KR20140125291A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, phase difference film, manufacturing method for the phase difference film, polymer and compound - Google Patents

Abstract

Provided is a liquid crystal aligning agent capable of obtaining a liquid crystal display device with improved various characteristics such as a voltage holding ratio or the like. To achieve this, a polymer (P) having a structure represented by the following formula (1) as a polymer component is contained in the liquid crystal aligning agent, wherein in formula (1), R1 is a hydrogen atom or a monovalent hydrocarbon group of 1-30 carbon atoms, X^1 and X^2 are each independently a divalent organic group, and two ″*″ represents a bonding hand bonded to mutually different groups.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal display device, a retardation film, a production method of a retardation film, a polymer and a compound , POLYMER AND COMPOUND}

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

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

As a liquid crystal display element, various properties such as a voltage holding ratio, a burn-in (after-image characteristic), heat resistance and the like are required to be good, and various liquid crystal aligning agents for obtaining a liquid crystal display element of high quality have been proposed See Patent Documents 1 and 2). Among them, Patent Document 1 discloses that a polyamic acid obtained by reacting a diamine having an aromatic ester structure with a tetracarboxylic acid derivative such as di (4-aminophenyl) hexane-1,6-dioate or the like as a polymer component of a liquid crystal aligning agent . Patent Document 2 discloses a polyamic acid or the like obtained by reacting a tetracarboxylic acid derivative with a diamine in which two aromatic rings are linked by an alkylene spacer structure such as 1,3-bis (4-amino-2-methylphenyl) As a polymer component of a liquid crystal aligning agent.

Various optical materials are used for the liquid crystal display element. Among them, the retardation film is used for the purpose of solving the coloring of the display, or for solving the viewing angle dependency that the display color and the contrast ratio change depending on the viewing direction . It is known that such a retardation film has a liquid crystal alignment film formed on the surface of a substrate such as a TAC film and a liquid crystal layer formed by curing the polymerizable liquid crystal on the surface of the liquid crystal alignment film. Recently, in the production of a liquid crystal alignment film in a retardation film, a photo alignment method of imparting liquid crystal alignment capability to a thin film by irradiating polarized or non-polarized radiation to the radiation-sensitive organic thin film formed on the substrate surface . In addition, various liquid crystal aligning agents for a retardation film for producing a liquid crystal alignment film by the photo alignment method have been proposed (for example, see Patent Document 3).

As a method for producing a phase difference film on an industrial scale, a roll-to-roll method has been proposed (see, for example, Patent Document 4). This method involves a process in which a film is drawn from a roll of a substrate film having a long shape and a liquid crystal alignment film is formed on the wound film, a process in which a polymerizable liquid crystal is applied on the liquid crystal alignment film Curing treatment and, if necessary, laminating the protective film are performed in successive steps, and the film after each step is recovered as a rolled film.

Japanese Patent Publication No. 4171543 Japanese Patent Publication No. 4779339 Japanese Laid-Open Patent Publication No. 2012-37868 Japanese Patent Application Laid-Open No. 2000-86786

2. Description of the Related Art In recent years, liquid crystal display devices have been used in various types of applications such as liquid crystal televisions, car navigation systems, mobile phones, smart phones, and information displays, as well as conventionally used display terminals for personal computers and the like. In addition, the demand for higher performance of the liquid crystal display device is further increased, and as the liquid crystal alignment film, it is required that various characteristics of the liquid crystal display device can be improved.

In addition, the retardation film can be easily produced on an industrial scale by employing the above-described roll-to-roll system. On the other hand, if the adhesion between the liquid crystal alignment film and the base film is insufficient, The orientation film sometimes peels off from the substrate film. In this case, the product yield is lowered.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal display element having various characteristics such as a voltage holding ratio and the like. Another object of the present invention is to provide a liquid crystal aligning agent capable of forming a liquid crystal alignment film for a phase difference film having good liquid crystal alignability and good adhesion to a substrate.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to achieve the above-described problems of the prior art. As a result, they found that the above problems can be solved by including a polymer having a specific structure as a polymer component in a liquid crystal aligning agent. It came to the following. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, production method of the retardation film, polymer and compound.

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

(In the formula (1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, X ¹ and X ² are each independently a divalent organic group; the two "*"Quot;)"

According to another aspect of the present invention, there is provided a liquid crystal alignment film formed using the liquid crystal aligning agent. Also provided is a liquid crystal display element comprising the liquid crystal alignment film and a retardation film comprising the liquid crystal alignment film. According to another aspect of the present invention, there is provided a method of manufacturing a liquid crystal display device, comprising the steps of: applying the liquid crystal aligning agent to a substrate to form a coated film; irradiating the coated film with light; The present invention also provides a method for producing a retardation film including the steps of:

In another aspect, the present invention provides a compound represented by the following formula (b-1). Further, there is provided a polymer obtained by reacting at least one compound selected from the group consisting of tetracarboxylic acid dianhydride and carbonic acid halide and an amine compound including a compound represented by the following formula (b-1):

(In the formula (b-1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, X ³ and X ⁴ are each independently a divalent organic group, and n is 0 or 1) .

According to the liquid crystal aligning agent containing the polymer having the structure represented by the above formula (1) as the polymer component, it is possible to form a liquid crystal alignment film with good liquid crystal alignability while satisfying the coating property with respect to the substrate. Further, according to the liquid crystal alignment film produced by the liquid crystal aligning agent of the present invention, it is possible to manufacture a liquid crystal display device having a high voltage holding ratio and good heat resistance and afterimage characteristics. Furthermore, the liquid crystal alignment film obtained using the liquid crystal aligning agent of the present invention has good adhesion to the substrate. Therefore, even when the film is stored as a winding, it is difficult for the liquid crystal alignment film and the substrate to be peeled off. Thus, for example, in the production of a retardation film, deterioration of product yield can be suppressed.

1 is a schematic configuration diagram of an FFS type liquid crystal cell.
2 is a schematic plan view of the top electrode. Fig. 2 (a) is a plan view of the top electrode, and Fig. 2 (b) is a partial enlarged view of the top electrode.

(Mode for carrying out the invention)

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

<Polymer Component>

The liquid crystal aligning agent of the present invention contains a polymer component and also contains a polymer (P) having a structure represented by the following formula (1) as the polymer component:

(In the formula (1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group of 1 to 30 carbon atoms, X ¹ and X ² are each independently a divalent organic group; "*"Quot;)&quot;

With regard to the formula (1), examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms in R ¹ include a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Herein, in the present specification, the term "chain hydrocarbon group" means a hydrocarbon group which does not contain a cyclic structure in its main chain and is composed of only a chain structure. However, the chain structure may be linear or branched. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only the structure of an alicyclic hydrocarbon and not containing an aromatic ring structure as the ring structure. However, it need not be composed of only the structure of an alicyclic hydrocarbon, and a part thereof may also have a chain structure. The term "aromatic hydrocarbon group" means a hydrocarbon group having an aromatic ring structure as a ring structure. However, it need not be constituted only of an aromatic ring structure, and a part thereof may contain a chain structure or a structure of an alicyclic hydrocarbon.

Specific examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms in R ¹ include linear hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, , A decyl group, a dodecyl group, a tetradecyl group and an eicosanyl group; An alkenyl group having 1 to 30 carbon atoms such as an ethynyl group, a propenyl group, and a butenyl group; And an alkynyl group having 1 to 30 carbon atoms such as an ethynyl group and a propynyl group. These groups may be linear or branched. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group and the like; Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a benzyl group, a phenethyl group and the like; Respectively.

Among them, R ¹ is preferably a hydrogen atom or a chain hydrocarbon group having 1 to 30 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms .

Examples of the main skeleton of the polymer (P) include polyamic acid, polyimide, polyamic ester, polyester, polyamide, polyorganosiloxane, cellulose derivative, polyacetal derivative, polystyrene derivative, poly (Meth) acrylate derivatives, and the like. The polymer (A) may be appropriately selected and used in accordance with the driving method and application of the liquid crystal display element, or one or more kinds of polymers having a skeleton selected therefrom. Further, (meth) acrylate means that it includes acrylate and methacrylate. The main skeleton of the polymer (P) is preferably a skeleton composed of at least one member selected from the group consisting of polyamic acid, polyimide and polyamic acid ester.

The polymer (P) preferably has a structure represented by the formula (1) (hereinafter also referred to as &quot; specific structure &quot;) in the main chain. In this case, X ¹ and X ² in the specific structure have a structure derived from the skeleton of the monomer used for the synthesis of the polymer.

The method for synthesizing the polymer (P) is not particularly limited. For example, a method of synthesizing at least one compound (a) selected from the group consisting of tetracarboxylic acid dianhydride and carbonic acid halide, an amine compound (b) . &Lt; / RTI &gt; Examples of the carbonic acid halide as the compound (a) include a dicarboxylic acid dihalide, a tetracarboxylic acid dihalide, and a tetracarboxylic acid diester dihalide. Examples of the halogen atom of the carbonic acid halide include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom, among which a chlorine atom is preferable.

[Polymer (P): polyamic acid]

When the polymer (P) is a polyamic acid, a polyamic acid having the specific structure (hereinafter also referred to as &quot; polyamic acid (P) &quot;) can be obtained, for example, by reacting a tetracarboxylic acid dianhydride b). &lt; / RTI &gt;

(Tetracarboxylic acid dianhydride)

Examples of the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid (P) include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-2 anhydride, bicyclo [2.2.1] heptane-2,3,5,6- Acid 2: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, 1,2,4,5- Cyclohexane tetracar An acid dianhydride, and bicyclo [2.2.2] loam-7-ene-2,3,5,6-tetracarboxylic acid dianhydride;

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

As the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid (P), 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro- Yl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane- 2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, Carboxynorbornane-2: 3,5: 6-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetra , Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, and pyromel To include at least one compound selected from the group consisting of acid dianhydride (hereinafter also referred to as "specific tetracarboxylic dianhydride") it is preferred. The amount of the specific tetracarboxylic acid dianhydride to be used is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total amount of the tetracarboxylic acid dianhydride used for the synthesis of the polyamic acid , And particularly preferably 20 mol% or more.

