TW201607989A - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element, in which a liquid crystal alignment film having improved friction resistance and a liquid crystal display element having improved endurance to external pressure are produced. The liquid crystal alignment agent provided by the present invention comprises at least one polymer (P) selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and an organic silicon compound having a nitrogen-containing structure represented by the formula (1a). In the formula (1a), "*1" is to bond with a hydrogen atom, a methylene group or a univalent alkyl group; R a and R b are respectively a bivalent organic group; "*1" and "*2" are bonds.

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

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

Conventionally, liquid crystal display devices have been developed with various types of liquid crystal display elements having different electrode structures, physical properties of liquid crystal molecules, and manufacturing steps, for example, known as twisted nematic (TN) type, or super twisted. Various liquid crystal display elements such as a SuperTwisted Nematic (STN) type, a Vertical Alignment (VA) type, an In-Plane Switching (IPS) type, and a fringe field switching (FFS) type. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As a material of the liquid crystal alignment film, polylysine or polyimide is usually used in terms of various properties such as heat resistance, mechanical strength, and affinity with liquid crystal.

In recent years, the popularity of small-sized display terminals such as mobile phones and tablet PCs, such as smart phones and personal digital assistants (PDAs), has been increasing, and the demand for high definition of liquid crystal panels has been further improved. Based on such a background, various liquid crystal alignment agents capable of improving the display quality or reliability of a liquid crystal panel have been proposed (for example, refer to Patent Document 1). Patent Document 1 discloses that an epoxy compound having a specific structure is contained in a liquid crystal alignment agent together with a polymer component of polyglycine or polyimine, and a liquid crystal alignment film is formed using the liquid crystal alignment agent. This improves liquid crystal alignment and reliability in the display element. In addition, in recent years, as the demand for flat-panel terminals or mobile terminals has increased, touch panel type liquid crystal displays have increased. [Prior Art Literature]

[Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-299318

[Problems to be solved by the invention]

In a liquid crystal display of a touch panel type, it is required that resistance to external pressure such as pressing of a pointing device such as a finger or a pen is high, that is, when an external pressure is applied, it is difficult to cause alignment failure or bright spot failure. Further, in recent years, in the flat type terminal or the mobile terminal, the weight reduction and the thinning are promoted, and in the panel assembling step at the time of manufacturing the liquid crystal display, strain of the panel is likely to occur, or stress is easily applied to the inside of the panel. The strain or stress of such a panel causes the alignment film to peel off from the substrate, and also causes a poor spot or poor alignment. Therefore, it is required that the liquid crystal alignment film is less likely to cause substrate peeling.

In particular, in recent years, with the increase in the definition of liquid crystal display elements, the size of one pixel has become smaller than in the past, and the step of the electronic component mounted on the substrate is on the substrate on which the liquid crystal alignment film is formed. increase the amount. Therefore, in recent years, the liquid crystal alignment film can be said to be easily subjected to high stress by the rubbing treatment, and it is easy to cause scratches or film peeling. On the other hand, since scratches or peeling on the liquid crystal alignment film cause display failure, the liquid crystal alignment film is required to have high abrasion resistance.

The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal alignment agent which can obtain a liquid crystal alignment film having excellent abrasion resistance and which can obtain a liquid crystal display element having high resistance to external pressure. [Technical means to solve the problem]

The inventors of the present invention have actively studied in order to solve the problems of the prior art as described above, and have found that a ruthenium compound having a specific structure is contained in a liquid crystal alignment agent to obtain abrasion resistance of a liquid crystal alignment film and liquid crystal display element. The effect of improving the resistance to external pressure has thus completed the present invention. Specifically, the present invention provides the following liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element.

An aspect of the present invention provides a liquid crystal alignment agent comprising: at least one polymer (P) selected from the group consisting of polyproline, polyphthalate, and polyamidene; The organic ruthenium compound having a nitrogen-containing structure represented by the formula (1a) (wherein "*1" in the following formula (1a) is bonded to a hydrogen atom, a methylene group or a monovalent hydrocarbon group).

[Chemical 1] (In the formula (1a), R ^a and R ^b are each independently a divalent organic group; "*1" and "*2" represent a bonding bond)

An aspect of the present invention provides a liquid crystal alignment agent comprising: at least one polymer (P) selected from the group consisting of polylysine, polyphthalate, and polyamidene; and organic germanium A compound having a nitrogen-containing structure represented by the formula (1a) and satisfying at least one of having a hydroxyl group in the molecule and R ^a in the formula (1a) being ^a carbonyl group.

Further, another aspect of the present invention provides a liquid crystal alignment film formed using the liquid crystal alignment agent and a liquid crystal display element including the liquid crystal alignment film. [Effects of the Invention]

By the liquid crystal alignment agent containing a specific organic ruthenium compound, a liquid crystal alignment film having excellent abrasion resistance can be obtained. Further, a liquid crystal display element having high resistance to external pressure can be obtained.

The liquid crystal alignment agent of the present disclosure is a liquid polymer composition in which the polymer component is preferably dissolved or dispersed in an organic solvent. Hereinafter, each component contained in the liquid crystal alignment agent of the present disclosure and other components arbitrarily formulated as needed will be described.

<Polymer (P)> The liquid crystal alignment agent of the present disclosure contains at least one polymer (P) selected from the group consisting of polyproline, polyimine, and polyphthalate as a polymer component.

[Polyuric Acid] The polyphthalic acid contained in the liquid crystal alignment agent of the present disclosure can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine. (Tetracarboxylic dianhydride) Examples of the tetracarboxylic dianhydride used in the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the tetracarboxylic dianhydride include aliphatic butane tetracarboxylic dianhydride: butane tetracarboxylic dianhydride; and alicyclic tetracarboxylic dianhydride: 1, 2, 3, and 4 - cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-di-oxo-tetrahydrofuran-3-yl)-3a, 4,5,9b- Tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-di-oxo-tetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b- Tetrahydronaphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran -2',5'-dione), 5-(2,5-di-oxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3 ,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6-dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2: 4,6:8-dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2:3,5:6-dianhydride, 4,9-dioxatricyclo[ 5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraketone, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene -2,3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, cyclopentane tetracarboxylic dianhydride, etc.;

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, ethylene glycol bis(trimellitic anhydride), 1,3-propanediol bis(trimellitic anhydride), and the like; The tetracarboxylic dianhydride described in JP-A-2010-97188 can be used. Further, the tetracarboxylic dianhydride used in the synthesis of the polyamic acid may be used alone or in combination of two or more.

The tetracarboxylic dianhydride preferably contains a compound selected from the group consisting of bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid in terms of liquid crystal alignment property and solubility in a solvent. 2:3,5:6-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5- Bis-oxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-di-oxo-tetrahydrofuran- 3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, bicyclo[3.3.0]octane-2,4 ,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, cyclohexanetetracarboxylic dianhydride, 1,3-propanediol bis(pellitic anhydride) and pyromellitic dianhydride At least one compound in the group. With respect to the total amount of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid, the amount of use of these preferred compounds (in the case of using two or more kinds thereof) is preferably 5 mol% or more. More preferably, it is 10 mol% or more, More preferably, it is 20 mol% or more.

(Diamine) Examples of the diamine used in the synthesis of the polyamic acid include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, and a diamine organosiloxane. Specific examples of the diamine include aliphatic m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. 1,3-bis(aminomethyl)cyclohexane or the like; examples of the alicyclic diamine include 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexylamine) )Wait;

Examples of the aromatic diamine include dodecyloxydiaminobenzene, tetradecyloxydiaminobenzene, pentadecyloxydiaminobenzene, hexadecyloxydiaminobenzene, and octadecene. Alkoxydiaminobenzene, cholestyloxydiaminobenzene, cholestyloxydiaminobenzene, cholesteryl diaminobenzoate, cholesteryl diaminobenzoate, Wool alkyl diaminobenzoate, 3,6-bis(4-aminobenzimidyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl) -4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-( (aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, N-(2,4-diaminophenyl)-4-(4-heptylcyclohexyl )benzamide, the following formula (D-1) [Chemical 2] (In the formula (D-1), X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, and R ^II is a single a bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1; wherein a and b do not simultaneously become 0 a diamine containing an alignment group such as a compound represented by a photo-alignment structure;

P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl sulfide, 4-aminobenzene 4- 4'-aminobenzoic acid ester, 4,4'-diaminoazobenzene, 1,5-bis(4-aminophenoxy)pentane, 1,7-bis(4-amine Phenoxy) heptane, bis[2-(4-aminophenyl)ethyl]adipate, N,N-bis(4-aminophenyl)methylamine, 1,5-diamine Naphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4 '-Diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2 - bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene di-extension) Isopropyl)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 2,4-Diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N,N'-double (4-Aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis-(4-aminobenzene Base)-pyridazine, 3,5-diaminobenzoic acid, 4,4'-[ Other diamines such as 4,4'-propane-1,3-diylbis(acridine-1,4-diyl)]diphenylamine, 4,4'-diaminotriphenylamine, etc.; Examples of the organic oxirane include 1,3-bis(3-aminopropyl)-tetramethyldioxane, and the like, and those described in JP-A-2010-97188 can also be used. Diamine.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _d -" in the formula (D-1) is preferably an alkyldiyl group having 1 to 3 carbon atoms, *-O-, *- COO- or *-OC ₂ H ₄ -O- (wherein the bond with "*" is bonded to the diaminophenyl group). The group "-C _c H _{2c +1"} may, for example, be 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 decyl group, a decyl group, a dodecyl group, or a decyl group. Trialkyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc., these groups are preferably linear. The two amine groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to the other groups.

