartz-based liquid crystal and the like. Further, to these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate and cholesteryl carbonate; 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 may be added and used.

(3-B) In the case of producing a PSA type liquid crystal display device, a liquid crystal cell is constructed in the same manner as in (3-A) except that a photopolymerizable compound is injected or dropped together with liquid crystal. Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage to be applied here may be DC or AC of 5 to 50 V, for example. As the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable. As the light source of the irradiation light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp and an excimer laser can be used. The ultraviolet ray in the above-mentioned preferable wavelength range can be obtained by a means for using the light source together with, for example, a filter diffraction grating or the like. The dose of light is preferably 1,000 to 200,000 J / m 2, and more preferably 1,000 to 100,000 J / m 2.

When a coating film is formed on a substrate by using a liquid crystal aligning agent containing a compound having a photopolymerizable group as a (3-C) polymer component or an additive, a liquid crystal cell is constructed in the same manner as in (3-A) Thereafter, a method may be employed in which the liquid crystal cell is irradiated with light in a state in which a voltage is applied between the conductive films of the pair of substrates to produce a liquid crystal display device. According to this method, the merit of the PSA mode can be realized with a small light irradiation amount. The voltage applied and the condition of the light to be irradiated can be applied to the description of (3-B) above.

A liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched polyvinyl alcohol is sandwiched by a cellulose acetate protective film or a polarizing plate made of H film itself .

The liquid crystal display of the present invention can be effectively applied to various apparatuses and can be applied to various devices such as a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, , Various monitors, liquid crystal televisions, information displays, and the like.

(Example)

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

In the following examples, the weight average molecular weight (Mw), the imidization ratio and the solution viscosity of the polymer solution of the polymer were measured by the following methods. Hereinafter, the compound represented by the formula X may be simply referred to as &quot; compound X &quot;.

[Weight average molecular weight (Mw) of polymer]

Mw is a polystyrene reduced value measured by GPC under the following conditions.

Column: TSKgelGRCXLII, manufactured by Toso Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

[Imidization Rate of Polymer]

The polyimide-containing solution was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, and dissolved in deuterated dimethyl sulfoxide. ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material. From the obtained ¹ H-NMR spectrum, the imidation rate was obtained using the following equation (1): &lt; EMI ID =

Imidization ratio (%) = (1-A ¹ / A ² × α) × 100 (One)

(In the formula (1), A ¹ is the peak area derived from the proton of the NH group near the chemical shift of 10 ppm, A ² is the peak area derived from the other proton, and? Is the peak area derived from the proton The ratio of the number of other protons to one proton in the NH group).

[Solution viscosity of polymer solution]

The solution viscosity (mPa s) of the polymer solution was measured at 25 캜 using an E-type rotational viscometer.

[Surface contact angle of membrane]

Approximately 2.0 μL of the droplet of ultra-pure water was dropped on the mold (ASL-400) using a contact angle meter DM-700 manufactured by Kyowa Kai Mengaku Co., Ltd. The image of the droplet after 30 seconds from the drop was subjected to image processing, .

<Synthesis of Compound>

[Synthesis Example 1-1: Synthesis of Compound (I)

Compound (I) was synthesized according to Reaction Scheme 1 below.

2.5 g of 4-nitro-N- (4-nitrophenyl) benzamide was suspended in 30 mL of THF, and 1.5 g of N, N-dimethylaminopyridine was added thereto. 3.95 g of di-tert-butyl dicarbonate (Boc ₂ O) was added to the solution. After stirring for 3 hours at room temperature, the suspended solid was filtered, and the solid was washed with ethanol. The solid was dried to obtain 2.2 g of the compound (i-1) in a purity of 99%.

And 0.3 g of Pd / C were purged with nitrogen, 40 ml of oxygen-deaerated THF was added thereto, and the mixture was stirred. 2.2 g of the compound (i-1) was placed in the vessel, cooled to 0 캜, and stirred for 5 minutes. Hydrogen gas was introduced thereinto, and the nitro group was reduced. After stirring for 3 hours in a hydrogen gas atmosphere, 50 mL of THF was added, the reaction solution was filtered, and the reaction solution was concentrated. The precipitated solid was recovered and, after drying, 1.7 g of the desired compound (I) was obtained in a purity of 99%.

[Synthesis Example 1-2: Synthesis of Compound (II)

Compound (II) was synthesized according to Reaction Scheme 2 below.

2.8 g of N ¹ , N ⁶ -bis (4-nitrophenethyl) adipamide was suspended in 40 mL of THF, and 2.5 g of N, N-dimethylaminopyridine was added thereto. To the solution was added 16 g of di-tert-butyl dicarbonate (Boc ₂ O). After stirring for 3 hours at room temperature, the suspended solid was filtered, and the solid was washed with ethanol. The solid was dried to obtain 3.5 g of compound (ii-1) in a purity of 98%.

And 0.5 g of Pd / C were purged with nitrogen, 100 ml of oxygen-deaerated THF was added thereto, and the mixture was stirred. 3.5 g of the compound (ii-1) was placed in the vessel, cooled to 0 캜 and stirred for 5 minutes. Hydrogen gas was introduced thereinto, and the nitro group was reduced. After stirring for 6 hours in a hydrogen gas atmosphere, 50 mL of THF was added, the reaction solution was filtered, and the reaction solution was concentrated. The precipitated solid was recovered and, after drying, 2.8 g of the aimed compound (II) was obtained in a purity of 99%.