(Amine compound)

The amine compound (b) used in the synthesis of the polyamic acid (P) preferably contains a compound having a group capable of introducing the specific structure into the main chain of the polymer. More specifically, the amine compound (b) It is preferred to include a compound:

(Where R ¹ has the same meaning as R ¹ in the formula (1) of the formula (b-1), X ³ and X ⁴ are, each independently represent a divalent organic group, and;; n is 0 or 1).

Examples of the divalent organic groups represented by X ³ and X ^{4 in} the above formula (b-1) include hydrocarbon groups such as divalent chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups, and carbon-carbon double bonds in the hydrocarbon group. (2) in which a functional group such as -O-, -COO-, -CO-, -NHCO-, -S- or -NH- is introduced into a carbon-carbon bond or a position adjacent to a carbonyl group in the formula And the like. X ³ and X ⁴ may have a substituent such as a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom).

Specific examples of X ³ and X ⁴ include divalent chain hydrocarbon groups such as methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, An alkanediyl group having 1 to 30 carbon atoms such as a nonanediyl group, a decanediyl group, a dodecanediyl group, a tetradecanediyl group and an eicosanediyl group; Divalent straight chain unsaturated hydrocarbon groups having 1 to 30 carbon atoms such as ethenylene group, propylene group, butenylene group, ethynylene group and propynylene group; These may be linear or branched. Examples of the divalent alicyclic hydrocarbon group include cyclohexylene group and the like; Examples of the bivalent aromatic hydrocarbon group include a phenylene group, a benzylene group, a phenetylene group and the like; Examples of the divalent group formed by introducing a functional group between the carbon-carbon bonds of the hydrocarbon group include groups having a heterocyclic ring such as piperidine, pyrrolidine, hexamethyleneimine, pyridine, and pyrazine; Respectively. X ³ and X ⁴ may be the same or different.

As X ³ and X ⁴ , it is preferable that at least one of X ³ and X ⁴ is a group having an aromatic ring from the viewpoints of the strength of the formed coating film and the voltage holding ratio, and from the viewpoint of affinity with the liquid crystal, Is more preferable. Specifically, as the compound (b-1), a compound represented by the following formula (b-1-1) can be preferably used:

(Formula (b-1-1) of, X ⁵ and X ⁶ are, each independently, a single bond or a divalent organic group, and; n is 0 or 1; R ¹ is R ¹ in the formula (1) and The same meaning).

Examples of the divalent organic groups represented by X ⁵ and X ⁶ in the formula (b-1-1) include those exemplified as X ³ and X ⁴ in the formula (b-1). The divalent organic group of X ⁵ and X ⁶ preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms.

n may be appropriately selected from 0 and 1 depending on the purpose of use and the like. Specifically, n = 1 is preferable from the viewpoint of increasing the voltage holding ratio, and n = 0 is preferable from the viewpoint of retaining the carboxyl group in the polymer after formation of the coating film and accordingly improving the relaxation speed of residual DC. When n = 0, it is preferable that R ¹ is an alkyl group having 1 to 5 carbon atoms. R ¹ in the formula (b-1) and formula (b-1-1) can be applied to the description of R ¹ in the formula (1).

Specific examples of the compound represented by the above formula (b-1-1) include, for example, the following compounds. In the synthesis of the polyamic acid (P) of the present invention, the compounds represented by the above formula (b-1) may be used singly or in combination of two or more.

In the synthesis of the polyamic acid (P), only the compound represented by the above formula (b-1) may be used as the amine compound (b), but other amines other than the above may be used together with the compound.

Examples of other amines that can be used herein include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include aliphatic diamines such as m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;

As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, Diaminodiphenylamine, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4 Diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-diaminobiphenyl, Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'- (m-phenylene diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4 ' -Bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6- Diaminocarbazole, N-methyl 3,6-diaminocarbazole, N, N'-bis (4-aminophenyl) -benzidine N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecanoxy- 2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy- 4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecaneoxy- Diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4 -Diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzene (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl (4 - ((aminophenyl) methyl) -3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl- Phenyl) -4-butylcyclohexane, 1,1-bis (4 - ((aminophenoxy) methyl) ) -4-heptylcyclohexane, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, Aminobenzylamine, 1- (2,4-diaminophenyl) piperazine-4-carboxylic acid, 4- (morpholin- Diamine, 1,3-bis (N- (4-aminophenyl) piperidinyl) propane,? -Amino-omega -aminophenyl alkylene, 1- , 3,3-trimethyl-1H-indene Aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 4-aminophenyl-4'- aminobenzoate, 4 , 4 '- [4,4'-propane-1,3-diylbis (piperidine-1,4-diyl)] dianiline, 4- (tetradecanoxy) benzene- (D-1):

( ^I ) wherein X ^I and X ^II each are a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, and 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, with the proviso that a and b do not become 0 at the same time;

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

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

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-3).

As other amines used for the synthesis of the polyamic acid, one or more of these compounds may be appropriately selected in accordance with the driving mode of the liquid crystal display element and the like.

The amine compound (b) used in the synthesis of the polyamic acid (P) of the present invention is advantageous in that it can form a coating film having good coating and rubbing resistance on the substrate, a liquid crystal display element having a good heat resistance and a relaxation speed of residual DC The proportion of the compound represented by the above formula (b-1) is preferably 0.5 mol% or more, more preferably 2 mol% or more, based on the total amount of the amine compound (b) , More preferably 5 mol% or more, and particularly preferably 10 mol% or more. The upper limit of the use ratio of the compound represented by the above formula (b-1) may be suitably set in accordance with the driving mode of the liquid crystal display element to which the compound is applied, Mol% or less, and when it is desired to improve the effect of addition of other amines (for example, to improve the voltage holding ratio and the liquid crystal alignability), the content is preferably 95 mol% or less.

The polymer (P) may be a polymer having a photo-orientable structure when the liquid crystal aligning ability is imparted to the coating film produced using the liquid crystal aligning agent of the present invention by the photo alignment method. Here, the photo-alignment structure is a concept including both the photo-alignment group and the decomposition-type photo-alignment unit. Specifically, as the photo-alignment structure, a group capable of optical orientation by photoisomerization, photo-dimerization, photolysis or the like can be adopted, and for example, an azobenzene-containing group containing azobenzene or a derivative thereof as basic skeleton, Containing group as a basic skeleton, a chalcone-containing group containing a derivative as a basic skeleton, a chalcone-containing group containing a chalcone or its derivative as a basic skeleton, benzophenone or a derivative thereof as a basic skeleton, coumarin or a derivative thereof And a polyimide-containing structure containing a coumarin-containing group, a polyimide or a derivative thereof as a skeleton as a basic skeleton.

When the polymer (P) comprises a polymer having a photo-orientable structure, the polymer (P) is preferably a polymer including a photo-degradable photo-alignment portion, and specifically, a bicyclo [2.2.2] octene skeleton or cyclo Butane skeleton. By having such a specific skeleton, the liquid crystal alignability of the coating film can be further improved. Further, such a polymer may contain at least one of, for example, cyclobutanetetracarboxylic acid dianhydride and bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride Can be obtained by reacting tetracarboxylic dianhydride with an amine compound containing the compound represented by the formula (b-1).

In the case where the liquid crystal aligning ability is imparted to the coating film by the photo alignment method, the ratio of the polymer having the photo-orientable structure and the specific structure is preferably set such that the total amount of the polymer (P) used for preparing the liquid crystal aligning agent of the present invention Is preferably 10% by weight or more, more preferably 30 to 100% by weight, and still more preferably 50 to 100% by weight.

[Molecular Weight Regulator]

In the synthesis of the polyamic acid (P), an endmodified polymer may be synthesized by using an appropriate molecular weight regulator together with the tetracarboxylic acid dianhydride and the amine compound (b) as described above. By using such a polymer having a terminal modification type, the coating property (printing property) of the liquid crystal aligning agent can be further improved without impairing the effect of the present invention.

Examples of the molecular weight regulator include acid monoanhydrides, monoamine compounds, and monoisocyanate compounds. Specific examples thereof include acid anhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride My back; As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine and the like; Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of tetracarboxylic acid dianhydride and diamine to be used.

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

The compound represented by the formula (b-1) can be synthesized by appropriately combining the methods of organic chemistry. As an example thereof, there can be mentioned, for example, a method of synthesizing a nitro intermediate having a nitro group in place of the primary amino group in the above formula (b-1) and then aminating the nitro group of the obtained nitro intermediate with a suitable reducing system .

The method for synthesizing the nitro intermediate may be appropriately selected depending on the desired compound. As an example thereof, there can be mentioned, for example, a method of reacting an amide compound having a corresponding X ³ and a nitro group with an acid chloride having a corresponding X ⁴ and a nitro group; A method of reacting an acid chloride having a corresponding X &lt; ³ &gt; and a nitro group with an amide compound having a corresponding X &lt; ⁴ &gt; A method of reacting ammonia with an acid chloride having a corresponding X &lt; ³ &gt; and a nitro group; And the like.

The reaction for obtaining the nitro intermediate is preferably carried out in an organic solvent. The organic solvent is not particularly limited as long as it is a solvent which does not affect the reaction. Examples of the organic solvent include methanol, ethanol, tetrahydrofuran, toluene, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, And the like. The reaction may be carried out in the presence of a catalyst, if necessary.

