TWI625323B - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, phase difference film and manufacturing method thereof, polymer and compound - Google Patents

Abstract

The present invention provides a liquid crystal alignment agent for forming a liquid crystal alignment film which can appropriately exhibit various characteristics required for a liquid crystal display element. The liquid crystal alignment agent contains at least one polymer (P) selected from the group consisting of polylysine, polyphthalate, and polyimine, and the polymer (P) is a tetracarboxylic acid. The acid derivative is obtained by a reaction with a diamine containing a compound represented by the following formula (1).

(R ^A is a divalent group having an oxygen atom or a sulfur atom at at least any position between a carbon-carbon bond of a hydrocarbon group and a position adjacent to the hydrocarbon group, and X ¹ and X ² are each independently a single bond, An oxygen atom, a sulfur atom or a divalent organic group.)

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, phase difference Membrane and its manufacturing method, polymer and compound

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, a retardation film, a method for producing the same, a polymer, and a compound.

Previously, liquid crystal display elements have developed various driving methods in which the electrode structure or the liquid crystal molecules used are different in physical properties, manufacturing steps, and the like, and for example, a twisted nematic (TN) type or a super twisted nematic (super- is known). Various liquid crystal display elements such as twisted nematic, STN) type, vertical alignment (VA) type, in-plane switching (IPS) type, and fringe field switching (FFS) type. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. In terms of various properties such as heat resistance, mechanical strength, and affinity with liquid crystal, the material of the liquid crystal alignment film is usually polyacrylic acid or polyimide.

In addition, in recent years, liquid crystal display elements have not only been used for personal electric power as before. A display terminal such as a brain, and is also used for various purposes such as a liquid crystal television or a car navigation system, a mobile phone, a smart phone, an information display, and the like. Against this background, the demand for higher performance of liquid crystal display elements has been further improved, and various characteristics required for liquid crystal display elements have been demanded as liquid crystal alignment films. In addition, a plurality of liquid crystal alignment agents for obtaining such a liquid crystal alignment film, or a polymer blended in the liquid crystal alignment agent, and a monomer for obtaining the polymer have been proposed (for example, refer to Patent Document 1 and Patent Document 2) .

Patent Document 1 discloses the use of 1,2-bis(4-(4-aminobenzyl)phenyl)B. Polyalkylenimine obtained by the reaction of a diamine having no polar group and a tetracarboxylic dianhydride, such as alkane or 1,6-bis(4-(4-aminobenzyl)phenyl)hexane, as a liquid crystal The polymer component of the alignment agent. Further, Patent Document 2 discloses the use of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,5-bis[4-(4-aminophenoxy)phenoxyl in the examples. Polylysine obtained by the reaction of pentane is used as a polymer component of a liquid crystal alignment agent.

In addition, a variety of optical materials are used in liquid crystal display elements, wherein the phase difference is The film is used for the purpose of eliminating the coloration of the display or for eliminating the dependence of the display color and contrast on the viewing angle depending on the visual direction. The retardation film is known to have a film having a liquid crystal alignment film formed on a surface of a substrate such as a triacetyl cellulose (TAC) film, and a liquid crystal layer through which the liquid crystal layer is passed. The surface of the liquid crystal alignment film is formed by curing the polymerizable liquid crystal. Further, in recent years, in the production of a liquid crystal alignment film of a retardation film, a photoalignment method is employed in which a liquid crystal alignment ability is imparted by irradiating a radiation-sensitive or non-polarized radiation to a radiation-sensitive organic thin film formed on a surface of a substrate, and Various liquid crystal alignment agents for retardation films for producing a liquid crystal alignment film by the above method have been proposed (for example, see Patent Document 3).

A method of producing a retardation film on an industrial scale proposes a roll-to-roll method (for example, refer to Patent Document 4). The method is a method in which the film is subjected to the following steps in a continuous step, and the film after the steps is formed into a wound body, and the treatment is carried out by winding up the wound body of the elongated substrate film. A film, a process of forming a liquid crystal alignment film on the rolled film, a process of applying a polymerizable liquid crystal on the liquid crystal alignment film and curing it, and a process of laminating a protective film as needed.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3658798

[Patent Document 2] International Publication No. 2004/053583

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-37868

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-86786

However, when the polyimide component described in Patent Document 1 is used as the polymer component of the liquid crystal alignment agent, the liquid crystal alignment agent tends to have poor coatability to the substrate. Further, when the liquid crystal alignment film of the FFS type liquid crystal display device is produced using the liquid crystal alignment agent, the pretilt angle is too high, and the viewing angle characteristics are poor. In the liquid crystal display device using the liquid crystal alignment agent containing the polyamic acid described in Patent Document 2, the voltage holding characteristics and the heat resistance are inferior.

In addition, the retardation film can be easily produced on an industrial scale by the above-described roll-to-roll method, but when the adhesion between the liquid crystal alignment film and the base film is insufficient, After the step is completed, the film is formed into a wound body At this time, there is a case where the liquid crystal alignment film is peeled off from the substrate film. In this case, there is a problem that the yield of the product is lowered.

The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal alignment agent for forming a liquid crystal alignment film capable of appropriately exhibiting various characteristics required for a liquid crystal display element. Further, another object of the present invention is to provide a liquid crystal alignment agent for forming a liquid crystal alignment film for a retardation film which is excellent in liquid crystal alignment and has good adhesion to a substrate.

The present inventors have conducted active research in order to achieve the problems of the prior art as described above, and as a result, have found that polylysine obtained by polycondensation of a diamine having a specific structure and a tetracarboxylic acid derivative, The present invention can be accomplished by solving at least the polymer of at least one of a polyphthalate and a polyimine. Specifically, the present invention provides the following liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, retardation film, a method for producing the same, a polymer, and a compound.

An aspect of the present invention provides a liquid crystal alignment agent containing at least one polymer (P) selected from the group consisting of polylysine, polyphthalate, and polyimine, the polymer (P) is obtained by including at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester compound, and tetracarboxylic acid diester dihalide, and the following formula ( 1) A diamine of the compound represented is obtained by a reaction.

(In the formula (1), R ^A is a divalent group having an oxygen atom or a sulfur atom between at least one of a carbon-carbon bond of a hydrocarbon group having 1 to 30 carbon atoms and a position adjacent to the hydrocarbon group. At least one of the hydrogen atoms of the hydrocarbon group may be substituted by a halogen atom; X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom or a divalent organic group; wherein, X ¹ and X ² are oxygen In the case where an atom and R ^A is -OR ¹ -O- (R ¹ is an alkanediyl group having 1 to 18 carbon atoms), the tetracarboxylic acid derivative is 1,2,3,4-cyclobutane IV Except in the case of carboxylic acid dianhydride.)

Another aspect of the present invention provides a liquid crystal alignment film which is formed using the liquid crystal alignment agent. Further, the present invention provides a liquid crystal display element including the liquid crystal alignment film and a retardation film. Further, another aspect of the present invention provides a method for producing a retardation film, comprising the steps of: applying the liquid crystal alignment agent onto a substrate to form a coating film; irradiating the coating film with light; The polymerizable liquid crystal is coated on the coating film after the light irradiation and hardened. Further, the present invention further provides a compound represented by the above formula (1), and a diamine containing the same, and a tetracarboxylic acid diester compound, a tetracarboxylic acid diester compound, and a tetracarboxylic acid diester dihalide. A polymer obtained by reacting at least one of the tetracarboxylic acid derivatives in the composed group.

By using a liquid crystal alignment agent containing a polymer obtained by a reaction of a diamine represented by the above formula (1) with a tetracarboxylic acid derivative, various characteristics which can appropriately exhibit various characteristics required for a liquid crystal display element can be formed. Liquid crystal alignment film. Further, according to the liquid crystal alignment agent of the present invention, a high quality liquid crystal display element can be produced. Further, the liquid crystal alignment film obtained by using the liquid crystal alignment agent of the present invention is bonded to the substrate. Good adhesion. Therefore, when the liquid crystal alignment film is formed into a wound body and stored, the liquid crystal alignment film and the substrate are also hardly peeled off. Therefore, for example, when a retardation film is produced, a decrease in product yield can be suppressed.

10‧‧‧Liquid display components

11a, 11b‧‧‧ glass substrate

12‧‧‧Liquid alignment film

13‧‧‧ top electrode

14‧‧‧Insulation

15‧‧‧ bottom electrode

16‧‧‧Liquid layer

D1‧‧‧ electrode line width

D2‧‧‧Distance between electrodes

Fig. 1 is a schematic configuration diagram of an FFS type liquid crystal display element.

2(a) and 2(b) are plan views of the top electrode. 2(a) is a plan view of the top electrode, and FIG. 2(b) is a partially enlarged view of the top electrode.

The liquid crystal alignment agent of the present invention comprises selected from the group consisting of polylysine and polyamidate And at least one polymer (P) in the group consisting of polyimine and, if necessary, other components. Hereinafter, each component contained in the liquid crystal alignment agent of the present invention and other components arbitrarily formulated as needed will be described.

<Polymer (P): Polylysine>

Polylysine (hereinafter also referred to as polyglycolic acid (P)) which is the polymer (P) of the present invention can be obtained by reacting a tetracarboxylic dianhydride with a diamine.

[tetracarboxylic dianhydride]

Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid (P) include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the tetracarboxylic dianhydride include aliphatic monocarboxylic dianhydride: 1,2,3,4-butanetetracarboxylic dianhydride; and alicyclic tetracarboxylic dianhydride. : 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro 8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[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-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6- Anhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ] Monoalkane-3,5,8,10-tetraketone, cyclohexanetetracarboxylic dianhydride, etc., and aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, etc. The tetracarboxylic dianhydride described in Japanese Laid-Open Patent Publication No. 2010-97188. Further, the tetracarboxylic dianhydride may be used alone or in combination of two or more.

The tetracarboxylic dianhydride used in the synthesis preferably contains at least one selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-three Carboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2- c] furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl) -naphtho[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-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3, 5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5, 8,10-tetraketone, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, and pyromellitic dianhydride. Moreover, from the viewpoint of transparency and solubility in a solvent, it is preferable to contain an alicyclic tetracarboxylic dianhydride, and it is preferable to contain an aromatic tetracarboxylic dianhydride from the viewpoint of electrical characteristics.

[diamine]

The diamine used for the synthesis of the polyamic acid (P) contains the compound represented by the formula (1).

R ^A in the formula (1) is a divalent group having an oxygen atom or a sulfur atom at at least any position between a carbon-carbon bond of a hydrocarbon group having 1 to 30 carbon atoms and a position adjacent to the hydrocarbon group. Here, the "hydrocarbon group" in the present specification means a meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" means a linear or branched hydrocarbon group which does not include a cyclic structure in the main chain but is composed only of a chain structure, and 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 including an aromatic ring structure. Among them, it is not necessary 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 necessary 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.

Specific examples of the hydrocarbon group having 1 to 30 carbon atoms include a methylene group, an ethylene group, a propane diyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, and a heptanediyl group. , octanediyl, decanediyl, decanediyl, dodecanediyl, tetradecanediyl, pentadecanediyl, hexadecandiyl, octadecyldiyl, etc., these hydrocarbyl groups may It is linear or branched. Further, examples of the alicyclic hydrocarbon group include cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, propylcyclohexane, pentylcyclohexane, dimethylcyclohexane, and the like. A group obtained by removing two hydrogen atoms, etc., and examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from benzene, toluene, xylene, ethylbenzene, propylbenzene or pentylbenzene. Mission and so on. Among them, the hydrocarbon group in R ^A preferably has a divalent chain hydrocarbon group, more preferably a divalent chain hydrocarbon group, and particularly preferably an alkanediyl group.