[Synthesis Example 1-3: Synthesis of Compound (III)

Compound (III) was synthesized according to Reaction Scheme 3 below.

2.5 g of 4-nitro-N- (4-nitrophenyl) benzamide was suspended in 30 mL of THF, and 1.5 g of N, N-dimethylaminopyridine was added thereto. To the solution was added 10.4 g of N- [2- (trimethylsilyl) ethoxycarbonyloxy] succinimide. After stirring for 3 hours at room temperature, the suspended solid was filtered, and the solid was washed with ethanol. The solid was dried to obtain 1.8 g of compound (iii-1) in a purity of 98%.

And 0.3 g of Pd / C were purged with nitrogen, 40 ml of oxygen-deaerated THF was added thereto, and the mixture was stirred. 1.8 g of the compound (iii-1) was placed in the vessel, cooled to 0 占 폚 and stirred for 5 minutes. Hydrogen gas was introduced thereinto, and the nitro group was reduced. After stirring for 3 hours in a hydrogen gas atmosphere, 50 mL of THF was added, the reaction solution was filtered, and the reaction solution was concentrated. The precipitated solid was recovered and, after drying, 1.5 g of the aimed compound (III) was obtained in a purity of 99%.

[Synthesis Example 1-4: Synthesis of Compound (IV)

Compound (IV) was synthesized according to Reaction Scheme 4 below.

5.0 g of bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,1'-biphenyl-4,4'-diyl was suspended in 60 mL of THF, And 0.5 g of N, N-dimethylaminopyridine. 40 g of di-tert-butyl dicarbonate (Boc ₂ O) was added to the solution. After stirring for 7 hours at room temperature, 10 mL of acetic anhydride was added and reacted for 5 hours. The suspended solid formed during the reaction was filtered, and the solid was washed with ethyl acetate. The solid was dried to obtain 4.5 g of compound (IV) in a purity of 97%.

[Synthesis Example 1-5: Synthesis of Compound (V)

Compound (V) was synthesized according to Reaction Scheme 5 below.

3.7 g of 4,4 '- (pentane-1,5-diylbis (oxy)) bis (N- (4-nitrophenyl) benzamide) was suspended in 60 ml of THF and thereto was added N, N-dimethylaminopyridine 2.7 g. 20 g of di-tert-butyl dicarbonate (Boc ₂ O) was added to the solution. After stirring for 5 hours at room temperature, the suspended solid was filtered, and the solid was washed with ethanol. This solid was dried to obtain 3.7 g of compound (v-1) in a purity of 98%.

And 0.3 g of Pd / C were purged with nitrogen, 100 ml of oxygen-deaerated THF was added thereto, and the mixture was stirred. 3.7 g of the compound (v-1) was placed in the vessel, cooled to 0 占 폚 and stirred for 5 minutes. Hydrogen gas was introduced thereinto, and the nitro group was reduced. After stirring for 6 hours in a hydrogen gas atmosphere, 80 mL of THF was added, the reaction solution was filtered, and the reaction solution was concentrated. The precipitated solid was recovered and, after drying, 3.0 g of the aimed compound (V) was obtained in a purity of 99%.

[Synthesis Example 1-6: Synthesis of Compound (VI)

Compound (VI) was synthesized according to Reaction Scheme 6 below.

25.4 g of the compound (vii-1), 300 mL of acetonitrile, 48.0 g of di-tert-butyl dicarbonate (Boc ₂ O) and 1.22 g of N, N-dimethylaminopyridine were added to a ₁ L egg- Lt; / RTI &gt; After completion of the reaction, the reaction solution was concentrated to 100 mL and then re-precipitated in 1 L of water. The resulting precipitate was recovered by filtration and dried to obtain 40.9 g of compound (VI).

[Synthesis Example 1-7: Synthesis of Compound (VII)

Compound (VII) was synthesized according to the following Reaction Scheme 7.

51.2 g of the compound (vii-1), 500 mL of acetonitrile, 48.0 g of di-tert-butyl dicarbonate (Boc ₂ O) and 1.22 g of N, N-dimethylaminopyridine were added to a ₁ L egg- Lt; / RTI &gt; After completion of the reaction, the reaction solution was concentrated to 150 mL, and then re-precipitated in 1 L of water. The resulting precipitate was recovered by filtration and dried to obtain 64.2 g of Compound (VII).

[Synthesis Example 1-8: Synthesis of Compound (VIII)

Compound (VIII) was synthesized according to Reaction Scheme 8 below.

4.54 g of 4-methacryloxybenzoic acid, and 1.08 g of 1,4-diaminobenzene were suspended in 30 mL of dichloromethane and ice-cooled. 5.76 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.488 g of N, N-dimethyl-4-aminopyridine were added thereto. After stirring for 6 hours at room temperature, the suspended solid was filtered and the solids were washed with ethanol. The solid was dried to obtain 3.4 g of compound (vii-1) in a purity of 99%.

3.0 g of the compound (vii-1) was suspended in 30 mL of THF, and 2.0 g of di-tert-butyl dicarbonate (Boc ₂ O) was dissolved in 30 mL of THF. To the solution was added 1.49 g of di-tert-butyl dicarbonate (Boc ₂ O). After stirring for 3 hours at room temperature, the solution was concentrated and the solid was dried to obtain 3.4 g of compound (VIII) in a purity of 99%.