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

[Synthesis of polyamic acid (P)] [

The ratio of the tetracarboxylic acid dianhydride and the amine compound (b) to be used in the synthesis reaction of the polyamic acid (P) of the present invention is such that the amino group (including the primary amino group and the secondary amino group) The ratio of the acid anhydride group of the tetracarboxylic acid dianhydride to the equivalent of the amino group reacting with the acid anhydride group of the tetracarboxylic dianhydride is preferably 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents .

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

Examples of the organic solvent include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like. Specific examples of these organic solvents include non-protonic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, Such as lactone, tetramethylurea, hexamethylphosphoric triamide and the like; As the phenolic solvent, for example, phenol, m-cresol, xylenol, halogenated phenol and the like;

As the alcohol, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether and the like; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like; Examples of the ester include esters such as ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, Isoamyl isobutyrate, and the like; Examples of the ether include diethyl ether, diisopentyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol n- Diethylene glycol dimethyl ether, glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, Ether acetate, tetrahydrofuran and the like; As halogenated hydrocarbons, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like; Examples of the hydrocarbons include hexane, heptane, octane, benzene, toluene, xylene and the like; Respectively.

Among these organic solvents, at least one kind selected from the group consisting of an aprotic polar solvent and a phenol type solvent (first group of organic solvents), or at least one kind selected from an organic solvent of the first group, It is preferable to use a mixture of at least one member selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). In the latter case, the ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less, based on the total amount of the organic solvent of the first group and the organic solvent of the second group By weight, more preferably not more than 30% by weight. The amount (?) Of the organic solvent used is preferably such that the total amount (?) Of the tetracarboxylic acid dianhydride and the amine compound (b) is 0.1 to 50% by weight relative to the total amount (? +?) Of the reaction solution Do.

As described above, a reaction solution obtained by dissolving the polyamic acid (P) is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent, or the polyamic acid (P) contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or the polyamic acid (P) May be provided later for preparation of the liquid crystal aligning agent. When the polyamic acid (P) is dehydrated and ring-closed to be polyimide, the reaction solution may be directly supplied to the dehydration ring-closing reaction, or the polyamic acid (P) contained in the reaction solution may be isolated and then subjected to a dehydration ring- , Or the purified polyamic acid (P) may be purified and then subjected to a dehydration ring-closing reaction. The polyamic acid can be isolated and purified by a known method.

[Polymer (P): polyamic acid ester]

The polyamic acid ester (hereinafter also referred to as a polyamic acid ester (P)) as the polymer (P) may be obtained by, for example, reacting a polyamic acid (P) obtained by the above-mentioned synthesis reaction with a hydroxyl group- (II) reacting a tetracarboxylic acid diester with an amine compound (b); (III) reacting a tetracarboxylic acid diester dihalide with an amine compound (b); Can be obtained by the method.

Examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; Phenols such as phenol and cresol, and the like. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, and 1,1,1-trifluoro-2-iodoethane. Examples of the epoxy group- , For example, propylene oxide, and the like. The tetracarboxylic acid diester used in the method [II] can be obtained by ring opening the tetracarboxylic acid dianhydride using the above-mentioned alcohols. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester thus obtained with a suitable chlorinating agent such as thionyl chloride. The amine compound (b) used in the methods [II] and [III] preferably contains the compound represented by the above formula (b-1), and other amines described above may be used as necessary. Further, the polyamic acid ester (P) may have only an amide ester structure, or may be a partial esterified product in which the amide structure and the amide ester structure coexist.

[Polymer (P): polyimide]

The polyimide (hereinafter also referred to as polyimide (P)) as the polymer (P) can be obtained, for example, by imidizing the polyamic acid (P) synthesized as described above by dehydration ring closure.

The polyimide (P) may be a completely imidized product in which all of the arboric acid structure of the polyamic acid (P) as a precursor thereof is dehydrated and closed, and only a part of the arid acid structure is subjected to dehydration ring closure, It may be a partially imide cargo. The imide ratio of the polyimide contained in the liquid crystal aligning agent of the present invention is preferably 30% or more, more preferably 40 to 99%, and further preferably 50 to 99%. The imidization rate is a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a part of the imide ring may be an isoimide ring.

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

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

In this way, a reaction solution containing the polyimide (P) is obtained. This reaction solution may be provided as it is in the preparation of a liquid crystal aligning agent, or may be supplied to the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. Alternatively, after the polyimide is isolated, Or may be added to the preparation of a liquid crystal aligning agent after purification of the isolated polyimide. These purification operations can be carried out according to a known method. In addition, polyimide (P) may be obtained by imidization of polyamic acid ester (P).

The polyamic acid, the polyamic acid ester and the polyimide as the polymer (P) thus obtained preferably have a solution viscosity of 10 to 800 mPa · s and a viscosity of 15 to 500 mPa · s s of solution viscosity. The solution viscosity (mPa 占 퐏) of the polymer is preferably 10 weight% or less by weight, which is prepared by using a good solvent of the polymer (for example,? -Butyrolactone, N-methyl- % Of the polymer solution at 25 占 폚 using an E-type rotational viscometer.

The weight average molecular weight (Mw) of the polyamic acid, polyamic acid ester and polyimide in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less. Within this molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

<Other components>

The liquid crystal aligning agent of the present invention contains the above-mentioned polymer (P), but may contain other components as necessary. The other components can be appropriately selected depending on the use of the liquid crystal aligning agent. For example, in the case of producing a liquid crystal alignment film for a liquid crystal display element using the liquid crystal aligning agent of the present invention, other components that may be added to the liquid crystal aligning agent include other polymers other than the polymer (P) (Hereinafter referred to as &quot; epoxy group-containing compound &quot;), a functional silane compound and the like.

[Other Polymers]

The other polymer may be used for improving solution characteristics and electrical properties. Examples of such other polymers include polyamides, polyimides, polyamic acid esters, polyesters, polyamides, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) (Meth) acrylate or the like as a main skeleton, and a polymer having no specific structure can be used. As the other polymer, at least one selected from the group consisting of polyamic acid, polyimide, polyamic acid ester and polysiloxane can be preferably used. The polyamic acid as the other polymer can be obtained, for example, by reacting the tetracarboxylic acid dianhydride exemplified in the explanation of the polyamic acid (P) with the other diamine, and the polyimide is obtained by reacting the polyamic acid And the polyamic acid ester can be obtained, for example, by esterification of the polyamic acid. The polyorganosiloxane as the other polymer can be obtained, for example, by a hydrolysis / condensation reaction of a hydrolyzable silane compound. The synthesis of these polymers can be carried out according to a known method.

When the other polymer is added to the liquid crystal aligning agent, the blending ratio thereof is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, more preferably 0.1 to 40 parts by weight based on 100 parts by weight of the total polymer in the composition. More preferably 30 parts by weight.

 [Epoxy group-containing compound]

The epoxy group-containing compound can be used for improving adhesion to the substrate surface in the liquid crystal alignment film. Examples of the 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 Diallyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromonopentyl glycol di N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidylaminomethylcyclohexane, N-diglycidyl-cyclohexylamine, epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598, and the like .

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

[Functional silane compound]

The functional silane compound can be used to improve the printability of the liquid crystal aligning agent. Examples of such a functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetri Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate , Methyl 9-triethoxysilyl-3,6-diazanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxy Silane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and the like. .

When the functional silane compound is added to the liquid crystal aligning agent, the blending ratio thereof is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight per 100 parts by weight of the total amount of the polymer.

In addition, antioxidants such as phenol-based antioxidants and amine-based antioxidants; Polyfunctional (meth) acrylates such as ethylene glycol diacrylate and 1,6-hexanediol diacrylate; May be added to the liquid crystal aligning agent.

Examples of other components that may be added to the liquid crystal aligning agent for the liquid crystal aligning agent for the retardation film include other polymers other than the polymer (P), a metal chelate compound, a curing accelerator, a surfactant, and the like have.

[Other Polymers]

The above-mentioned other polymer which may be added to the liquid crystal aligning agent for the retardation film may be used for improvement of the solution property and the like. Specific examples of the other polymer which may be added to the liquid crystal aligning agent for liquid crystal display elements Polymers and the like.

As the other polymer, a polymer having a photo-orientable structure can be preferably used, and specifically, a polymer having a photo-orientable group is preferably included, and a polymer having a group having a cinnamic acid structure as a photo- . Among them, a polyorganosiloxane having a cinnamic acid structure can be preferably used because it is easy to introduce a photo-orientable group into a polymer.

Further, the polymer having a photo-orientable group can be synthesized by a conventionally known method. For example, the polyorganosiloxane having a photo-orientable group as the other polymer can be obtained by reacting a polyorganosiloxane having an epoxy group and a carbonic acid having a photo-orientable group in an organic solvent such as an ether, ester, In the presence of a catalyst such as an alkylammonium salt or the like.

When the other polymer is added to the liquid crystal aligning agent, the blending ratio thereof is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and most preferably 0.1 to 40 parts by weight, based on 100 parts by weight of the total polymer in the composition. To 30 parts by weight.

 [Metal chelate compound]

The metal chelate compound is contained in the liquid crystal aligning agent in order to ensure the mechanical strength of the film formed by the low temperature treatment when the polymer component of the liquid crystal aligning agent has an epoxy structure. As the metal chelate compound, an acetylacetone complex or acetoacetic acid complex of a metal selected from aluminum, titanium and zirconium is preferably used. Specific examples include diisopropoxyethylacetoacetate aluminum, tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (Acetylacetonate) titanium, tri-n-butoxyethylacetoacetate zirconium, and di-n-butoxybis (ethylacetoacetate) zirconium. The amount of the metal chelate compound to be used is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and 1 to 30 parts by weight based on 100 parts by weight of the total of the components including the epoxy structure More preferable.