Further, at least one of the hydrogen atoms of the hydrocarbon group in R ^A may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The number (total count) of the oxygen atom and the sulfur atom which the R ^A has is not particularly limited, and can be appropriately selected depending on the carbon number of R ^A from the viewpoint of low pretiltability or improved solubility of the polymer. It is preferably from 1 to 5, more preferably from 1 to 3. Further, when R ^A has a plurality of these hetero atoms (oxygen atoms or sulfur atoms), it may have only one of an oxygen atom and a sulfur atom, or may have two of these atoms.

The position at which the oxygen atom or the sulfur atom is introduced may be between the carbon-carbon bonds of the hydrocarbon group, the position adjacent to the hydrocarbon group, or both. In addition, the term "between carbon-carbon bonds of a hydrocarbon group" means ^{a case where} the position of the hetero atom X ^a is "-R ¹⁰ -X ^a -R ¹¹ -" (wherein R ¹⁰ and R ¹¹ are a hydrocarbon group), so-called " The position adjacent to the hydrocarbon group means that the position of the hetero atom X ^a becomes "*-X ^a -R ¹² -" (wherein R ¹² is a hydrocarbon group, and "*" is a benzene ring bonded to R ^A The case of combining keys).

X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom or a divalent organic group. Here, examples of the "divalent organic group" in X ¹ and X ² include a substituted or unsubstituted alkanodiyl group, a substituted or unsubstituted alkenediyl group, and a carbonyl group. An ester group (-COO-), a guanamine group (-CO-NH-) or the like is preferred as a specific example. The alkanediyl group of X ¹ and X ² preferably has a carbon number of 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3. Further, the enediyl group is preferably a carbon number of 2 to 10, more preferably 2 to 5, particularly preferably 2 to 3. Further, examples of the substituent introduced to the alkanediyl group and the alkenediyl group include an oxygen atom (-O-), a sulfur atom (-S-), and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.). ), hydroxyl, and the like.

Among them, X ¹ and X ^{2 are} preferably an oxygen atom, an ester group, a decylamino group, an alkanediyl group having 1 to 10 carbon atoms or an enediyl group having 2 to 10 carbon atoms, more preferably an oxygen atom and a carbon number of 1 to 5. The alkanediyl group or the alkenediyl group having 2 to 5 carbon atoms is particularly preferably an oxygen atom, a methylene group, an ethylene group or a vinylidene group.

In the compound, the compound represented by the formula (1) is preferably a compound represented by the following formula (1-1).

(In the formula (1-1), R ² is a divalent hydrocarbon group having 1 to 30 carbon atoms, X ³ is an oxygen atom or a sulfur atom, X ⁴ is a single bond, an oxygen atom or a sulfur atom; and X ¹ and X ² are The above formula (1) is the same meaning.)

Specific examples of R ² in the formula (1-1) can be explained by using a hydrocarbon group having 1 to 30 carbon atoms of R ^A of the formula (1). R ² is preferably a divalent chain hydrocarbon group, and more preferably an alkanediyl group. The carbon number of the alkanediyl group is preferably from 1 to 20, more preferably from 1 to 11, and particularly preferably from 1 to 8.

X ³ is an oxygen atom or a sulfur atom, and is preferably an oxygen atom. Further, X ⁴ is a single bond, an oxygen atom or a sulfur atom, and is preferably a single bond or an oxygen atom.

Preferable specific examples of the compound represented by the formula (1) include, for example, a compound represented by the following formula (DA-1) to formula (DA-15).

[Chemical 3]

From the viewpoint of sufficiently obtaining the effects of the present invention, the use ratio of the compound represented by the formula (1) is preferably set to 1 mol% with respect to the total amount of the diamine used in the synthesis of the polyamic acid. ~100% of the range of moles. The lower limit is more preferably 5 mol% or more, particularly preferably 15 mol% or more, and particularly preferably 20 mol% or more. The compound represented by the formula (1) may be used alone or in combination of two or more. Used in combination.

Further, in the compound represented by the formula (1), since the group "R ^A " between the two benzene rings is a hydrocarbon group having an oxygen atom or a sulfur atom, it is presumed that the polymer obtained by using the compound passes polarity. The improvement of the solubility of the polymer is improved, and the coating property of the liquid crystal alignment agent on the substrate is improved. Further, it is presumed that the rotatability of the molecule is improved and the frictional elongation is improved, whereby the low pretilt of the liquid crystal alignment film (increased viewing angle) can be exhibited. The compound represented by the formula (1) has a polymer which can form a liquid crystal alignment film having various properties such as liquid crystal alignment property, voltage holding property, and heat resistance by polycondensation with a tetracarboxylic anhydride or the like. The same effect. Therefore, compounds not described in the following examples can also be used in the present invention.

[Synthesis of the compound represented by the formula (1)]

The compound represented by the formula (1) can be synthesized by appropriately combining a common method of organic chemistry. An example thereof is a method of synthesizing a dinitro intermediate having a nitro group instead of the primary amino group in the formula (1), and then, using a suitable reduction system, the nitro group of the obtained dinitro intermediate Amination is carried out.

The method of synthesizing the dinitro intermediate can be appropriately selected depending on the target compound. As an example, for example, when X ¹ and X ² are oxygen atoms, the dihydro compound can be synthesized by synthesizing a dihydro compound represented by HO-Ph-R ^A -Ph-OH (Ph is a phenylene group). Obtained by reaction with halogenated nitrobenzene. Further, when X ¹ and X ² are a methylene group, the obtained reaction product can be obtained by reacting a compound represented by Bz-R ^A -Bz (Bz is a phenyl group) with nitrobenzylidene chloride. It is obtained by reducing a carbonyl group to a methylene group. In the case where X ¹ and X ² are ester groups, it can be obtained by reacting the dihydrogen compound with nitrobenzylidene chloride.

The reduction reaction of the dinitro intermediate is preferably in an organic solvent, for example using It is carried out by a catalyst such as palladium carbon, platinum oxide, zinc, iron, tin or nickel. Examples of the organic solvent used herein include ethyl acetate, toluene, tetrahydrofuran, and alcohol. However, the synthesis formula of the compound represented by the formula (1) is not limited to the method.

[Other diamines]

The diamine used in the synthesis of the polyamic acid (P) may be used singly as the compound represented by the formula (1), or other diamines other than the compound may be represented by the formula (1). The compound is used in combination.

Here, examples of the other diamine include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organic decane, and the like. Specific examples of the diamine compound include aliphatic m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. An amine, 1,3-bis(aminomethyl)cyclohexane or the like; examples of the alicyclic diamine include 1,4-diaminocyclohexane and 4,4'-methylenebis(cyclohexyl) Amine) and the like; examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, and 1,5-diamine. Naphthyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,7 -2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9, 9-9-bis(4-aminophenyl)fluorene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene Diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3, 4-diaminopyridine, 2,4-diamine Pyridine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminoguanidine Oxazole, N-phenyl-3,6-diamino Carbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4 - bis-(4-aminophenyl)-pyridazine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-5-amine , 1-(4-Aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indol-6-amine, 3,5-diaminobenzoic acid, cholestane Cholestoyl oxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholesteryl-2,4- Diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate , 3,5-diaminobenzoic acid lanthanum alkyl ester, 3,6-bis(4-aminobenzylideneoxy)cholestane, 3,6-bis(4-aminophenoxy) Cholestane, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzonitrileoxy) Cyclohexyl-3,5-diaminobenzoate, 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, 2,4-diamino-N,N-diene Propyl aniline, 4-aminobenzylamine, 3-aminobenzylamine, 1,3-diamino-4-octadecyloxybenzene, 3-(3,5-diaminobenzoic acid醯oxy)cholestane, 3,6-bis(4-aminobenzylideneoxy)cholestane, and the following formula (D-1)

(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 n is 0 or 1; wherein a and b are not 0 at the same time )

Examples of the compound to be represented, and examples of the diamine-based organodecane oxide include 1,3-bis(3-aminopropyl)-tetramethyldioxane, etc., and other patents can be used. The diamine described in the '97188 publication.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _n -" in the formula (D-1) is preferably an alkanediyl group having a carbon number of 1 to 3, *-O-, * -COO- or *-OC ₂ H ₄ -O- (wherein the bond labeled "*" is bonded to the diaminophenyl group).

Specific examples of the group "-C _c H _2c+1 " include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl , n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nine Alkyl, n-icosyl, and the like. The two amine groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to 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-1-5), and the like.

In addition, the diamine used in the synthesis of the poly-proline (P) may be used alone or in combination of two or more.

In the case where the liquid crystal alignment agent of the present invention is used for producing a TN type, STN type or vertical alignment type liquid crystal display element, the other diamine preferably contains a group having a ability to impart a pretilt angle to the coating film (hereinafter, Also known as "pretilt imparting group" diamines. Examples of the pretilt angle-imparting group include an alkyl group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, and a group having a steroid skeleton having 17 to 51 carbon atoms. A group having a polycyclic structure or the like.

Specific examples of the diamine having a pretilt angle-imparting group include, for example, dodecane Oxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, tetradecyloxy-2, 5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-di Aminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, 3,5-diaminobenzoic acid lanthanum alkyl ester, 3,6-bis(4-aminobenzylideneoxy)cholesterane, 4-(4'-trifluoromethoxybenzhydryloxy) Cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzyloxy)cyclohexyl-3,5-diaminobenzoate, 1, 1-bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)) -4-heptylcyclohexane, a diamine represented by the formula (D-1), and the like. Further, the diamine may be used alone or in combination of two or more.

When a diamine having a pretilt angle imparting group is used, from the viewpoint of exhibiting sufficiently high pretilt characteristics, the use ratio of the diamine is preferably set to 5 mol% or more based on the entire diamine. More preferably, it is set to 10 mol% or more. In addition, The upper limit of the use ratio is not particularly limited, but from the viewpoint of not impairing the effect of the use of the compound represented by the above formula (1), it is preferably set to 99 mol with respect to all diamines. It is at most or less than the ear, and more preferably at 95% by mole or less.

[Molecular weight regulator]

When the polyamic acid (P) is synthesized, a terminal-modified polymer can be synthesized using a suitable molecular weight modifier together with the tetracarboxylic dianhydride and the diamine as described above. By forming the terminal-modified polymer, the coating property (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention.

Examples of the molecular weight modifier include an acid monoanhydride, a monoamine compound, and a monoisocyanate compound. Specific examples of the compound include, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, and the like. Examples include tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, and the like; examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, and n-heptylamine. Examples of the monoisocyanate compound include n-octylamine, n-dodecylamine, n-octadecylamine, and the like. Examples of the monoisocyanate compound include phenyl isocyanate and 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.

[Synthesis of polyglycine]

The ratio of the tetracarboxylic dianhydride to the diamine to be used in the synthesis reaction of the polyamic acid (P) is preferably 1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 equivalent. The ratio of 2 equivalents is more preferably a ratio of 0.3 equivalents to 1.2 equivalents. Further, the synthesis reaction of polyamic acid (P) 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.