[Synthesis Example 1-9: Synthesis of Compound (C-1)] [

Compound (C-1) was synthesized according to Reaction Scheme 9 below.

30.2 g of the compound (C-1a), 200 mL of thionyl chloride and 0.1 mL of N, N-dimethylformamide were added to a 500 mL eggplant-shaped flask equipped with a stirrer, a nitrogen inlet tube and a reflux tube and refluxed for 1 hour. After completion of the reaction, the mixture was concentrated and dried. The viscous liquid obtained was recrystallized from cyclohexane, filtered and dried to obtain 27.1 g of the compound (C-1).

[Synthesis Example 1-10: Synthesis of Compound (ADBA1)] [

Compound (ADBA1) was synthesized according to the following Reaction Scheme (13).

28.6 g of compound (DA1), 300 mL of acetonitrile, 45.8 g of di-tert-butyl dicarbonate (Boc ₂ O) and 1.01 g of triethylamine were added to a 1 L eggplant-shaped flask and reacted at room temperature for 6 hours. After the completion of the reaction, the reaction solution was concentrated to 100 mL, then reprecipitated in 1 L of water, and the resulting precipitate was recovered by filtration and dried to obtain 43.8 g of a compound (ADBA1).

[Synthesis Example 1-11: Synthesis of compound (ADC1)] [

A compound (ADC1) was synthesized according to the following Reaction Scheme 14.

27.0 g of compound (DC1), 200 mL of thionyl chloride and 0.1 mL of N, N-dimethylformamide were added to a 500 mL eggplant-shaped flask equipped with a stirrer, a nitrogen inlet tube and a reflux tube and refluxed for 1 hour. After completion of the reaction, the mixture was concentrated and dried. The viscous liquid obtained was recrystallized from cyclohexane, filtered and dried to obtain 27.6 g of a compound (ADC1).

[Synthesis Example 1-12: Synthesis of Compound (3-7)] [

Compound (3-7) was synthesized according to Reaction Scheme 17 below.

Synthesis of compound (3-7A)

16.6 g of nitrophenethylamine, 200 mL of acetonitrile, 43.7 g of di-tert-butyl dicarbonate (Boc ₂ O) and 1.22 g of N, N-dimethylaminopyridine were added to a 1 L eggplant-shaped flask, Lt; / RTI &gt; After completion of the reaction, the reaction solution was concentrated to 100 mL and then re-precipitated in 1 L of water. The resulting precipitate was recovered by filtration and dried to obtain 24.0 g of Compound (3-7A).

Synthesis of compound (3-7C)

24.3 g of the compound (3-7A), 17.3 g of the compound (3-7B) and 500 mL of dichloromethane were added to a 1 L three-necked flask equipped with a reflux condenser and a nitrogen inlet tube and refluxed for 20 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to 100 mL, and then eluted with an alumina column (eluent: hexane: ethyl acetate = 6: 4), followed by concentration and drying to obtain 22.9 g of compound (3-7C).

Synthesis of compound (3-7)

Into a 2 L autoclave were added 22.9 g of the compound (3-7C), 200 mL of tetrahydrofuran, 200 mL of ethanol and 1.15 g of 5% Pd / C. Next, hydrogen was blown to 1.4 kg / cm &lt; 2 &gt;, followed by reaction at room temperature for 20 hours. After completion of the reaction, the filtrate was subjected to Celite filtration. The resulting filtrate was concentrated under reduced pressure to 50 mL, and the obtained solution was reprecipitated with 1 L of water. The precipitate was collected by filtration, washed with methanol, and then vacuum-dried to obtain 17.9 g of the compound (3-7).

&Lt; Synthesis of Polymer &

[Synthesis Example 2-1: Synthesis of Polymer (P1)] [

100 moles of pyromellitic dianhydride (PMDA) and 100 moles of compound (I) as diamine were dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at room temperature for 6 hours. % Solution. A small amount of the obtained polyamic acid solution was collected, and the solution viscosity was 92 mPa · s as measured by adding NMP to a solution having a polyamic acid concentration of 10 wt%. The polyamic acid thus obtained was used as the polymer (P1).

[Synthesis Example 2-2 to Synthesis Example 2-23, Synthesis Example 2-27 and Synthesis Example 2-28]

A polyamic acid was synthesized in the same manner as in Synthesis Example 2-1 except that the type and amount of the tetracarboxylic acid dianhydride and the diamine to be used were changed as shown in Table 1 below. For the synthetic examples 2-2, 2-5, 2-6, 2-8, 2-10-2-12, 2-14-2-18, and 2-20-2-23, The polymer (P5), the polymer (P6), the polymer (P8), the polymer (P10) to the polymer (P12), the polymer (P14) to the polymer (P18) did.

With regard to Synthesis Examples 2-3, 2-4, 2-7, 2-9, 2-13, 2-19, 2-27 and 2-28, pyridine and acetic anhydride were added to the obtained polyamic acid solution , And chemical imidization. The reaction solution after the chemical imidization was concentrated to prepare NMP so that the concentration became 10% by weight.

In Table 1, the values in parentheses of the tetracarboxylic dianhydrides indicate the ratio (molar ratio) of the tetracarboxylic dianhydrides used in the synthesis of the polymer to the total of 100 moles. The numerical value in () of the diamine represents the ratio (molar amount) of the tetracarboxylic acid dianhydride used in the synthesis of the polymer to the total of 100 moles. The abbreviations of acid anhydrides and diamines in Table 1 indicate the following compounds, respectively.