[Curing accelerator]

When the polymer component in the liquid crystal aligning agent has an epoxy structure, the curing accelerator is contained in the liquid crystal aligning agent to ensure the stability of the formed liquid crystal alignment film with respect to the mechanical strength and the liquid crystal alignability with time. As the curing accelerator, for example, a compound having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carbonic acid anhydride group and the like can be used. Among them, a compound having a phenol group or a silanol group is preferable Do. Specific examples thereof include compounds having a phenol group such as cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol and the like; Examples of the compound having a silanol group include trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis (hydroxydimethylsilyl) benzene , Triphenylsilanol, tri (p-tolyl) silanol, diphenylsilanediol, and the like. The proportion of the curing accelerator to be used is preferably 50 parts by weight or less, more preferably 0.1 to 40 parts by weight, and more preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of the components including the epoxy structure Do.

[Surfactants]

The surfactant may be contained in the liquid crystal aligning agent for the purpose of improving the coating property of the liquid crystal aligning agent to the substrate. Examples of such a surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants. The proportion of the surfactant to be used is preferably 10 parts by weight or less, more preferably 1 part by weight or less, based on 100 parts by weight of the total amount of the liquid crystal aligning agent.

<Solvent>

The liquid crystal aligning agent of the present invention is prepared as a liquid composition in which the above-mentioned polymer (P) and other components which are optionally used are dispersed or dissolved in an appropriate solvent.

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

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

Particularly preferable range of the solid concentration varies depending on the use of the liquid crystal aligning agent and the method used when applying the liquid crystal aligning agent to the substrate. For example, when the liquid crystal aligning agent for a liquid crystal alignment film is applied to a substrate by the spinner method, the solid concentration (the ratio of the total weight of the components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) Is in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable to set the solid concentration in the range of 3 to 9% by weight and the solution viscosity in the range of 12 to 50 mPa · s accordingly. In the case of the inkjet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, and the solution viscosity is in the range of 3 to 15 mPa · s. The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 10 to 50 占 폚, more preferably 20 to 30 占 폚. In the liquid crystal aligning agent for the retardation film, the solid concentration of the liquid crystal aligning agent is preferably in the range of 0.2 to 10% by weight from the viewpoint of making the coating property of the liquid crystal aligning agent and the film thickness of the formed coating film appropriate, , And more preferably 3 to 10 wt%.

<Liquid crystal display element and retardation film>

By using the above-described liquid crystal aligning agent of the present invention, a liquid crystal alignment film can be produced. Further, the liquid crystal alignment film formed using the liquid crystal aligning 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 phase difference 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 comprises a liquid crystal alignment film formed using the liquid crystal aligning agent. The operation mode of the liquid crystal display device of the present invention is not particularly limited and may be, for example, TN type, STN type, VA type (including VA-MVA type and VA-PVA type), IPS type, FFS type, And the like can be applied to various 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). Process (I-1) differs from substrate to be used in accordance with a desired operation mode. Processes (I-2) and (I-3) are common to each operation mode.

[Process (I-1): Formation of coating film]

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

(I-1A) For example, when a liquid crystal display device of a TN type, an STN type or a VA type is manufactured, two substrates on which a patterned transparent conductive film is formed are paired, The liquid crystal aligning agent of the present invention is preferably applied by offset printing, spin coating, roll coatering, or inkjet printing. Examples of the substrate include glass such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film to be formed on one surface of the substrate, an ITO film made of NESA film (a registered trademark of PPG Corporation of the US) or indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) . The patterned transparent conductive film can be obtained, for example, by forming a transparent conductive film without a pattern and then forming a pattern by photoetching; A method using a mask having a desired pattern when forming a transparent conductive film; And so on. In the application of the liquid crystal aligning agent, a functional silane compound, a functional titanium compound and the like are previously coated on the surface of the substrate surface on which the coating film is to be formed, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film Or may be carried out prior to the processing.

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

(I-1B) In the case of producing an IPS or FFS type liquid crystal display element, the electrode formation surface of the substrate on which the electrode made of the transparent conductive film or the metal film patterned in the comb shape is formed, The liquid crystal aligning agent of the present invention is applied to one side of the counter substrate, and then each coated side is heated to form a coated film. The material and the method of application of the transparent conductive film, the heating conditions after coating, the method of patterning the transparent conductive film or metal film, the pretreatment of the substrate, and the preferable film thickness of the formed film are the same as those of the above (I-1A) . As the metal film, for example, a film made of a metal such as chromium can be used.

In any of the cases (I-1A) and (I-1B), a liquid crystal aligning agent is coated on a substrate, and then an organic solvent is removed to form a coating film to be an alignment film. At this time, when the polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imidazole ring structure and an arboric acid structure, the dehydration ring- , Or a more imaged coating film may be used.

[Process (I-2): Orientation-imparting treatment]

In the case of producing a liquid crystal display element of TN type, STN type, IPS type or FFS type, as a treatment for imparting liquid crystal alignability to the coating film formed in the above step (I-1), the coating film is, for example, A rubbing process is performed in which a cloth made of fibers such as cotton is wound in a predetermined direction. Accordingly, 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, when a VA type liquid crystal display element is produced, the coating film formed in the above step (I-1) can be used as it is as a liquid crystal alignment film, but the coating film may be rubbed. Further, it is also possible to use a treatment for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film to the rubbed liquid crystal alignment film, or a process for forming a resist film on a part of the surface of the liquid crystal alignment film The rubbing treatment may be performed in a direction different from the rubbing treatment, and then the treatment for removing the resist film may be performed so that the liquid crystal alignment film has different liquid crystal aligning ability for each region. In this case, it is possible to improve the visual field characteristic of the obtained liquid crystal display element. Further, a liquid crystal alignment film suitable for VA type liquid crystal display elements can be suitably used for liquid crystal display devices of the PSA (polymer sustained alignment) type. As the treatment for imparting the liquid crystal aligning ability to the coating film, a treatment by the photo alignment method may be employed instead of the rubbing treatment.

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

Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and the liquid crystal is arranged between the two substrates arranged opposite to each other to manufacture a liquid crystal cell. To produce a liquid crystal cell, for example, the following two methods can be used. The first method is a conventionally known method. First, two substrates are opposed to each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other. The peripheral portions of the two substrates are bonded together using a sealant, After the liquid crystal is filled and filled in the cell gap, the liquid crystal cell can be manufactured by sealing the injection port. The second method is a method called ODF (One Drop Fill) method. For example, an ultraviolet curable sealant is applied to a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed and the liquid crystal is dropped to a predetermined number of places on the liquid crystal alignment film surface, The liquid crystal cell can be manufactured by spreading the liquid crystal on the entire surface of the substrate and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealing agent. Regardless of the method, it is preferable to heat the liquid crystal cell produced as described above to a temperature at which the liquid crystal used is isotropic, and then gradually cool to room temperature to remove the flow alignment at the time of filling the liquid crystal Do.

As the sealing agent, for example, an epoxy resin containing a curing agent and an aluminum oxide sphere as a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Of these, nematic liquid crystals are preferable, and examples thereof include a cypher base liquid crystal, an agar watch liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexane liquid crystal, Based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, quartz-based liquid crystal and the like. Further, to these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate and cholesteryl carbonate; Chiral agents such as those sold under the trade names "C-15" and "CB-15" (Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, or the like may be added and used.

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

[Retardation film]

When a retardation film is produced using the liquid crystal aligning agent of the present invention, it is possible to form a uniform liquid crystal alignment film while suppressing the generation of dust or static electricity during the process. By using a photomask suitable for irradiation of radiation, It is preferable to use the photo alignment method in that a plurality of regions having different liquid crystal alignment directions can be arbitrarily formed on the substrate. Specifically, it can be produced through the following steps (II-1) to (II-3).

[Process (II-1): Formation of coating film by liquid crystal aligning agent]

First, the liquid crystal aligning agent of the present invention is coated on a substrate to form a coating film. Examples of the substrate used here include a substrate made of synthetic resin such as triacetylcellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyamide, polyimide, polymethyl methacrylate, polycarbonate and the like A transparent substrate can be suitably exemplified. Among them, TAC is generally used as a protective layer of a polarizing film in a liquid crystal display element. In addition, polymethylmethacrylate can be preferably used as a substrate for a retardation film in terms of low hygroscopicity of a solvent, good optical characteristics, and low cost. In addition, with respect to the substrate used for coating the liquid crystal aligning agent, the surface of the substrate on which the coating film is formed may be subjected to a pretreatment known in the prior art in order to improve the adhesion between the substrate surface and the coating film.

In most cases, the retardation film is used in combination with a polarizing film. At this time, it is necessary to precisely control the angle with respect to the polarization axis of the polarizing film in a specific direction so as to exhibit the expected optical characteristics, and to bond the retardation film. Therefore, here, a liquid crystal alignment film having a liquid crystal aligning ability in a predetermined angle direction is formed on a substrate such as a TAC film or polymethylmethacrylate, thereby joining the retardation film to the polarizing film while controlling the angle thereof Can be omitted. Thus, the productivity of the liquid crystal display element can be improved. In order to form a liquid crystal alignment film having a liquid crystal aligning ability in the direction of a predetermined angle, it is preferable to conduct the alignment by the photo alignment method using the liquid crystal aligning agent of the present invention.