Specific examples of the compound represented by the formula (D-1) include a compound represented by the following formula (D-1-1) to formula (D-1-4), and the like. [Chemical 3] Further, the diamine used in the synthesis of the polyamic acid may be used singly or in combination of two or more kinds.

When it is applied to a liquid crystal alignment agent for a TN type, an STN type, or a vertical alignment type liquid crystal display element, a group capable of imparting liquid crystal alignment ability to a coating film can be introduced into a side chain of polyphthalic acid (orthogonal group) ). Examples of such an aligning group include a group having a linear structure, a group having a liquid crystal original skeleton, and a group having a bulky structure. Specific examples thereof include an alkyl group having 4 to 20 carbon atoms and carbon. 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, a group having a plurality of rings bonded directly or via a linking group, and the like. The polyamic acid having an alignment group can be obtained, for example, by polymerization of a diamine containing an alignment group in a monomer composition. When a diamine containing an alignment group is used, the ratio of the ratio of the diamine containing the alignment group to the total amount of the diamine used in the synthesis is preferably set so that the liquid crystal alignment property is good. 3 mol% or more, more preferably 5 mol% to 70 mol%.

(Synthesis of Polylysine) Polyproline can be obtained by reacting a tetracarboxylic dianhydride and a diamine as described above with a molecular weight modifier as needed. The ratio of the tetracarboxylic dianhydride to the diamine to be used in the synthesis reaction of the poly-proline is preferably 1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents. More preferably, it is a ratio of 0.3 equivalent to 1.2 equivalent. Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride; monoamine compounds such as aniline, cyclohexylamine, n-butylamine, and stearylamine; and isocyanic acid; A monoisocyanate compound such as a phenyl ester or a naphthyl isocyanate. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine to be used.

The synthesis reaction of polylysine is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. Further, the reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

Examples of the organic solvent used in the reaction include an aprotic polar solvent, a phenol-based solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenol-based solvent (the first group of organic solvents), or selected from the first group of organic solvents are preferably used. One or more kinds of a mixture of one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (the second group of organic solvents). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, and more preferably 40% by weight based on the total amount of the organic solvent of the first group and the organic solvent of the second group. Hereinafter, it is especially preferably 30% by weight or less.

A particularly preferred organic solvent is preferably selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, gamma-butyl One or more of a group consisting of lactone, tetramethylurea, hexamethylphosphonium triamine, m-cresol, xylenol, and halogenated phenol is used as a solvent, or these organic solvents are used within the range of the ratio. a mixture of more than one of the other organic solvents. The amount (a) of the organic solvent to be used is preferably in an amount of from 0.1% by weight to 50% by weight based on the total amount (a+b) of the reaction solution, and the total amount (b) of the tetracarboxylic dianhydride and the diamine.

A reaction solution obtained by dissolving polylysine was obtained in the manner as described above. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or the poly-proline acid contained in the reaction solution may be separated and then supplied to the preparation of the liquid crystal alignment agent, or the separated polyamic acid may be purified. Provided to the preparation of a liquid crystal alignment agent. In the case where polylysine is subjected to dehydration ring closure to form a polyimine, the reaction solution may be directly supplied to the dehydration ring closure reaction, or the polylysine contained in the reaction solution may be separated and then provided. The dehydration ring closure reaction is carried out, or the separated polyamic acid can also be purified and then supplied to the dehydration ring closure reaction. The separation and purification of polylysine can be carried out according to a known method.

[Polyurethane] Polyphthalate can be obtained, for example, by the following method: [I] a method of reacting a polylysine obtained by the synthesis reaction with an esterifying agent; [II] a method of reacting a tetracarboxylic acid diester with a diamine; [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine, and the like. Further, the term "tetracarboxylic acid diester" as used herein means a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified, and the other two are carboxyl groups. The "tetracarboxylic acid diester dihalide" means a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified and the other two are halogenated.

The esterifying agent used in the method [I] may, for example, be a hydroxyl group-containing compound, an acetal compound, a halide or an epoxy group-containing compound. Specific examples of the compound include a hydroxyl group-containing compound such as an alcohol such as methanol, ethanol or propanol, or a phenol such as phenol or cresol. Examples of the acetal compound include N,N-dimethyl group. Hydrazine diethyl acetal, N,N-diethylformamide diethyl acetal, etc.; halides, for example, methyl bromide, bromoethane, octadecane, methyl chloride, Examples of the epoxy group-containing compound include chloroacetyl octadecane and 1,1,1-trifluoro-2-iodoethane.

The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by subjecting the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid to ring opening using the alcohol. Further, in the method [II], the tetracarboxylic acid derivative to be used may be only a tetracarboxylic acid diester, or a tetracarboxylic dianhydride may be used in combination. The diamine used in the synthesis of the method [II] may, for example, be a diamine exemplified in the synthesis of polylysine. The reaction of the method [II] is preferably carried out in an organic solvent in the presence of a suitable dehydration catalyst. The organic solvent is exemplified as an organic solvent exemplified as an organic solvent used for the synthesis of polyglycine. Examples of the dehydration catalyst include 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium halide, carbonylimidazole, and phosphorus-based condensing agent. .

The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting a tetracarboxylic acid diester obtained in the above manner with a suitable chlorinating agent such as sulfinium chloride. Further, in the method [III], the tetracarboxylic acid derivative to be used may be only a tetracarboxylic acid diester dihalide, or a tetracarboxylic dianhydride may be used in combination. The diamine used in the synthesis of the method [III] may, for example, be a diamine exemplified in the synthesis of polylysine. The reaction of the method [III] is preferably carried out in an organic solvent in the presence of a suitable base. The organic solvent is exemplified as an organic solvent exemplified as an organic solvent used for the synthesis of polyglycine. As the base, for example, a tertiary amine such as pyridine or triethylamine can be preferably used. Further, the polyphthalate contained in the liquid crystal alignment agent may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist.

The reaction solution obtained by dissolving the polyamidate may be directly supplied to the preparation of the liquid crystal alignment agent, or the polyphthalate contained in the reaction solution may be separated and then supplied to the preparation of the liquid crystal alignment agent, or may be The isolated polyphthalate is purified and then supplied to the preparation of the liquid crystal alignment agent. The separation and purification of the polyamidite can be carried out according to a known method.

[Polyimide] Polyimine can be obtained, for example, by subjecting polylysine synthesized in the above manner to dehydration ring closure and ruthenium imidization.

The polyimine may be a fully ruthenium imide formed by dehydration ring closure of the proline structure of the polyglycolic acid as its precursor, or may be a dehydration ring closure only for a part of the proline structure. And a part of the quinone imide compound which has a structure of a proline and a quinone ring structure. The ruthenium imidization ratio of the polyimine used in the reaction is preferably 20% or more, more preferably 30% to 99%, and particularly preferably 40% to 99%. The ruthenium imidation ratio is a total of the number of the guanidine structure of the polyimine and the number of the quinone ring structure, and the ratio of the number of the quinone ring structure is expressed as a percentage. Here, a part of the quinone ring may also be an isoindole ring.

The dehydration ring closure of polylysine is preferably carried out by a method of heating polylysine; or dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, A method of heating is required. Among them, a method using the latter is preferred.

In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of poly-proline, the dehydrating agent may be, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The amount of the dehydrating agent to be used is preferably from 0.01 mol to 20 mol based on 1 mol of the proline structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. The amount of the dehydration ring-closure catalyst used is preferably set to 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent to be used. The organic solvent used for the dehydration ring-closure reaction is exemplified as an organic solvent exemplified as an organic solvent used for the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

A reaction solution containing polyienimine was obtained in the manner described. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the dehydration agent and the dehydration ring closure catalyst can be removed from the reaction solution, and then supplied to the preparation of the liquid crystal alignment agent, or the polyphthalimide can be separated and then supplied to the liquid crystal alignment. The preparation of the agent, or the separation of the separated polyimine, may be further provided to the preparation of the liquid crystal alignment agent. These purification operations can be carried out in accordance with a known method. In addition to this, polyimine can also be obtained by hydrazylation of a polyphthalate.