&Lt; Tetracarboxylic acid dianhydride >

A-1: pyromellitic acid dianhydride

A-2: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

A-3: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

A-4: 1R, 2S, 4S, 5R-1,2,4,5-cyclohexanetetracarboxylic acid dianhydride

A-5: p-phenylenebis (trimellitic acid monoester anhydride)

<Diamine>

D-1: p-phenylenediamine

D-2: 4-Aminophenyl-4'-aminobenzamide

D-3: N- (4-aminophenyl) -N-phenylbenzene-1,4-diamine

D-4: 4-Aminophenyl-4'-aminobenzoate

D-5: 3- (3,5-diaminobenzoyloxy) cholestane

[Synthesis Example 2-24: Synthesis of polymer (P19)] [

A polymer (P19) was synthesized according to the following reaction formula (10).

4.55 g of the compound (VI), 50 mL of tetrahydrofuran and 0.2 mL of N, N-dimethylformamide were added to a 100 mL three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer. Next, 3.39 g of the compound (C-1) was added, and 2.84 g of N-ethyl-N, N-diisopropylamine was added slowly, and then the temperature was returned to room temperature and polymerization was carried out one day and a night. After the completion of the reaction, 100 mL of cyclopentanone was added, and 100 mL of water was subjected to washing three times. Then, 100 mL of N-methyl-2-pyrrolidone was added to the organic layer and the mixture was concentrated to 70 g. 100 mL of pyrrolidone was added and then concentrated to 70 g to obtain an N-methyl-2-pyrrolidone solution (solid concentration: 10% by weight) of the polymer (P19). The polymer (P19) had a weight average molecular weight of 5,500.

[Synthesis Example 2-25: Synthesis of Polymer (P20)] [

A polymer (P20) was synthesized according to the following Reaction Scheme 11.

7.12 g of compound (VII), 70 mL of tetrahydrofuran and 0.2 mL of N, N-dimethylformamide were added to a 100 mL three-necked flask equipped with a thermometer, a nitrogen inlet tube and a thermometer. Next, 3.25 g of the compound (A-6) was added, then 2.84 g of N-ethyl-N, N-diisopropylamine was added slowly, and then the temperature was returned to room temperature and polymerization was carried out overnight. After completion of the reaction, 140 mL of cyclopentanone was added, and 140 mL of water was washed three times with water. Then, 140 mL of N-methyl-2-pyrrolidone was added to the organic layer and the mixture was concentrated to 92 g. 140 mL of pyrrolidone was added, and the mixture was concentrated to 92 g to obtain an N-methyl-2-pyrrolidone solution (solid concentration: 10% by weight) of the polymer (P20). The polymer (P20) had a weight average molecular weight of 6,100.

[Synthesis Example 2-26: Synthesis of Polymer (R6)] [

A polymer (R6) was synthesized according to the following Reaction Scheme 12.

2.54 g of the compound (vi-1), 50 mL of chloroform, 50 mL of water and 0.8 g of sodium hydroxide were placed in a 200 mL three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube. Next, 3.39 g of the compound (C-1) was added and stirred vigorously for 4 hours to obtain a white precipitate. This precipitation was insoluble in tetrahydrofuran and N-methyl-2-pyrrolidone.

[Synthesis Example 2-29: Synthesis of Polymer (AP3)] [

A polymer (AP3) was synthesized according to the following Reaction Scheme 15.

4.87 g of the compound (ADBA1), 25 mL of tetrahydrofuran and 4.8 g of sodium hydride were added to a 100 mL three-necked flask equipped with a dropping funnel, a nitrogen inlet tube, and a thermometer. Next, a solution prepared by dissolving 2.70 g of the compound (ADC1) in 25 mL of tetrahydrofuran was slowly added dropwise, and then the mixture was returned to room temperature and polymerized for one day and night. After completion of the reaction, 100 mL of cyclopentanone was added, and 100 mL of water was washed three times with water. 100 mL of cyclopentanone was added to the organic layer, and the mixture was concentrated to 61 g. Thereafter, 100 mL of cyclopentanone was added again, and then the mixture was concentrated to 61 g to obtain a cyclopentanone solution (solid concentration: 10% by weight) of the polymer (AP3). The polymer (AP3) had a weight average molecular weight of 5,000.

[Synthesis Example 2-30: Synthesis of Polymer (AP4)] [

A polymer (AP4) was synthesized according to the following reaction scheme (16).

60 mL of N, N-dimethylacetamide, 0.5 g of cupric chloride, 20 mL of pyridine and 7.24 g of the compound (V) were placed in a 500 mL three-necked flask equipped with a thermometer, Then, 248 mL of oxygen was introduced, and the reaction was allowed to proceed at room temperature for 2 hours. After completion of the reaction, 100 mL of cyclopentanone was added, and the mixture was washed three times with 100 mL of water. Next, 72 g of cyclopentanone was added to the organic layer, and the mixture was concentrated under reduced pressure to 72 g. Then, 72 g of cyclopentanone was added again and the mixture was concentrated to 72 g to obtain a cyclopentanone solution (solid concentration: 10% &Lt; / RTI &gt; The polymer (AP4) had a weight average molecular weight of 14,000.