Here, examples of the organic solvent include an aprotic polar solvent and a phenol system. Solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Specific examples of the organic solvent include, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl. Pyridinium, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide, etc.; examples of the phenolic solvent include phenol, m-cresol, xylenol, halogenated phenol, and the like. ;

Examples of the alcohol include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, and ethylene glycol monomethyl ether; and examples of the ketone include acetone, methyl ethyl ketone, and methyl isobutyl ketone. And the ester may, for example, be ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate or the like; Examples of the ether include diethyl ether, diisoamyl ether, ethylene glycol methyl ether, ethylene glycol diethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, and ethylene glycol. Alcohol ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran, etc.; halogenated hydrocarbons, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, Chlorobenzene or the like; examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, xylene, and the like.

Among these organic solvents, it is preferred to use an aprotic polar solvent selected from the group consisting of And one or more of the group consisting of the phenolic solvent (the organic solvent of the first group), or one or more selected from the organic solvents of the first group and selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons And a group consisting of hydrocarbons (the second group of organic solvents) More than one mixture. In the latter case, the ratio of the organic solvent of the second group is preferably 50% by weight or less, 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. In addition, the amount (α) of the organic solvent to be used is preferably 0.1% by weight to 50% by weight based on the total amount (α + β) of the reaction solution, and the total amount (β) of the tetracarboxylic dianhydride and the diamine. the amount.

As described above, a reaction solution obtained by dissolving polylysine (P) was obtained. 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 isolated and then supplied to the preparation of the liquid crystal alignment agent, or the isolated 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 a dehydration ring-closure reaction, or the polylysine contained in the reaction solution may be isolated and then supplied to The dehydration ring closure reaction, or the isolated polyamic acid can also be purified and then supplied to the dehydration ring closure reaction. The isolation and purification of polylysine can be carried out according to a known method.

<Polymer (P): Polyphthalate>

The polyglycolate (hereinafter also referred to as polyphthalate (P)) which is the polymer (P) of the present invention can be obtained, for example, by the following method: [I] obtained by the synthesis reaction a method for synthesizing polyamine acid (P) with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like; [II] a method for reacting a tetracarboxylic acid diester compound with a diamine; [III] A method of reacting a tetracarboxylic acid diester dihalide with a diamine.

Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol, and propanol; and phenols such as phenol and cresol. In addition, halides can be listed, for example. For example: methyl bromide, bromoethane, stearyl bromide, methyl chloride, chlorooctadecane, 1,1,1-trifluoro-2-iodoethane, etc., containing epoxy Examples of the compound of the group include propylene oxide and the like. The tetracarboxylic acid diester compound used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid (P) by using the alcohol. Further, the tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting, for example, a tetracarboxylic acid diester compound obtained in the above manner with a suitable chlorinating agent such as sulfinium chloride. The diamine used in the method [II] and the method [III] contains the compound represented by the formula (1). Further, the other amines may be used as needed. Further, the polyperurate may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist.

<Polymer (P): Polyimine >

The polyimine (hereinafter also referred to as "polyimine (P)") which is a polymer (P) contained in the liquid crystal alignment agent of the present invention can be obtained by the poly-proline which is synthesized in the manner described ( P) The dehydration ring closure is carried out and obtained by hydrazine imidization.

The polyimine (P) may be a polyglycolic acid to be its precursor The complete ruthenium imide formed by dehydration ring closure of the proline structure may be a dehydration ring closure of only a part of the proline structure and the phthalate structure, and the proline structure and the guanamine At least one of the acid ester structures is a partial quinone imide that coexists with the quinone ring structure. The imidization ratio of the polyimine (P) is preferably 30% or more, more preferably 40% to 99%, and particularly preferably 50% to 99, in terms of an increase in voltage holding ratio. %. The ruthenium imidization ratio is a total of the amount of the guanidine structure of the polyimine, the number of the phthalate structure, and the number of the quinone ring structure, and the number of the quinone ring structure is The ratio is expressed as a percentage. Here, a part of the quinone ring may be 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, it is preferred to use the latter method.

In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to a solution of polyglycolic acid to carry out hydrazine imidation, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. 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 polyglycolic acid. As the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, collidine, lutidine or triethylamine can be used. The amount of the dehydration ring-closure catalyst to be used is preferably 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent to be used. The organic solvent used in the dehydration ring closure reaction is exemplified as an organic solvent exemplified as an organic solvent for synthesizing polyamic acid. 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 polyiminoimine (P) was obtained in the above manner. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the dehydration agent can be removed from the reaction solution and the dehydration ring-closing catalyst can be supplied to the liquid crystal alignment agent, or the polyimine can be isolated and then supplied to the liquid crystal alignment. The preparation of the agent, or the isolated polyimine can also be purified and then supplied to the preparation of the liquid crystal alignment agent. These purification operations can be carried out in accordance with a known method.

<Solid viscosity and weight average molecular weight of polymer>

Polylysine, polyphthalate as polymer (P) obtained in the manner described And the polyimine is preferably 10 mPa when it is made into a solution having a concentration of 10% by weight. s~800mPa. The solution viscosity of s is more preferably 15 mPa. s~500mPa. s solution viscosity of the compound. Further, the solution viscosity (mPa.s) of the polymer is a concentration of 10% by weight prepared for a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer. The polymer solution was measured at 25 ° C using an E-type rotational viscometer. Further, the poly-proline, polyphthalate, and polyimine contained in the liquid crystal alignment agent of the present invention are converted to polystyrene by gel permeation chromatography (GPC). The weight average molecular weight (Mw) is preferably from 500 to 100,000, more preferably from 1,000 to 50,000.

100 parts by weight of the total of the polymer component in the liquid crystal alignment agent, The use ratio of the polymer (P) is preferably from 50 parts by weight to 100 parts by weight. If it is less than 50 parts by weight, there is a concern that the effects of the present invention cannot be sufficiently obtained. It is more preferably 60 parts by weight or more, and particularly preferably 70 parts by weight or more. The polymer (P) may be used alone or in combination of two or more.

<Other ingredients>

The liquid crystal alignment agent of the present invention may contain other components as needed. Examples of the other component include a polymer other than the polymer (P), a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound"), a functional decane compound, and the like. A metal chelate compound, a hardening accelerator, a surfactant, and the like.

[Other polymers]

The other polymers may be used to improve solution properties or electrical properties. The other polymer may, for example, be a poly-proline which is obtained by a reaction of a diamine which does not contain the compound represented by the formula (1) with a tetracarboxylic dianhydride, and which is removed by the polyamic acid. Polyimine obtained by ring closure of water, polyphthalamide as polyester derivative, polyorganosiloxane, polyester, polyamine, cellulose derivative, polycondensation An aldehyde, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate, or the like.

Further, in the case where the liquid crystal alignment agent of the present invention is used for a retardation film, the other polymer may preferably use a polymer having a photo-alignment structure. Here, the photo-alignment structure is a concept including both a photo-alignment group and a decomposable photo-alignment unit. Specific examples include a structure in which photo-alignment is exhibited by photo-isomerization, photodimerization, photodecomposition, or the like, and examples thereof include azobenzene, cinnamic acid, and chalcone. Benzophenone, coumarin, and polyimine and derivatives of these compounds are used as a basic skeleton group and the like. Among these polymers, a polymer having a photo-alignment group is preferable, and a polymer containing a group having a cinnamic acid structure (cinnamic acid or a derivative thereof) introduced therein is more preferable. Among them, in view of the fact that the photo-alignment group is easily introduced into the polymer, a polyorganosiloxane having a cinnamic acid structure can be preferably used.

Further, the polymer having a photo-alignment group can be synthesized by a conventionally known method. For example, a polyorganosiloxane having a photo-alignment group as another polymer may be a polyorganosiloxane having an epoxy group and a carboxylic acid having a photo-alignment group, preferably an ether, an ester, a ketone, or the like. In the organic solvent, the reaction is carried out in the presence of a catalyst such as a quaternary ammonium salt to synthesize.

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 ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and new Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol 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-aminomethyl ring Hexane, N,N-diglycidyl-cyclohexylamine and the like are preferred compounds. 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 compound is added to the liquid crystal alignment agent, the compounding ratio of the epoxy compound is preferably 40 parts by weight or less based on 100 parts by weight of the total of the polymers contained in the liquid crystal alignment agent. More preferably, it is 0.1 weight part - 30 weight part.

[functional decane compound]

The functional decane compound 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 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltriethoxysilane Decane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-triethoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1,4,7- Triazanonane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, methyl 9-trimethoxydecyl-3,6-diazadecanoate, N-benzyl 3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, glycidoxymethyltrimethoxydecane, 2-glycidoxyethyltrimethoxy Basear, 3-glycidoxypropyltrimethoxydecane, and the like.

In the case where the functional decane compound is added to the liquid crystal alignment agent, the compounding ratio of the functional decane compound is preferably 2 parts by weight based on 100 parts by weight of the total of the polymer contained in the liquid crystal alignment agent. Hereinafter, it is more preferably 0.02 parts by weight to 0.2 parts by weight.

[metal chelate compound]

The metal chelate compound is contained in a liquid crystal alignment agent (especially a phase difference) for the purpose of ensuring mechanical strength of a film formed by low-temperature treatment in the case where the polymer component of the liquid crystal alignment agent has an epoxy structure. In the liquid crystal alignment agent for film). The metal chelate compound is preferably an acetalacetone complex or an etodoacetate complex using a metal selected from the group consisting of aluminum, titanium, and zirconium. Specific examples thereof include aluminum diisopropoxyethylacetate, aluminum tris(acetylsulfonate), aluminum tris(ethylacetate), and diisopropoxy bis(ethyl group B). Indoleacetic acid) titanium, titanium diisopropoxy bis(ethyl sulfonate), zirconium tri-n-butoxyethyl acetoacetate, zirconium di-n-butoxy bis(ethyl acetonitrile), and the like. In the case of adding the metal chelate compound, the metal chelate compound is preferably used in an amount of 50 parts by weight or less, more preferably 0.1% by weight based on 100 parts by total of the total of the constituent components containing the epoxy structure. It is -40 parts by weight, particularly preferably 1 part by weight to 30 parts by weight.

[hardening accelerator]

In the case where the polymer component in the liquid crystal alignment agent has an epoxy structure, the hardening accelerator is contained in the liquid crystal alignment agent in order to ensure the mechanical strength of the formed liquid crystal alignment film and the temporal stability of the liquid crystal alignment property ( In particular, it is used in a liquid crystal alignment agent for retardation film. As the hardening accelerator, for example, a compound having a phenol group, a stanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic anhydride group or the like can be used, and among them, a compound having a phenol group or a stanol group is preferable. Specific examples of the compound having a phenol group include cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol, and the like; and compounds having a stanol group; For example, trimethyl decyl alcohol, triethyl stanol, 1,1,3,3-tetraphenyl-1,3-dioxane diol, 1,4-bis(hydroxy dimethyl decane) Benzene, triphenyl decyl alcohol, tris(p-tolyl) decyl alcohol, diphenyl decane diol, and the like. When the curing accelerator is added, the curing accelerator is preferably used in an amount of 50 parts by weight or less, more preferably 0.1 parts by weight to 40 parts by weight, based on 100 parts by weight of the total of the constituent components containing the epoxy structure. It is especially preferably 1 part by weight to 30 parts by weight.