The polymer (P) obtained in the above manner is preferably a solution having a solution viscosity of 20 mPa·s to 1,800 mPa·s when it is made into a solution having a concentration of 15% by weight, more preferably 50 mPa·s. ～1,500 mPa·s solution viscosity. Further, the solution viscosity (mPa·s) of the polymer (P) is a concentration of 15 which is prepared by using a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer (P). The weight % of the polymer solution was measured at 25 ° C using an E-type rotational viscometer. The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (P) measured by Gel Permeation Chromatography (GPC) is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, and more preferably 10 or less. By being in the molecular weight range as described above, good alignment and stability of the liquid crystal display element can be ensured.

<Organic ruthenium compound> The liquid crystal alignment agent of the present invention contains an organic ruthenium compound having a nitrogen-containing structure represented by the following formula (1a) in addition to the polymer (P) (hereinafter also referred to as "specific oxime" The compound ") is used as an additive. [Chemical 4] (In the formula (1a), R ^a and R ^b are each independently a divalent organic group; "*1" and "*2" represent a bonding bond)

In the above formula (1a), examples of the divalent organic group of R ^a and R ^b include a carbonyl group, a divalent hydrocarbon group, and a heterocyclic group. Here, the "hydrocarbon group" in the present specification means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" means a linear hydrocarbon group and a branched hydrocarbon group which are not composed of a chain structure but a chain structure. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. Among them, it is not necessarily required to be composed only of the structure of the alicyclic hydrocarbon, and also includes a hydrocarbon group having a chain structure in a part thereof. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. Among them, it is not necessarily required to be composed only of an aromatic ring structure, and a structure of a chain structure or an alicyclic hydrocarbon may be contained in a part thereof.

The specific ruthenium compound contained in the liquid crystal alignment agent of the present disclosure is further such that "*1" in the formula (1a) is bonded to a hydrogen atom, a methylene group or a monovalent hydrocarbon group, or satisfies a hydroxyl group in the molecule and R ^a in the formula (1a) is at least one compound of the carbonyl group. By including such an organic cerium compound in a liquid crystal alignment agent, a liquid crystal alignment film having excellent abrasion resistance or resistance to external pressure can be obtained.

Here, in the case where "*1" in the formula (1a) is bonded to a methylene group, the methylene group may form at least a part of a ring structure together with the nitrogen atom and R ^b in the formula (1a). . Further, the specific hydrazine compound is a compound having at least one nitrogen-containing structure represented by the formula (1a) and the "*1" in the formula (1a) is bonded to a hydrogen atom, a methylene group or a monovalent hydrocarbon group. In the case of the above, a compound having at least one of a hydroxyl group in the molecule and R ^a in the formula (1a) as ^a carbonyl group may be further satisfied. In view of the fact that the effect of the present invention is sufficiently obtained, the specific ruthenium compound is preferably selected from the group consisting of a ruthenium compound having a nitrogen-containing structure represented by the formula (1a) and a hydroxyl group, and a ruthenium compound having a urea structure. At least one of the groups.

In the case where the specific hydrazine compound is a hydrazine compound having a nitrogen-containing structure represented by the above formula (1a) and a hydroxy group, the compound may, for example, be a group having a group selected from the group consisting of a primary amine group and a secondary amine group. An amine compound of at least one of (hereinafter also referred to as "specific amine group") and a reaction containing at least one reactive group selected from the group consisting of an acid anhydride group, an epoxy group and an oxetanyl group A compound obtained by reacting a compound of a base. Further, at least one of the amine compound and the reactive group-containing compound is a compound having a halogen atom. In this case, only one of the amine compound and the reactive group-containing compound may have a ruthenium atom, or the amine compound and the reactive group-containing compound may each have a ruthenium atom. .

Specific examples of the case where a specific ruthenium compound is synthesized by the reaction of the amine compound with the reactive group-containing compound include, for example, the following [1] to [4]: [1] using a specific amine a method of reacting these compounds with the ruthenium compound (s-1) as the amine compound and using the compound (t-1) having an acid anhydride group as the reactive group-containing compound; An acid anhydride group ruthenium compound (s-2) is used as the reactive group-containing compound to react with the amine compound; [3] a ruthenium compound having an epoxy group or an oxetanyl group is used ( S-3) a method of reacting the reactive group-containing compound with the amine compound; [4] using a ruthenium compound (s-1) having a specific amine group as the amine compound, and using A compound (e-1) having an epoxy group or an oxetanyl group is used as the reactive group-containing compound, and a method of reacting these compounds.

Examples of the hydrazine compound (s-1) used in the above [1] and [4] include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-amino group. Propylmethyldiethoxydecane, 3-aminopropylmethyldimethoxydecane, 3-aminopropylethyldimethoxydecane, 3-aminopropylethyldiethoxylate Decane, 3-aminopropyldimethylethoxydecane, 3-aminopropyldiethylmethoxydecane, 3-aminopropyldiethylethoxydecane, N-(2-amine Benzyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl , 3-aminopropyltriethoxydecane, 4-aminobutyldimethylmethoxydecane, and the like. The hydrazine compound (s-1) may be used alone or in combination of two or more.

Examples of the hydrazine compound (s-2) used in the formula [2] include trimethoxydecyl propyl succinic anhydride, triethoxy decyl propyl succinic anhydride, and methyl dimethoxy decane. Propyl succinic anhydride, methyl diethoxy decyl propyl succinic anhydride, and the like. The hydrazine compound (s-2) may be used alone or in combination of two or more.

The oxime compound (s-3) having an epoxy group or an oxetanyl group used in the above [3] may, for example, be 3-glycidoxypropyltrimethoxydecane or 3-glycidoxypropane. Triethoxy decane, 3-glycidoxy propyl methyl dimethoxy decane, 3-glycidoxy propyl methyl diethoxy decane, 3-glycidoxy propyl dimethyl Methoxydecane, 3-glycidoxypropyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 2-(3,4-epoxy ring An epoxy group-containing decane compound such as hexyl)ethyltriethoxydecane; the following formula (s-3-1) [Chemical 5] An oxetan compound containing an oxetanyl group such as a compound represented by the above. The hydrazine compound (s-3) may be used alone or in combination of two or more.

The compound (t-1) having an acid anhydride group used in the above [1] is not particularly limited as long as it has at least one acid anhydride group in one molecule. Specifically, examples of the compound having one acid anhydride group in one molecule include maleic anhydride, phthalic anhydride, itaconic anhydride, 2,3-pyridinecarboxylic anhydride, and the like; and two or more in one molecule. Examples of the acid anhydride group-containing compound include a compound exemplified as the tetracarboxylic dianhydride used in the synthesis of the polyamic acid. The compound (t-1) having an acid anhydride group may be used alone or in combination of two or more.

The amine compound used in the above [2] and [3] is not particularly limited as long as it has at least one specific amine group in one molecule. Specifically, examples of the compound having a primary amino group in one molecule include aniline, cyclohexylamine, propylamine, butylamine, pentylamine, hexylamine and the like; and a compound having a secondary amine group in one molecule can be exemplified, for example. : dimethylamine, diethylamine, dipropylamine, dibutylamine, dodecamethylene imine, acridine, pyrrolidine, hexamethyleneimine, heptamethyleneimine, dicyclohexylamine, N -methylbenzylamine, bis-(2-ethylhexyl)amine, diallylamine, morpholine or the like; a compound having two or more primary amine groups in one molecule is exemplified as the polyamic acid A compound exemplified as the diamine used in the synthesis, and the like, and a compound having two or more secondary amine groups in one molecule may, for example, be a pyridazine or the like. The amine compound may be used alone or in combination of two or more.

Examples of the compound (e-1) having an epoxy group or an oxetanyl group used in the above [4] include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether. 1,6-hexanediol diglycidyl ether, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzyl Alkylamine, N,N-diglycidyl-aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, and the like. The compound (e-1) may be used alone or in combination of two or more.

The ratio of the amine compound to the reactive group-containing compound to be used in the synthesis reaction of the specific hydrazine compound is preferably 1 equivalent to the specific amine group of the amine compound, and the reactive group of the reactive group-containing compound is 0.2 equivalent to 2.5. The ratio of the equivalent is more preferably 0.3 to 2.2 equivalents. The reaction of the amine compound with the reactive group-containing compound is preferably carried out in an organic solvent. The organic solvent to be used in the reaction may be any solvent which is inert to the amine compound and the reactive group-containing compound, and may dissolve the compound. Examples thereof include N-methyl-2-pyrrolidone. The reaction temperature is preferably 0 ° C to 80 ° C, and more preferably 10 ° C to 70 ° C. The reaction time is preferably from 1 hour to 60 hours, more preferably from 10 hours to 30 hours.