[Synthesis Example 2-31: Synthesis of polymer (P21)] [

Cyclohexanetetracarboxylic acid dianhydride as a diamine, 70 molar parts of the compound (I) and 30 mol of the compound (3-7) as tetracarboxylic dianhydrides, and 100 molar parts of 1R, 2S, 4S, 5R- Was dissolved in N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at room temperature for 6 hours to obtain a solution containing 20 wt% of polyamic acid. A small amount of the obtained polyamic acid solution was collected and NMP was added thereto to obtain a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 89 mPa · s. The polyamic acid thus obtained was designated as polymer (P21).

[Example 1]

&Lt; Preparation of liquid crystal aligning agent &

NMP and butyl cellosolve (BC) were added as an organic solvent to the polymer (P1) obtained in Synthesis Example 2-1 as a polymer and the solvent composition was NMP: BC = 50:50 (weight ratio) . This solution was filtered using a filter having a pore diameter of 1 mu m to prepare a liquid crystal aligning agent.

<Evaluation of Storage Stability>

The liquid crystal aligning agent prepared above was placed in a sample bottle and left for one week in an oven at a temperature of 40 캜 to measure a change in viscosity (mPa s). The viscosity was measured at 25 DEG C using an E-type rotational viscometer. The storage stability was evaluated as &quot; acceptable (A) &quot; when the viscosity change was less than 5% and the storage stability was evaluated as &quot; (X) &quot;. As a result, the storage stability was judged to be &quot; good &quot; in this example.

&Lt; Production of Liquid Crystal Display Device for Rubbing Orientation >

As a substrate, a liquid crystal aligning agent prepared as described above was applied by a spinner on a glass substrate having two lines of metal electrodes (electrode A and electrode B) made of chrome and patterned in the form of a comb, Baked on a hot plate at 230 DEG C for 10 minutes to form a coating film having a thickness of about 800 ANGSTROM. The rubbing process was carried out using a rubbing machine having a roll coated with a nylon cloth against the formed coating film surface at a roll rotation speed of 1,000 rpm, a stage moving speed of 25 mm / sec, and a hair embroidering length of 0.4 mm , And liquid crystal aligning ability. The substrate was ultrasonically cleaned in ultrapure water for 1 minute and dried in a 100 ° C clean oven for 10 minutes to produce a substrate having a liquid crystal alignment film on the surface having a comb-like chromium electrode. The substrate having this liquid crystal alignment film was referred to as &quot; substrate A &quot;.

Separately, a coating film of a liquid crystal aligning agent was formed and rubbed on one side of a 1 mm-thick glass substrate having no electrode, washed and dried to obtain a substrate having a liquid crystal alignment film on one side, . The substrate having this liquid crystal alignment film was referred to as &quot; substrate B &quot;.

Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 탆 was applied to the outer edge of the surface having the rubbed liquid crystal alignment film of the substrate, and then the two liquid crystal alignment films were laminated so that the rubbing direction in each liquid crystal alignment film was anti- A and B were disposed to face each other with a space therebetween, and outer edges were abutted and pressed to cure the adhesive. Subsequently, a nematic liquid crystal (MLC-2042, manufactured by Merck Ltd.) was charged between a pair of substrates from the liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic photo-curable adhesive to produce a liquid crystal cell of a transverse electric field system.

&Lt; Evaluation of afterimage characteristic (burn-in characteristic)

A liquid crystal display element of a transverse electric field system was manufactured by the same method as the above-mentioned &quot; Production of liquid crystal display element for rubbing orientation &quot;. This transverse electric field type liquid crystal display element was placed under an environment of 25 占 폚 and 1 atmospheric pressure, and a voltage of 3.5 V of an AC voltage and 5 V of a DC voltage of 5 V was applied to the electrode A for 2 hours without applying a voltage to the electrode B. Immediately thereafter, a voltage of 4 V of AC was applied to both the electrode A and the electrode B. The time from when the voltage of 4 V of AC was started to be applied to both electrodes until the difference in light transmittance between the electrode A and the electrode B became visually confirmed was measured. (?) &Quot;, the afterimage characteristic is &quot; feasible (?) &Quot; when the time is less than 100 seconds and the afterimage characteristic is &quot; I appreciated. As a result, it was evaluated as &quot; good &quot; in this embodiment.

[Examples 2 to 9, 27 and Comparative Examples 2, 3, 5]

A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the type and amount of the polymer used were changed as shown in Table 2 below. Using the prepared liquid crystal aligning agent, evaluation of storage stability, production of liquid crystal display element for rubbing alignment, and evaluation of after-image characteristics were carried out in the same manner as in Example 1, respectively. The results are shown in Table 2 below.

In Table 2, the numerical value of the polymer blend ratio represents the orientation ratio (parts by weight) to the total 100 parts by weight of the polymer components used for preparing the liquid crystal aligning agent.

[Examples 10 to 22, 28, 32, 33, 36 and Comparative Examples 1 and 4]

A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the kind and amount of the polymer used were changed as shown in Table 2 above. Using the prepared liquid crystal aligning agent, evaluation of storage stability, production of liquid crystal display element for rubbing alignment, and evaluation of after-image characteristics were carried out in the same manner as in Example 1, respectively. The results are shown in Table 2 above.