[Surfactant]

The surfactant may be contained in a liquid crystal alignment agent (particularly, a liquid crystal alignment agent for retardation film) for improving the coating property of the liquid crystal alignment agent on the substrate. Examples of such a surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, anthrone surfactants, polyalkylene oxide surfactants, and fluorine-containing surface active agents. Agents, etc. The use ratio of the surfactant is preferably 10 parts by weight or less, and more preferably 1 part by weight or less, based on 100 parts by weight of the total amount of the liquid crystal alignment agent.

Further, other components may have at least one in the molecule in addition to the components. An oxetane group compound or an antioxidant or the like.

<solvent>

The liquid crystal alignment agent of the present invention is prepared such that the polymer (P) and, if necessary, other components are preferably dispersed or dissolved in a suitable solvent to form a liquid composition.

Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butylidene, N,N-dimethylformamide, and N,N-dimethyl B. Indoleamine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene Alcohol 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, B Glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethyl Glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate and the like. These solvents may be used singly or in combination of two or more.

The solid content concentration in the liquid crystal alignment agent of the present invention (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) is appropriately selected in consideration of viscosity, volatility, and the like, and is preferably selected. It is in the range of 1% by weight to 10% by weight. In other words, the liquid crystal alignment agent of the present invention 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 exists. The tendency to increase the coating property is increased.

A particularly preferred range of solid component concentrations is based on the use of a liquid crystal alignment agent. The method used when applying the liquid crystal alignment agent on the substrate is different. For example, when the liquid crystal alignment agent for a liquid crystal alignment film is applied to a substrate by a spinner method, the solid content concentration (the total weight of all components other than the solvent in the liquid crystal alignment agent is in the total weight of the liquid crystal alignment agent) The proportion is particularly preferably in the range of 1.5% 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% by weight to 9% by weight, thereby setting the solution viscosity to 12 mPa. s~50mPa. The scope of 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 3 mPa. s~15mPa. The scope of s. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 10 ° C to 50 ° C, and more preferably from 20 ° C to 30 ° C. In the liquid crystal alignment agent for a retardation film, the solid content concentration of the liquid crystal alignment agent is preferably 0.2% by weight to 10% from the viewpoint of applicability of the liquid crystal alignment agent and the film thickness of the formed coating film. The range of % is more preferably in the range of 3% by weight to 10% by weight.

<Liquid crystal display element and retardation film>

The liquid crystal alignment film can be produced by using the liquid crystal alignment agent of the present invention described above. In addition, the liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention can be preferably applied to a liquid crystal alignment film for a liquid crystal display element and a liquid crystal alignment film for a retardation film. Hereinafter, the liquid crystal display element and the retardation film of the present invention will be described.

[Liquid Crystal Display Element]

The liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The mode of operation of the liquid crystal display device of the present invention is not particularly limited. For example, it can be applied to TN type, STN type, VA type (including Vertical Alignment-Multidomain Vertical Alignment (VA-MVA) type, Vertical Alignment-Patterned Vertical Alignment (VA). -PVA), IPS type, FFS type, optically compensated bend (OCB) type and other driving methods. The liquid crystal display element of the present invention can be produced, for example, by the following steps (I-1) to (I-3). Step (I-1) uses different substrates depending on the desired mode of operation. Step (I-2) and step (I-3) are shared in each operation mode.

[Step (I-1): Formation of Coating Film]

First, a liquid crystal alignment agent of the present invention is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate.

(I-1A) 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, and each of the transparent conductive films On the forming surface, the liquid crystal alignment agent of the present invention is preferably applied by offset printing, spin coating, roll coater or ink jet printing. For the substrate, for example, glass such as float glass or soda glass; plastics including polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly(alicyclic olefin), and the like can 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 containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). Indium tin oxide (ITO) film. 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, a method of using a mask having a desired pattern when forming a transparent conductive film, and the like may be employed. . 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. Pre-processing.

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 smoldering (post-baking) step is carried out for the purpose of completely removing the solvent and thermally amidating the proline structure present in the polymer as needed. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 300 ° C, and more preferably 120 ° C 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 formed film is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

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

In any of the above (I-1A) and (I-1B), the coating film is formed by coating a liquid crystal alignment agent on a substrate and then removing the organic solvent to form an alignment film or an alignment film. At this time, the polymerization contained in the liquid crystal alignment agent of the present invention When the material is polyamic acid, or is a polyphthalate, or is a quinone imidized polymer having a quinone ring structure and a proline structure, it can also be further heated after the coating film is formed. The dehydration ring-closing reaction is carried out to prepare a more imidized coating film.

[Step (I-2): Orientation ability treatment]

In the case of manufacturing a TN type, STN type, IPS type, or FFS type liquid crystal display element, as a process of imparting a liquid crystal alignment ability to the coating film formed in the above step (I-1), the following rubbing treatment is performed: A roll of a cloth containing fibers such as nylon, rayon, cotton, or the like is wound, and the coating film is rubbed in a certain direction. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. On the other hand, in the case of producing a VA liquid crystal display element, the coating film formed in the above step (I-1) can be directly used as the liquid crystal alignment film, but the coating film may be subjected to a rubbing treatment. Further, the liquid crystal alignment film after the rubbing treatment may be further subjected to a treatment of changing a pretilt angle of a partial region of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays, or forming a resistance on a part of the surface of the liquid crystal alignment film. After the etchant film, the rubbing treatment is performed in a direction different from the rubbing treatment, and then the treatment of the resist film is removed; thereby, the liquid crystal alignment film has different liquid crystal alignment capabilities in each region. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved. Further, the liquid crystal alignment film suitable for the VA liquid crystal display element can also be applied to a polymer sustained alignment (PSA) type liquid crystal display element. The treatment for imparting liquid crystal alignment ability to the coating film may be a treatment using a photo-alignment method instead of the rubbing treatment.

[Step (I-3): Construction of Liquid Crystal Cell]

By preparing two substrates in which the liquid crystal alignment film was formed as described above, liquid crystal cells were formed by disposing liquid crystal between the two substrates arranged in the opposite direction. When manufacturing a liquid crystal cell, an example The following two methods can be cited. 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 sealing material, and are divided by the surface of the substrate and the sealing material. After the filling liquid crystal is injected into the cell gap, the injection hole is sealed, thereby manufacturing a liquid crystal cell. In addition, the second method is a method called a One Drop Fill (ODF) method. Applying, for example, an ultraviolet curable sealing material to a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed, and further adding liquid crystal to a predetermined number of portions on the liquid crystal alignment film surface, The 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, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealing material, thereby manufacturing a liquid crystal cell. In the case of using any of the methods, it is preferred to remove the liquid crystal cell by heating the liquid crystal cell produced in the above manner to a temperature at which the liquid crystal used becomes an isotropic phase, and then slowly cooling to room temperature. The flow alignment at the time.

As the sealing material, for example, an epoxy resin containing a hardener and an alumina ball as a spacer can be used. Further, the liquid crystal may be a nematic liquid crystal or a smectic liquid crystal, and among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal or an oxidized azo (for example) may be used. Azoxy) liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane An alkane liquid crystal, a cubane liquid crystal, or the like. In addition, it is also possible to use the following substances in these liquid crystals: for example, cholesterol liquid crystal such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate (cholesteric) Liquid crystal); a chiral agent sold under the trade names "C-15", "CB-15" (manufactured by Merck); p-methoxybenzylidene-p-amino-2-yl Ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate.

Then, it can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. A liquid crystal display element of the present invention. The polarizing plate which is bonded to the outer surface of the liquid crystal cell is a polarizing plate in which a polarizing film called "H film" is sandwiched by a cellulose acetate protective film, and the "H film" is made to extend polyvinyl alcohol. A film obtained by absorbing iodine to one side; or a polarizing plate containing the H film itself.

[Relativity film]

In the case where the retardation film is produced by using the liquid crystal alignment agent of the present invention, not only dust or static electricity generation can be suppressed in the step, but also a uniform liquid crystal alignment film can be formed, and it can be suitably used by irradiation of radiation. In terms of a light mask and a plurality of regions having different liquid crystal alignment directions are arbitrarily formed on the substrate, it is preferable to use a photoalignment method. Specifically, the production method including the following steps (II-1) to (II-3) can be mentioned.

[Step (II-1): Formation of Coating Film Using Liquid Crystal Aligning Agent]

First, the liquid crystal alignment agent of the present invention is applied onto a substrate to form a coating film. The substrate used herein may be suitably exemplified to include triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polyamine, polyimine, poly A transparent substrate of a synthetic resin such as methyl methacrylate or polycarbonate. Among these substrates, TAC is generally used as a protective layer of a polarizing film in a liquid crystal display element. Further, in terms of low hygroscopicity of the solvent, good optical properties, and low cost, In other words, polymethyl methacrylate can be preferably used as a substrate for a retardation film. Further, in order to make the substrate for coating the liquid crystal alignment agent more excellent in adhesion between the surface of the substrate and the coating film, a conventionally known pretreatment may be performed on the surface on which the coating film is formed on the surface of the substrate.

In most cases, the retardation film is used in combination with a polarizing film. At this time, in order to exhibit desired optical characteristics, it is necessary to precisely control the angle of the polarizing axis with respect to the polarizing film to a specific direction to bond the retardation film. Therefore, by forming a liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle on a substrate such as a TAC film or a polymethyl methacrylate, it is possible to omit the retardation film while controlling the angle thereof. The step on the polarizing film. In addition, it is thereby possible to contribute to improvement in productivity of the liquid crystal display element. In order to form a liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle, it is preferably carried out by a photoalignment method using the liquid crystal alignment agent of the present invention.

The coating of the liquid crystal alignment agent on the substrate can be carried out by a suitable coating method, for example, a roll coater method, a spinner method, a printing method, an inkjet method, a bar coater method, or an extrusion die method. , direct gravure coater method, chamber doctor coater method, offset gravure coater method, single roll kiss coater method, small use Reverse gravure coater method, three reverse roll coater methods, four trans roll coater methods, slot die method, air knife coater method, A positive rotary roll coater method, a blade coater method, a knife coater method, an impregnation coater method, an MB coater method, an MB trans coater method, and the like.

After coating, the coated surface is heated (baked) to form a coating film. The heating temperature at this time is preferably 40 to 150 ° C, and more preferably 80 to 140 ° C. heating The time is preferably set to 0.1 minute to 15 minutes, and more preferably set to 1 minute to 10 minutes. The film thickness of the coating film formed on the substrate is preferably from 1 nm to 1,000 nm, and more preferably from 5 nm to 500 nm.

[Step (II-2): Light irradiation step]

Then, the coating film formed on the substrate in the manner described above is irradiated with light to impart a liquid crystal alignment ability to the coating film. Here, examples of the light to be irradiated include ultraviolet rays, visible rays, and the like which include light having a wavelength of 150 nm to 800 nm. Among these lights, ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. The illumination light may be polarized or non-polarized. The polarized light is preferably a light containing linearly polarized light.

When the light to be used is polarized, the substrate may be irradiated with light from a vertical direction, or light may be irradiated from an oblique direction, or these irradiations may be combined. In the case of irradiating non-polarized light, it is necessary to irradiate the substrate surface from the oblique direction.