The application of the liquid crystal aligning agent onto the substrate can be carried out by a suitable coating method. For example, a roll coating method, a spinner method, a printing method, an ink jet method, a bar coater method, an extrusion die method, a direct gravure coater method, A reverse kiss coater method using a small diameter gravure roll, a three reverse roll coater method, a four reverse roll coater method, a slot die method, an air knife coater method, A doctor coater method, a forward rotation roll coater method, a blade coater method, a knife coater method, an impregnation coater method, an MB coater method, and an MB reverse coater method.

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

[Process (II-2): light irradiation process]

Subsequently, the coating film formed on the substrate is irradiated with light as described above, thereby imparting liquid crystal alignment capability to the coating film. Here, examples of the light to be irradiated include ultraviolet rays including visible light having a wavelength of 150 to 800 nm, visible light, and the like. Of these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferred. The irradiation light may be polarized light or unpolarized light. As the polarized light, it is preferable to use light including linearly polarized light.

When light to be used is polarized light, irradiation of light may be performed in a direction perpendicular to the substrate surface, or may be performed in an oblique direction, or may be performed in combination. In the case of irradiating unpolarized light, it is necessary to perform the irradiation from the oblique direction with respect to the substrate surface.

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

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

[Process (2-3): Formation of liquid crystal layer]

Subsequently, the polymerizable liquid crystal is coated on the coating film after light irradiation as described above to cure it. Thus, a coating film (liquid crystal layer) containing a polymerizable liquid crystal is formed. The polymerizable liquid crystal used herein is a liquid crystal compound or a liquid crystal composition which undergoes polymerization by at least one of heating and light irradiation. As such polymerizable liquid crystals, conventionally known liquid crystal materials can be used. Specific examples thereof include non-patent document 1 (&quot; UV curable liquid crystal and its application &quot;, Liquid Crystal, Vol. 3, No. 1 (1999) 42) can be used as the nematic liquid crystal. Also, cholesteric liquid crystals; Discotic liquid crystal; Or a twisted nematic alignment type liquid crystal to which a chiral agent is added. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may also be a composition containing a known polymerization initiator, a suitable solvent, and the like.

In order to apply the above-mentioned polymerizable liquid crystal on a coating film formed using a liquid crystal aligning agent, a suitable coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, or an ink jet method may be employed.

Subsequently, the coating film of the polymerizable liquid crystal thus formed is subjected to at least one treatment selected from heating and light irradiation to cure the coating film to form a liquid crystal layer. It is preferable that these treatments are carried out in an overlapping manner because good orientation can be obtained.

The heating temperature of the coating film should be appropriately selected depending on the kind of the polymerizable liquid crystal used. For example, in the case of using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40 to 80 占 폚. The heating time is preferably 0.5 to 5 minutes.

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

The thickness of the liquid crystal layer to be formed is suitably set in accordance with a desired optical characteristic. For example, in the case of producing a 1/2 wavelength plate in visible light having a wavelength of 540 nm, the thickness is selected such that the retardation of the formed retardation film is 240 to 300 nm, and if it is a 1/4 wavelength plate, Is selected to be 120 to 150 nm. The thickness of the liquid crystal layer in which the objective phase difference is obtained differs depending on the optical characteristics of the polymerizable liquid crystal used. For example, in the case of using RMS03-013C manufactured by Merck, the thickness for producing a 1/4 wavelength plate is in the range of 0.6 to 1.5 占 퐉.

The retardation film thus obtained can be suitably applied as a retardation film of a liquid crystal display element. The liquid crystal display element to which the retardation film produced using the liquid crystal aligning agent of the present invention is applied is not limited to a driving method thereof and may be a known liquid crystal display element such as TN type, STN type, IPS type, FFS type, It can be applied to various methods. The retardation film is used by adhering the substrate side of the retardation film to the outer surface of the polarizing plate disposed on the visual side (viewing side) of the liquid crystal display element. Therefore, it is preferable that the substrate of the retardation film is made of a TAC or acrylic base material, and the substrate of the retardation film functions also as a protective film of the polarizing film.

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

[Example]

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

In the following Examples and Synthesis Examples, the weight average molecular weight Mw, the imidization rate and the epoxy equivalent of the polymer, and the solution viscosity of the polymer solution were measured by the following methods.

[Weight average molecular weight Mw of the polymer]

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

Column: TSKgelGRCXLII, manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68 ㎏f / ㎠

[Imidization Rate of Polymer]

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

Imidization rate (%) = {(1-A ¹ ) / (A ² × α)} × 100 (One)

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

[Epoxy equivalent]

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

[Solution viscosity of polymer solution]

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

&Lt; Synthesis of amine compound >

[Example 1-1; Synthesis of Compound (DA-1)

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

147.2 g (0.69 mol) of 3- (4-nitrophenyl) propanoic acid chloride and 500 ml of tetrahydrofuran (THF) were added to a 3 L three-necked flask equipped with a thermometer, a three-way cock and a dropping funnel. Subsequently, 1,000 ml of a 25% ammonia aqueous solution was slowly added dropwise. The mixture was reacted at 30 DEG C for 2 hours, mixed with 1500 mL of ethyl acetate, and then washed with an aqueous solution of sodium hydrogencarbonate and distilled water. Subsequently, the organic layer was concentrated to precipitate a solid. The obtained solid was recrystallized from ethyl acetate and hexane, collected by filtration, and dried to obtain 113.8 g (0.59 mol) of 3- (4-nitrophenyl) propanamide.

Next, to a 2 L three-necked flask equipped with a thermometer, a three-way cock, and a dropping funnel were added 99.0 g (0.51 mol) of 3- (4-nitrophenyl) 106.8 g (0.50 mol) of chloride, and 1000 ml of THF were added, cooled to 5 캜 in an ice bath, and mixed by stirring. Subsequently, 80 ml of pyridine was slowly dropped from the dropping funnel. During the dropwise addition, the mixture was cooled in an ice bath so as not to exceed 10 ° C and reacted at 0 ° C to 10 ° C for 1 hour and then at room temperature for 4 hours. After the reaction, the resultant mixture was mixed with 1000 ml of ethyl acetate, and then separated by distilled water. The obtained organic layer was concentrated to precipitate a solid. The precipitated solid was recrystallized from ethanol, collected by filtration and dried to obtain 102.5 g (0.28 mol) of a nitro intermediate (DA-1-1).

Subsequently, 102.5 g of the above nitro intermediate (DA-1-1), 10 g of 5% Pd / C, 280 mL of ethanol and 280 mL of tetrahydrofuran were added to a 2 L autoclave under nitrogen flow, , And reacted in the presence of hydrogen at room temperature. The reaction was followed by HPLC to confirm the progress of the reaction, followed by filtration. The filtrate and 3000 mL of ethyl acetate were mixed, and then separated by distillation. The solvent was removed from the obtained organic layer by distillation under reduced pressure to precipitate a solid. The precipitated solid was recrystallized from ethanol to obtain 75.6 g (0.24 mol) of the compound (DA-1).

[Examples 1-2; Synthesis of compound (DA-2)

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

30 g (0.50 mol) of urea, 224.3 g (1.05 mol) of 3- (4-nitrophenyl) propanoic acid chloride and 500 ml of THF were added to a 2 L three-necked flask equipped with a thermometer, The mixture was cooled to 5 캜 and mixed with stirring. Subsequently, 160 ml of pyridine was slowly added dropwise from the dropping funnel. During the dropwise addition, the mixture was cooled in an ice bath so as not to exceed 10 ° C and reacted at 0 ° C to 10 ° C for 1 hour and then at room temperature for 4 hours. After the reaction, the mixture was mixed with 3000 ml of ethyl acetate, and then the solution was separated and washed with distilled water. Subsequently, the organic layer was concentrated to precipitate a solid. The precipitated solid was recrystallized from ethanol, collected by filtration and dried to obtain 151.2 g (0.37 mol) of the nitro intermediate (DA-2-1).

Subsequently, 151.2 g of the above nitro intermediate (DA-2-1), 10 g of 5% Pd / C, 400 mL of ethanol and 400 mL of tetrahydrofuran were added to a 2 L autoclave under nitrogen flow, , And reacted in the presence of hydrogen at room temperature. The reaction was followed by HPLC to confirm the progress of the reaction, followed by filtration. After filtration, the filtrate and 2000 mL of ethyl acetate were mixed, followed by separation and purification by distilled water. The obtained organic layer was subjected to vacuum distillation to remove the solvent to precipitate a solid. The precipitated solid was recrystallized from ethanol to obtain 103.4 g (0.33 mol) of the compound (DA-2).

[Examples 1-3; Synthesis of Compound (DA-3)

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

100 g (0.51 mole) of 3- (4-nitrophenyl) propanamide synthesized by the same procedure as in Example 1-1, 10 g of 5% Pd / C, 500 mL of ethanol and tetra 500 mL of hydrofuran was added, and the mixture was replaced with hydrogen again, and the reaction was carried out at room temperature in the presence of hydrogen. The reaction was followed by HPLC to confirm the progress of the reaction, followed by filtration. The filtrate and 2000 mL of ethyl acetate were mixed, and then separated by distillation. The obtained organic layer was subjected to vacuum distillation to remove the solvent to precipitate a solid. The precipitated solid was recrystallized from ethanol to obtain 71.9 g (0.44 mol) of the compound (DA-3).

[Examples 1-4; Synthesis of compound (DA-4)

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

(0.53 mol) of 4-nitrofluorobenzene, 64.1 g (0.5 mol) of isonipecotamide and 207.3 g (0.5 mol) of isobutanol were added to a 2 L three-necked flask equipped with a thermometer, 1.5 mol) and 1000 ml of N, N-dimethylformamide (DMF) were added and mixed. After reacting at 80 DEG C for 5 hours, the reaction mixture was mixed with 700 mL of ethyl acetate, and then the reaction solution was separated and washed with distilled water. Subsequently, the organic layer was concentrated to precipitate a solid. The obtained solid was recrystallized from ethanol, collected by filtration and dried to obtain 97.8 g (0.39 mol) of intermediate (DA-4-1).