Specific examples of the specific hydrazine compound obtained by the above reaction include, for example, a compound represented by the following formula (1). [Chemical 6] (In the formula (1), R ¹⁹ is a hydrogen atom or a monovalent hydrocarbon group, or a divalent hydrocarbon group formed by two R ¹⁹ bonds in the molecule; R ²⁰ is a trivalent organic group, and R ²¹ is a divalent organic group, R ²² and R ²³ are each independently a monovalent hydrocarbon group, R ²⁴ is a (h+i) valent organic group; A ¹ is a single bond or a carbonyl group, and A ² is a single bond, a carbonyl group or an alkyldiyl group having 1 to 3 carbon atoms; B ¹ and B ² are each independently a carbonyl group or an alkanediyl group having 1 to 3 carbon atoms; and e, f, g, and i are each independently an integer of 0 to 4, and e+f+g≧1 and e+i≧ 1; h is an integer of 1 to 4, and j is an integer of 1 to 3; wherein, when R ²⁰ , R ²² , R ²³ , A ¹ , A ² , B ¹ and B ² are respectively present, R ²⁰ , R ²² , R ²³ , A ¹ , A ² , B ¹ and B ² independently have the definition)

In the formula (1), the monovalent hydrocarbon group of R ¹⁹ may, for example, be a linear chain such as 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 decyl group or a fluorenyl group. Or a branched alkyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a benzyl group; and the like. In these groups, R ^{19 is} preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Further, in the case of R ¹⁹ in one molecule two or more of memory, two R ¹⁹ in the molecule may be bonded to each other and constitute a part of the ring. In this case, a ring is formed from "-R ¹⁹ -nitrogen atom -B ² -R ²⁴ -B ² -nitrogen atom-R ¹⁹ -" in the formula (1). The ring formed by the bonding of R ¹⁹ is a nitrogen-containing hetero ring having two nitrogen atoms, and examples thereof include a pyridazine ring and the like.

The trivalent organic group of R ²⁰ may, for example, be a hydrocarbon group having 1 to 10 carbon atoms, and preferably a chain hydrocarbon group having 1 to 3 carbon atoms. Examples of the divalent organic group of R ²¹ include an alkanediyl group having 1 to 6 carbon atoms or a divalent group in which a methylene group of the alkanediyl group is substituted with -O-. The monovalent hydrocarbon group of R ²² and R ²³ may be exemplified as the monovalent hydrocarbon group of R ¹⁹ . It is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Examples of R ²⁴ include a hydrocarbon group having 1 to 20 carbon atoms, a group in which a methylene group of the hydrocarbon group is substituted with -O-, -CO-, -COO-, -NH-, -NHCO- or the like, and hydrogen of a hydrocarbon group. A group in which an atom is substituted with a halogen atom (preferably a fluorine atom) or the like.

In the case of e=0, it is preferred that at least one of B ¹ and B ² is a carbonyl group, and A ¹ is a carbonyl group. In this case, the specific ruthenium compound has a structure in which a hydroxyl group and a nitrogen-containing structure of a specific ruthenium compound are bonded to a carbonyl group, respectively. Further, in the case where a hydroxyl group is bonded to a carbonyl group, a specific hydrazine compound has a carboxyl group, and in the case where a nitrogen-containing structure is bonded to a carbonyl group, a specific hydrazine compound has a guanamine bond (-CO-NR-). Among them, the specific hydrazine compound may further have a hydroxyl group in addition to the carboxyl group, and may further have -NR- in addition to the guanamine bond.

Specific examples of the compound represented by the formula (1) include a compound represented by the following formula (1-1) to formula (1-5), and the like.

[Chemistry 7] (In the formula (1-1), R ¹ is a tetravalent organic group, R ² is a divalent organic group, R ³ and R ⁴ are each independently a monovalent hydrocarbon group, and a is an integer of 1 to 3; R ² may be the same or different; when there are a plurality of R ³ and R ⁴ respectively, a plurality of R ³ and a plurality of R ⁴ may be the same or different)

[化8] (In the formula (1-2), R ⁵ and R ⁷ are each independently a divalent organic group, R ⁶ is a trivalent organic group, and R ⁸ and R ⁹ are each independently a monovalent hydrocarbon group, and b is 1 to 3, respectively. An integer; wherein, a plurality of R ⁶ may be the same or different; and when there are a plurality of R ⁸ and R ⁹ respectively, the plurality of R ⁸ and the plurality of R ⁹ may be the same or different)

[Chemistry 9] (In the formula (1-3), R ¹⁰ and R ¹¹ are each independently a divalent organic group, and R ¹² and R ¹³ are each independently a monovalent hydrocarbon group, and c is an integer of from 1 to 3; wherein, in R ¹² and When there are a plurality of R ¹³ respectively, the plurality of R ¹² and the plurality of R ¹³ may be the same or different)

[化10] (In the formula (1-4), R ¹⁴ is a monovalent organic group, R ¹⁵ is a trivalent organic group, R ¹⁶ is a divalent hydrocarbon group, and R ¹⁷ and R ¹⁸ are each independently a monovalent hydrocarbon group, and d is 1 to 3 An integer; wherein, when there are a plurality of R ¹⁷ and R ¹⁸ respectively, the plurality of R ¹⁷ and the plurality of R ¹⁸ may be the same or different)

[11] (In the formula (1-5), R ²⁵ is a hydrogen atom or a monovalent hydrocarbon group, or a divalent hydrocarbon group formed by two R ²⁵ bonds in the molecule; R ²⁶ is a divalent organic group, and R ²⁷ is a trivalent organic group. , R ³⁰ is a divalent organic group, R ²⁸ and R ²⁹ are each independently a monovalent hydrocarbon group, and k is an integer of 1 to 3; and A ³ is a single bond, a carbonyl group or an alkanediyl group having 1 to 3 carbon atoms; in the molecule a plurality of R ^25, R ^27, R ³⁰ and a ³ may be the same or different; when there are a plurality of R ²⁸ and R ^29, R ²⁸ and a plurality of a plurality of R ²⁹ may be the same , can also be different)

The compound represented by the formula (1-1) can be synthesized by the method of the above [1], and specifically, an amine group-containing decane compound can be used as the oxime compound (s-1), and tetracarboxylic acid. The acid dianhydride is obtained as a compound (t-1) having an acid anhydride group by reacting these compounds. Here, in the formula (1-1), the tetravalent organic group of R ^{1 is} a tetravalent group derived from a tetracarboxylic dianhydride; and the divalent organic group of R ² is an amine group-containing decane compound. Examples of the divalent group to be derived include an alkanediyl group having 1 to 6 carbon atoms, a divalent group having -NH- between carbon-carbon bonds of the alkanediyl group, and the like. The monovalent hydrocarbon group of R ³ and R ⁴ may be exemplified as the monovalent hydrocarbon group of R ¹⁹ in the formula (1). It is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

The compound represented by the formula (1-2) can be synthesized by the method of the above [2], specifically, by using an acid anhydride group-containing decane compound as the hydrazine compound (s-2), and a diamine. These amine compounds are obtained by reacting these compounds. Here, in the formula (1-2), the divalent organic group of R ⁵ is a divalent group derived from a diamine. The divalent organic group of R ⁷ is a divalent organic group derived from an acid anhydride group-containing decane compound, and examples thereof include an alkyldiyl group having 1 to 6 carbon atoms. R ⁶ is a trivalent organic group having a carbon number include, for example, a chain hydrocarbon group having 1 to 5. The monovalent hydrocarbon group of R ⁸ and R ⁹ may be exemplified as the monovalent hydrocarbon group of R ¹⁹ in the formula (1). It is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

The compound represented by the formula (1-3) can be synthesized by the method of the above [1], specifically, by using an amine group-containing decane compound as the oxime compound (s-1), and an acid sheet. An anhydride is obtained as a compound (t-1) having an acid anhydride group by reacting these compounds. In the above formula (1-3), the divalent organic group of R ¹⁰ is a divalent group derived from an acid monoanhydride, and examples thereof include a divalent hydrocarbon group having 2 to 20 carbon atoms. The divalent organic group of R ¹¹ is a divalent group derived from an amine group-containing decane compound, and examples thereof include an alkyldiyl group having 1 to 6 carbon atoms and -NH- between carbon-carbon bonds of the alkanediyl group. The divalent base and so on. R ¹² and R ¹³ is a monovalent hydrocarbon group include the embodiment as illustrated in (1) of the formula R ^{19 is} a monovalent hydrocarbon group. It is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