Examples of the light source to be used include a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, a mercury-xenon lamp (Hg-Xe lamp), and the like. The polarized light can be obtained by a method in which these light sources are used in combination with, for example, a filter, a diffraction grating, or the like.

The amount of light irradiation is preferably 0.1 mJ/cm ² or more and less than 1,000 mJ/cm ² , more preferably 1 mJ/cm ² to 500 mJ/cm ² , and particularly preferably ² mJ/cm ² to 200 mJ/cm. ² .

[Step (II-3): Formation of liquid crystal layer]

Then, the polymerizable liquid crystal is applied and cured on the coating film which has been irradiated with light in the above manner. Thereby, a coating film (liquid crystal layer) containing a polymerizable liquid crystal is formed. The polymerizable liquid crystal used herein is processed by at least one of heating and light irradiation. A liquid crystal compound or a liquid crystal composition which is polymerized. As the polymerizable liquid crystal, a conventionally known liquid crystal can be used. Specifically, for example, Non-Patent Document 1 ("UV-Curable Liquid Crystals and Their Application", "Liquid Crystal", The nematic liquid crystal described in Volume 3, No. 1 (1999), pages 34 to 42). Further, it may be: cholesteric liquid crystal; disc-shaped liquid crystal; twisted nematic alignment type liquid crystal to which a chiral agent is added. The polymerizable liquid crystal may also be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may also be a composition further containing a known polymerization initiator or a suitable solvent.

When the polymerizable liquid crystal as described above is applied onto the coating film formed using the liquid crystal alignment agent, for example, a suitable coating such as a bar coater method, a roll coater method, a spinner method, a printing method, or an inkjet method can be employed. method.

Then, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more treatments selected from the group consisting of heating and light irradiation, whereby the coating film is cured to form a liquid crystal layer. These processes are superposed and are preferred because a good alignment can be obtained.

The heating temperature of the coating film should be appropriately selected depending on the type of the polymerizable liquid crystal to be used. For example, in the case of using RMS03-013C manufactured by Merck, it is preferred to carry out heating at a temperature ranging from 40 °C to 80 °C. The heating time is preferably from 0.5 minutes to 5 minutes.

As the irradiation light, non-polarized ultraviolet rays having a wavelength in the range of 200 nm to 500 nm can be preferably used. The amount of light irradiation is preferably 50 mJ/cm ² to 10,000 mJ/cm ² , and more preferably 100 mJ/cm ² to 5,000 mJ/cm ² .

The thickness of the formed liquid crystal layer is appropriately set in accordance with desired optical characteristics. For example, in the case of producing a 1/2 wavelength plate of visible light having a wavelength of 540 nm, the phase difference of the formed retardation film is selected to be a thickness of 240 nm to 300 nm, and is 1/4. For the wavelength plate, the phase difference is selected to be 120 nm to 150 nm. The thickness of the liquid crystal layer in which the target phase difference can be obtained varies depending on the optical characteristics of the polymerizable liquid crystal to be used. For example, in the case of using RMS03-013C manufactured by Merck, the thickness for producing a quarter-wave plate is in the range of 0.6 μm to 1.5 μm.

The retardation film obtained in the above manner can be preferably applied as a retardation film of a liquid crystal display element. The liquid crystal display element to which the retardation film produced by using the liquid crystal alignment agent of the present invention is applied is not limited, and can be applied to various known methods such as TN type, STN type, IPS type, FFS type, and VA type. . The retardation film is used by attaching a surface on the substrate side of the retardation film to the outer surface of the polarizing plate disposed on the viewing side of the liquid crystal display element. Therefore, it is preferable that the substrate of the retardation film is made of TAC or an acrylic substrate, and the substrate of the retardation film functions as a protective film of the polarizing film.

The liquid crystal display element of the present invention can be effectively applied to various devices, for example, can be used for: a timepiece, a portable game machine, a word processor, a note type personal computer, a car navigation system, and a photo. Various display devices such as a camcorder, a personal digital assistant (PDA), a digital camera, a mobile phone, a smart phone, various monitors, a liquid crystal television, and an information display.

[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 examples and synthesis examples, the weight average molecular weight Mw of the polymer, the oxime imidization ratio, and the epoxy equivalent, and the solution viscosity of the polymer solution are advantageous. It was measured by the following method.

[weight average molecular weight Mw of polymer]

Mw is a polystyrene-converted value measured by gel permeation chromatography under the following conditions.

Pipe column: manufactured by Tosoh (stock), TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf/cm ²

[Polylination rate of polymer]

The solution containing the polyimine is put into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl hydrazine, using tetramethyl decane as a reference substance at room temperature. measured at ¹ H- nuclear magnetic resonance ^{(1 H-Nuclear magnetic resonance,} 1 H-NMR). From the obtained ¹ H-NMR spectrum, the following formula (1) was used to determine the ruthenium iodide ratio.

醯 imidization rate (%) = (1-A ¹ /A ² ×α)×100...(1)

(In the formula (1), A ¹ is the peak area of the proton derived from the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of other protons relative to the polymer The ratio of the number of protons of the NH group in (polyglycine).)

[epoxy equivalent]

The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

[Solid viscosity of polymer solution]

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

<Synthesis of diamine> [Example 1-1: Synthesis of Compound (DA-1)]

The compound represented by the formula (DA-1) (hereinafter referred to as the compound (DA-1)) was synthesized according to the following Scheme 1.

In a 3 L three-necked flask equipped with a thermometer and a three-way cock, 105.1 g (0.53 mol) of 4-(benzyloxy)phenol, 57.5 g (0.25 mol) of 1,5-dibromopentane, and 138.2 g of potassium carbonate were added. (1.0 mol) and 1250 ml of dimethylformamide (DMF) were mixed. Then, the temperature was raised to 60 ° C, and the reaction was carried out for 6 hours, and then mixed with 2000 ml of ethyl acetate, followed by liquid separation washing with distilled water. Then, the organic layer was concentrated to precipitate a solid. The obtained solid was recrystallized from ethyl acetate and hexane, collected by filtration, and dried, whereby the formula (DA-1-1) was obtained. The compound represented (expressed as compound (DA-1-1)) was 99.6 g (0.21 mol).

Next, 99.6 g (0.21 mol) of the obtained compound (DA-1-1) and 10 g of 5% Pd/C were weighed in a 2 L three-necked flask equipped with a thermometer, a three-way cock, and a dropping funnel. The system was vacuum degassed and replaced with nitrogen. Then, 1000 ml of tetrahydrofuran (THF) was added, and while cooling at a temperature not exceeding 10 ° C, the crucible was slowly added dropwise. Monohydrate 100 ml. Then, the reaction was carried out for 6 hours at room temperature. Further, the solvent used in the reaction was previously subjected to nitrogen substitution. After the reaction, the inorganic salt was removed by filtration, and 1000 ml of ethyl acetate was mixed in the filtrate, followed by liquid separation washing with distilled water. Then, the organic layer was concentrated to precipitate a solid. The obtained solid was recovered and dried to obtain 56.4 g (0.20 mol) of the compound represented by the formula (DA-1-2) (expressed as compound (DA-1-2)).

Next, in a 1 L three-necked flask equipped with a thermometer and a three-way cock, The compound (DA-1-2) obtained was added 56.4 g (0.20 mol), 4-fluoronitrobenzene 56.5 g (0.40 mol), potassium carbonate 108.1 g (0.78 mol), and dimethylformamidine. Amine (DMF) 500 ml was mixed. Then, the temperature was raised to 60 ° C, and the reaction was carried out for 6 hours, and then mixed with 1000 ml of ethyl acetate, followed by liquid separation washing with distilled water. Then, the organic layer was concentrated to precipitate a solid. The obtained solid was recrystallized from ethyl acetate and hexane, and recovered by filtration and dried to obtain a compound represented by the formula (DA-1-3) (expressed as a dinitro intermediate (DA-1) -3)) 74.7g (0.14 m).

Next, 74.7 g (0.14 mol) of the dinitro intermediate (DA-1-3), 7.5 g of 5% Pd/C, 200 mL of ethanol, and 800 mL of tetrahydrofuran were added to a 2 L autoclave under a nitrogen stream. The replacement was repeated with hydrogen, and the reaction was carried out at room temperature in the presence of hydrogen. Perform liquid chromatography to trace the reaction and confirm the progress of the reaction. After filtering. The filtrate was mixed with 3,000 mL of ethyl acetate, and then subjected to liquid separation purification using distilled water. The solvent was removed from the obtained organic layer by distillation under reduced pressure to precipitate a solid. Compound (DA-1) 58.3 g (0.12 mol) was obtained by recrystallizing the precipitated solid in ethanol.

[Example 1-2: Synthesis of Compound (DA-2)]

The compound represented by the formula (DA-2) (hereinafter referred to as the compound (DA-2)) was synthesized according to the following Scheme 2.

Add 3-benzene to a 3L three-necked flask equipped with a thermometer and a three-way cock 99.5 g (0.5 mol) of propyl bromide, 51.8 g (0.55 mol) of phenol, 207.3 g (1.5 mol) of potassium carbonate, and 2000 ml of dimethylformamide (DMF) were mixed. Then, the temperature was raised to 60 ° C, and the reaction was carried out for 6 hours, and then mixed with 2000 ml of ethyl acetate, followed by liquid separation washing with distilled water. Then, the organic layer is concentrated to precipitate the solid Out. The obtained solid was recrystallized in ethanol, recovered by filtration, and dried, whereby the compound represented by the formula (DA-2-1) (expressed as the compound (DA-2-1)) 77.5 g (0.37 Mo) was obtained. ear).

Next, 243.3 g (1.83 mol) of aluminum chloride and 1000 mL of dichloromethane were mixed in a 2 L three-necked flask equipped with a thermometer and a three-way cock, and 4-nitrobenzidine chloride 162.6 g was placed under cooling in an ice bath. (0.88 moles) to dissolve. Then, 400 mL of a dichloromethane solution containing 77.5 g (0.37 mol) of the compound (DA-2-1) was slowly added dropwise. After completion of the dropwise addition, the reaction was carried out for 6 hours while returning to room temperature. After confirming the completion of the reaction by liquid chromatography, the reaction solution was poured into a mixture of 10 equivalents of hydrochloric acid and ice, followed by extraction with chloroform. Then, it washed with sodium bicarbonate aqueous solution, brine, and distilled water, and dried the organic layer by magnesium sulfate. Then, the solvent was removed by distillation under reduced pressure, and the crystals were sufficiently precipitated and then filtered. The filtrate was washed successively with water, ethanol and toluene, and dried under reduced pressure to give the compound (DA-2-2) (yield as compound (DA-2-2)) 95.0 g ( 0.19 moles).

Next, 95.0 g of the compound (DA-2-2) and 500 mL of dichloromethane were added to a 1 L three-necked flask equipped with a thermometer, a dropping funnel, and a three-way cock, and trifluoromethanesulfonic acid was slowly added dropwise under ice-cooling. 120g. Then, 120 g of triethyl decane was slowly added dropwise. After completion of the dropwise addition, the reaction was carried out for 10 hours while returning to room temperature. After confirming the completion of the reaction by liquid chromatography, the reaction solution was neutralized with an aqueous sodium carbonate solution and washed with water. The organic layer is concentrated, and the solid is precipitated and then recrystallized in a toluene solvent to obtain the compound represented by the formula (DA-2-3) (expressed as a dinitro intermediate (DA-2-3)). 71.9g (0.15 m).