Next, 97.8 g of the intermediate (DA-4-1) obtained above, 87.4 g (0.47 mol) of 4-nitrobenzoyl chloride and 500 ml of THF were added to a 2 L three-necked flask equipped with a thermometer, In addition, the mixture was cooled to 5 캜 in an ice bath and stirred and mixed. Subsequently, 65 ml of pyridine was slowly dropped from the dropping funnel. During the dropwise addition, the mixture was cooled in an ice bath so as not to exceed 10 ° C and reacted at 0 ° C to 10 ° C for 1 hour and then at room temperature for 4 hours. After the reaction, the resultant mixture was mixed with 1000 ml of ethyl acetate, and the solution was washed with an aqueous solution of sodium hydrogencarbonate and distilled water. Subsequently, the organic layer was concentrated and solid precipitated. The precipitated solid was recrystallized from ethanol, collected by filtration and dried to obtain 70.5 g (0.18 mol) of a nitro intermediate (DA-4-2).

Subsequently, 70.5 g of the above nitro intermediate (DA-4-2), 7 g of 5% Pd / C, 180 mL of ethanol and 180 mL of tetrahydrofuran were added to a 2 L autoclave under nitrogen flow, , And reacted in the presence of hydrogen at room temperature. The reaction was followed by HPLC to confirm the progress of the reaction, followed by filtration. The organic layer was subjected to vacuum distillation to remove the solvent to precipitate a solid. The precipitated solid was recrystallized from ethanol to obtain 43.1 g (0.13 mol) of the compound (DA-4).

[Examples 1-5; Synthesis of Compound (DA-5)

A compound represented by the following formula (DA-5) (hereinafter referred to as a compound (DA-5)) was synthesized according to the following Reaction Scheme 5.

In the same manner as in Example 1-3 except that N-methyl-3- (4-nitrophenyl) propanamide was used in place of 3- (4-nitrophenyl) propanamide in Example 1-3 , Compound (DA-5) were obtained.

&Lt; Synthesis of Polymer &

[Example 2-1; Synthesis of Polymer (PA-1)

11.84 g of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride as a tetracarboxylic acid dianhydride (98 mole parts based on 100 moles of the total amount of the amine compound used in the synthesis) and 4-aminophenyl-4 16.97 g (90 molar parts) of the compound (DA-1) were dissolved in 170 g of N-methyl-2-pyrrolidone (NMP) For 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The collected precipitate was washed with methanol and then dried at 40 캜 for 15 hours under reduced pressure to obtain 28.1 g of polyamic acid (hereinafter referred to as polymer (PA-1)). The obtained polymer (PA-1) was adjusted to 10 wt% in NMP, and the viscosity of the solution was measured to be 1,051 mPa · s. The polymer solution was allowed to stand at 20 占 폚 for 3 days. As a result, the polymer solution was not gelated and the storage stability was good.

[Examples 2-2 to 2-8; Synthesis of polymer (PA-2) to polymer (PA-8)

A polymer was obtained in the same manner as in Example 2-1 except that the kind and the amount of the tetracarboxylic acid dianhydride and the amine compound used in the reaction were changed as shown in Table 1 below. The values in Table 1 indicate the ratio (molar%) of the tetracarboxylic acid dianhydride to the total amount of the tetracarboxylic acid dianhydride used in the reaction, and the total amount of the amine compounds used in the reaction (% By mol) of the total amount of the composition. Each of the polymer solutions obtained in the Examples was allowed to stand at 20 占 폚 for 3 days. As a result, none of the polymer solutions became gel, and storage stability was good.

The abbreviations of tetracarboxylic dianhydrides and amine compounds in Table 1 are as follows.

(Tetracarboxylic acid dianhydride)

AN-1; 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride

AN-2; Pyromellitic dianhydride

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

AN-4; Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-2 anhydrous

AN-5; Methyl-3a, 4,5,9b-tetrahydronaphtho [l, 2-c] furan-l, 3-dione

(Amine compound)

DA-6; Paraphenylenediamine

DA-7; 4,4'-diaminodiphenylmethane

DA-8; 4-aminophenyl-4'-aminobenzoate

DA-9; 2,4-diamino-N, N-diallylaniline

DA-10; 4,4'-diaminodiphenylamine

DA-11; 3,5-diaminobenzoic acid

DA-12; 3,5-diaminobenzoic acid cholestanyl

DA-13; 4- (tetradecanoxy) benzene-1,3-diamine

[Synthesis Example 1; Synthesis of Polymer (PI-1)

1.6 g of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride as a tetracarboxylic acid dianhydride (9.8 moles per 100 moles of the total amount of the amine compound used in the synthesis) and bicyclo [3.3.0] octane-2 , 18.36 g (86.2 molar equivalents) of 4,6,8-tetracarboxylic acid 2: 4, 6: 8-2 anhydride and 1.8 g (20 molar equivalents) of paraphenylenediamine as an amine compound, 4,4'- (10 molar parts) of 2,4-diamino-N, N-diallylaniline and 1.66 g (10 molar equivalents) of 4,4'-diaminodiphenylamine, ) Was dissolved in 198.3 g of NMP, and the reaction was carried out at room temperature for 6 hours. Subsequently, 266.7 g of NMP was added, and 16.12 g of pyridine and 20.81 g of acetic anhydride were added, followed by dehydration ring-closure reaction at 100 ° C for 5 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol and then dried at 40 캜 for 15 hours under reduced pressure to obtain a polyimide (PI-1) having an imidization rate of about 85%. The obtained polyimide (PI-1) was adjusted to 10 wt% in NMP. The viscosity of this solution was measured and found to be 844 mPa · s.

[Synthesis Example 2; Synthesis of polyorganosiloxane]

100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, And mixed at room temperature. 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted at 80 DEG C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out, washed with a 0.2 wt% aqueous ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane having an oxiranyl group As a viscous transparent liquid. As a result of ¹ H-NMR analysis of the polyorganosiloxane having the oxiranyl group, a peak based on the oxiranyl group was obtained near the chemical shift (?) = 3.2 ppm as the theoretical intensity, It was confirmed that the side reaction did not occur. The epoxy equivalent of the polyorganosiloxane having the oxiranyl group was measured and found to be 186 g / equivalent.

Subsequently, in a 100 mL three-necked flask, 9.3 g of the polyorganosiloxane having the oxirane group obtained above, 26 g of methyl isobutyl ketone, 3 g of 4-phenoxycinnamic acid and 0.10 g of UCAT 18X (trade name, manufactured by SANA PRO) And the reaction was carried out at 80 占 폚 for 12 hours with stirring. After completion of the reaction, the reaction mixture was poured into methanol to recover precipitates. The resulting precipitates were dissolved in ethyl acetate to prepare a solution. The solution was washed three times with water and then the solvent was distilled off to obtain an oxiranyl group and a cinnamic acid structure (S-1) as a white powder. The polyorganosiloxane (S-1) had a weight average molecular weight Mw of 3,500 in terms of polystyrene as measured by gel permeation chromatography.

&Lt; Preparation and evaluation of liquid crystal aligning agent >

[Example 3-1: FFS type liquid crystal display element]

(1) Preparation of liquid crystal aligning agent

100 parts by weight of the polymer (PA-1) obtained in Example 2-1 as a polymer was dissolved in a mixed solvent consisting of? -Butyrolactone (GBL), NMP and butyl cellosolve (BC) (GBL: NMP: BC = 40:20 (weight ratio)) to obtain a solution having a solid content concentration of 4.0% by weight. This solution was filtered with a filter having a pore diameter of 0.2 탆 to prepare a liquid crystal aligning agent (R-1).

(2) Evaluation of application property

The liquid crystal aligning agent (R-1) prepared above was coated on a glass substrate using a spinner, pre-baked on a hot plate at 80 DEG C for 1 minute, and then heated in an oven at 200 deg. (Post-baking) by a time heating to form a coating film having an average film thickness of 1,000 ANGSTROM. This coating film was observed under a microscope at a magnification of 100 times to examine whether the film thickness was uneven or pinholes were present. The evaluations were carried out in such a manner that when both of the film thickness unevenness and the pinholes were not observed, the coating performance was evaluated as &quot; good &quot;, and at least one of the film thickness unevenness and pinholes was clearly observed. In the present example, both of the film thickness irregularity and the pinhole were not observed, and the coating property was "good".

(3) Evaluation of rubbing resistance

The coating film obtained above was subjected to rubbing treatment seven times with a rubbing machine having a roll covered with a cotton cloth at a roll rotation speed of 1000 rpm, a stage moving speed of 20 cm / sec and a piercing length of 0.4 mm. The foreign substance (piece of coating film) caused by the rubbing cut on the substrate thus obtained was observed with an optical microscope, and the number of foreign substances in the area of 500 mu m x 500 mu m was measured. In the evaluation, rubbing resistance was evaluated as "good" when the number of foreign matters was 3 or less, "good" was evaluated as 4 or more and 7 or less, and rubbing resistance was evaluated as "poor" when the number of foreign matters was 8 or more. As a result, the rubbing resistance of this coating film was &quot; good &quot;.