The compound represented by the formula (1-4) can be synthesized by the method of the above [2], specifically, by using an acid anhydride group-containing decane compound as the hydrazine compound (s-2), and a monoamine. These amine compounds are obtained by reacting these compounds. Here, in the formula (1-4), the monovalent organic group of R ¹⁴ is a monovalent group derived from a monoamine. Examples of the trivalent organic group of R ¹⁵ include a chain hydrocarbon group having 1 to 5 carbon atoms. The divalent organic group of R ¹⁶ is a divalent organic group derived from an acid anhydride group-containing decane compound, and examples thereof include an alkyldiyl group having 1 to 6 carbon atoms. The monovalent hydrocarbon group of R ¹⁷ and R ¹⁸ may be exemplified as the monovalent hydrocarbon group of R ¹⁹ in the formula (1). It is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

The compound represented by the formula (1-5) can be synthesized by the method of the above [3], and specifically, by using an epoxy group-containing decane compound or an oxetanyl group-containing decane compound as The hydrazine compound (s-3) and the exemplified compound are obtained as a reaction of these compounds as the amine compound. Here, in the formula (1-5), the divalent organic group of R ²⁶ is a divalent group derived from an amine compound. The trivalent organic group of R ²⁷ may, for example, be a chain hydrocarbon group having 1 to 5 carbon atoms. The divalent organic group of R ³⁰ is a divalent group derived from an epoxy group-containing decane compound or an oxetanyl group-containing decane compound, and examples thereof include an alkyl 2 group having 1 to 5 carbon atoms or The carbon-carbon bond of the group has a divalent group of -O- or the like. The monovalent hydrocarbon group of R ²⁵ , R ²⁸ and R ²⁹ may be exemplified as the monovalent hydrocarbon group of R ¹⁹ in the formula (1). It is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. A ³ is preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms.

A preferred example of the case where the specific hydrazine compound is a hydrazine compound having a urea structure is, for example, a compound represented by the following formula (2). [化12] (In the formula (2), R ³¹ and R ³² are each independently a monovalent hydrocarbon group, R ³³ is a divalent organic group, R ³⁴ is a monovalent organic group; t is an integer of 1 to 3; wherein, in R ³¹ , In the case where there are a plurality of R ³² , a plurality of R ³¹ and R ³² independently have the definition)

In the formula (2), R ³¹ and R ^{32 are} preferably a methyl group or an ethyl group. R ³³ methylene carbon atoms and examples thereof include an alkanediyl group having 1 to 6 or two of the alkyl group is substituted by a divalent group -O-. R ³⁴ may, for example, be a monovalent hydrocarbon group or a monovalent alicyclic group. Specific examples of the compound represented by the formula (2) include 1-(pyridin-2-yl)-3-(3-triethoxydecyl)propyl)urea and 1-(pyridine). -2-yl)-3-(3-trimethoxydecyl)propyl)urea, 1-(pyridin-2-yl)-3-(3-methyldiethoxydecyl)propyl)urea Wait. Further, the ruthenium compound having a urea structure may be used alone or in combination of two or more.

Among the compounds, the specific ruthenium compound contained in the liquid crystal alignment agent of the present disclosure may particularly preferably be selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2). At least one of the groups. Further, the specific hydrazine compound may be used alone or in combination of two or more.

The compounding ratio of the specific cerium compound is preferably from 0.01 part by weight to 50 parts by weight based on 100 parts by weight of the total of the polymer components of the liquid crystal alignment agent. The reason for this is that if it is less than 0.01 parts by weight, it is difficult to obtain an effect of improvement due to the addition of the organic cerium compound, and if it is more than 50 parts by weight, the liquid crystal alignment property tends to be lowered. It is more preferably 0.05 parts by weight to 40 parts by weight, particularly preferably 0.1 parts by weight to 35 parts by weight, particularly preferably 0.1 parts by weight to 30 parts by weight. Further, a specific hydrazine compound may be used alone or in combination of two or more.

<Other Components> The liquid crystal alignment agent of the present disclosure may contain a polymer (P) and other components other than the specific ruthenium compound as needed. Examples of the other component include a polymer other than polyglycine, polyimine, and polyphthalate, and a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound"). ), a functional decane compound other than a specific hydrazine compound, and the like.

[Other Polymers] The other polymers can be used to improve solution properties or electrical properties. The other polymer may, for example, be a polyorganosiloxane, a polyester, a polyamine, a cellulose derivative, a polyacetal, a polystyrene derivative, or a poly(styrene-phenyl cis-butane) in the main skeleton. A polymer such as an enediamine derivative or a polymer such as poly(meth)acrylate. When the other polymer is added to the liquid crystal alignment agent, the compounding ratio of the other polymer is preferably 50 parts by weight or less, based on 100 parts by weight of the total of the polymer contained in the liquid crystal alignment agent. It is preferably 0.1 parts by weight to 40 parts by weight, and particularly preferably 0.1 parts by weight to 30 parts by weight or less.

[Epoxy group-containing compound] The epoxy group-containing compound can be used to improve the adhesion or electrical properties of the liquid crystal alignment film to the surface of the substrate. Examples of such an epoxy group-containing compound include the following compounds: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol II. Glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl Alcohol diglycidyl ether, N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl- Aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, and the like. In addition to the above, examples of the epoxy group-containing compound include the epoxy group-containing polyorganosiloxane having the disclosure of WO 2009/096598. When the epoxy group-containing compound is added to the liquid crystal alignment agent, the compounding ratio of the epoxy group-containing compound is preferably set to 100 parts by weight based on the total of the polymer contained in the liquid crystal alignment agent. 40 parts by weight or less, more preferably 0.1 parts by weight to 30 parts by weight.

[Other Functional Halogen Compounds] Other functional decane compounds can be used for the purpose of improving the printability of the liquid crystal alignment agent. Examples of such a functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyl group. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Baseline, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-triethoxy Nonylalkyltriethylenetriamine, 10-trimethoxydecyl-1,4,7-triazanonane, 9-trimethoxydecyl-3,6-diazadecyl acetate , 9-trimethoxydecyl-3,6-diazanonanoate, N-benzyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxy Basear, glycidoxymethyltrimethoxydecane, 2-glycidoxyethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, and the like. When the other functional decane compound is added to the liquid crystal alignment agent, the compounding ratio of the other functional decane compound is preferably set to 100 parts by weight based on the total of the polymer contained in the liquid crystal alignment agent. 2 parts by weight or less, more preferably 0.02 parts by weight to 0.2 parts by weight.

Further, other components may be, in addition to the compound, a compound having at least one oxetanyl group in the molecule or an antioxidant, a metal chelate compound, a hardening accelerator, a surfactant, a filler, a dispersing agent, Sensitizers, etc.

<Solvent> The liquid crystal alignment agent of the present disclosure is prepared by dissolving or dissolving a polymer (P), a specific hydrazine compound, and other components as needed, preferably in a suitable solvent.

Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, and N,N-dimethyl B. Indamine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, Ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol Ethyl 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, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethyl carbonate, propyl carbonate, and the like. These organic solvents may be used singly or in combination of two or more.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1 weight. A range of % to 10% by weight. In other words, the liquid crystal alignment agent is applied to the surface of the substrate as described later, and is preferably heated to form a coating film as a liquid crystal alignment film or a coating film to be a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small, and it is difficult to obtain a favorable liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and it is difficult to obtain a favorable liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coating property decreases. tendency.

A particularly preferable range of the solid content concentration differs depending on the method when the liquid crystal alignment agent is applied onto the substrate. For example, when it is applied to a substrate by a spinner method, the solid content concentration (the ratio of the total weight of all the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is particularly preferably 1.5. The range of % by weight to 4.5% by weight. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3 to 9 wt%, thereby setting the solution viscosity to a range of 12 mPa·s to 50 mPa·s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1% by weight to 5% by weight, thereby setting the solution viscosity to a range of 3 mPa·s to 15 mPa·s. The temperature at which the liquid crystal alignment agent is prepared is preferably from 10 ° C to 50 ° C, and more preferably from 20 ° C to 30 ° C.

<Liquid Crystal Display Element> The liquid crystal display element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The operation mode of the liquid crystal display element is not particularly limited, and can be applied to, for example, a TN type, an STN type, or a VA type (including a Vertical Alignment-Multidomain Vertical Alignment (VA-MVA) type, a vertical alignment-pattern. Vertical Alignment (Picture Alignment Alignment, VA-PVA), etc.), IPS type, FFS type, Optically Compensated Bend (OCB) type and other modes of operation.

The liquid crystal display element can be manufactured, for example, by a method including the following steps (1) to (3). Step (1) uses different substrates depending on the desired mode of operation. Step (2) and step (3) are shared in each operation mode.