Next, the dinitro intermediate was added to a 2 L autoclave under a nitrogen stream. (DA-2-3) 71.9 g (0.15 mol), 7.2 g of 5% Pd/C, 200 mL of ethanol, and 800 mL of tetrahydrofuran were replaced with hydrogen, and the reaction was carried out at room temperature in the presence of hydrogen. The reaction was traced by high performance liquid chromatography (HPLC), and it was confirmed that the reaction was carried out, followed by filtration. The filtrate was mixed with 3,000 mL of ethyl acetate, and then subjected to liquid separation purification with distilled water. The solvent was removed from the obtained organic layer by distillation under reduced pressure to precipitate a solid. Compound (DA-2) 53.3 g (0.13 mol) was obtained by recrystallizing the precipitated solid in ethanol.

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

The compound represented by the formula (DA-3) (hereinafter referred to as the compound (DA-3)) was synthesized according to the following Scheme 3.

In a 3L three-necked flask equipped with a thermometer and a three-way cock, add 4- Hydroxyl-4'-nitrobiphenyl 180.8 g (0.84 mol), 1,3-dibromopropane 80.8 g (0.4 mol), potassium carbonate 221.1 g (1.6 mol) and dimethylformamide (DMF) ) 2000ml, mixed. Then, the temperature was raised to 60 ° C, and the reaction was carried out for 6 hours, and then mixed with 4000 ml of ethyl acetate, followed by liquid separation washing with distilled water. Then, the organic layer was concentrated to precipitate a solid. The resulting solid is recrystallized in ethanol. It was collected by filtration and dried to obtain 103.5 g (0.22 mol) of the compound represented by the formula (DA-3-1) (expressed as dinitro intermediate (DA-3-1)).

Next, 10 mL of the dinitro intermediate (DA-3-1) (0.22 mol), 10.3 g of 5% Pd/C, 100 mL of ethanol, and 500 mL of tetrahydrofuran were added to a 2 L autoclave under a nitrogen stream. The replacement was repeated with hydrogen, and the reaction was carried out at room temperature in the presence of hydrogen. The reaction was traced by HPLC, and it was confirmed that the reaction was carried out, followed by filtration. The filtrate was mixed with 1000 mL of ethyl acetate, and then subjected to liquid separation purification with distilled water. The solvent was removed from the obtained organic layer by distillation under reduced pressure to precipitate a solid. The compound (DA-3) 151.7 g (0.37 mol) was obtained by recrystallizing the precipitated solid in ethanol.

[Example 1-4: Synthesis of Compound (DA-4)]

The compound represented by the formula (DA-4) (hereinafter referred to as the compound (DA-4)) was synthesized according to the following Scheme 4.

1L three-necked flask with thermometer, three-way cock and dropping funnel Among the compounds (DA-1-2) obtained in the same manner as in the above Example 1-1, 43.4 g (0.15 mol), triethylamine (TEA) 60.7 g (0.6 mol), and 300 ml. The THF was mixed, and a solution of 69.6 g (0.38 mol) of 4-nitrobenzimid chloride in 400 ml of THF was slowly added dropwise under ice-cooling. After the dropwise addition, the reaction was carried out for 12 hours at room temperature, and then mixed with 1000 ml of ethyl acetate, followed by liquid separation washing with distilled water. Then, the organic layer was concentrated to precipitate a solid. The obtained solid was recrystallized from ethyl acetate and hexane, and recovered by filtration and dried to obtain a compound represented by the formula (DA-4-1) (expressed as a dinitro intermediate (DA-4) -1)) 39.6g (0.07 mol).

Then, 39.6 g (0.07 mol) of the dinitro intermediate (DA-4-1), 4 g of 5% Pd/C, 100 mL of ethanol, and 250 mL of tetrahydrofuran were added to a 2 L autoclave under a nitrogen stream to obtain The hydrogen gas was replaced again, and the reaction was carried out at room temperature in the presence of hydrogen. The reaction was traced by HPLC, and it was confirmed that the reaction was carried out, followed by filtration. The solvent was removed from the organic layer by distillation under reduced pressure to precipitate a solid. Compound (DA-4) 27.4 g (0.05 mol) was obtained by recrystallizing the precipitated solid in ethanol.

<Synthesis of Polymer> [Example 2-1: Synthesis of polymer (PA-1)]

10.7 g of pyromellitic dianhydride as a tetracarboxylic dianhydride (93 moles relative to 100 moles of the total amount of the diamine used in the synthesis), and a compound (DA-1) as a diamine 12.41 g (50 moles relative to 100 moles of total diamine used in the synthesis), 4-aminophenyl-4'-aminobenzoate 4.82 g (relative to synthesis) The total amount of diamine used is 100 moles to 40 moles) and 4,4'-[4,4'-propane-1,3-diylbis(acridine-1,4-diyl) Diphenylamine 2.07g (as opposed to The total amount of the diamine used in the synthesis is 100 moles to 10 moles, dissolved in N-methyl-2-pyrrolidone (NMP) 85g and γ-butyrolactone ( In a mixed solvent of γ-butyllactone, GBL) and 85 g, the reaction was carried out at 30 ° C for 6 hours. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. The precipitate thus collected was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain 28.2 g of polylysine (hereinafter referred to as polymer (PA-1)). The obtained polymer (PA-1) was prepared in a solvent composition of NMP:GBL=50:50 to prepare 15% by weight, and the viscosity of the solution was measured and found to be 550 mPa. s. Further, the polymer solution was allowed to stand at 20 ° C for 3 days, and as a result, gelation did not occur, and storage stability was good.

[Example 2-2 to Example 2-5, Example 2-7, Synthesis Example 1, Synthesis Example 2]

In the same manner as in Example 2-1, the polymerization was carried out in the same manner as in Example 2-1 except that the type and amount of the tetracarboxylic dianhydride and the diamine used in the reaction were changed as described in Table 1 below. Things. Further, regarding the tetracarboxylic dianhydride, the numerical values in Table 1 indicate the use ratio (mol%) with respect to the total amount of the tetracarboxylic dianhydride used in the reaction, and regarding the diamine, the numerical values in Table 1 are relative to The ratio of use of the total amount of diamine used in the reaction (% by mole). After the polymer solution obtained in the examples was allowed to stand at 20 ° C for 3 days, gelation did not occur, and the storage stability was good.

The abbreviations of the tetracarboxylic dianhydride and the diamine in Table 1 are as follows.

(tetracarboxylic dianhydride)

AN-1:1,2,3,4-cyclobutane tetracarboxylic dianhydride

AN-2: pyromellitic dianhydride

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

AN-4: ethylenediaminetetraacetic acid dianhydride

AN-5: 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2 -c]furan-1,3-diketone

(diamine)

Da-1: a compound represented by the following formula (da-1)

Da-2: 4-aminophenyl-4'-aminobenzoate

Da-3: 4,4'-diaminodiphenylmethane

Da-4:4,4'-[4,4'-propane-1,3-diylbis(acridine-1,4-diyl)]diphenylamine

Da-5: 2,4-diamino-N,N-diallylaniline

Da-6:4,4'-diaminodiphenylamine

Da-7:3,5-diaminobenzoic acid

Da-8: cholesteryl 3,5-diaminobenzoate

Da-9: 4-(tetradecyloxy)benzene-1,3-diamine

Da-10: the compound represented by the formula (DA-15)

Da-11: 1,4-bis-(5-amino-pyridin-2-yl)-pyridazine

[Example 2-6: Synthesis of Polymer (PI-1)]

16.58 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride (98 mol parts relative to 100 mol parts of the total amount of diamine used in the synthesis), and as The diamine compound (DA-2) 25.52 g (80 mol parts relative to 100 mols of the total amount of the diamine used in the synthesis) and the 3,5-diaminobenzoic acid cholesteryl 7.89 g (20 mol parts based on 100 mols of the total amount of the diamine used in the synthesis), dissolved in 200 g of NMP, and reacted at room temperature for 6 hours. Then, 250 g of NMP was added, and 11.7 g of pyridine and 15.11 g of acetic anhydride were added, and a dehydration ring-closure reaction was carried out at 80 ° C for 5 hours. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. After the recovered precipitate was washed with methanol, it was dried at 40 ° C for 15 hours under reduced pressure, thereby obtaining a quinone imine. A polyimine (about polymer (PI-1)) having a rate of about 65%. The obtained polymer (PI-1) was prepared to 15% by weight using NMP. The viscosity of the solution was measured and found to be 890 mPa. s.

[Synthesis Example 3: Synthesis of polyorganosiloxane]

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 500 g of methyl isobutyl ketone, and three to three were charged. 10.0 g of the amine was mixed at room temperature. Thereto, 100 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and then the reaction was carried out at 80 ° C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure, thereby being in the form of a viscous transparent liquid. A polyorganosiloxane having an oxirane group is obtained. ¹ H-NMR analysis of the polyorganosiloxane having an oxiranyl group revealed that a peak based on the oxirane group was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm as determined by the theoretical strength. A side reaction of the oxirane group was not produced. The epoxy equivalent of the polyorganosiloxane having an oxiranyl group was measured and found to be 186 g/eq.

Then, 9.3 g of the obtained polyorganosiloxane having an oxirane group, 26 g of methyl isobutyl ketone, 3 g of 4-phenoxycinnamic acid, and UCAT 18X were placed in a 100 mL three-necked flask. 0.10 g, manufactured by San-Apro Co., Ltd., and reacted at 80 ° C for 12 hours while stirring. After completion of the reaction, the reaction mixture was poured into methanol, and the resulting precipitate was collected, and the precipitate was dissolved in ethyl acetate to prepare a solution. After washing the solution three times, the solvent was distilled off, thereby In the form of a white powder, 6.3 g of polyorganosiloxane (S-1) having an oxiranyl group and a cinnamic acid structure was obtained. For the polyorganosiloxane (S-1), The polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography was 3,500.

<Preparation and evaluation of liquid crystal alignment agent> [Example 3-1: FFS type liquid crystal display element] (1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PA-1) obtained in Example 2-1 as a polymer was dissolved in a mixed solvent containing γ-butyrolactone (GBL), NMP, and butyl cellosolve (BC) (GBL: NMP) : BC = 40: 40: 20 (weight ratio)), a solution having a solid concentration of 3.5% by weight was prepared. This solution was filtered using a screening procedure having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent.

(2) Evaluation of coating properties

The prepared liquid crystal alignment agent was applied onto a glass substrate by a spinner, prebaked on a hot plate at 80 ° C for 1 minute, and then heated in a 200 ° C oven in which the inside of the chamber was purged with nitrogen for 1 hour. (post-baking), thereby forming a coating film having an average film thickness of 1,000 Å. The coating film was observed with a microscope having a magnification of 100 times, and the film thickness unevenness and the presence or absence of pinholes were ascertained. The evaluation was carried out in such a manner that the film thickness unevenness and the pinhole were not observed, and the coating property was evaluated as "good", and at least one of the film thickness unevenness and the pinhole was observed. The evaluation was "poor" in coating properties. In the present embodiment, both the film thickness unevenness and the pinhole were not observed, and the coatability was "good".