(4) Fabrication of FFS type liquid crystal display device

A liquid crystal display element of the FFS type liquid crystal display element shown in Fig. 1 was produced. First, two systems of combination electrodes, in which a bottom electrode 12 having no pattern, a silicon nitride film 13 as an insulating layer, and a top electrode 14 patterned in the form of a comb are formed in this order, The glass substrate 11a having the transparent electrodes 12 and 14 and the opposing glass substrate 11b on which the electrodes are not formed are arranged in a pair so that the surface of the glass substrate 11a having the transparent electrodes 12 and 14 and the surface of the opposed glass substrate 11b (R-1) prepared in the above (1) was coated on one surface with a spinner to form a coating film. Subsequently, this coating film was pre-baked on a hot plate at 80 DEG C for 1 minute, and then heated (post baking) at 230 DEG C for 15 minutes in an oven where the inside of the tube was replaced with nitrogen to form a coating film having an average thickness of 1,000 ANGSTROM. A schematic plan view of the top electrode 14 is shown in Fig. 2 (a) is a plan view of the top electrode 14, and Fig. 2 (b) is an enlarged view of a portion C1 surrounded by a broken line in Fig. 2 (a). In this embodiment, the line width d1 of the electrode 14 is 4 mu m and the distance d2 between the electrodes is 6 mu m.

Then, each surface of the coated film formed on the glass substrate was rubbed with cotton. In Fig. 2 (b), the rubbing direction of the coating film formed on the glass substrate 11a is indicated by an arrow. These substrates were bonded to each other with a spacer having a diameter of 3.5 m interposed therebetween so that the rubbing directions of the substrates were antiparallel, and liquid crystal MLC-6221 (manufactured by Merck Ltd.) was injected. A polarizing plate was bonded to both sides of the substrate so that the polarizing directions of the two polarizing plates were orthogonal to each other, thereby producing a liquid crystal display device.

(5) Evaluation of alignment of liquid crystal

With respect to the FFS type liquid crystal display device manufactured as described above, the presence or absence of an abnormal domain in a change of light and dark when a voltage of 5 V was turned ON / OFF (applied / released) was observed with a microscope at a magnification of 50 times. In the evaluation, the case where the abnormal domain was not observed was designated as &quot; good liquid crystal alignability &quot;, and the case where the abnormal domain was observed was determined as &quot; poor &quot; In this liquid crystal display element, the liquid crystal alignment property was &quot; good &quot;.

(6) Evaluation of Voltage Conservation Rate

As a result of measuring the voltage holding ratio (VHR) at 167 milliseconds after the application of the voltage of 5 V at 23 deg. C for an application time of 60 microseconds and a span of 167 milliseconds to the FFS type liquid crystal display device manufactured as described above 99.1%. As a measuring apparatus, VHR-1 (manufactured by Toyotecnica Co., Ltd.) was used.

(7) Evaluation of heat resistance

With respect to the FFS type liquid crystal display device manufactured as described above, the voltage holding ratio was measured in the same manner as in (6), and the value was regarded as an initial VHR (VHR _BF ). Subsequently, the liquid crystal display element after the initial VHR measurement was left to stand in an oven at 100 캜 for 300 hours. Thereafter, the liquid crystal display element was allowed to stand at room temperature and gradually cooled to room temperature, and then the voltage holding ratio (VHR _AF ) was measured as described above. Further, the rate of change (? VHR (%)) of the voltage holding ratio before and after application of heat stress was determined by the following formula (EX-1).

? VHR = ((VHR _BF - VHR _AF ) / VHR _BF ) x 100 ... (EX-1)

The evaluation of the heat resistance was carried out under the conditions that the change rate? VHR was less than 4% in the heat resistance &quot; good &quot;, 4% to less than 5% in the good condition, and 5% or more in the heat resistance &quot; poor &quot;. As a result, the? VHR of the liquid crystal display element of this example was 2.1%, and the heat resistance was "good".

(8) Evaluation of relaxation speed of residual DC (evaluation of after-image characteristics)

With respect to the liquid crystal display device manufactured as described above, the relaxation rate of the residual DC was measured by a dielectric (dielectric) absorption method using a 6254C liquid crystal physical property evaluation apparatus manufactured by Toyo Technica Co., Ltd. The measurement was performed under an environment of 60 占 폚, a direct current voltage of 10 V was applied for 30 minutes, a discharge was performed for 1 second, and residual DC for 30 minutes was then measured. The relaxation rate of the residual DC was obtained by calculating the average residual DC relaxation rate from the residual DC value one minute after the time showing the maximum value and the maximum value of the residual DC. The residual DC damping resistance was evaluated as "good" when the damping rate of the residual DC was 4 mV / sec or more, the residual DC damping resistance was evaluated as "good" when the damping rate was less than 4 mV / sec and 2 mV / It was done as sex "bad". Further, the faster the relaxation rate of the residual DC is, the less the afterimage is generated and the better the afterimage characteristic is. The relaxation speed of the residual DC of the liquid crystal display element of the present embodiment was 4.2 mV / sec, and it was judged that the residual DC relaxation was &quot; good &quot;.

[Examples 3-2 to 3-6 and Comparative Example 1]

A liquid crystal aligning agent was prepared in the same manner as in Example 3-1 except that each of the polymers shown in Table 2 below was used as the polymer in Example 3-1, and an FFS type liquid crystal display device was produced, And evaluated. The evaluation results are shown in Table 2 below.

Liquid crystal aligning agent Coat Liquid crystal cell polymer
Application property
Rubbing
tolerance
Liquid crystal
Orientation

Voltage
Conservation rate
[%] Heat resistance Residual DC damping rate Kinds amount
(Parts by weight) ΔVHR
[%] Judgment Residual DC damping rate
[mV / sec] Judgment Example 3-1 PA-1 100 Good rainfall Good 99.1 2.1 rainfall 4.2 rainfall Example 3-2 PA-2 100 Good rainfall Good 99.3 2.2 rainfall 4.8 rainfall Example 3-3 PA-3 100 Good rainfall Good 99.1 2.3 rainfall 5.2 rainfall Example 3-4 PA-4 100 Good rainfall Good 99.0 2.9 rainfall 5.3 rainfall Example 3-5 PA-5 100 Good rainfall Good 98.4 3.9 rainfall 3.4 Good Examples 3-6 PA-6 100 Good rainfall Good 98.8 2.2 rainfall 4.1 rainfall Comparative Example 1 PI-1 100 Bad Good Good 98.0 4.1 Good 2.7 Good

As shown in Table 2, in Examples 3-1 to 3-6, favorable results were obtained for both the coating properties of the liquid crystal aligning agent and the rubbing resistance of the coating film. In addition, the results were "good" or "good" with respect to the liquid crystal alignability, the voltage holding ratio, the heat resistance, and the relaxation speed of residual DC. On the other hand, in Comparative Example 1, the coating property of the liquid crystal aligning agent was &quot; poor &quot; and the rubbing resistance of the coating film was also inferior to those of Examples. Further, in the liquid crystal display element of Comparative Example 1, the liquid crystal alignability, the voltage holding ratio, the heat resistance, and the relaxation speed of the residual DC were all lower than those in Examples.

[Example 3-7: TN type liquid crystal display element]

(1) Preparation of liquid crystal aligning agent

100 parts by weight of the polymer (PA-7) obtained in Example 2-7 as a polymer was dissolved in a mixed solvent of NMP and BC (NMP: BC = 50: 50 (weight ratio)) to prepare a solution having a solid concentration of 6.5% by weight. This solution was sufficiently stirred, and then filtered through a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (R-7).

(2) Evaluation of printability

The liquid crystal aligning agent (R-7) prepared in the above (1) was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of ITO film using a liquid crystal alignment film printing machine (manufactured by Nihon Shinsengaten Co., Ltd.) (Pre-baked) on a hot plate for 1 minute to remove the solvent, and then heated on a hot plate at 200 DEG C for 10 minutes (post baking) to form a coating film having an average film thickness of 600 ANGSTROM. This coating film was observed under a microscope with a magnification of 20 times to examine whether there was uneven printing or pinholes. In the evaluation, printing was evaluated as "good" in cases where both printing irregularities and pinholes were not observed, "printability" in the case where at least one of printing irregularities and pinholes were observed slightly, printing unevenness, In the case of a large amount of printing was determined as &quot; poor &quot; in printability. In the present embodiment, both the unevenness in printing and the pinhole were not observed, and the printability was &quot; good &quot;.

(3) Production of TN type liquid crystal cell

The liquid crystal aligning agent (R-7) prepared in the above (1) was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of ITO film using a liquid crystal alignment film printing machine (manufactured by Nihon Shinsengaten Co., Ltd.) (Pre-baked) on a hot plate for 1 minute to remove the solvent, and then heated on a hot plate at 200 DEG C for 10 minutes (post baking) to form a coating film having an average film thickness of 600 ANGSTROM. The coating film was subjected to a rubbing treatment with a rubbing machine having a roll covered with a rayon hot spring at a roll rotation speed of 500 rpm, a stage moving speed of 3 cm / sec, and a padded indentation length of 0.4 mm to give a liquid crystal alignment capability. Thereafter, ultrasonic cleaning was performed for 1 minute in ultrapure water, and then the substrate was dried in a 100 占 폚 clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. Further, the above operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film.

Next, on one of the pair of substrates, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied to the outer edge of the surface having the liquid crystal alignment film, and then the pair of substrates was laminated on the liquid crystal alignment film So that the surfaces are opposed to each other, and the adhesive is cured. Subsequently, a nematic liquid crystal (MLC-6221 manufactured by Merck Ltd.) was filled between a pair of substrates from the liquid crystal injection port, and then a liquid crystal injection port was sealed with an acrylic light-curable adhesive to produce a TN type liquid crystal cell.