&Lt; Evaluation of Phase Separation >

The liquid phase aligning agent obtained by blending two kinds of polymers was evaluated for the phase separation property between the polymers. First, two types of liquid crystal aligning agents having different types of polymers were prepared by carrying out the same operations as in Example 1 except that only one kind of the two kinds of polymers was used. Subsequently, for each of the prepared liquid crystal aligning agents, a fired film was prepared and the surface contact angle (reference contact angle A1, A2 [deg.]) Of the film was measured. Also, with respect to the liquid crystal aligning agent prepared as described above, a baked film was produced by the same operation, and the contact angle B [degrees] of the surface of the film was measured. When the phase separation property of the polymer is good, since the two types of polymers are divided into the upper layer and the lower layer, the surface contact angle B of the sintered film containing two kinds of polymers is preferably such that the surface contact angle (A1 or A2 ). When the phase separation is not so good, it is considered that the value becomes close to the middle of the two kinds of polymers. Therefore, when the surface contact angle B of the fired film containing two kinds of polymers is close to any of the reference contact angles A 1 and A 2, it is considered that the phase separation property is good and the surface contact angle B and the two reference contact angles A 1 and A 2 (?), The case where the difference? Is less than 5% is referred to as good (?), The case where the difference is less than 10% is defined as? The evaluation results of the respective examples are shown in Table 2 above. In addition, Δθ used the value represented by the following formula (2):

?? [%] = (| B-A | / B) 占 100 (2)

Wherein A is a reference contact angle A1 or A2 and B is a surface contact angle of a bake film produced using a liquid crystal aligning agent containing two kinds of polymers.

[Example 23]

&Lt; Preparation of liquid crystal aligning agent &

A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the type and amount of the polymer used were changed as shown in Table 2 above.

<Evaluation of Storage Stability>

Using the prepared liquid crystal aligning agent, the storage stability of the liquid crystal aligning agent was evaluated in the same manner as in Example 1 above. As a result, it was evaluated as &quot; possible &quot; in this embodiment.

&Lt; Production of optical alignment liquid crystal display element (1) >

The liquid crystal aligning agent prepared above was formed on the surface of a glass substrate having two lines of metal electrodes (electrode A and electrode B) consisting of chromium-patterned combs on one side and an opposing glass substrate on which electrodes were not provided, Coated with a spinner so that the film thickness became 0.1 탆, and dried in a hot oven at 80 캜 for 1 minute and at 200 캜 in a clean oven for 1 hour to form a coating film. On the surface of this coating film, 10,000 J / m 2 of polarized light including a 254 nm bright line was irradiated from the normal direction of the substrate using a Hg-Xe lamp to form a liquid crystal alignment film. Next, with respect to the pair of substrates subjected to the light irradiation treatment, the epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 mu m was applied by screen printing while leaving the liquid crystal injection hole at the edge of the surface on which the liquid crystal alignment film was formed, Was bonded to the substrates so that the projection directions of the polarization axes of the substrates to the substrate surface were antiparallel to each other, and the adhesive was thermally cured at 150 DEG C for 1 hour. Subsequently, a nematic liquid crystal (MLC-7028, manufactured by Merck Ltd.) was charged from a pair of substrates through a liquid crystal injection port, and then a liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated at 150 占 폚 and slowly cooled to room temperature. Next, a polarizing plate was bonded to both outer sides of the substrate to produce a transverse electric field type liquid crystal display element.

&Lt; Evaluation of after-image characteristic &

A liquid crystal display element of a transverse electric field system was manufactured in the same manner as the above-mentioned "Production of liquid crystal display element for photo-alignment (1)", and the after-image characteristics were evaluated in the same manner as in Example 1. As a result, in this example, it was difficult to generate afterimage, and the evaluation was &quot; good &quot;.

[Examples 24 to 26]

A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the kind and amount of the polymer used were changed as shown in Table 2 above. The storage stability was evaluated in the same manner as in Example 1 using the prepared liquid crystal aligning agent. A liquid crystal display element for photo alignment was produced in the same manner as in Example 23 except that the used liquid crystal aligning agent was changed respectively, and in the same manner as in Example 1, Respectively. In Examples 25 and 26 in which two kinds of polymers were blended to prepare a liquid crystal aligning agent, the phase separation property of the two kinds of polymers was evaluated by the same method as the < phase separation evaluation >. The results are shown in Table 2 above.

[Examples 29, 30]

&Lt; Preparation of liquid crystal aligning agent &

A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the type and amount of the polymer used were changed as shown in Table 2 above.

<Evaluation of Storage Stability>

Using the prepared liquid crystal aligning agent, the storage stability was evaluated in the same manner as in Example 1 above. As a result, both of Examples 29 and 30 were evaluated as &quot; good &quot;.

&Lt; Production of optical alignment liquid crystal display element (2) >

Each of the liquid crystal aligning agents prepared above was used as a pair of a glass substrate having two lines of metal electrodes (electrode A and electrode B) made of chrome patterned in comb shape on one side and an opposing glass substrate on which electrodes were not provided The coating was applied to the substrate surface using a spinner so that the film thickness became 0.1 mu m and fired on a hot plate at 80 DEG C for 1 minute. Next, on the surface of the coating film, 10,000 J / m 2 of polarized light including a 254-nm bright line was irradiated from the substrate normal direction using a Hg-Xe lamp, and then dried in a 200 o C clean oven for 1 hour to form a liquid crystal alignment film did. Next, with respect to the pair of substrates, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 mu m was applied by screen printing to leave a liquid crystal injection hole at the edge of the surface on which the liquid crystal alignment film was formed, And the adhesive was thermally cured at 150 DEG C for 1 hour. Subsequently, a nematic liquid crystal (MLC-7028, manufactured by Merck Ltd.) was charged from a pair of substrates through a liquid crystal injection port, and then a liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated at 150 占 폚 and slowly cooled to room temperature. Thereafter, a polarizing plate was bonded to both outer sides of the substrate to produce a transverse electric field type liquid crystal display element.