(3) Evaluation of friction resistance

With respect to the obtained coating film, the rubbing treatment was performed 7 times using a friction machine having a roller wound with a cotton cloth at a roll rotation speed of 1000 rpm, a table moving speed of 20 cm/sec, and a hair press-in length of 0.4 mm. Using an optical microscope to observe the resulting substrate The foreign matter (the fragments of the coating film) caused by the rubbing was removed, and the number of foreign matter in the region of 500 μm × 500 μm was calculated. The evaluation was performed in such a manner that the number of foreign matter was three or less, and the abrasion resistance was "good", and four or more and seven or less cases were evaluated as "may", and eight or more cases were evaluated as resistant. Frictional "bad". As a result, the abrasion resistance of the coating film was "good".

(4) Manufacture of FFS type liquid crystal display elements

The FFS type liquid crystal display element shown in Fig. 1 was produced. First, a pair of glass substrates 11a having two electrode pairs on one side and a pair of opposite glass substrates 11b not provided with electrodes are formed as a pair, and the electrode pairs of the two systems are sequentially formed with a bottom electrode 15 having no pattern as The tantalum nitride film of the insulating layer 14 and the top electrode 13 patterned into a comb-tooth shape are coated on the surface of the glass substrate 11a having the transparent electrode and the surface facing the glass substrate 11b by using a rotator. The liquid crystal alignment agent prepared in the above (1) forms a coating film. Then, the coating film was prebaked on a hot plate at 80 ° C for 1 minute, and then heated in an oven which was purged with nitrogen in the chamber at 230 ° C for 15 minutes (post-baking) to form an average film thickness of 1,000 Å coating. A schematic plan view of the top electrode 13 is shown in FIG. 2(a) is a plan view of the top electrode 13, and FIG. 2(b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2(a). In the present embodiment, the line width d1 of the electrode was set to 4 μm, and the distance d2 between the electrodes was set to 6 μm.

Then, each surface of the coating film formed on the glass substrate was subjected to a rubbing treatment using cotton to form a liquid crystal alignment film 12. In Fig. 2(b), the direction in which the coating film formed on the glass substrate 11a is rubbed is indicated by an arrow. These substrates were bonded to each other with a spacer having a diameter of 3.5 μm so that the rubbing directions of the substrate 11a and the substrate 11b were anti-parallel, and the liquid crystal MLC-6221 (manufactured by Merck) was injected. The liquid crystal layer 16 is formed. Further, on the outer surfaces of the substrate 11a and the substrate 11b, a polarizing plate (not shown) is attached so that the polarization directions of the two polarizing plates are orthogonal to each other, whereby the liquid crystal display element 10 is produced.

(5) Evaluation of liquid crystal alignment

For the manufactured FFS type liquid crystal display element, use a microscope to observe when the magnification is 50 times. Turns off (ON.OFF) (applies.releases) the presence or absence of an abnormal area in the change in brightness and darkness at a voltage of 5V. The evaluation was performed by evaluating the case where the abnormal region was not observed as the liquid crystal alignment property "good", and the case where the abnormal region was observed as the liquid crystal alignment property "bad". The liquid crystal alignment property in the liquid crystal display element is "good".

(6) Evaluation of voltage retention rate

With respect to the manufactured FFS-type liquid crystal display device, a voltage of 5 V was applied at 23 ° C for an application time of 60 μsec and a span of 167 msec, and then the voltage holding ratio (VHR) after 167 msec from the application release was measured. The result was 99.2%. Further, VHR-1 manufactured by Toyo Technica Co., Ltd. was used as a measuring device.

(7) Evaluation of heat resistance

With respect to the manufactured FFS type liquid crystal display device, the voltage holding ratio was measured in the same manner as in the above (6), and the value was defined as the initial VHR (VHR _BF ). Then, the liquid crystal display element after the initial VHR measurement was allowed to stand in an oven at 100 ° C for 300 hours. Then, the liquid crystal display element was allowed to stand at room temperature and left to cool to room temperature, and then the voltage holding ratio (VHR _AF ) was measured in the same manner as described above. Moreover, the rate of change of the voltage holding ratio (ΔVHR (%)) before and after the application of the thermal stress is obtained by the following mathematical expression (2).

△VHR=((VHR _BF -VHR _AF )÷VHR _BF )×100...(2)

The evaluation of the heat resistance was carried out by evaluating the case where the rate of change ΔVHR was less than 4% as "good", and the case of 4% or more and less than 5% as "may", and the case of 5% or more. It was evaluated as "poor" in heat resistance. As a result, the liquid crystal display element of the present example had a ΔVHR of 1.9% and a heat resistance of "good".

(8) Pretilt characteristics

With respect to the manufactured liquid crystal display element, the angle at which the liquid crystal molecules were inclined from the substrate surface was measured by a crystal rotation method using He-Ne laser light, and this value was defined as a pretilt angle θ. The crystal rotation method is based on Non-Patent Document 1 (TJ Scheffer et al., Journal of Applied Physics, J. Appl. Phys., Vol. 48, p. 1783 (1977)) and Non-Patent Document 2 (F. Nakano et al., Japanese Journal of Applied Physics, JPN. J. Appl. Phys., Vol. 19, p. 2013 (1980)) The method described is carried out.

The evaluation was performed in such a manner that the pretilt angle θ was less than 1.0°, and the pretilt angle evaluation was “good”, and the case of 1.0° or more was evaluated as the pretilt angle evaluation “bad”, and as a result, the pretilt angle of the liquid crystal display element was changed. The rate was 0.3°, and it was judged that the pretilt stability was "good".

(9) Contrast evaluation after driving stress (evaluation of residual current characteristics of alternating current (AC))

An FFS type liquid crystal cell was produced in the same manner as in the above (4) except that the polarizing plate was not bonded to both sides of the substrate. For the FFS type liquid crystal cell, after being driven at an alternating voltage of 10 V for 30 hours, it is used between the light source and the light amount detector. A device equipped with a polarizer and an analyzer is used to measure the minimum relative transmittance (%) expressed by the following mathematical expression (3).

Minimum relative transmittance (%) = (β - B ⁰ ) / (B ¹⁰⁰ - B ⁰ ) × 100 (3)

(In Mathematical Formula (3), B ⁰ is the amount of light transmitted in a blank state and under a crossed Nicols; B ¹⁰⁰ is the amount of light transmitted in a blank state and under a parallel Nicol prism ? is the minimum amount of light transmitted by sandwiching the liquid crystal display element between the polarizer and the analyzer under a crossed Nicol prism.)

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element. In the FFS type liquid crystal display element, the smaller the black level in the dark state, the more excellent the contrast. The case where the minimum relative transmittance was less than 0.5% was evaluated as "good", the case where 0.5% or more and less than 1.0% was evaluated as "OK", and the case where 1.0% or more was evaluated as "poor". As a result, the minimum relative transmittance of the liquid crystal cell was 0.2%, and it was judged as "good".

[Example 3-2 to Example 3-5 and Comparative Example 1 and Comparative Example 2]

In the above Example 3-1, a liquid crystal alignment agent was prepared in the same manner as in Example 3-1 except that the components of the type shown in Table 2 below were used as the polymer, respectively, and an FFS type liquid crystal display element was produced. To carry out various evaluations. The evaluation results are shown in Table 2 below.

As shown in Table 2, in Examples 3-1 to 3-5, regarding liquid crystal alignment Both the coatability of the agent and the abrasion resistance of the coating film gave good results. Further, the alignment properties, voltage holding ratio, heat resistance, pretilt characteristics, and AC afterimage characteristics of the liquid crystal molecules in the liquid crystal display element are also good results. On the other hand, in Comparative Example 1, the coating property of the liquid crystal alignment agent was "poor", and the abrasion resistance of the coating film was inferior to that of the examples. Further, in the liquid crystal display device of Comparative Example 1, the voltage holding ratio, the pretilt angle characteristics, and the AC afterimage characteristics were inferior to those of the examples. In Comparative Example 2, a polymer obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride with the compound (DA-1) was used, but the voltage holding ratio was low, and the heat resistance of the liquid crystal cell was used. Sex is "bad".

[Example 3-6: TN type liquid crystal display element] (1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PA-7) obtained as the polymer in Example 2-5 was dissolved in a mixed solvent of NMP and BC (NMP: BC = 50:50 (weight ratio)) to prepare a solid. A solution having a component concentration of 6.5% by weight. After the solution was thoroughly stirred, it was filtered using a screening procedure having a pore size of 0.2 μm to prepare a liquid crystal alignment agent.

(2) Evaluation of printability

The liquid crystal alignment agent prepared in the above (1) was applied onto a transparent electrode surface of a glass substrate having a transparent electrode including an ITO film at a temperature of 80 ° C using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). The hot plate was preheated (prebaked) for 1 minute to remove the solvent, and then heated (post-baked) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å. The coating film was observed with a microscope having a magnification of 20 times to find uneven printing and the presence or absence of pinholes. The evaluation is as follows In the formula, it was evaluated that the printing unevenness and the pinhole were not observed as "good", and that a small amount of printing unevenness and at least one of the pinholes were evaluated as printability. "Yes", it was found that a large amount of printing unevenness and at least one of the pinholes were evaluated as "defective" in printability. In the present embodiment, neither printing unevenness nor pinholes were observed, and the printability was "good".

(3) Manufacture of TN type liquid crystal cell

The liquid crystal alignment agent prepared in the above (1) was applied onto a transparent electrode surface of a glass substrate having a transparent electrode including an ITO film at a temperature of 80 ° C using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). The hot plate was preheated (prebaked) for 1 minute to remove the solvent, and then heated (post-baked) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å. This coating film was subjected to a rubbing treatment using a rubbing machine having a roll of rayon cloth wound thereon at a roll rotation speed of 500 rpm, a table moving speed of 3 cm/sec, and a hair press-in length of 0.4 mm to impart 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 above operation was repeated to obtain a pair of (two pieces) substrates having a liquid crystal alignment film.

Next, 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. The method is to laminate a pair of substrates and crimp them to harden the adhesive. Then, a nematic liquid crystal (manufactured by Merck & Co., MLC-6221) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed by an acrylic photocurable adhesive, thereby manufacturing a TN type liquid crystal cell. .

(4) Evaluation of liquid crystal alignment

For the TN type liquid crystal cell manufactured in the above (3), in a crossed Nicol prism Under the microscope, use a magnification of 50 times to observe when turned on. The presence or absence of an abnormal area when the 5V voltage is disconnected. The evaluation was carried out in the same manner as (5) of the above Example 3-1. As a result, the liquid crystal alignment in the liquid crystal cell is "good".

(5) Evaluation of pretilt stability

With respect to the TN type liquid crystal cell manufactured in the above (3), the angle at which the liquid crystal molecules are inclined from the substrate surface is measured by a crystal rotation method using He-Ne laser light, and this value is taken as the initial pretilt angle θ _IN . The crystal rotation method is based on Non-Patent Document 1 (TJ Scheffer et al., Journal of Applied Physics, J. Appl. Phys., Vol. 48, p. 1783 (1977)) and Patent Document 2 (F. Nakano et al., Japanese Journal of Applied Physics, JPN. J. Appl. Phys., Vol. 19, p. 2013 (1980)) The way to proceed.