[Step (1): Formation of Coating Film] First, a liquid crystal alignment agent is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate. (1-A) In the case of manufacturing, for example, a TN type, STN type or VA type liquid crystal display element, first, two substrates provided with a patterned transparent conductive film are used as a pair, preferably by offset printing, A liquid crystal alignment agent is applied to each of the transparent conductive film formation surfaces of the substrate by a spin coating method, a roll coater method, or an inkjet printing method. For the substrate, for example, glass such as float glass or soda glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and poly(alicyclic olefin) may be used. Transparent substrate. The transparent conductive film provided on one side of the substrate may be a Neisser (NESA) film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA), and contains indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). Indium Tin Oxide (ITO) film or the like. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, and a method of using a mask having a desired pattern when forming a transparent conductive film may be employed. Wait. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, the surface on which the coating film is formed on the surface of the substrate may be coated with a functional decane compound or a functional titanium compound. Pretreatment.

After the liquid crystal alignment agent is applied, it is preferable to perform preheating (prebaking) for the purpose of preventing the sag of the applied liquid crystal alignment agent. The prebaking temperature is preferably from 30 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C, and particularly preferably from 40 ° C to 100 ° C. The prebaking time is preferably from 0.25 minutes to 10 minutes, more preferably from 0.5 minutes to 5 minutes. Then, the simmering (post-baking) step is carried out for the purpose of completely removing the solvent, and if necessary, the hydrazine imidization of the proline structure present in the polymer. The calcination temperature (post-baking temperature) at this time is preferably 80 to 300 ° C, and more preferably 120 to 250 ° C. The post-baking time is preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 100 minutes. The film thickness of the film formed in the above manner is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

(1-B) In the case of manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate including an electrode patterned with a comb-shaped transparent conductive film or a metal film, and an electrode not provided A liquid crystal alignment agent is applied to one surface of the counter substrate, and then each coated surface is heated to form a coating film. Material of the substrate and the transparent conductive film used at this time, a coating method, heating conditions after coating, a method of patterning a transparent conductive film or a metal film, pretreatment of a substrate, and a preferred film of the formed coating film The thickness is the same as the above (1-A). As the metal film, for example, a film containing a metal such as chromium can be used.

In either case of the above (1-A) and (1-B), a liquid crystal alignment film is removed by coating a liquid crystal alignment agent on a substrate, and a liquid crystal alignment film or a coating film of a liquid crystal alignment film is formed. At this time, by further heating after the formation of the coating film, the poly-proline, the polyphthalate, and the polyimine which are formulated in the liquid crystal alignment agent may be subjected to a dehydration ring-closure reaction to form a further ruthenium imine. Coating film.

[Step (2): Orientation ability imparting treatment] When a TN type, STN type, IPS type or FFS type liquid crystal display element is manufactured, the treatment for imparting liquid crystal alignment ability to the coating film formed in the step (1) is carried out. . Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. The alignment ability imparting treatment may be a rubbing treatment or a photoalignment treatment in which the coating film is wiped in a predetermined direction by using a roll wound with a cloth containing fibers such as nylon, rayon, cotton or the like; The light alignment treatment is radiation that irradiates the coating film with polarized light or non-polarized light. In particular, the liquid crystal alignment film formed of the liquid crystal alignment agent has high abrasion resistance, and when rubbing treatment is employed as the alignment ability imparting treatment, it is also difficult to cause scratches or film peeling. On the other hand, in the case of producing a VA liquid crystal display element, the coating film formed in the above step (1) can be directly used as a liquid crystal alignment film, and the alignment film imparting treatment can be performed on the coating film.

Further, the liquid crystal alignment film after the rubbing treatment may be further subjected to the following treatment so that the liquid crystal alignment film has different liquid crystal alignment ability in each region: a part of the liquid crystal alignment film is irradiated by irradiating a part of the liquid crystal alignment film with ultraviolet rays. The treatment of changing the pretilt angle of the region; or the treatment of removing the resist film after performing a rubbing treatment in a direction different from the previous rubbing treatment after forming a resist film on a part of the surface of the liquid crystal alignment film. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved. A liquid crystal alignment film suitable for a VA type liquid crystal display element can also be suitably used for a polymer sustained alignment (PSA) type liquid crystal display element.

[Step (3): Construction of Liquid Crystal Cell] Two substrates in which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal was placed between the two substrates arranged in the opposite direction to manufacture a liquid crystal cell. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. The first method is a previously known method. First, the two substrates are opposed to each other via a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, and are divided by the surface of the substrate and the sealant. After the filling liquid crystal is injected into the cell gap, the injection hole is sealed, whereby the liquid crystal cell can be manufactured. In addition, the second method is a method called a One Drop Fill (ODF) method. a predetermined portion on one of the two substrates on which the liquid crystal alignment film is formed, for example, an ultraviolet curable sealant is applied, and then liquid crystal is dropped on a predetermined portion of the liquid crystal alignment film surface, The liquid crystal alignment film is bonded to the other substrate in a facing manner, and the liquid crystal is spread over the entire surface of the substrate. Then, the entire surface of the substrate is irradiated with ultraviolet light to harden the sealing agent, whereby the liquid crystal cell can be manufactured. In the case of using any of the methods, it is preferable to heat the liquid crystal cell produced in the above manner to a temperature at which the liquid crystal used is obtained to obtain an isotropic phase, and then gradually cool to room temperature, thereby eliminating the liquid crystal. Flow alignment when filling.

As the sealant, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer can be used. The liquid crystal may be a nematic liquid crystal or a liquid crystal. Among them, a nematic liquid crystal is preferable. For example, a Schiff base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, or a phenyl group can be used. A cyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, or the like. In addition, the following substances may be added to these liquid crystals: for example, cholesteryl chloride, cholesteryl nonanoate, cholesteric liquid crystal, etc.; Chiral agent sold under the names "C-15", "CB-15" (manufactured by Merck); p-nonylbenzylidene-p-amino-2-methylbutyl cinnamate Wait for ferroelectric liquid crystals, etc.

Next, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. The polarizing plate to be bonded to the outer surface of the liquid crystal cell may be a polarizing plate in which a polarizing film called "H film" is sandwiched by a cellulose acetate protective film or a polarizing plate including the H film itself. The H film is a film obtained by absorbing iodine while extending the polyvinyl alcohol.

The liquid crystal display element of the present disclosure can be effectively applied to various devices, for example, can be used for: clocks, portable game machines, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (Personal Digital Assistance, Various display devices such as PDAs, digital cameras, mobile phones, smart phones, tablet PCs, various monitors, LCD TVs, information displays, and the like. [Examples]

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

In the following synthesis examples, the weight average molecular weight Mw and the ruthenium iodide ratio of the polymer and the solution viscosity of the polymer solution were measured by the following methods. Further, in the following, the compound represented by the formula X may be simply referred to as "compound X". [Weight Average Molecular Weight Mw of Polymer] Mw is a polystyrene-converted value measured by GPC under the following conditions. Pipe column: manufactured by Tosoh (stock), TSKgelGRCXLII solvent: tetrahydrofuran temperature: 40 ° C pressure: 68 kgf / cm ² [polymerization rate of ruthenium iodide] Put the solution containing polyimine into pure water, The obtained precipitate was sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl hydrazine, and tetramethyl decane was used as a reference material to measure ¹ H-nuclear magnetic resonance at room temperature ( ¹ H-Nuclear Magnetic Resonance, ¹ H-NMR). From the obtained ¹ H-NMR spectrum, the oxime imidization ratio was determined using the following formula (1).醯imination rate (%)=(1-A ¹ /A ² ×α)×100 (1) (In the formula (1), A ¹ is an NH-based proton which occurs near a chemical shift of 10 ppm. The peak area, A ^{2 is} the peak area from other protons, and α is the ratio of the number of protons of other protons relative to the NH group in the precursor of the polymer (polyproline). Solution Viscosity of Solution] The solution viscosity (mPa·s) of the polymer solution was measured at 25 ° C using an E-type rotational viscometer.

<Synthesis of an organic hydrazine compound> [Synthesis Example 1-1: Synthesis of Compound (Si-1)] 3-aminopropyltriethoxysilane (APTES) and 1, 2, 3, 4 - 1,2,3,4-cyclobutane tetracarboxylic dianhydride (CB), added to N-methyl-2- at a compounding ratio of APTES:CB=2:1 (mole ratio) Pyrrolidone (N-methyl-2-pyrrolidone (NMP)) was stirred and reacted at 25 ° C for 6 hours to obtain a solution containing the compound (Si-1) as an organic ruthenium compound.

[Synthesis Example 1-2 to Synthesis Example 1-6] The same operation as in Synthesis Example 1-1 except that the compound (precursor) used in the reaction and the compounding ratio thereof were changed as shown in Table 1 below. A solution containing the compound (Si-2) to the compound (Si-6) as an organic ruthenium compound was obtained.