&Lt; Evaluation of after-image characteristic &

A liquid crystal display element of a transverse electric field system was manufactured by the same method as the above-mentioned "Production of liquid crystal display element for photoadjustment (2)", and the characteristics of afterimage were evaluated by the same method as in Embodiment 1. As a result, it was evaluated as "good" in Example 29 and "possible" in Example 30.

<Phase Separation Evaluation>

Using the prepared liquid crystal aligning agent, the phase separation property of the two kinds of polymers was evaluated by the same operation as the < phase separation evaluation >. As a result, both of Examples 29 and 30 were evaluated as &quot; good &quot;.

As shown in Table 2, by using the polymer (P) having an amide bond protected, the storage stability could be improved while the afterimage characteristics were not impaired. In addition, even when a polymer having a high imidization ratio (for example, a polymer having an imidization ratio of 90% or more) was used, good results were obtained regarding storage stability. In addition, the polymer having a high hydrogen bonding property such as the polymer (P20) has poor storage stability, but it has been found that the introduction of a protecting group improves solubility in a solvent and improves storage stability. Good results were obtained as the afterimage characteristic of the liquid crystal display element. This is presumably because the protective groups introduced into the polymer are desorbed by heat, resulting in regeneration of the highly oriented structure after post-baking.

With respect to the phase separation of a system in which a plurality of polymers were blended, all of the examples were satisfactory. This is presumed to be because the hydrophobicity of the polymer (P) increases due to the introduction effect of the protecting group, and the polarity difference is generated between the polymer and the polymer having no protecting group. For this reason, phase separation is caused even when a polymer having a poor liquid crystal alignability such as the polymer (R1) is mixed with a polymer which tends to lower the afterimage characteristic of the liquid crystal display element, and a film having a high orientation It is presumed that good results were obtained in the evaluation of the afterimage characteristic.

[Example 31]

&Lt; Preparation of liquid crystal aligning agent &

NMP and butyl cellosolve (BC) were added as an organic solvent to a solution containing the polymer (R5) obtained in Synthesis Example 2-23 as a polymer component, and furthermore, the compound synthesized in Synthesis Example 1-8 (VIII) was added in an amount of 20 parts by weight based on 100 parts by weight of the polymer (R5) to obtain a solution having a solvent composition of NMP: BC = 50:50 (weight ratio) and a solid concentration of 6.0% by weight. This solution was filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent.

&Lt; Evaluation of printability >

The liquid crystal aligning agent prepared above was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printing machine (manufactured by Nippon Sha Shingen Co., Ltd.) and heated on a hot plate at 80 캜 for 1 minute (Prebaked) to remove the solvent, and then heated (post baking) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å. This coating film was observed under a microscope with a magnification of 20 times to examine whether there was uneven printing or pinholes. The evaluation was made based on the printability &quot; good &quot; (&quot; good &quot;) when print unevenness and pinholes were not observed, the printability &quot; (X) &quot; in the case where at least one of the pinhole and the pinhole was observed. In this example, neither print unevenness nor pinholes were observed, and the printability was &quot; good &quot;.

&Lt; Production of liquid crystal display element &

On the respective electrode surfaces of a pair of glass substrates each having an ITO electrode patterned in a slit shape as shown in Fig. 1 and partitioned into a plurality of regions, the liquid crystal aligning agent prepared above was applied to a liquid crystal alignment film printing machine (Post-baking) on a hot plate at 200 ° C for 10 minutes to obtain a film having an average film thickness of 600 Å Was formed. The coating film was subjected to a rubbing treatment with a rubbing machine having a roll around which a rayon spring was wound at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a piercing indentation length of 0.1 mm. Thereafter, the substrate was ultrasonically cleaned in ultrapure water for 1 minute and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film. The rubbing treatment described above is a weak rubbing treatment performed for the purpose of controlling the collapse of the liquid crystal and performing the orientation division in a simple manner.

Next, for one of the pair of substrates, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 mu m was applied to the outer edge of the surface having the liquid crystal alignment film, and then the pair of substrates was bonded And the adhesive was cured. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled between the pair of substrates from the liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic-based photo-curable adhesive to manufacture a liquid crystal cell. An AC voltage of 10 V was applied between the electrodes at an AC voltage of 10 V and the liquid crystal was driven. An ultraviolet ray irradiation apparatus using a metal halide lamp was used as the light source. Ultraviolet rays were irradiated at an irradiation dose of 10,000 J / did. This irradiation dose is a value measured using a photometer which is measured based on a wavelength of 365 nm.

&Lt; Evaluation of after-image characteristic &

The liquid crystal display device prepared above was placed under an environment of 25 占 폚 and 1 atmospheric pressure, and an AC voltage of 10 V was applied to the electrode A for 300 hours without applying voltage to the electrode B. After a lapse of 300 hours, a voltage of 3 V of alternating current was applied to both the electrode A and the electrode B, and the difference? T [%] of the light transmittance between both electrodes was measured. At this time, the afterimage characteristic is evaluated as "acceptable (?)" When the ΔT is less than 2%, the afterimage characteristic is "acceptable" when the residual image characteristic is "good" did. As a result, it was evaluated as &quot; good &quot; in this embodiment.