Then, an AC voltage of 5 V was applied to the liquid crystal cell after the initial pretilt angle θ _IN was measured for 100 hours. Then, the pretilt angle was measured again in the same manner as described above, and this value was taken as the pretilt angle θ _AF after voltage application. These measured values were substituted into the following formula (4), and the amount of change in the pretilt angle (Δθ (°)) before and after the voltage application was obtained.

Δθ=| θ _AF -θ _IN |...(4)

The case where Δθ is less than 3% is evaluated as “good” for pretilt stability, the case where 3% or more and less than 4% is evaluated as “pretilt stability”, and the case where 4% or more is evaluated as pretilt stability. "Poor", as a result, the pretilt angle change rate of the liquid crystal cell was 2.8%, and it was judged that the pretilt angle stability was "good".

(6) Evaluation of voltage retention rate and heat resistance

The voltage holding ratio (VHR _BF ) was measured in the same manner as (6) of the above-described Example 3-1, and the voltage before and after the heat stress was given in the same manner as (7) of the embodiment 3-1. The heat resistance of the liquid crystal display element was evaluated by the rate of change of the retention ratio. As a result, the VHR _BF was 98.9%. Further, ΔVHR was 2.9%, and it was judged that the heat resistance was "good".

[Example 3-7: VA type liquid crystal display element] (1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PI-1) obtained in Example 2-6 as a polymer was added to NMP and BC to prepare a solid concentration of 6.5% by weight, and the solvent mixture ratio was NMP:BC= 50:50 (by weight) solution. After the solution was thoroughly stirred, it was filtered using a screening procedure having a pore size of 0.2 μm to prepare a liquid crystal alignment agent.

(2) Evaluation of printability

Using the liquid crystal alignment agent prepared in the above (1), the printability was ascertained in the same manner as in the above (2) of Example 3-5, and as a result, uneven printing and pinholes were not observed. The printability is "good".

(3) Manufacture of VA type liquid crystal cell

The prepared liquid crystal alignment agent was applied onto a transparent electrode surface of a glass substrate (thickness: 1 mm) having a transparent electrode containing an ITO film using a liquid crystal alignment film printer (manufactured by Nippon Photographic Co., Ltd.) at 80 The plate was heated (prebaked) for 1 minute on a hot plate of ° C, and further heated (post-baked) on a hot plate at 200 ° C for 60 minutes to form a coating film (liquid crystal alignment film) having an average film thickness of 800 Å. This operation was repeated to obtain a pair of (two pieces) glass substrates having a liquid crystal alignment film on the transparent conductive film. Next, one of the pair of substrates is on the outer edge of the surface having the liquid crystal alignment film After coating an epoxy resin adhesive to which alumina balls having a diameter of 5.5 μm were applied, a pair of substrates were superposed and pressure-bonded so that the liquid crystal alignment film faces were opposed to each other to harden the adhesive. Then, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) 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 VA liquid crystal cell.

(4) Evaluation of liquid crystal alignment, voltage retention and heat resistance

In the VA liquid crystal cell produced in the above (3), the liquid crystal alignment property was evaluated in the same manner as in (5) of Example 3-1, and as a result, the liquid crystal alignment property of the liquid crystal cell was "good". Further, the voltage holding ratio (VHR _BF ) was measured in the same manner as (6) of Example 3-1, and heat resistance was performed in the same manner as (7) of Example 3-1 (before and after thermal stress imparting) Evaluation of the rate of change of the voltage holding rate). As a result, the VHR _BF was 99.2%. Further, ΔVHR was 2.4%, and it was judged that the heat resistance was "good".

[Example 3-8: retardation film] (1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PA-2) obtained in Example 2-2 and 5 parts by weight of the polyorganosiloxane (S-1) obtained in Synthesis Example 3 were dissolved in a mixed solvent containing NMP and BC. (NMP: BC = 50:50 (weight ratio)), a solution having a solid concentration of 3.5% by weight was prepared. This solution was filtered using a screening procedure having a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent.

(2) Fabrication of retardation film

The prepared liquid crystal alignment agent was applied to one surface of the TAC film as a substrate by using a bar coater, and baked at 120 ° C for 2 minutes in an oven to form a coating film having a film thickness of 100 nm. Subsequently, the coating film surface, using Hg-Xe lamp and a Glan-Taylor prism, since ultraviolet radiation polarized perpendicular to the normal to the substrate comprising an open wire 313nm 10mJ / cm ^2. Then, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck) was filtered using a screening program having a pore size of 0.2 μm, and then the polymerizable liquid crystal was applied onto the coating film after light irradiation by a bar coater. A coating film of a polymerizable liquid crystal is formed. After baking for 1 minute in an oven adjusted to a temperature of 50 ° C, a non-polarized ultraviolet ray of 1,000 mJ/cm ² containing an open line of 365 nm was irradiated from the vertical direction using a Hg-Xe lamp to make polymerizability. The liquid crystal is hardened to form a liquid crystal layer, thereby producing a retardation film.

(3) Evaluation of liquid crystal alignment

In the retardation film produced in the above (2), the liquid crystal alignment property was evaluated by observing the presence or absence of an abnormal region by visual observation under a crossed Nicols and a polarizing microscope (magnification: 2.5 times). The evaluation was carried out in such a manner that the alignment was good under visual observation, and the case where no abnormal region was observed under a polarizing microscope was evaluated as "good" liquid crystal alignment; no abnormal region was observed under visual observation, but in a polarizing microscope The case where the abnormal region was observed was evaluated as "liquid crystal alignment", and the case where the abnormal region was observed under both the visual observation and the polarizing microscope was evaluated as "liquid crystal alignment" "defect". As a result, the retardation film was evaluated as "good" in liquid crystal alignment.

(4) Adhesion

The adhesion between the coating film formed of the liquid crystal alignment agent and the substrate was evaluated using the retardation film produced in the above (2). First, a spacer having an interval of a guide was used, and a slit was cut from the surface on the liquid crystal layer side of the retardation film by a dicing blade, and 10 × 10 lattice patterns were formed in a range of 1 cm × 1 cm. The depth of each slit is from the midpoint of the thickness of the liquid crystal layer to the thickness of the substrate. Then, the cellophane tape is adhered so as to cover the entire surface of the lattice pattern, and then the cellophane tape is peeled off. The notch portion of the lattice pattern after peeling was observed by visual observation under crossed Nicols, and the adhesion was evaluated. The evaluation was performed in such a manner that the peeling was not confirmed in the case where the portion along the incision line and the intersection of the lattice pattern was not observed, and the adhesion was "good"; the number of the entire lattice pattern was observed in the portion. When the number of the peeled lattices is less than 15%, the adhesion is "corresponding"; and the number of the lattices observed in the portion is 15% or more in the case where the number of the lattice patterns is 15% or more. Sexual "bad". As a result, the retardation film was "good" in adhesion.

Claims (13)

A liquid crystal alignment agent comprising at least one polymer (P) selected from the group consisting of polylysine, polyphthalate, and polyamidiamine, the polymer (P) being And at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester compound, and tetracarboxylic acid diester dihalide, and represented by the following formula (1) Obtained by reacting a diamine of the compound, In the formula (1), R ^A is a divalent group having an oxygen atom or a sulfur atom between at least one of a carbon-carbon bond of a hydrocarbon group having 1 to 30 carbon atoms and a position adjacent to the hydrocarbon group. At least one of the hydrogen atoms of the hydrocarbon group may be substituted by a halogen atom; X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom or a divalent organic group; wherein, X ¹ and X ² are In the case of an oxygen atom and R ^A is -OR ¹ -O- (R ¹ is an alkanediyl group having 1 to 18 carbon atoms), the tetracarboxylic acid derivative is 1,2,3,4-cyclobutane Except in the case of tetracarboxylic dianhydride. The liquid crystal alignment agent according to claim 1, wherein the diamine further comprises an aromatic diamine. The liquid crystal alignment agent according to the first aspect of the invention, wherein the diamine represented by the formula (1) is a diamine represented by the following formula (1-1). In the formula (1-1), R ² is a divalent hydrocarbon group having 1 to 30 carbon atoms, and X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom or a divalent organic group, and X ³ is an oxygen atom or a sulfur atom, X ⁴ is a single bond, an oxygen atom or a sulfur atom; wherein, when X ¹ , X ² , X ³ and X ⁴ are oxygen atoms, and R ² is an alkanediyl group having 1 to 18 carbon atoms, The case where the tetracarboxylic acid derivative is 1,2,3,4-cyclobutanetetracarboxylic dianhydride is excluded. The liquid crystal alignment agent according to claim 3, wherein the R ² is an alkanediyl group having 1 to 11 carbon atoms. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein X ¹ and X ² are each independently an oxygen atom, an alkanediyl group having 1 to 10 carbon atoms, An alkenediyl group, an ester group or a decylamino group having 2 to 10 carbon atoms. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the tetracarboxylic acid derivative comprises at least one selected from the group consisting of the following compounds, that is, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-( Tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro- 8-Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[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-dioxotetrahydro-3-furan 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4 , 9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraketone, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylate Acid dianhydride, ethylenediaminetetraacetic acid dianhydride, and pyromellitic dianhydride. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein the polymer (P) comprises a side chain structure having a pretilt performance ability. A liquid crystal alignment film characterized in that it is used as the first patent application scope The liquid crystal alignment agent according to any one of item 7, wherein the liquid crystal alignment agent is formed. A liquid crystal display element comprising the liquid crystal alignment film according to item 8 of the patent application. A retardation film comprising the liquid crystal alignment film according to item 8 of the patent application. A method for producing a retardation film, comprising the steps of: applying a liquid crystal alignment agent according to any one of claims 1 to 7 to a substrate to form a coating film; The film is irradiated with light; and the polymerizable liquid crystal is coated on the coating film after the light irradiation and hardened. A polymer characterized by comprising at least one tetracarboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester compound, and tetracarboxylic acid diester dihalide The diamine of the compound represented by the formula (1) is obtained by reacting, In the formula (1), R ^A is a divalent group having an oxygen atom or a sulfur atom between at least one of a carbon-carbon bond of a hydrocarbon group having 1 to 30 carbon atoms and a position adjacent to the hydrocarbon group. At least one of the hydrogen atoms of the hydrocarbon group may be substituted by a halogen atom; X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom or a divalent organic group; wherein, X ¹ and X ² are In the case of an oxygen atom and R ^A is -OR ¹ -O- (R ¹ is an alkanediyl group having 1 to 18 carbon atoms), the tetracarboxylic acid derivative is 1,2,3,4-cyclobutane Except in the case of tetracarboxylic dianhydride. A compound represented by the following formula (1), which is characterized by: In the formula (1), R ^A is a divalent group having an oxygen atom or a sulfur atom between at least one of a carbon-carbon bond of a hydrocarbon group having 1 to 30 carbon atoms and a position adjacent to the hydrocarbon group. At least one of the hydrogen atoms of the hydrocarbon group may be substituted by a halogen atom; X ¹ and X ² are each independently a single bond, an oxygen atom, a sulfur atom or a divalent organic group; wherein, X ¹ and X ² are The oxygen atom and R ^A are -OR ¹ -O- (wherein R ¹ is an alkanediyl group having 1 to 18 carbon atoms).