[Table 1]

In Table 1, the abbreviations of the precursors are as follows. (Precursor 1: decane compound) C-1: 3-aminopropyltriethoxydecane (APTES) C-2: 3-trimethoxydecylpropyl succinic anhydride C-3: 3-glycidol Hydroxypropyltrimethoxydecane (Precursor 2: Other Compounds) AN-1: Pyromellitic dianhydride AN-2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CB) DA-1: p-phenylenediamine B-1: maleic anhydride B-2: 2,3-pyridinedicarboxylic anhydride B-3: azine

<Synthesis of Polymer> [Synthesis Example 2-1: Synthesis of Polymer (PAA-1)] 100 mol parts of pyromellitic dianhydride as tetracarboxylic dianhydride, and 100 mol as a diamine The bis[2-(4-aminophenyl)ethyl]adipate in the ear was dissolved in N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C for 6 hours to obtain a solid concentration. It is a 15% by weight polylysine solution. The obtained polyaminic acid solution was fractionated, and the obtained solution had a viscosity of 420 mPa·s.

[Synthesis Example 2-2 to Synthesis Example 2-7] In the synthesis example 2-1, the type and amount of the tetracarboxylic dianhydride and the amine (diamine and monoamine) used in the reaction were changed as follows Polylysine was obtained in the same manner as in Synthesis Example 2-1 except the conditions described in Table 2. Further, with respect to Synthesis Example 2-2 to Synthesis Example 2-7, the numerical values in Table 2 indicate the use ratio (molar parts) with respect to 100 moles of the total amount of the tetracarboxylic dianhydride used in the reaction.

[Table 2]

The abbreviations of the tetracarboxylic dianhydride and the diamine in Table 2 are as follows. (tetracarboxylic dianhydride) AN-1: pyromellitic dianhydride AN-2: 1,2,3,4-cyclobutane tetracarboxylic dianhydride AN-3: 2,3,5-tricarboxyl ring Amyl acetal dianhydride AN-4: bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride AN-5:5-(2,5- Bilateral oxytetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione AN-6:1,3- Propylene glycol bis(trimellitic anhydride) AN-7: dimethyl-1,3-bis(chlorocarbonyl)cyclobutane-2,4-carboxylate AN-8: dimethyl-1,3-double (chlorocarbonyl)cyclopentane-2,4-carboxylate [Chemical 13]

(diamine) DA-1: p-phenylenediamine DA-2: 4,4'-diaminodiphenylmethane DA-3: 4,4'-diaminodiphenylamine DA-4:1, 5-bis(4-aminophenoxy)pentane DA-5: 4-aminophenyl-4'-aminobenzoate DA-6: bis[2-(4-aminophenyl) Ethyl]adipate DA-7: 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl DA-8: 4,4'-diaminotriphenylamine DA -9: Compound DA-10 represented by the following formula (DA-9): 4-(tetradecyloxy)benzene-1,3-diamine DA-11: stearylamine DA-12:1, 3-bis(3-aminopropyl)-tetramethyldioxane DA-13: 3,6-bis(4-aminobenzimidyloxy)cholestane DA-14: the following formula Compound DA-15 represented by (DA-14): a compound represented by the following formula (DA-15) [Chemical Formula 14]

[Synthesis Example 2-8: Synthesis of Polymer (PI-8)] 100 mol parts of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride, and as a diamine 80 moles of p-phenylenediamine, 10 moles of 4,4'-diaminodiphenylmethane and 10 moles of 2,2'-bis(trifluoromethyl)-4,4' The diaminobiphenyl was dissolved in NMP, and the reaction was carried out for 6 hours at room temperature to obtain a polyaminic acid solution having a solid concentration of 15% by weight. NMP was added to the polyamic acid solution to have a solid content concentration of 10% by weight, and 100 moles of pyridine and acetic anhydride were added to each of 100 tetramers of tetracarboxylic dianhydride. The dehydration ring closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement using a new NMP to obtain a solution containing a polyamidimide (polymer (PI-8)) having a ruthenium iodide ratio of 75%. The viscosity of the obtained polymer (PI-8) adjusted to 15% by weight by NMP was measured and found to be 520 mPa·s.

[Synthesis Example 2-9: Synthesis of Polymer (PI-9)] In addition to the synthesis examples 2-8, the types and amounts of tetracarboxylic dianhydride and diamine used in the reaction, and pyridine and B were used. The amount of the acid anhydride was changed to the same operation as in Synthesis Example 2-9 except that the amount of the acid anhydride was changed, thereby obtaining a polyimine (polymer (PI-9)). Further, regarding Synthesis Examples 2 to 9, the numerical values in Table 2 indicate the use ratio (molar parts) with respect to 100 moles of the total amount of the tetracarboxylic dianhydride used in the reaction. The viscosity of the obtained polymer (PI-9) adjusted to 15% by weight by NMP was measured and found to be 520 mPa·s.

[Synthesis Example 2-10: Synthesis of Polymer (PAE-10)] 6.92 g of p-phenylenediamine as a diamine was added (80 mol with respect to 100 mol of the total amount of the diamine used in the synthesis) Ears and 3.17 g (20 moles relative to 100 moles of total diamine used in the synthesis) of 4,4'-diaminodiphenylmethane, and 15 ml of pyridine and 505 ml of N-methyl-2-pyrrolidone (NMP) and dissolved. While the solution was stirred with water, a solution of 2.975 g (97 moles relative to 100 moles of the total amount of the diamine used in the synthesis) of dimethyl-1,3-bis(chlorocarbonyl) was added. The cyclobutane-2,4-carboxylate was further added with NMP so that the solid content concentration was 5% by weight, and the mixture was stirred for 4 hours while being water-cooled. The solution was poured into 250 g of water to precipitate a polymer, which was filtered by suction filtration, washed again with 250 g of water, and washed 3 times with 63 g of methanol at 40 ° C. Drying under reduced pressure was carried out, whereby 28 g of a poly phthalate powder was obtained. The polyglycolate (polymer (PAE-10)) had a weight average molecular weight of Mw = 27,000. Further, with respect to Synthesis Examples 2 to 10, the numerical values in Table 2 indicate the use ratio (molar parts) with respect to the tetracarboxylic acid derivative relative to the total amount of 100 moles of the tetracarboxylic acid derivative used in the reaction. The diamine is used in a ratio (molar) relative to the total amount of 100 parts of the diamine used in the reaction.

[Synthesis Example 2-11: Synthesis of Polymer (PAE-11)] In addition to the synthesis examples 2 to 10, the types and amounts of the tetracarboxylic acid diester dihalide and the diamine used in the reaction, and The amount of pyridine and acetic anhydride was changed to the same operation as in Synthesis Example 2-10 except that the amount of pyridine and acetic anhydride was changed, thereby obtaining a polyphthalate (polymer (PAE-11)). Further, with respect to Synthesis Example 2-11, the numerical values in Table 2 have the same meanings as in Synthesis Example 2-10.

<Preparation and evaluation of liquid crystal alignment agent> [Example 1] (1) Preparation of liquid crystal alignment agent 100 parts by weight of the polymer (PAA-1) obtained in Synthesis Example 2-1 as a polymer, and organic 2 parts by weight of the hydrazine compound of the compound (Si-1) obtained in Synthesis Example 1-1, dissolved in γ-butyrolactone (GBL), NMP and diethylene glycol diethyl ether (diethylene glycol diethyl) A mixed solvent (GBL: NMP: DEDG = 55:30:15 (weight ratio)) of ether, DEDG) was prepared as a solution having a solid concentration of 6.0% by weight. This solution was filtered using a filter having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent.

(2) Evaluation of abrasion resistance Using the liquid crystal alignment agent prepared in the above (1), a coating film was formed on a quartz substrate, and then a friction device having a roller wound with a rayon cloth was used, and the following Table 3 was used. The two conditions (condition (A) and condition (B)) described are subjected to rubbing treatment. The coating film (liquid crystal alignment film) after the rubbing treatment was washed with isopropyl alcohol, and the peeling of the alignment film from the substrate and the presence or absence of the rubbing flaw were visually confirmed. In this case, any of the peeling and the rubbing flaw of the liquid crystal alignment film was not observed as the abrasion resistance "good (○)", and at least one of the peeling and the rubbing flaw of the liquid crystal alignment film was observed. The situation was evaluated as "bad (x)". As a result, in the examples, no peeling of the liquid crystal alignment film and frictional scratches were observed under any of the conditions (A) and (B), and the rubbing resistance was "good".