[Comparative Examples 6 and 7]

A liquid crystal aligning agent was prepared in the same manner as in Example 31 except that the kinds and amounts of additives used were changed as shown in Table 3 below. Evaluation of printability, manufacture of a liquid crystal display element, and evaluation of afterimage characteristics were carried out in the same manner as in Example 31, using the prepared liquid crystal aligning agent. The results are shown in Table 3 below.

In Table 3, the numerical value of the blending ratio of the polymer and the additive represents the blend ratio (parts by weight) to the total 100 parts by weight of the polymer components used for preparing the liquid crystal aligning agent. The abbreviations of the additives are as follows.

Add-1: Compound represented by the following formula (Add-1)

Add-2: Compound represented by the following formula (Add-2)

As shown in Table 3, in Example 31, by using a compound having a protecting group introduced into the amide bond portion as the photopolymerizable compound, the printability can be improved while maintaining the afterimage characteristic of the liquid crystal display element. On the other hand, in Comparative Example 6 in which a protecting group was not introduced in the amide bond portion, the printability was "poor" and in Comparative Example 7 having no nitrogen atom, the afterimage characteristics were inferior to those in Examples.

[Example 34]

&Lt; Preparation of liquid crystal aligning agent &

NMP and butyl cellosolve (BC) were added as an organic solvent to the polymer (AP3) obtained in Synthesis Example 2-29 as a polymer and the solvent composition was NMP: BC: cyclopentanone = 20: 50: , And a solid concentration of 5.0 wt%. This solution was filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent.

<Evaluation of Storage Stability>

Using the prepared liquid crystal aligning agent, the storage stability of the liquid crystal aligning agent was evaluated in the same manner as in Example 1 above. As a result, in this example, the storage stability was evaluated as &quot; good &quot;.

&Lt; Production of optical alignment liquid crystal display element (3) >

The liquid crystal aligning agent prepared above was formed on the surface of a glass substrate having two lines of metal electrodes (electrode A and electrode B) consisting of chromium-patterned combs on one side and an opposing glass substrate on which electrodes were not provided, Using a spinner so that the film thickness became 0.1 mu m, and dried in a 200 DEG C clean oven for 1 hour to form a coating film.

On the surface of this coating film, 5,000 J / m 2 of polarized light including a bright line of 365 nm was irradiated from the normal line direction of the substrate using a Hg-Xe lamp to form a liquid crystal alignment film. Next, with respect to the pair of substrates subjected to the light irradiation treatment, the epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 mu m was applied by screen printing while leaving the liquid crystal injection hole at the edge of the surface on which the liquid crystal alignment film was formed, Was bonded to the substrates so that the projection directions of the polarization axes of the substrates to the substrate surface were antiparallel to each other, and the adhesive was thermally cured at 150 DEG C for 1 hour. Subsequently, a nematic liquid crystal (MLC-7028, manufactured by Merck Ltd.) was charged from a pair of substrates through a liquid crystal injection port, and then a liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated at 150 占 폚 and slowly cooled to room temperature. Next, a polarizing plate was bonded to both outer sides of the substrate to produce a transverse electric field type liquid crystal display element.

&Lt; Evaluation of after-image characteristic &

A liquid crystal display element of a transverse electric field system was manufactured by the same method as the above-mentioned "Production of liquid crystal display element for photo-alignment (3)", and the after-image characteristics were evaluated by the same method as in Embodiment 1. As a result, in this example, it was difficult to generate afterimage, and the evaluation was &quot; good &quot;.

[Example 35]

A liquid crystal aligning agent was prepared in the same manner as in Example 34 except that the polymer (AP4) was used instead of the polymer (AP3). Further, evaluation was carried out in the same manner as in Example 34 using the obtained liquid crystal aligning agent. The results are shown in Table 4 below.

As shown in Table 4, even when a polymer having an azobenzene structure in its main chain was used as the polymer (P), the storage stability of the liquid crystal aligning agent was good. Good results were also obtained in the evaluation of the afterimage characteristic of the liquid crystal display element.

A, B: glass substrate

Claims (9)

A liquid crystal aligning agent containing a compound (P) having a partial structure represented by the following formula (1)

(In the formula (1), Y ¹ represents a protecting group, and "*" represents a bonding hand). The method according to claim 1,
The compound (P) is a polymer having a partial structure represented by the formula (1). 3. The method of claim 2,
Wherein the compound (P) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyamide. The method according to claim 1,
A liquid crystal aligning agent containing at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyamide and the above compound (P) as an additive. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 4. A liquid crystal display element comprising the liquid crystal alignment film according to claim 5. A polymer having a main structure of polyamic acid, polyamic acid ester, polyimide or polyamide and having a partial structure represented by the following formula (1):

(In the formula (1), Y ¹ represents a protecting group, and "*" represents a bonding hand). A diamine having a partial structure represented by the following formula (1):

(In the formula (1), Y ¹ represents a protecting group, and "*" represents a bonding hand). Tetracarboxylic dianhydride having a partial structure represented by the following formula (1):

(In the formula (1), Y ¹ represents a protecting group, and "*" represents a bonding hand).

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