(4) Evaluation of liquid crystal orientation

With respect to the liquid crystal cell prepared in (3) above, the presence or absence of an abnormal domain when a voltage of 5 V was turned on / off under Cross Nicol was observed at a magnification of 50 by a microscope. Evaluation was carried out in the same manner as in (5) of Example 3-1. As a result, in this liquid crystal display element, the liquid crystal alignment property was "good".

(5) Evaluation of Pretilt Angle Stability

For the liquid crystal cell prepared in (3) above, the angle of inclination of the liquid crystal molecules from the substrate surface was measured by the crystal rotation method using He-Ne laser light, and this value was defined as the initial pretilt angle? _IN . The crystal rotation method is disclosed in Non-Patent Document 1 (TJ Scheffer et al., J. Appl. Phys. Vol. 48, p. 1783 (1977)) and Non-Patent Document 2 (F. Nakano et al., JPN J. Appl. Phys. , p2013 (1980)).

Subsequently, an AC voltage of 5 V was applied to the liquid crystal display element after the initial pretilt angle? _IN was measured for 100 hours. Thereafter, the pretilt angle was again measured by the same method as described above, and this value was defined as a pretilt angle? _AF after voltage application. These measured values were substituted into the following formula (EX-2), and the amount of change (?? (°)) of the pretilt angle before and after voltage application was obtained.

_{Δθ = | θ AF -θ IN |} ... (EX-2)

The pretilt angle stability was evaluated as "good" when Δθ was less than 3%, the pretilt angle stability was evaluated as "good" when it was less than 3% and less than 4%, and "preliminary tilt angle stability" As a result, the change rate of the pretilt angle of this liquid crystal display element was 2.8%, and it was judged that the pretilt angle stability was "good".

(6) Evaluation of voltage holding ratio and heat resistance

The initial voltage holding ratio VHR _BF was measured in the same manner as in Example 3-1 (6), and in the same manner as in (7) of Example 3-1, the change rate of the voltage holding ratio before and after the application of heat stress To evaluate the heat resistance of the liquid crystal display element. As a result, the initial voltage holding ratio VHR _BF was 98.9%. Also, the? VHR was 2.9%, and the heat resistance was judged as "good".

[Example 3-8: VA type liquid crystal display device]

(1) Preparation of liquid crystal aligning agent

100 parts by weight of the polymer (PA-8) obtained in Example 2-8 as a polymer was added with NMP and BC to obtain a solution having a solid concentration of 6.5% by weight and a solvent mixture ratio of NMP: BC = 50: 50 (weight ratio). This solution was sufficiently stirred and then filtered through a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (R-8).

(2) Evaluation of printability

The printability was examined in the same manner as in item (2) of Example 3-7 by using the liquid crystal aligning agent (R-8) prepared in the above (1). As a result, both the unevenness in printing and the pinhole were not observed, Sex was "good".

(3) Production of VA type liquid crystal cell

The liquid crystal aligning agent (R-8) prepared above was coated on a transparent electrode surface of a glass substrate (1 mm thick) having a transparent electrode made of an ITO film using a liquid crystal alignment film printing machine (manufactured by Nihon Shinsengaten Co., Ltd.) (Post-baking) on a hot plate at 80 ° C for 1 minute and then heated (post baking) for 60 minutes on a hot plate at 200 ° C to form a coating film (liquid crystal alignment film) with an average film thickness of 800 Å. This operation was repeated to obtain a pair of glass substrates (two pieces) having a liquid crystal alignment film on the transparent conductive film.

Next, on one of the pair of substrates, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 mu m was applied to the outer edge of the surface having the liquid crystal alignment film, and then the liquid crystal alignment film surface was opposed to the pair of substrates They were superposed and squeezed, and the adhesive was cured. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled between a pair of substrates from the liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic photo-curable adhesive to produce a VA type liquid crystal cell.

(4) Evaluation of liquid crystal orientation, voltage holding ratio and heat resistance

The liquid crystal cell prepared in (3) above was evaluated for liquid crystal alignability in the same manner as in (4) of Example 3-7. As a result, the liquid crystal alignability of this liquid crystal display element was found to be &quot; good &quot;. The initial voltage holding ratio VHR _BF was measured in the same manner as in Example 3-1 (6), and in the same manner as in (7) of Example 3-1, the heat resistance (voltage holding ratio before and after applying heat stress Change rate) was evaluated. As a result, the initial voltage holding ratio VHR _BF was 99.2%. Also, the? VHR was 2.4% and the heat resistance was judged as "good".

[Example 3-9: retardation film]

(1) Preparation of liquid crystal aligning 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 2 were mixed in a mixed solvent of NMP and BC (NMP: BC = 50: 50 (weight ratio)) to obtain a solution having a solid content concentration of 3.5% by weight. This solution was filtered with a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (R-9).

(2) Production of retardation film

The liquid crystal aligning agent (R-9) prepared above was applied to one surface of a TAC film as a substrate using a bar coater and baked at 120 DEG C for 2 minutes in an oven to form a 100 nm thick coating film. Subsequently, polarizing ultraviolet rays including 313 nm bright line of 10 mJ / cm 2 were vertically irradiated onto the surface of the coating film from the substrate normal using an Hg-Xe lamp and a Glane Taylor prism. Subsequently, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck Ltd.) was filtered with a filter having a pore size of 0.2 mu m, and then the polymerizable liquid crystal was coated on the coated film by the bar coater to form a coating film of the polymerizable liquid crystal did. After baking for 1 minute in an oven adjusted to a temperature of 50 캜, 1,000 mJ / cm 2 of unpolarized ultraviolet light including a bright line of 365 nm was irradiated from a direction perpendicular to the coated film surface using an Hg-Xe lamp, The liquid crystal was cured to form a liquid crystal layer, whereby a retardation film was produced.

(3) Evaluation of liquid crystal orientation

The retardation film prepared in (2) above was evaluated for its liquid crystal alignability by observing the presence of an abnormal domain by naked eyes under a cross-nicol and a polarizing microscope (magnification 2.5 times). In the evaluation, when the orientation was good in the naked eye and the abnormal domain was not observed under a polarizing microscope, the case where the abnormal domain was observed with a polarizing microscope was evaluated as &quot; good &quot; , And the case where the abnormal domain was observed with a naked eye and a polarizing microscope was defined as &quot; poor &quot; in the liquid crystal alignment property. As a result, this retardation film was evaluated as &quot; good &quot; in liquid crystal alignment property.

(4) Adhesion

Using the retardation film prepared in (2) above, the adhesion of the coating film formed by the liquid crystal aligning agent to the substrate was evaluated. At first, a uniform gap spacer with a guide was used to cut through the surface of the liquid crystal layer side of the retardation film with a cutter knife, and 10 x 10 grid patterns were formed. The depth of each infeed was set so as to reach the middle of the thickness of the substrate from the surface of the liquid crystal layer. Subsequently, the cellophane tape was closely contacted to cover the entire surface of the grid pattern, and then the cellophane tape was peeled off. The notched portion of the grid pattern after peeling was observed by naked eye under Cross Nicol to evaluate the adhesion. In the evaluation, the case where no peeling was confirmed at the portion along the cut-off line and the intersection of the lattice pattern was evaluated as the adhesion "good" and the number of lattice peaks observed in the portion was less than 15% , The adhesion was evaluated as &quot; poor &quot;, and the case where the number of lattice planes in which the peeling was observed was 15% or more with respect to the total number of lattice patterns was evaluated as &quot; poor &quot;. As a result, the retardation film had good adhesion.

10: liquid crystal cell
11a and 11b: glass substrate
12: bottom electrode
13: Silicon nitride film
14: Top electrode
15a and 15b: a liquid crystal alignment film

Claims (11)

A liquid crystal aligning agent comprising a polymer (P) having a structure represented by the following formula (1)

(In the formula (1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, X ¹ and X ² are each independently a divalent organic group; the two "*"Quot;)&quot; The method according to claim 1,
Wherein the polymer (P) is at least one selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester. The method according to claim 1,
The polymer (P) is a polymer obtained by reacting at least one compound (a) selected from the group consisting of a tetracarboxylic acid dianhydride and a carbonic acid halide and an amine compound (b)
A liquid crystal aligning agent comprising the compound in which the amine compound (b) is represented by the following formula (b-1)

(In the formula (b-1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, X ³ and X ⁴ are each independently a divalent organic group, and n is 0 or 1) . The method of claim 3,
Wherein the compound (a) is a tetracarboxylic acid dianhydride,
As the tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b- (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 [ 3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'- dione), 5- (2,5- dioxotetrahydro- 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane 2: 3,5: 6-2 anhydride, 4,9- Tricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic acid 2 &lt; / RTI &gt; anhydride. The method of claim 3,
Wherein the compound represented by the above formula (b-1) is a compound represented by the following formula (b-1-1)

(In the formula (b-1-1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, X ⁵ and X ⁶ are each independently a single bond or a divalent organic group; n Is 0 or 1). A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 5. A liquid crystal display element comprising the liquid crystal alignment film according to claim 6. A retardation film comprising the liquid crystal alignment film according to claim 6. A method for manufacturing a liquid crystal display device, comprising the steps of: applying the liquid crystal aligning agent according to any one of claims 1 to 5 onto a substrate to form a coated film;
Irradiating the coating film with light,
Applying a polymerizable liquid crystal on the coating film after the light irradiation and curing the coating film. A tetracarboxylic acid dianhydride and a carbonic acid halide, and an amine compound containing a compound represented by the following formula (b-1):

(In the formula (b-1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, X ³ and X ⁴ are each independently a divalent organic group, and n is 0 or 1) . A compound represented by the following formula (b-1):

(In the formula (b-1), R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, X ³ and X ⁴ are each independently a divalent organic group, and n is 0 or 1) .

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