[table 3]

(3) Production of Liquid Crystal Cell The liquid crystal alignment agent prepared in the above (1) was applied to a ITO electrode having a comb-tooth shape by using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). The electrode surface of a 1 mm glass substrate was heated (prebaked) on a hot plate at 80 ° C for 1 minute to remove the solvent, and then heated (post-baked) on a hot plate at 200 ° C for 10 minutes to form an average film thickness. It is a coating film of 0.06 μm. The coating film was subjected to a rubbing treatment using a rubbing machine having a roll wound with a rayon cloth at a roll rotation number of 500 rpm, a table moving speed of 3 cm/sec, and a hair press-in length of 0.4 mm to impart a liquid crystal alignment ability. Then, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. Further, the operation was repeated for a glass substrate having a thickness of 1 mm and having a circular photosensitive spacer having a height of 5 μm and a diameter of 5 μm at an area ratio of 0.1%. A pair (two pieces) of a substrate having a liquid crystal alignment film was obtained. Then, for one of the pair of substrates, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and then the liquid crystal alignment film surface is opposite. In a manner, a pair of substrates are overlapped and crimped to harden the adhesive. Then, a nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-2042) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell. .

(4) Evaluation of the bright spot defect of the liquid crystal cell Using a push pull gauge (manufactured by Imada), the center portion of the liquid crystal cell manufactured in the above (3) was changed to 40 N The way to apply pressure for 5 seconds. This was repeated 100 times, and the case where no bright spot was observed by a polarizing microscope was evaluated as "good (○)", and the case where one to nine bright spots were observed was evaluated as "may (?)", and 10 were observed. The case of the above highlights was evaluated as "bad (x)". As a result, no bright spots were observed in this example, which was a "good" result.

(5) Evaluation of liquid crystal alignment property A The liquid crystal cell produced in the above (3) was observed by a polarizing microscope for the presence or absence of the flow alignment of the liquid crystal, and was observed by a polarizing microscope to be repeatedly turned on and off (applied and released). The presence or absence of an abnormal region in the change of light and dark at a voltage of 5 V, thereby evaluating the liquid crystal alignment property. The evaluation was carried out in the following manner: the case where the flow alignment and the abnormal region were not observed was evaluated as the liquid crystal alignment "good (○)", and although the flow alignment was not observed, the case where the abnormal region was observed was evaluated as "may" △)", the case where the flow alignment was found was evaluated as "bad (x)". As a result, the liquid crystal alignment property of this example was evaluated as "good".

(6) Evaluation of liquid crystal alignment B (resistance at high temperature) The two liquid crystal cells were prepared by the method of the above (3), and one of them (component A) was applied under a backlight at 60 ° C. An alternating voltage of 10 V was applied for 20 hours, and an alternating voltage of 1 V was applied to the other (element B) for 20 hours. Then, the luminance difference between the element A and the element B observed when the voltage application is converted into a DC voltage of 2.5 V is expressed by 256 steps, and the afterimage resistance in a high temperature environment is evaluated based on the luminance difference. The case where the luminance difference was less than 5 was evaluated as "good" with respect to the afterimage resistance, and the case of 5 or more and less than 10 was evaluated as "resistance", and the case of exceeding 10 was evaluated as "resistance". As a result, in this example, the evaluation of the "good" afterimage resistance was obtained.

(7) Evaluation of electrical characteristics (voltage holding ratio) The liquid crystal cell manufactured by the method (3) was subjected to application of a voltage of 5 V at an application time of 60 μsec and a span of 167 msec at 40 ° C. The voltage holding ratio (VHR) after 167 milliseconds since the application was released. Further, the measuring device was VHR-1 manufactured using Toyo Technica Co., Ltd. The electric characteristics of the liquid crystal cell were evaluated as "good" when the voltage holding ratio was 98% or more, "may" when 95% or more and less than 98%, and "bad" when 95% or less was used. ". As a result, this example is an evaluation of "good" electrical characteristics.

[Examples 2 to 12 and Comparative Examples 1 to 5] In the first embodiment, the types and amounts of the polymers and additives used were as shown in Table 4 below. The preparation of the liquid crystal alignment agent and the production of the liquid crystal cell were carried out in the same manner as in Example 1, and various evaluations were carried out. The evaluation results are shown in Table 4 below.

[Table 4]

In Table 4, the abbreviations of the additives are as follows. Add-1: N, N, N', N'-tetraglycidyl-4, 4'-diaminodiphenylmethane Add-2: 3-glycidoxypropyltrimethoxydecane Add- 3: 3-aminopropyltriethoxydecane Si-7: a compound represented by the following formula (si-7) [Chem. 15]

As shown in Table 4, in the liquid crystal alignment agent of Examples 1 to 12 containing the organic ruthenium compound having the nitrogen-containing structure represented by the above formula (1a), the rubbing resistance of the liquid crystal alignment film formed using the same is used. good. Further, the liquid crystal cells of Examples 1 to 12 are "difficult to produce bright spots, evaluation of liquid crystal alignment (presence or absence of liquid crystal alignment and presence or absence of abnormal regions), image resistance at high temperatures, and electrical characteristics. Good or "can" results, and a balance of various characteristics. On the other hand, in the comparative example, at least one of the rubbing resistance of the liquid crystal alignment film, the difficulty in producing a bright spot defect in the liquid crystal cell, and the liquid crystal alignment property were inferior to those of the examples.

no

no

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Claims (10)

A liquid crystal alignment agent comprising: at least one polymer (P) selected from the group consisting of polylysine, polyphthalate, and polyimine; and having the formula (1a) The organic ruthenium compound having a nitrogen-containing structure in which "*1" in the following formula (1a) is bonded to a hydrogen atom, a methylene group or a monovalent hydrocarbon group; In the formula (1a), R ^a and R ^b are each independently a divalent organic group; "*1" and "*2" represent a bond. The liquid crystal alignment agent according to claim 1, wherein the organic ruthenium compound is a compound which further satisfies at least one of a hydroxyl group in the molecule and ^a carbonyl group in the formula (1a). A liquid crystal alignment agent comprising: at least one polymer (P) selected from the group consisting of polylysine, polyphthalate, and polyimine; and having the formula (1a) An organic ruthenium compound having a nitrogen-containing structure and satisfying a hydroxyl group in the molecule and at least one of R ^a in the formula (1a) is ^a carbonyl group: In the formula (1a), R ^a and R ^b are each independently a divalent organic group; "*1" and "*2" represent a bond. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the organic ruthenium compound is selected from the group consisting of a ruthenium compound having the nitrogen-containing structure and a hydroxyl group, and a ruthenium compound having a urea structure. At least one of the group consisting of. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the organic hydrazine compound is at least one selected from the group consisting of a primary amine group and a secondary amine group. An amine compound obtained by reacting a reactive group-containing compound having at least one selected from the group consisting of an acid anhydride group, an epoxy group, and an oxetanyl group, and the amine compound and the At least one of the reactive group-containing compounds is a compound having a halogen atom. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the organic hydrazine compound has a hydroxyl group, and at least one of the hydroxyl groups of the organic hydrazine compound is bonded to a carbonyl group. The liquid crystal alignment agent according to any one of the above aspects, wherein the organic hydrazine compound is selected from the group consisting of a compound represented by the following formula (1) and represented by the following formula (2) At least one of the groups consisting of compounds, In the formula (1), R ¹⁹ is a hydrogen atom or a monovalent hydrocarbon group, or a divalent hydrocarbon group formed by two R ¹⁹ bonds in the molecule; R ²⁰ is a trivalent organic group, and R ²¹ is a divalent organic group, R ²² And R ²³ are each independently a monovalent hydrocarbon group, R ²⁴ is a (h+i) valent organic group; A ¹ is a single bond or a carbonyl group, and A ² is a single bond, a carbonyl group or an alkyldiyl group having 1 to 3 carbon atoms, B ¹ and B ² are each independently a carbonyl group or a C alkanediyl group having 1 to 3; e, f, g and i are each independently an integer of 0 to 4, e + f + g ≧ 1 and e + i ≧ 1 h is an integer of 1-4, and j is an integer of 1-3; wherein, when there are a plurality of R ²⁰ , R ²² , R ²³ , A ¹ , A ² , B ^{1 ,} and B ² respectively, a plurality of R ²⁰ , R ²² , R ²³ , A ¹ , A ² , B ¹ and B ² independently have the definition; In the formula (2), R ³¹ and R ³² are each independently a monovalent hydrocarbon group, R ³³ is a divalent organic group, R ³⁴ is a monovalent organic group; t is an integer of 1 to 3; wherein, R ³¹ and R ^In the case where there are a plurality of ³² , a plurality of R ³¹ and R ³² independently have the definition. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the compounding ratio of the organic cerium compound is 0.1 part by weight to 100 parts by weight of the polymer (P). 30 parts by weight. A liquid crystal alignment film which is formed using the liquid crystal alignment agent according to any one of claims 1 to 8. A liquid crystal display element comprising the liquid crystal alignment film according to claim 9 of the patent application.